Determination of diflubenzuron and chlorbenzuron in fruits by combining acetonitrile‐based extraction with dispersive liquid–liquid microextraction followed by high‐performance liquid chromatography

In this study, a simple and low‐organic‐solvent‐consuming method combining an acetonitrile‐partitioning extraction procedure followed by “quick, easy, cheap, effective, rugged and safe” cleanup with ionic‐liquid‐based dispersive liquid–liquid microextraction and high‐performance liquid chromatography with diode array detection was developed for the determination of diflubenzuron and chlorbenzuron in grapes and pears. Ionic‐liquid‐based dispersive liquid–liquid microextraction was performed using the ionic liquid 1‐hexyl‐3‐methylimidazolium hexafluorophosphate as the extractive solvent and acetonitrile extract as the dispersive solvent. The main factors influencing the efficiency of the dispersive liquid–liquid microextraction were evaluated, including the extractive solvent type and volume and the dispersive solvent volume. The validation parameters indicated the suitability of the method for routine analyses of benzoylurea insecticides in a large number of samples. The relative recoveries at three spiked levels ranged between 98.6 and 109.3% with relative standard deviations of less than 5.2%. The limit of detection was 0.005 mg/kg for the two insecticides. The proposed method was successfully used for the rapid determination of diflubenzuron and chlorbenzuron residues in real fruit samples.     

中空纤维膜液相微萃取-GC-MS测定水果和蔬菜中三唑类杀菌剂残留量

研究了一种直接快速测定水果和蔬菜等固体样品中5种三唑类杀菌剂残留量的新方法,以气相色谱-质谱联用技术为基础,利用中空纤维膜液相微萃取提取固体样品中目标物。通过实验确定最佳萃取条件为：萃取剂为环己烷,固体样品与水的比例为1：3（总质量为10g）,超声震荡5min后以500r/min的搅拌速率在40℃下萃取20min。萃取后取1μL有机溶剂直接进样进行气相色谱质谱分离检测。在此条件下,水果和蔬菜中的三唑酮和多效唑的线性范围为0.5—25mg/kg,腈菌唑、烯唑醇和丙环唑的线性范围为1—25mg/kg;5种目标物的检出限均低于0.210mg/kg;相对标准偏差在4.7%—8.1%之间。该方法可以用于水果和蔬菜等固体样品中三唑类杀菌剂的快速测定。     

Design of a compressed air modulator to be used in comprehensive multidimensional gas chromatography and its application in the determination of pesticide residues in grapes

In this study, a new modulator that is simple, robust and presents low operation costs, was developed. This modulator uses compressed air to cool two small portions in the first centimeters of the second chromatographic column of a comprehensive multidimensional gas chromatography (GC × GC) system. The results show a variation in the peak area less than 3 and 5% to alkanes and pesticides, respectively. The standard deviations for the retention times in the first and second dimension are around 0.05 min and 0.05 s for all the compounds. The system was optimized with n-alkanes. The GC × GC system proposed was applied in the determination of pyrethroid pesticides (bifenthrin, cypermethrin, deltamethrin, fenvalerate, esfenvalerate, cis- and trans-permethrin) in grape samples. Samples were extracted by the mini-Luke modified method and pesticides were quantified by comprehensive multidimensional gas chromatography with micro electron-capture detection (μECD). The values of method limit of quantification (LOQ) were 0.01–0.02 mg kg⁻¹ for all studied pyrethroid and the values of recovery were between 94.3 and 115.2%, with good precision (RSD < 18.4%), demonstrating that the performance of the total method consisting of a modified Luke extraction method and determination by GC × GC-μECD are satisfactory. This study also showed that the system using a modulator with a double jet of compressed air has the potential for application in the analysis of a wider range of pesticide residues in other commodities since it provides low values of LOQ with acceptable accuracy and precision.     

Impact of sonolytic ozonation (O3/US) on degradation of pesticide residues in fresh vegetables and fruits: Case study of Faisalabad,Pakistan

