Residues of the fungicide famoxadone in grapes and its fate during wine production.

Famoxadone is a recently applied fungicide to vines that belongs to the oxazolidinedione family. The fate of famoxadone was studied by considering the decay ratio of this fungicide during the maturation of grapes and wine production. The main factors affecting the presence of fungicide residues such as fruit growth, photodegradation, evaporation, thermodegradation and co-distillation were studied with model systems. An experimental field was treated with a commercial product containing famoxadone at the recommended dose. After this application, residues of famoxadone were found in grapes at 0.27 +/- 0.06 mg kg(-1). In this field experiment, the half-life t(1/2) of famoxadone, which is described by pseudo-first-order kinetics (R2 = 0.74), was 18 +/- 6 days, resulting from the photodegradation. The famoxadone residue levels in grapes were below the established maximum residues level for Europe (2 mg kg(-1)), whilst levels in wine, carried out with and without maceration, were below the calculated limit of detection of the method.

Residues of azoxystrobin, fenhexamid and pyrimethanil in strawberry following field treatments and the effect of domestic washing.

Residues of the pesticides azoxystrobin, fenhexamid and pyrimethanil were determined in strawberry after field treatment. The effect of 'home' washing with tap water and a commercially available vegetable detergent on residue levels was also studied. After treatment, azoxystrobin and pyrimethanil residues on strawberry were on average 0.55 and 2.98 mg kg(-1), respectively, values below the maximum residue level (MRL) fixed by the European Union (2.0 and 5 mg kg(-1), respectively), while fenhexamid residues were on average 2.99 mg kg(-1), which is very close to the MRL of 3.0 mg kg(-1), but some samples were over the MRL. Thereafter, all residues declined, with a half-life of about 8 days (azoxystrobin and fenhexamid) and 4.8 days (pyrimethanil). Washing the fruit with tap water reduced the residues of azoxystrobin and fenhexamid but did not affect pyrimethanil residues. Finally, when fruits were washed with a commercial detergent, greater amounts were removed (about 45% of azoxystrobin and pyrimethanil and 60% of fenhexamid).

The effect of simulated rain on folpet and mancozeb residues on grapes and on vine leaves.

Artificial rainfalls were used to determine the effect of the amount of the rainfall and the time interval between pesticide application and rainfall event, on folpet and mancozeb residues on grapes and vine leaves. Forty-five mm of rain were administered to the vineyard in different amounts (45; 30+15; 15+15+15 mm). Folpet showed good rainfastness on the grapes and on the leaves. A modest decrease was observed only in the experiments that had received 45 mm of rain at one go. Mancozeb showed a lower rainfastness, since a portion of the deposit was easily washed off also by a modest rainfall. The percentage of this portion was higher in the grapes (38%) than in the leaves (20%). The data obtained in these experiments show that, in the case of folpet, it is not necessary to repeat the treatment when it rains the day after, while it is recommendable to repeat it in the case of mancozeb.

Persistence and effectiveness of pyrethroids in plastic strips against Varroa jacobsoni (Acari: Varroidae) and mite resistance in a Mediterranean area.

An apiary trial was conducted in 1997 in Sardinia, Italy, to verify the effectiveness of fluvalinate in polyvinyl chloride strips and flumethrin in polyethylene strips against Varroa jacobsoni Oudemans. Two indices to evaluate the efficacy of the treatments were adopted: percentage change in mite infestation of worker-sealed brood cells considering only treated hives and percentage change in mite mortality, and the natural variation in mite populations recorded in control hives during the trial. All acaricide treatments reduced the level of mite infestation of both sealed brood and adult bees. However, their effectiveness was slightly reduced in comparison to previous studies because of mite resistance phenomena. Portions of polyethylene strips of flumethrin from treated hives were sampled weekly to determine acaricide persistence using gas chromatography. After 4 wk, a slight reduction (approximately 9%) of the active ingredient content was observed. A laboratory bioassay also was performed to establish the resistance of adult female mites to fluvalinate. Mites were sampled from the experimental apiary and from various Sardinian apiaries which had primarily been subjected to fluvalinate applications in plastic strips or wood inserts for years. Mite resistance varied from 0 to 96%, depending on the acaricide management adopted. The lowest resistance level occurred in an apiary where pyrethroids had never been used, whereas the highest level occurred in an apiary, with intensive use of fluvalinate in wood inserts.

Fenhexamid residues in grapes and wine.

