Pesticide residues in fresh and processed edible mushrooms from Czech markets.

The occurrence of pesticide residues, their metabolites and degradation products in 49 edible mushrooms (fresh, dried, canned and frozen) was investigated. Using QuEChERS extraction, followed by liquid and gas chromatography coupled with tandem mass spectrometry, the samples collected from Czech markets were tested for 427 analytes. A total of 21 pesticide residues, their metabolites and pesticide synergists were found in quantifiable concentrations. The most frequently detected pesticide residues included prochloraz and its metabolites, metrafenone and carbendazim. Two mushroom samples were found to be in violation of the maximum residue level. In addition, the fate of 13 pesticides during the processing of fresh mushrooms was investigated. The processing factors calculated from the data ranged from 6.0 to 12.3 for drying and from 0.3 to 1.3 for deep-freezing. The results showed that most of the pesticide residues tested were stable under the conditions of mushroom processing.

Assessment of pesticide residues in citrus fruit on the Czech market.

When assessing citrus fruit quality, besides natural health-promoting compounds, attention also has to be paid to residues of chemicals used to protect fruit against various pests. A set of 49 samples of different types of citrus fruits collected at the Czech market were analysed for 460 pesticide residues using LC-MS/MS and GC-MS/MS methods. While no residues were detected in citruses from organic farming, altogether 38 various pesticide residues were detected in conventional production samples. Buprofezin in two grapefruit samples and fenbutatin oxide in one tangerine sample exceeded maximum residue limits (MRLs). Depending on the pesticide group, 10-70% of residues were found in pulp, this means that their processing factors calculated for peeling are in the range of 0.02-0.76. In the case of a beverage prepared from unpeeled lemon slices, the transfer of residues from contaminated fruit into infusion was, depending on the beverage type and processing conditions, in the range of 8-61%.

Pesticide Residues and Their Metabolites in Grapes and Wines from Conventional and Organic Farming System.

In this study, the occurrence of pesticide residues and their metabolites in grapes and wines was investigated. A targeted analysis of 406 pesticide residues in 49 wine and grape samples from organic and conventional production were performed using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) extraction method, followed by ultra-high-performance liquid chromatography coupled with tandem mass spectrometry. Multiple residues (>4 residues/sample) were detected in 22 tested samples. The most commonly detected residues were fungicides (e.g., boscalid) and insecticides (e.g., methoxyfenozide). An ultra-high-performance liquid chromatography-high resolution mass spectrometry method (UHPLC-(HR)MS) was used for screening of pesticide metabolites. We also provide a method and database for detecting pesticide metabolites (extending our previously published database to 49 metabolites originating from 25 pesticides). An introduced strategy of targeted screening of pesticide metabolites was applied for authentication of 27 organic grapes and wines. In total, 23 samples were free of quantifiable residues/detected metabolites or contained residues approved for organic production.

Can Occurrence of Pesticide Metabolites Detected in Crops Provide the Evidence on Illegal Practices in Organic Farming?

Modern pesticides rapidly degrade after their application due to both physicochemical factors and through biotransformation. Consequently, pesticide residues in samples might be either undetectable or detected at low concentrations (≤10 µg/kg). Under such conditions, a monitoring of pesticide metabolites in samples might be a conceivable solution enabling the documentation of earlier pesticide use. Analysis of metabolites might pose analytical challenges because pesticide degradation leads to the production of a number of metabolites, differing somewhat in their structure and polarity. This study was focused on the determination of pesticide residues and their metabolites in samples of grapevine and wine using ultrahigh-performance liquid chromatography coupled with high-resolution mass spectrometry, with the objective of supporting the possibility of the verification of the method of farming. It documents the identification of pesticide metabolites commonly used in conventional farming and provides a characterization of pesticide degradation during grapevine growth, maturation, and during the wine-making process.

Food fraud in oregano: Pesticide residues as adulteration markers.

Oregano, a widely used and popular herb, is particularly vulnerable to fraud. Less valued plants, adulterants that are often used for dilution, may introduce into this commodity additional contaminants such as pesticide residues. In this study, more than 400 pesticides were screened in a representative set of 42 genuine and 34 adulterated dried oregano samples collected from various locations across Europe. The results obtained by advanced mass spectrometry-based methods, showed, that some pesticide residues could be detected in virtually all tested samples, nevertheless, on average, higher contamination was found in the adulterated oregano samples. Increased incidence of insecticides such as cyfluthrin, permethrin and cyhalothrin was typical for these samples, moreover, pyriproxyfen was detected exclusively in adulterated samples. Thus, based on a critical assessment of pesticide profiles, suspected adulterated oregano samples can be selected for follow up authenticity testing.