Pesticides In Vegetable Samples Research Articles

Coupled‐column liquid chromatography method with photochemically induced derivatization for the direct determination of benzoylureas in vegetables

The coupled-column (LC-LC) system, consisting of a first column packed with internal surface reversed phase (ISRP) (50 x 4.6mm ID) and a Chrompack C18 (100 x 4.6 mm ID) as second column, allowed the simultaneous determination of five benzoylurea insecticides in dichloromethane (CH2Cl2) extracts of vegetable samples without any clean-up step. This system was combined with a photochemically induced fluorescence (PIF) post-column derivatization in order to provide strongly fluorescent photoproducts from the non-fluorescent benzoylureas. Limits of detection ranged from 0.21 to 0.98 microg L(-1) of pesticide (equivalent to 0.14-0.65 microg kg(-1) in vegetable samples) and limits of determination ranged from 4.0 to 10.0 microg L(-1) (equivalent to 2.7-6.7 microg kg(-1)). Linearity of the method was established between 2 and 1800 microg L(-1), depending upon the compound. Validation of the total method was performed by randomly analyzing recoveries of four vegetable samples (aubergine, cucumber, green bean, and tomato) spiked at two levels of concentration (10.0 and 33.3 microg kg(-1)). The combination of the LC-LC system with PIF detection provides a sensitive, selective, and rapid method for the determination of pesticides in vegetable samples at levels lower than the maximum residue levels (MRLs) established for these compounds by Spanish legislation.

One-year routine application of a new method based on liquid chromatography–tandem mass spectrometry to the analysis of 16 multiclass pesticides in vegetable samples

An analytical procedure has been developed for determining a group of 16 multiclass pesticides most commonly used in crop protection. The extraction step is performed with a mixture of ethyl acetate and sodium sulphate, in the presence of 6.5 M NaOH. After evaporation, a final extract containing 1 mg sample/ml extract, is obtained in methanol. Analysis of the methanolic extract, without additional clean-up steps, is performed by liquid chromatography–electrospray ionisation-tandem mass spectrometry combining positive and negative ion mode. The analytical performance of the method has been validated for three different matrices: pepper, lettuce and aubergine. Mean recoveries obtained were between 70 and 110% in most of the cases with a precision of <28%. Linearity of response over 2 orders of magnitude was demonstrated ( r ≥ 0.99) with limits of detection ≤0.01 mg/kg in all the cases. No significant matrix effects were observed with the exception of triflumizol that presented a drastic decrease in response as a consequence of an ion formation suppression effect in the presence of pepper matrix. The method has been applied to the analysis of 560 vegetable samples, as a part of the monitoring programme of the Association of Producers and Exporters of Fruits and Vegetables of Almerı́a (COEXPHAL). The unambiguous confirmation of the positive findings by comparison of the product ion mass spectra of the peaks in samples and standards, demonstrated the applicability of the method in routine analysis.

Assessment of matrix effects in gas chromatography electron capture pesticide-residue analysis

The analysis of pesticide residues in vegetable samples leads in most cases to different results when solvent or matrix-matched calibration is used for quantitation. Matrix effects in GC-ECD analysis of pesticides in vegetable samples have been assessed by comparing calibration curves prepared in solvent and in blank matrix extracts. Eight different vegetables have been considered among the most common commodities in routine pesticide residue laboratories.

Multicomponent determination of pesticides in vegetables by gas chromatography with mass spectrometric detection and multivariate calibration

Three multivariate calibration methods, partial least squares (PLS-1 and PLS-2) and principal component regression (PCR), were applied for the first time to the simultaneous determination of a mixture of six pesticides in vegetables samples by gas chromatography with mass spectrometric detection (GC-MS). PLS-1 method showed better prediction ability than PLS-2 and PCR methods. The GC-MS chromatograms obtained of vegetable samples spiked with the target pesticides were used to build the calibration matrix. The PLS-1 models were evaluated by predicting the concentrations of independent test samples. Also, the proposed models were successfully applied for the determination of these pesticides in vegetable samples after an extraction step with dichloromethane. By using the first derivative signals in PLS-1 models, simultaneous determination of the compounds was not improved.

