Comparative study of the main top-down approaches for the estimation of measurement uncertainty in multiresidue analysis of pesticides in fruits and vegetables.

Practical "top-down" approaches appear to be the most suitable for the evaluation of measurement uncertainty in pesticide residue testing laboratories, where analytical procedures are routinely applied to a large number of pesticide/food combinations. The opposite approach, "bottom-up" evaluation of measurement uncertainty, leads to great difficulties in evaluating all of the pesticides in a consistent way. Among the top-down approaches, there are two main ways in which measurement uncertainty can be estimated: One is based on default values, which are based on previous extensive interlaboratory experience and the proven accuracy of the laboratory; these include the Horwitz equation or the fit-for-purpose relative standard deviation (FFP-RSD). The other is based on experimental data from the quality control work of the laboratory: within-laboratory reproducibility, interlaboratory validation, or a combination of results obtained in proficiency tests. The principal existing guidelines from various bodies (Eurachem, Nordtest, and Eurolab) all propose different approaches for calculating measurement uncertainty. In this paper, the main top-down approaches are evaluated and compared using the data from the European Proficiency Test Database for Fruits and Vegetables and the Multiresidue Method validation databases obtained from the National Reference and Official Laboratories in Europe. The main conclusion of the comparative study is that a default expanded measurement uncertainty value of 50% could satisfy all of the requirements for facilitating and harmonizing, worldwide, the intercomparability of the pesticide residue confidence results between laboratories.

Analysis of pesticide residues in fruit and vegetables with ethyl acetate extraction using gas and liquid chromatography with tandem mass spectrometric detection.

A multiresidue method based on extraction with ethyl acetate has been used at the Swedish National Food Administration since 1989 to monitor pesticide residues in fruit and vegetables. The method has been continuously adjusted, resulting in simple and quick analyses of pesticide residues. To recover basic pesticides, the addition of an alkali is necessary. The addition of sodium hydrogen carbonate has been shown to recover all pesticides effectively without any degradation. The liquid chromatography (LC) with tandem mass spectrometry (MS/MS) technique has made it possible to analyse more polar pesticides and to replace many single methods. The latest development in the multiresidue method, comprising the use of gas chromatography (GC) with MS/MS, has further improved the analysis by replacing the conventional GC detectors. The need for cleanup has been reduced or eliminated entirely. Consequently, the method has been simplified in a way that makes it possible to recover all included analytes in many different matrices in one single extraction and to detect them either with GC-MS/MS or with LC-MS/MS.

A new multi-residue method for analysis of pesticide residues in fruit and vegetables using liquid chromatography with tandem mass spectrometric detection.

A new multi-residue method for determination of pesticide residues in a wide variety of fruit and vegetables, using the National Food Administration (NFA) ethyl acetate extraction and determination by means of LC-MS/MS, is presented. The method includes pesticides normally detected by LC-UV or LC-fluorescence such as benzimidazoles, carbamates, N-methylcarbamates and organophosphorus compounds with an oxidisable sulphide group as well. After extraction with ethyl acetate, the extract is concentrated and an aliquot of the extract is evaporated to dryness and redissolved in methanol before injection on LC-MS/MS. The method has been validated for 57 different pesticides and metabolites. Representative species from different commodity groups were chosen as matrices in order to study the influence from different matrices on recoveries. The fortification levels studied were 0.01-0.5 mg kg(-1). Matrix effects were tested for all matrices by means of standard addition to blank extracts. The matrix effect, expressed as signal in solvent compared to signal in matrix, was in general found to be small. The obtained recoveries are, with a few exceptions, in the range 70-100%. The proposed method is quick and straightforward and no additional clean-up steps are needed. The method can be used for the analysis of all 57 pesticides in one single determination step at 0.01 mg kg(-1).

Pressurised fluid extraction (PFE) as an alternative general method for the determination of pesticide residues in rape seed.

A pressurised fluid extraction (PFE) multi-method has been developed for the determination of pesticide residues in rape seed. The method was validated for 25 different pesticides and metabolites. The reliability and efficiency of PFE for extracting pesticide residues from rape seed was investigated. The traditional extraction solvent, hexane saturated with acetonitrile, was used at elevated temperature and pressure. With increased temperature, the extraction kinetics were improved but at the same time more co-extractives were obtained in the form of lipids. When 1 g of rape seed was extracted at temperatures from 60 degrees C to 150 degrees C, the lipid content extracted was found to be as high as 17-26%. An additional clean-up step was therefore required and lipid co-extractives were effectively removed by gel permeation chromatography. The interpretation of the chromatograms and the quantification of the results were satisfactorily improved by the removal of interfering lipids. The developed method was used to extract vinclozolin and iprodione from incurred samples, resulting in a concentration in accordance with the results using conventional liquid-liquid extraction (LLE) between hexane and acetonitrile and also supercritical fluid extraction (SFE) using carbon dioxide. The results of the present study suggest that PEE is a good alternative extraction technique for the determination of pesticide residues in oil seed. Despite the necessity for a lipid-removal clean-up step, the PFE technique facilitated the extraction process by faster extractions and the possibility of automated analysis.