High pesticide residues in fresh produce is a serious food safety issue. This study was aimed at assessing the pesticides residues in some important vegetables and fruits marketed in Faisalabad, Pakistan and the impact of sonolytic ozonation (O₃/US) treatment in removing these contaminants. From a short grower’s survey, five registered and mostly used pesticides (acetamiprid, carbendazim, imidacloprid, thiacloprid and thiamethoxam) were identified. A time optimization trial of O₃/US application (05, 10 and 15 min) on okra, showed that 10 min treatment significantly reduced three identified chemicals (thiamethoxam 100 %, imidacloprid and thiacloprid 97.17 %), without any adverse effect on its quality. In follow up trial, five fresh vegetables (cauliflower, chillies, cucumber, spinach and tomato) three fresh fruits (grapes, guava and peach) collected from three markets of Faisalabad, were pooled together to have uniform samples. Vegetables and fruits were treated with O₃/US for 10 and 6 min, respectively, along with control (simple tap wash) for determining the impacts on pesticides degradation. Samples were processed for extraction, clean up and analysis using HPLC-UV–Vis in isocratic mode. The data revealed the presence of five mentioned chemicals, with an accumulative mean residue of 9.006 and 1.921 µg/g in tested vegetables and fruits, respectively. After subjecting to O₃/US, the accumulative chemical residues were reduced to 3.214 µg/g (64.313 %) and 1.064 (44.6 %) in treated vegetables and fruits respectively. Irrespective of fresh produce, the mean residues of thiamethoxam, imidachloprid, acetamiprid and thiachloprid and carbendazim were reduced by 99.3 %, 52.6 %, 65.2 %, 87.3 % and 72% respectively. It was concluded that sonolytic ozonation treatment was effective in significant reduction of pesticide residues from vegetables and fruits and thus can be employed as a good food safety practice at culinary level to reduce the associated health hazardous risks.     

Evaluation of sample processing and sub-sampling performance

A methodology for the estimation of sample processing and sub-sampling performance based on the comparison of the global method experimental dispersion of results with the uncertainty estimated from developed models for the subsequent analytical steps is presented. This approach is a valuable alternative to the evaluation of adequate experimental information using a classical ANOVA, since the significance of the sample processing and sub-sampling is evaluated with a higher number of degrees of freedom for the same number of experimental assays, due to the high number of degrees of freedom associated with the uncertainty estimated for the subsequent analytical steps from the combination of the involved sources of uncertainty.Considering the construction of a model to describe the performance of the analytical steps following sample processing and sub-sampling over a broad concentration range, the experimental assays involved at the evaluation of the sample processing and sub-sampling can be performed at any concentration meeting the previously validated range and several months after the development of that model once its adequacy has been proven over time.This approach, which also allows the construction of a detailed performance model for the global analytical method over a broad concentration range, was applied to the determination of pesticide residues in apples by gas-chromatography with electron capture detector.Considering that no information was available regarding the samples heterogeneity, sub-sampling performance was evaluated considering a sample representing the worst expectable homogeneity. This was accomplished by spiking just one out of the 10 halves of apples processed in each sample.The developed model for the performance of the analytical method was successfully and easily applied to routine analysis through an automated link between the information generated by the chromatograph software with a file containing the model.     

Automatic determination of phylloquinone in vegetables and fruits using on-line photochemical reduction and fluorescence detection via solid phase extraction and flow injection

A very simple, rapid and highly sensitive flow injection fluorimetric method was developed for the determination of phylloquinone. The assay was based on the on-line reduction of phylloquinone in dodecylsulfate micelles after irradiation with UV light. The micellar medium enhanced the fluorescence and stability of the reduced phylloquinone. Under optimum experimental conditions, the range of application of the technique was between 0.09 and 45.0 μg mL⁻¹ and the detection limit was 0.05 μg mL⁻¹. The sample throughput was 90 injections per hour. The reliability of the method for the routine analysis of phylloquinone in vegetables and fruits is demonstrated. Extractions were made with hexane, and an automated solid phase extraction system was used to purify the sample extracts prior to injection into the flow injection manifold.     

Solid-phase microextraction (SPME) for the determination of pyrethroids in cucumber and watermelon using liquid chromatography combined with post-column photochemically induced fluorimetry derivatization and fluorescence detection

A sensitive and efficient solid-phase microextraction (SPME) method for the determination of seven pyrethroid insecticides including fenpropathrin, λ-cyhalothrin, deltamethrin, fenvalerate, permethrin, τ-fluvalinate and bifenthrin in cucumber and watermelon samples using high performance liquid chromatography combined with post-column photochemically induced fluorimetry derivatization and fluorescence detection (SPME-HPLC-PIF-FD) was developed and validated. The optimum SPME conditions were used for the extraction of samples of both matrices (extraction time 30 min, stirring rate 1100 rpm, extraction temperature 65 °C, sample pH 3, soaking time 7 min, desorption time 5 min, ACN content 25%, desorption and soaking solvent was the mobile phase and in static mode). The method was validated in terms of limits of detection (LODs) and the limits of quantification (LOQs) in both IUPAC and EURACHEM criteria. LODs and LOQs were achieved in values lower than the maximum residue levels (MRLs) established in the Spanish regulations for all pesticides in this study (MRLs range between 0.01 and 0.1 mg kg⁻¹ for all pyrethroid insecticides in both matrices). LOQs according to the second criterion were between 1.5 and 5 μg kg⁻¹ for cucumber; and between 1.3 and 5 μg kg⁻¹ for watermelon samples. Precision and recovery studies were evaluated at two concentration levels for each matrix. Good precision was obtained and relative standard deviation values were less than 10% in all cases. Recovery values were calculated at 0.05 and 0.5 mg kg⁻¹ levels (n = 6) and they ranged between 93% and 108% for cucumber and between 91% and 110% for watermelon samples. Applicability of the method to pyrethroids in cucumber and watermelon of commercial samples was demonstrated.     