The behaviour of the fungicide, fenhexamid, on grapes, and during wine-making, as well as its effect on the microflora of alcoholic and malolactic fermentation has been studied. After treatment, the residue on grapes decreased rapidly to one-third of the initial level after the first week, while it remained constant during the following two weeks. At harvest, in the wine obtained by vinification without skins, the fungicide residue decreased on average by 49%, while in the wine obtained by vinification with skins, the decrease was on average 62%. The presence of this fungicide on grapes and in the wine did not affect alcoholic and malolactic fermentation, nor did fermentation cause any degradation of the fungicide. A simple and rapid gas chromatograhic method (GC-NPD) for the determination of fenhexamid residues in grapes, must and wine is described.

Acephate and buprofezin residues in olives and olive oil.

Field trials were carried out to study the persistence of acephate and buprofezin on olives. Two cultivars, pizz'e carroga and pendolino, with very large and small fruits respectively were used. After treatment, no difference was found between the two pesticide deposits on the olives. The disappearance rates, calculated as pseudo first order kinetics, were similar for both pesticides (on average 12 days). Methamidophos, the acephate metabolite, was always present on all olives, and in some pendolino samples it showed higher residues than the maximum residue limit (MRL). During washing, the first step of olive processing, the residue level of both pesticides on the olives did not decrease. After processing of the olives into oil, no residues of acephate or methamidophos were found in the olive oil, while the residues of buprofezin were on average four times higher than on olives.

Distribution of folpet on the grape surface after treatment.

Field trials were carried out to evaluate whether folpet sprayed on grapevines penetrated the epicuticular wax and cell walls of grapes. Folpet showed poor penetration into the epicuticular wax; it was found almost totally on the surface. Despite its low solubility in water, perhaps due to the presence of adjuvants, its residues showed such a high resistance to washing that the action of rain was negligible in decreasing residues.

Fate of quinoxyfen residues in grapes, wine, and their processing products.

Quinoxyfen is a new fungicide that belongs to the family of the quinolines, recently introduced to control powdery mildew (Uncinula necator). In this paper the fate of quinoxyfen residues from vine to wine and in their processing products was studied. After the last of four applications at the recommended rate, 0.38 mg/kg of residue was found on the grapes, which is under the legal limit fixed in Italy (0.5 mg/kg). The degradation rate was according to a pseudo-first-order kinetics (r = 0.964) and the half-life was 7.24 days. Vinification was carried out with and without maceration. During the vinifications without maceration <50% of the residues passed from the grapes to the musts. Separation of the lees (8%) from the must by centrifugation caused no detectable residues in centrifuged must. At the end of fermentation with and without maceration no quinoxyfen residues were determinable in the wine. No effect on the alcoholic or malolactic fermentation was observed even in the presence of higher quinoxyfen concentrations than those found in the grapes at harvest time. During fermentation, the yeasts partially degraded the pesticides and completly adsorbed them. Bacteria, on the other hand, do not have any degradative effect on the pesticides. The raisins obtained by sun-drying did not contain any residues, whereas those obtained by oven-drying show the same amount of residues as in the fresh grapes. During the sun-drying process the fruit weight decreased by a factor of 4; the decrease in the oven-drying was equivalent. Samples of dregs and liquid lees, fortified with high levels of quinoxyfen. were double-distilled. The first dregs distillate, with an alcohol content of 32.1%, did not show any residues, whereas the first lees distillate, with an alcohol content of 34.5%, showed 7% of the initial residues. After the second lees distillation, the obtained product showed an alcoholic content of 81.2% and no residues of quinoxyfen (<0.01 mg/kg).

Factors affecting imazalil and thiabendazole uptake and persistence in citrus fruits following dip treatments.

The effect of concentration, temperature, and length of treatment with imazalil (IMZ) and thiabendazole (TBZ) was studied with application to citrus fruit. The amount of residues retained by fruit after "home" washing was also monitored. IMZ uptake in citrus fruit was related to treatment duration, whereas TBZ residues was not. Residues of IMZ or TBZ fungicides were significantly correlated with dip temperature (r = 0.943 for IMZ; r = 0.911 for TBZ). Treatment at 50 degrees C produced a deposition approximately 8 and approximately 2.5 times higher than when treatments were carried out at 20 degrees C in IMZ and TBZ, respectively. No significant differences in terms of IMZ deposition were detected after treatments carried out alone or in combination. Uptake of the two fungicides was associated with their physicochemical characteristics as well as different formulation types. IMZ residues showed a great persistence during storage when applied separately, and >83% of active ingredient was present after 9 weeks of storage. IMZ residues increased with dip length, doubling when dip time increased from 0.5 to 3 min. In contrast, TBZ residues did not change with the different dip times. Following postharvest dip treatments of citrus fruit at 20 or 50 degrees C, home washing removed approximately 50% of the IMZ and approximately 90% of the TBZ.

Pesticides in fermentative processes of wine.

