This work aimed to investigate the bio-distribution and the persistence of fipronil and its primary metabolite fipronil sulfone after oral and dermal administration by simulating natural farming conditions. Fipronil and fipronil sulfone detection and quantification were performed in different poultry matrices using an LC-MS/MS method coupled with modified QuEChERS extraction. After oral administration, fipronil was detected in feathers at each sampling time, in eggs for 28 days, and in the internal organs at the end of the experiment. After dermal administration, high levels of fipronil were detected in feathers, accounting for 195.85 ± 8.54 mg/kg, which were reduced by a third after 60 days. No traces of fipronil were detected in the eggs or internal organs. In addition, fipronil sulfone showed remarkable residues in all samples in trial 2. The data obtained confirmed that inappropriate use of unauthorized pesticides can lead to severe contamination of entire poultry farms. The contemporary presence of fipronil sulfone in feathers and eggs associated with the lack of fipronil in eggs suggests recent dermal contamination or past oral contamination. Moreover, simultaneous analysis of hens’ feathers and eggs could represent a new method to improve large-scale monitoring programs and animal welfare, limiting their slaughter.
Vernaccia is a white grape mostly used to produce a distinct wine protected by the controlled designation of origin (DOC) recognition. It is very susceptible to fungal disease, and it is subjected to a defined management protocol in the field. Winemaking could influence pesticide residues through different mechanisms. This work investigated the influence on pesticide residues of the winemaking process at the industrial level of the wine Vernaccia di Oristano. Thirty-five samples of grapes, two musts, and two vines (both liquid fraction and pellets) were analyzed by using a validated multiresidue LC-MS/MS (Liquid Chromatography with tandem mass spectrometry) method. Data obtained showed the presence in grapes juice of 16 pesticides (8 not allowed in the EU) with mandipropamid and mepanipyrim, the only ones with values higher than their MRL (maximum residue level). Pesticide residues decrease in must was related to the dilution effect due to mixing the grape samples. However, pellets analysis also confirmed the high affinity of pesticides for the suspended material (fenhexamid), whereas the increase in wine to a re-solubilization process from the lees during the fermentation step. The present paper highlighted the effectiveness of the technological process of winemaking to decrease pesticide residues compared to the raw material.
Fourth-range products are those types of fresh fruit and vegetables that are ready for raw consumption or after cooking, and belong to organic or integrated cultivations. These products are subject to mild post-harvesting processing procedures (selection, sorting, husking, cutting, and washing), and are afterwards packaged in packets or closed food plates, with an average shelf life of 5–10 days. Artichokes are stripped of the leaves, stems and outer bracts, and the remaining heads are washed with acidifying solutions. The A LC-MS/MS analytical method was developed and validated following SANTE guidelines for the detection of 220 pesticides. This work evaluated the distribution of pesticide residues among the fraction of artichokes obtained during the industrial processing, and the residues of their wastes left on the field were also investigated. The results showed quantifiable residues of one herbicide (pendimethalin) and four fungicides (azoxystrobin, propyzamide, tebuconazole, and pyraclostrobin). Pendimethalin was found in all samples, with the higher values in leaves 0.046 ± 8.2 mg/kg and in field waste 0.30 ± 6.7 mg/kg. Azoxystrobin was the most concentrated in the outer bracts (0.18 ± 2.9 mg/kg). The outer bracts showed the highest number of residues. The industrial waste showed a significant decrease in the number of residues and their concentration.
Insecticide\'s disappearance after field treatments could be ascribed to different factors such as sunlight photodegradation, dilution effect due to fruit growth, co-distillation during fruit respiration and evaporation. Moreover, the epicuticular waxes could speed or slow down the degradation rate, and the cultivation in an open field or greenhouses could affect the residues dramatically. After harvest, the processing techniques to produce byproducts deeply influence insecticide residues. For example, fruit drying, winemaking, the industrial processing of tomatoes to produce purée, triple-concentrated paste, fine pulp, diced, olive processing to obtain table olive and olive oil, and other industrial applications on fruits affect residues and their half-life time. The scope of this chapter is to highlight the major factors responsible for the disappearance of insecticides after treatment. Moreover, the chapter intends to review the influence of the industrial processes on insecticide behaviour when the raw material is transformed into its byproducts.
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