Abstract

This paper investigated the possibility of leaving out the traditional clean-up step in the QuEChERS procedure and analysing non-cleaned extracts from fruit, vegetables and cereals with a combination of gas chromatography-tandem mass spectrometry (GC-MS/MS), back-flush technology and large-volume injection. By using calibration standards in cucumber matrix, recovery and precision were calculated in lettuce, orange and wheat for 109 pesticides at 0.01 and 0.1 mg kg−1 in two sets of samples: one with and one without clean-up. For both spiking levels, 80–82% of the pesticides in the non-cleaned extracts and 80–84% of the pesticides in the cleaned extracts were within the acceptable recovery range of 70–120%. Precision data for both levels showed that 95% of the pesticides in the non-cleaned extracts and 93–95% of the pesticides in the cleaned extracts had RSDs below 20%. Recovery and precision data were determined using a two tailed t-test (p = 0.05). By using calibration standards in the respective matrix, we studied if the non-cleaned calibration standards gave an extra matrix effect compared with the cleaned standards by using the slope from calibration graphs and plotting the calculated extra matrix effect minus 100 for each compound. The results showed that for 79% of the pesticides, the extra matrix effect minus 100 was within the acceptable range of −20% to 20%. Five European Union proficiency tests on rye, mandarin, rice, pear and barley, respectively, from 2010 to 2012 were reanalysed omitting the clean-up step and showed satisfactory results. At least 70 injections of non-cleaned extracts were made without detecting any increased need for maintenance during the experimental period. Analysing non-cleaned QuEChERS extracts of lettuce, orange and wheat are possible under the conditions described in this paper because recovery, precision and specificity showed satisfactory results compared with samples subjected to traditional dispersive clean-up.

Abstract

The gas chromatography mass spectrometry (GC-MS) deconvolution reporting software (DRS) from Agilent Technologies has been evaluated for its ability as a screening tool to detect a large number ofpesticides in incurred and fortified samples extracted with acetone/dichloromethane/light petroleum(Mini-Luke method). The detection of pesticides is based on fixed retention times using retention timelocking (RTL) and full scan mass spectral comparison with a partly customer built automated massspectral deconvolution and identification system (AMDIS) database. The GC-MS was equipped with a programmable temperature vaporising (PTV) injector system which enables more sample to be injected.In a blind study of 52 real samples a total number of 158 incurred pesticides were found. In addition to the 85 pesticides found by manual interpretation of GC-NPD/ECD chromatograms, the DRS revealed 73 morepesticides (+46%). The DRS system also shows its potential to discover pesticides which are normally notsearched for (EPN in long beans from Thailand). A spiking experiment was performed to blank matricesof apple, orange and lettuce with 177 different pesticides at concentration levels 0.02 and 0.1 mg/kg. The samples were analysed on GC-MS full scan and the AMDIS match factor was used as a mass spectralquality criterion. The threshold level of the AMDIS match factor was set at 20 to eliminate most of thefalse positives. AMDIS match factors from 20 up to 69 are regarded only as indication of a positive hit andmust be followed by manual interpretation. Pesticides giving AMDIS match factors at ≥70 are regarded as identified. To simplify and decrease the large amount of data generated at each concentration level,the AMDIS match factors ≥20 was averaged (mean AMF) for each pesticide including the commodities and their replicates. Among 177 different pesticides spiked at 0.02 and 0.1 mg/kg level, the percentage of mean AMF values ≥70 were 23% and 80%, respectively. For 531 individual detections of pesticides (177pesticides×3 replicates) giving AMDIS match factor 20 in apple, orange and lettuce, the detection rates at 0.02 mg/kg were 71%, 63% and 72%, respectively. For the 0.1 mg/kg level the detection rates were 89%,85% and 89%, respectively. In real samples some manual interpretation must be performed in addition. However, screening by GC-MS/DRS is about 5-10 times faster compared to screening with GC-NPD/ECDbecause the time used for manual interpretation is much shorter and there is no need for re-injection on GC-MS for the identification of suspect peaks found on GC-NPD/ECD.

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Abstract

Although the sulfonylurea herbicides have been used for many years worldwide, few field studies have been performed and little is known about the occurrence, fate and transport of sulfonylureas in the field. This report presents results from the first controlled field and laboratory-studies on the fate of sulfonylurea herbicides in Norway and a method for sample preparation and LC-MS/MS analysis of sulfonylurea herbicides in water samples is also presented.