The influence of six fungicides (azoxystrobin, cyprodinil, fludioxonil, mepanipyrim, pyrimethanil, and tetraconazole) on the fermentative activity of two yeasts (Saccharomyces cerevisiae and Kloeckeraapiculata) and two lactic bacteria (Leuconostoc oenos and Lactobacillus plantarum) was studied. The possibility of their being degraded by these yeasts and bacteria was also investigated. The presence of the pesticides did not affect alcoholic fermentation, not even with levels higher than those normally found in grapes in field experiments. On the contrary, their presence stimulated the yeast, especially K. apiculata, to produce more alcohol. The fermentative process did not affect the amount of pesticides either by degradation or by adsorption. During malolactic fermentation by Le. oenos, malic acid decreased slightly less (by approximately 15%) in the presence of all pesticides, except mepanipyrim. A lower effect ( approximately 5%) was found during the fermentative process with La. plantarum. The bacteria studied did not show a degradative effect on pesticides during malolactic fermentation.

Gas chromatographic determination of azoxystrobin, fluazinam, kresoxim-methyl, mepanipyrim, and tetraconazole in grapes, must, and wine.

Azoxystrobin, fluazinam, kresoxim-methyl, mepanipyrim, and tetraconazole were determined in grapes, must, and wine by a gas chromatographic method with nitrogen-phosphorus (NP) and mass spectrometric (MS) detectors. Pesticides were isolated from the matrixes by online microextraction with acetone-hexane (50 + 50, v/v). Because of the high selectivity of NP and MS detectors, no interferent peaks were present and no cleanup was necessary. Recoveries from fortified grapes, must, and wine ranged from 80 to 111%, with coefficients of variation ranging from 1 to 14%. Limits of determination were 0.05 mg/kg for kresoxim-methyl and 0.10 mg/kg for the other compounds.

Gas chromatographic determination of cyprodinil, fludioxonil, pyrimethanil, and tebuconazole in grapes, must, and wine.

A rapid and simple gas chromatographic method for determinating cyprodinil, fludioxonil, pyrimethanil, and tebuconazole in grapes, must, and wine is described. An on-line microextraction method was used with a one-step extraction-partition procedure. Nitrogen-phosphorus and mass spectrometric detectors were used, because of their low sensitivity and high selectivity. Because of high selectivity of detector, no cleanup was necessary and the extract was concentrated 5 times. Recoveries from fortified grapes, must, and wine ranged from 93 to 110%. Limits of determination were 0.05 mg/kg for cyprodinil and pyrimethanil and 0.10 mg/kg for fludioxonil and tebuconazole.

Pesticide residues in artichokes: effect of different head shape.

Residues of three pesticides (dimethoate, parathion, and pyrazophos) in two artichoke cultivars, Masedu and Spinoso sardo, were investigated. The amount of pesticides in artichokes was greatly affected by the head shape. In the case of the calix-shaped Masedu artichoke, the residues in whole heads at commercial ripening were on average about twice higher than those of the pagoda-shaped Spinoso sardo artichoke. In the heart this ratio was 4 to 42 times greater. Residue decay rates were very fast, mainly owing to the dilution effect due to head growth.

[Polychlorobiphenyl content in adipose tissue of subjects not exposed professionally]. / Contenuto di PCB nel tessuto adiposo di soggetti non esposti professionalmente.

Polychlorinated biphenyl (PCB) levels were determined in 52 samples of adipose tissue removed during surgery from patients residing in a central region of Sardinia who had no previous occupational exposure. The average PCB value of the whole group was 0.72 microgram/g (range 0.11-2.81 micrograms/g); in males the average value (means = 0.97 microgram/g) was significantly higher than in females (means = 0.60 microgram/g). A positive correlation was observed between age and PCB levels in adipose tissue. This analysis could be usefully performed in occupationally exposed subjects so as to better assess the exposure level.

[Isoflurane pollution in operating rooms]. / Inquinamento da isoflurano nelle sale operatorie.

In three operating rooms of a Sardinian hospital, the Authors have measured the air levels of isoflurane using static samplers. Anaesthetic mean daily concentrations ranged from 3.5 to 41.5 ppm in room A, from 4.1 to 24.4 ppm in room B, from 9.5 to 30.4 ppm in room C above all depending on the length and the number of surgical operations. The Authors emphasize the need of suitable prevention measures.

[An episode of extraoccupational lead poisoning]. / Su un episodio di intossicazione extraprofessionale da piombo.

An episode of non occupational lead intoxication observed in the four members of family is described. While three of them had only biochemical signs of abnormal lead absorption, the remaining subject presented the serious clinical features of plumbism. The source of intoxication was contaminated wine. The importance, for diagnostical and medico-preventive purposes, of a possible non occupational absorption of lead is stressed.