Pesticide residues in grapes and during vinification process
Introduction
The occurrence and concentrations of pesticide residues in grapes and consequently in wines depend on grapevine pests characteristic of each vine-growing region, type of grape growing (traditional, integrated, organic), pesticide concentrations at spraying, time period and climatic conditions from the last spraying until harvest. In Slovenia in 2007, 9.063 hectares of vineyards were cultivated by integrated crop management, which represents half of total Slovenian grape production and 183 ha by organic viticulture. One of the major differences of all types of production concerns crop protection.
Baša Česnik, Gregorčič, and Čuš (2008) monitored pesticide residues in 47 samples of wine grapes from the 2006 vintage from the vineyards included in integrated crop management. The results showed that folpet (97.9%), cyprodinil (51.1%), dithiocarbamates (44.7%), chlorothalonil (23.4%), chlorpyriphos (19.1%) and pyrimethanil (14.9%) were the most frequently found pesticides in grapes. Soleas and Goldberg (2000) assayed 26 pesticides in 1827 raw juices prior to alcoholic fermentation and 1537 wines from nine major wine-producing regions (Australia, Canada, Central Europe, France, Italy, South America, South Africa, Spain and USA). The most frequently found pesticides in the samples of raw juices were folpet (14.5%) and captan (13.9%), followed by guthion (4.8%), carbaryl (3.5%) and dimethoate (2.5%). In the samples of wines, carbaryl (7.9%), malathion (3.5%) and dimethoate (2.5%) were detected at the highest percentages.
Many authors have also shown that the proper use of pesticides does not cause a contravention of Maximum Residue Limits (MRLs) in grapes (Cabras and Angioni, 2000, Farris et al., 1992, Navarro et al., 2001). There are data for dissipation rates of some pesticides in wine grapes. Review of Cabras and Angioni (2000) showed that pyrimethanil residues are constant up to harvest, whereas, azoxystrobin, cyprodinil, fludioxonil and tebuconazole show different disappearance rates. The residues of fenhexamid in grapes decreased rapidly to one-third of the initial concentrations after almost one week after the application (Cabras et al., 2001). The decay rates of the organophosphorus insecticides are also very fast (Cabras et al., 1995). Navarro et al. (2001) studied the disappearance of six pesticides (chlorpyrifos, fenarimol, metalaxyl, mancozeb, penconazole and vinclozolin), which are widely used in vineyards to control European grapevine moths (Eupoecilia ambiguella Hübn. and Lobesia botrana Den. & Schiff.) (chlorpyrifos), powdery mildew (Uncinula necator (Schwein.) Burrill) (fenarimol and penconazole), downy mildew (Plasmopara viticola ((Berk et M.A. Curtis) Berl. et de Toni)) (metalaxyl and mancozeb) and grey mould (Botryotinia fuckeliana de Bary (Whetzel) (vinclozolin). The order of dissipation rates in grapes was: chlorpyrifos > vinclozolin > fenarimol > metalaxyl > penconazole > mancozeb.
There are also data for dissipation rates of some pesticides from grapes to wine (Cabras et al., 1997a, Cabras et al., 1997b, Garcia-Cazorla and Xirau-Vayreda, 1994, Navarro et al., 1999). Among the most frequently found pesticide residues in grapes (Baša Česnik et al., 2008) and must (Soleas & Goldberg, 2000) is folpet, but Cabras et al. (1997a) showed that, during the winemaking process, the residues of folpet is degraded by photolytic and hydrolytic reactions, and at the end of fermentation, only phthalimide was still present in wines. Garcia-Cazorla and Xirau-Vayreda (1994) studied the persistence of dicarboximidic fungicide residues (iprodione, procymidone and vinclozoline) in grapes, must and wine. The results showed that residual levels of dicarboximidic fungicides decreased during the winemaking process, however the detectable levels of residues were found in wines. Sala et al. (1996) also confirmed the persistence of iprodione, procymidone and vinclozoline during the vinification of white and red grapes. The disappearance of the fungicides cyprodinil, fludioxonil, procymidone and vinclozoline from commercially sterilized white grape juice was studied during the storage at 40 °C for about 2 months (Pose-Juan, Cancho-Grande, Rial-Otero, & Simal-Gándara, 2006). The half-lives at 40 °C for vinclozoline, procymidone, fludioxonil and cyprodinil were found to be 11, 20, 33 and 44 days, respectively. The effect of winemaking processes on the concentrations of chlorpyrifos, penconazole, fenarimol, vinclozolin, metalaxyl and mancozeb in red wines has been studied by (Navarro et al., 1999). They found fenarimol and metalaxyl to be the most persistent pesticides in their vinification process. Among the residual levels of cyprodinil, fludioxonil, pyrimethanil and quinoxyfen compared in the study of Fernandez, Oliva, Barba, and Camara (2005), the decrease in levels of pyrimethanil was the slowest in processes with or without maceration. Pesticide residues in wine after fermentation are generally always smaller than those in the grapes and must, except for those pesticides that did not have a preferential partition between liquid and solid phase (i.e. azoxystrobin, dimethoate and pyrimethanil). In some cases (i.e. chlorpyrifos, chlozolinate, diclofluanid, fluazinam and mepanipyrim), no detectable residues were found in wine at the end of fermentation despite having been found in the grapes and must (Cabras et al., 2000; Sala et al., 1996). The important decrease in levels of pesticide residues during the winemaking process occurs with the separation of solid (cake and lees) and liquid phases (must, wine) (Cabras et al., 2000; Cabras et al., 1997b, Ruediger et al., 2004).
Numerous analytical methods for determining pesticide residues in grapes/must/wine/vineyard soils have been published until now. Gas chromatography (Angioni et al., 2005, Gonzalez-Rodriguez et al., 2009a, Gonzalez et al., 2003, Navarro et al., 2000, Otero et al., 2002, Rial-Otero et al., 2004) and liquid chromatography (Juan-García et al., 2004, Rial Otero et al., 2003, Teixeira et al., 2004) are the two most powerful techniques (Gandara et al., 1993, Lehotay et al., 2005, Pang et al., 2006) that were used in the study. Pre-concentration step can be done by liquid–liquid extraction (Gonzalez-Rodriguez et al., 2009a) or by solid-phase microextraction (SPME) (Otero et al., 2002).
The aim of the present study was to investigate the occurrence and concentrations of pesticide residues in grapes during ripening period and in vinification process of different grapevine varieties in Slovenia.
Section snippets
Crop protection
Crop protection in the experimental vineyards was done with consideration of good agriculture practice. Timetable of sprayings and the active ingredients used are shown in Table 2. The concentrations of pesticides at sprayings were those proposed by the manufacturers.
Sampling in current study
Samples of Blaufränkisch (red), Malvasia (white), Pinot Gris (white) and Refosco (red) grapes were taken in 15–25 days intervals during ripening period. The experimental vineyards were chosen in coastal (Malvasia and Refosco) and
Results and discussion
All pesticides used in the spraying programs, with the exception of dinocap and Fosetyl-Al, were monitored with the listed analytical methods.
Acknowledgements
The authors would like to thank the producers concerned with the samplings and those who contributed to the work: Mateja Fortuna and co-workers at the Central Laboratories of the Agricultural Institute of Slovenia. This research was supported by the Slovenian Public Research Agency and by the Ministry of Agriculture, Forestry and Food, Republic of Slovenia (Project No. V4-0323).
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