Multi-residue method for determination of pesticides in vegetable samples by GC-MS-MS

A method for detection, quantification, and confirmation of 30 multi-class pesticide residues in fresh vegetables by gas chromatography-tandem mass spectrometry (GC-MS-MS) has been developed. The optimum ionization mode, electron impact (El-MS-MS) or chemical ionization (Cl-MS-MS), was used for different groups of pesticides in a single run. The residues were previously extracted from vegetables with dichloromethane. A 10μL aliquot of the extract can be injected in routine analysis without a clean up step when the glass liner is used with Carbofrit. Recovery efficiencies ranged 70–119% at the two different fortification levels studied and the relative standard deviation was <16.9% for all compounds. The limit of detection of each compound was 30 ng Kg−1−6 μg Kg−1. The proposed method was applied to the routine analysis of pesticides in vegetables grown in an important greenhouses area located in El Ejido (Almeria, Spain).

Matrix-effects of vegetable commodities in electron-capture detection applied to pesticide multiresidue analysis

The influence of the sample matrix in the analysis of pesticides in vegetable samples has been studied in order to determine if the matrix content introduces a systematic or proportional (or both) bias in the measurements. Experiments have been carried out during a 4-month period, in which calibration curves, prepared in solvent and in vegetable matrix, were prepared and analysed. A statistical treatment has been applied in order to: (i) check the stability of such calibrations during the period studied; (ii) compare both solvent and matrix-matched calibrations; and (iii) obtain a correction function. Applying the correction function to the results obtained with a solvent calibration it is possible to make a prediction of the values obtained applying a matrix-matched calibration. The performance of the correction function has been validated with recovery data. Finally the uncertainty derived from the use of each calibration plot and the correction function has been calculated.

Detection of organophosphate and carbamate pesticides in vegetable samples by a photothermal biosensor

Previously developed photothermal biosensor was optimised by determining the most suitable enzyme substrate (acetylthiocholine iodide) and the optimal carrier buffer (0.05 M phosphate buffer, pH 8.0). Excitation laser operating at 488 nm and 120 mW power provided the highest biosensor sensitivity. The biosensor was tested for detection of toxic organophosphate and carbamate compounds present in samples of salad, iceberg lettuce, and onion. Sufficient sensitivities to different pesticides (carbofuran, propamocarb, oxydemeton–methyl and parathion–ethyl) were achieved without time-consuming sample preparation procedures. The results show good agreement with the concentrations of pesticides determined with standard GC-MS detection method. The developed photothermal biosensor offers new low cost means to detect low concentrations of pesticides in vegetable samples with high throughput and little or no sample pretreatment.

Gas chromatographic determination of pesticides in vegetable samples by sequential positive and negative chemical ionization and tandem mass spectrometric fragmentation using an ion trap analyser.

A selective and sensitive chromatographic method is described for the determination of nine organochlorine and organophosphorus pesticides in vegetable samples by gas chromatography-mass spectrometry. The proposed method combines the use of positive and negative chemical ionisation and tandem mass spectrometric fragmentation, resulting in a significant increase in selectivity and allowing the simultaneous confirmation and quantification of trace levels of pesticides in complex vegetable matrices. Parameters relative to ionisation and fragmentation processes were optimised to obtain maximum sensitivity. Repeatability and reproducibility studies yielded relative standard deviations lower than 25% in all cases. Identification criteria, such as retention time and relative abundance of characteristic product ions, were also evaluated in order to guarantee the correct identification of the target compounds. The method was applied to real vegetable samples to demonstrate its use in routine analysis.

Detection of carbamate pesticides in vegetable samples using cholinesterase‐based biosensors

AbstractBiosensors for determination of carbamates in vegetables based on five different cholinesterase as biorecognition elements and a screen‐printed electrode system as an amperometric transducer were developed. Measurements were simply performed by dropping solutions (either sample or substrate) directly on the biosensor. The response of biosensors to selected carbamates (aldicarb, carbaryl, carbofuran, methomyl and propoxur) was characterized. The performance was evaluated on extracts of potatoes and carrots, the results from the AChE biosensor and a standard HPLC procedure were compared. Finally, the biosensor was used for the direct analysis of vegetable juices without any pretreatment steps. In this case, 10 μg/L levels of added carbofuran and propoxur were reliably identified. The whole procedure takes less than 20 min including 10 min incubation with samples. The concentrations of carbamates determined with biosensor agreed well for carbofuran. Lower response was observed for propoxur.