Outer product analysis of electronic nose and visible spectra: application to the measurement of peach fruit characteristics

Visual aspect and aroma are among the most important features of fruit that determine consumer preferences. Electronic nose and spectroscopic techniques have shown positive results in evaluating some basic analytical parameters of fruit and global features such as the cultivar.In this paper, we illustrate and discuss a study aimed at evaluating the improvement derived by the fusion of visible spectra and electronic nose data. These experiments were performed on a population of yellow peaches belonging to two cultivars. Each sample was measured by visible optical spectroscopy and by electronic nose. In addition, a number of reference parameters were also measured by conventional destructive methodologies.Collected data were analysed individually and then fused together in order to classify the two cultivars and to estimate the reference parameters. Data fusion was performed building the outer product matrix for each measurement. The set of matrices was then successively unfolded and analysed by conventional chemometrics tools.Results were improved using outer products, for instance in classification average percentage errors of 25, 10, and 7 for electronic nose, spectra, and outer product, respectively was achieved. Regression analysis provides the evidence of a substantial orthogonal appearance of the datasets, which offer former hidden information on fruit classification.     

Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in combination with gas and liquid chromatography and tandem mass spectrometric detection

The Quick Easy Cheap Effective Rugged and Safe multiresidue method (QuEChERS) has been validated for the extraction of 80 pesticides belonging to various chemical classes from various types of representative commodities with low lipid contents. A mixture of 38 pesticides amenable to gas chromatography (GC) were quantitatively recovered from spiked lemon, raisins, wheat flour and cucumber, and determined using gas chromatography-tandem mass spectrometry (GC-MS/MS). An additional mixture of 42 pesticides were recovered from oranges, red wine, red grapes, raisins and wheat flour, using liquid chromatography-tandem mass spectrometry (LC-MS/MS) for determination. The pesticides chosen for this study included many of the most frequently detected ones and/or those that are most often found to violate the maximum residue limit (MRL) in food samples, some compounds that have only recently been introduced, as well as a few other miscellaneous compounds. The method employed involved initial extraction in a water/acetonitrile system, an extraction/partitioning step after the addition of salt, and a cleanup step utilizing dispersive solid-phase extraction (D-SPE); this combination ensured that it was a rapid, simple and cost-effective procedure. The spiking levels for the recovery experiments were 0.005, 0.01, 0.02 and 0.2 mg kg(-1) for GC-MS/MS analyses, and 0.01 and 0.1 mg kg(-1) for LC-MS/MS analyses. Adequate pesticide quantification and identity confirmation were attained, even at the lowest concentration levels, considering the high signal-to-noise ratios, the very good accuracies and precisions, as well as the good matches between the observed ion ratios. Mean recoveries mostly ranged between 70 and 110% (98% on average), and relative standard deviations (RSD) were generally below 10% (4.3% on average). The use of analyte protectants during GC analysis was demonstrated to provide a good alternative to the use of matrix-matched standards to minimize matrix-effect-related errors. Based on these results, the methodology has been proven to be highly efficient and robust and thus suitable for monitoring the MRL compliance of a wide range of commodity/pesticide combinations.     

Monitoring multi-class pesticide residues in fresh fruits and vegetables by liquid chromatography with tandem mass spectrometry

A new analytical method was developed using liquid chromatography with tandem mass spectrometry for the routine analysis of 31 multi-class pesticide residues and applied to approximately 50 fresh fruit and vegetable samples (green bean, cucumber, pepper, tomato, eggplant, watermelon, melon and zucchini). Extraction of the pesticides with ethyl acetate was carried out. The optimal ionisation conditions were selected for each pesticide in the same run. The procedure was validated and the values of some merit figures, such as recovery, precision, linear range, detection limit and quantification limit for each pesticide were calculated together with its calculated expanded uncertainty (U). The average recoveries in cucumber obtained for each pesticide ranged between 74 and 105% at two different fortification levels (n = 10 each) that ranged between 9 and 250 ng g(-1) (depending on the pesticide). The uncertainty associated to the analytical method was lower than 23% for all compounds tested. The calculated limits of detection and quantitation were typically <1 ng g(-1) that were much lower than the maximum residue levels established by European legislation.