REVIEWS Pesticide Residues in Grapes, Wine, and Their Processing Products Paolo Cabras* and Alberto Angioni Dipartimento di Tossicologia, Universita ` di Cagliari, viale Diaz 182, 09126 Cagliari, Italy In this review the results obtained in the 1990s from research on the behavior of pesticide residues on grapes, from treatment to harvest, and their fate in drying, wine-making, and alcoholic beverage processing are reported. The fungicide residues on grapes (cyproconazole, hexaconazole, kresoxim- methyl, myclobutanil, penconazole, tetraconazole, and triadimenol), the application rates of which were of a few tens of grams per hectare, were very low after treatment and were not detectable at harvest. Pyrimethanil residues were constant up to harvest, whereas fluazinam, cyprodinil, mepanipyrim, azoxystrobin, and fludioxonil showed different disappearance rates (t 1/2 ) 4.3, 12, 12.8, 15.2, and 24 days, respectively). The decay rate of the organophosphorus insecticides was very fast with t 1/2 ranging between 0.97 and 3.84 days. The drying process determined a fruit concentration of 4 times. Despite this, the residue levels of benalaxyl, phosalone, metalaxyl, and procymidone on sun-dried grapes equalled those on the fresh grape, whereas they were higher for iprodione (1.6 times) and lower for vinclozolin and dimethoate (one-third and one-fifth, respectively). In the oven-drying process, benalaxyl, metalaxyl, and vinclozolin showed the same residue value in the fresh and dried fruit, whereas iprodione and procymidone resides were lower in raisins than in the fresh fruit. The wine-making process begins with the pressing of grapes. From this moment onward, because the pesticide on the grape surface comes into contact with the must, it is in a biphasic system, made up of a liquid phase (the must) and a solid phase (cake and lees), and will be apportioned between the two phases. The new fungicides have shown no effect on alcoholic or malolactic fermentation. In some cases the presence of pesticides has also stimulated the yeasts, especially Kloeckera apiculata, to produce more alcohol. After fermentation, pesticide residues in wine were always smaller than those on the grapes and in the must, except for those pesticides that did not have a preferential partition between liquid and solid phase (azoxystrobin, dimethoate, and pyrimethanil) and were present in wine at the same concentration as on the grapes. In some cases (mepanipyrim, fluazinam, and chlorpyrifos) no detectable residues were found in the wines at the end of fermentation. From a comparison of residues in wine obtained by vinification with and without skins, it can be seen that their values were generally not different. Among the clarifying substances commonly used in wine (bentonite, charcoal, gelatin, polyvinylpolypyrrolidone, potassium caseinate, and colloidal silicon dioxide), charcoal allowed the complete elimination of most pesticides, especially at low levels, whereas the other clarifying substances were ineffective. Wine and its byproducts (cake and lees) are used in the industry to produce alcohol and alcoholic beverages. Fenthion, quinalphos, and vinclozolin pass into the distillate from the lees only if present at very high concentrations, but with a very low transfer percantage (2, 1, and 0.1%, respectively). No residue passed from the cake into the distillate, whereas fenthion and vinclozolin pass from the wine, but only at low transfer percentages (13 and 5%, respectively). Keywords: Pesticides; residues; grapes; raisins; wine; alcoholic beverage APRIL 2000 VOLUME 48, NUMBER 4 © Copyright 2000 by the American Chemical Society 10.1021/jf990727a CCC: $19.00 © 2000 American Chemical Society Published on Web 03/30/2000