Targeted and untargeted mass spectrometric approaches in discrimination between Myrtus communis cultivars from Sardinia region.

In the present study, the discrimination of phytochemical content of Myrtus communis berries from different geographical origin and cultivars was explored by Liquid Chromatography-Electrospray Ionization-Fourier Transform-Mass Spectrometry (LC-ESI-FT-MS) metabolic profiling and quantitative analysis. Experiments were carried on myrtle plants grown in an experimental area of Sardinia region, obtained by the germination of seeds taken from berries collected in each part of the region. A preliminary untargeted approach on fruit's extracts was realized by collecting LC-ESI-FT-(Orbitrap)-MS data obtained by operating in negative ion mode and performing principal component analysis with the result of differentiation of samples. In a second step, targeted analysis with a reduced number of variables was realized. A data matrix was obtained by the data fusion of positive and negative ionization LC-ESI-MS results, by using as variables the peak areas of each known compounds. By the observation of principal component analysis, results found that anthocyanins, and mainly derivatives of cyanidin, are the principal marker compounds responsive for the discrimination of samples based on the geographical origin of the seeds. Based on this finding, finally, an LC-diode array detector method was developed, validated and applied for the quantitative analysis of berries' extracts based on 11 commercial standard compounds corresponding to the identified markers. Copyright © 2016 John Wiley & Sons, Ltd.

Influence of post-harvest treatments with fludioxonil and soy lecithin co-application in controlling blue and grey mould and fludioxonil residues in Coscia pears.

The residue levels of fludioxonil (FLU) were determined in Coscia pear following a 1-, 2- or 4-min dip in an aqueous mixture of FLU containing 300 or 100 mg l(-1) (active ingredient, a.i.) at 20 and 50 degrees C, respectively, with or without 2% soy lecithin. The efficacy of heat treatment with water and FLU mixtures was investigated on artificially inoculated pears for the control of post-harvest decay caused by blue (Penicillium expansum Link) and grey (Botrytis cinerea Pers. ex Fr.) mould. Treatment with 300 mg l(-1) FLU at 20 degrees C increased residues significantly when treatment time rose from 1 to 2 min; no further increase was recorded when dip time raised from 2 to 4 min. FLU residue rates were unaffected by treatment time when 300 mg l(-1) a.i. was applied in combination with lecithin at 20 degrees C. While treatment with 100 mg l(-1) a.i. at 50 degrees C for 1 and 2 min resulted in similar residue levels, significantly higher residues were detected when dip time increased from 1 to 4 min. Co-application of lecithin significantly decreased FLU residues with respect to fruit treated with FLU alone. Treatments with FLU at 20 or 50 degrees C effectively controlled decay over 10 days of incubation. While co-application of lecithin did not affect the efficacy of FLU at 300 mg l(-1)and 20 degrees C, treatment efficacy decreased when lecithin was applied in combination with 100 mg l(-1) FLU and 50 degrees C for 4 min and to a greater extent when dip time was 1-2 min.

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.

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.

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.

Photolysis of pesticides: influence of epicuticular waxes from Persica laevis DC on the photodegradation in the solid phase of aminocarb, methiocarb and fenthion.

Pesticides with N,N-dimethyl and thiomethyl moieties (aminocarb, methiocarb and fenthion) were irradiated under artificial light (lambda > 290 nm) in an amorphous wax phase from Persica laevis DC. The effect of the presence of the wax on the photolysis rate differed in the three pesticides, increasing it in aminocarb, having little effect in methiocarb and slowing it down in fenthion. The presence of the wax affected the qualitative photodegradation behaviour of all the pesticides. The data obtained were compared with those for pirimicarb, which had been studied earlier.

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.

Phenolic compounds in virgin olive oil. 2. Reappraisal of the extraction, HPLC separation, and quantification procedures.

The extraction procedures (solid/liquid SPE and liquid/liquid LLE) and HPLC separation and quantification methods of polyphenolic compounds have been checked in virgin olive oils in order to explain the differences in content reported in the literature. The work has been carried out on oils prepared from one cultivar and produced under the same protocol. The extraction methods are practically equivalent, but the SPE technique is more favorable because it is faster and simpler. It has been proved that the chromatographic features and the method of chemical expression of the concentrations may greatly affect the final values. Thus, under the same analytical method, the total concentration values of polyphenols of the same oil show variations from 18% to 80%, according to the formality of expression as gallic acid, caffeic acid, or tyrosol equivalents. The role of the nature and spectrophotometric features of the phenols and of the internal standard is also discussed, and it was found to be an important source of reported variation. A gradient separation with an eluent mixture acetonitrile-sulfuric acid (0.1 mol/L), detection at 225 nm, and quantitative calculation of polyphenolic compounds in oils (expressed as tyrosol equivalents, THY(eq)) is proposed.

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.

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.