M. A. Cámara

Removal of famoxadone, fluquinconazole and trifloxystrobin residues in red wines: Effects of clarification and filtration processes

The effects of six clarification agents [egg albumin, blood albumin, bentonite + gelatine, charcoal, polyvinylpolypyrrolidine (PVPP) and silica gel] on the removal of residues of three fungicides (famoxadone, fluquinconazole and trifloxystrobin) applied directly to a racked red wine, elaborated from Monastrell variety grapes from the D.O. Region of Jumilla (Murcia, Spain) were studied. The clarified wines were filtered with 0.45 μ m nylon filters to determine the influence of this winemaking process in the disappearance of fungicide residues. Analytical determination of fluquinconazole and trifloxystrobin was performed by gas chromatography with electron captor detector (ECD), while that of famoxadone using an HPLC equipped with a diode array detector (DAD). Generally, trifloxystrobin is the fungicide that is the lowest persistent one in wines, except in the egg albumin study whereas, the most persistent one is fluquinconazole. The elimination depends on the nature of the active ingredient, though the water stability in the presence of light within it has more influence than the solubility and polarity of the product itself. The most effective clarifying agents were the charcoal and PVPP. The silica gel and bentonite plus gelatine were not enough to reduce considerably the residual contents in the wine clarified with them. In general terms, filtration is not an effective step in the elimination of wine residues. The greatest removal after filtration is obtained in wines clarified with egg albumine and bentonite plus gelatine, and the lowest in those clarified with PVPP.

Dissipation of insect growth regulators in fresh and canned fruits

The objective of the study was to determine the dissipation of insect growth regulators in fresh and canned mandarin and apricot to determine the exposure to them. Field studies were carried out in the preharvest period with good agricultural practices (GAP) and in critical agricultural practices. The processing studies were carried out in each relevant step in a pilot plant. A validated methodology was developed (limit of quantification of 0.05 mg kg−1 for apricots, 0.10 mg kg−1 for mandarin) including acetone–dichloromethane extraction, cleanup, and liquid chromatography-diode array detection. The pesticides complied with the maximum residue limits (MRLs) except pyriproxyfen, which has not been authorized in apricots, and it did not comply with its MRL for peaches. The dissipation rates (t 1/2) with GAP were fenoxycarb-apricot > pyriproxyfen-apricot > fenoxycarb-mandarin > pyriproxyfen-mandarin. In the processing studies, there was only residue transference in the canning of apricots. All final cans contained residues much lower than the MRLs.

Influence of the matrix in bioavailability of flufenoxuron, lufenuron, pyriproxyfen and fenoxycarb residues in grapes and wine

The aim of this study is to ascertain the in vitro bioavailablity of pesticides that regulate and inhibit the growth of insects--flufenoxuron, lufenuron, pyriproxyfen and fenoxycarb--in grapes grown under good agricultural practice (GAP), while respecting the pre-harvest intervals (PHI) for critical conditions (CAP), in the most unfavorable conditions. The bioavailability of wines obtained from grapes in each assay and in standard solutions is also studied in order to establish matrix-related differences. Human gastric digestion, intestinal digestion and absorption were imitated. Porcine pepsin, porcine pancreatin, bile salts and semipermeable cellulose dialysis tubing were used. The analysis of the residues of the insecticides studied was performed by extraction with the QuEChERS method, and determination was with HPLC-MS. In all cases it was observed that the pesticides can be ordered according to their dialyzation capacity: fenoxycarb>pyriproxyfen>lufenuron>flufenoxuron. The different matrices can also be ordered according to the matrix effect they impose on the dialysis: grape>wine>standards. The highest percentages of dialyzation for grape and wine matrices are achieved for fenoxycarb (3.27%) and pyriproxifen (2.04%) in wine.

Influence of several fungicides on the antioxidant activity of red wines (var. Monastrell)

The antioxidant activity of wines obtained from grapes treated with six fungicides (famoxadone, fenhexamid, fluquinconazole, kresoxim-methyl, quinoxyfen and trifloxystrobin) was investigated. Two field trials in triplicate were carried out for each formulation of the fungicide at the recommended dose of the manufacturer. The first trial was carried out under good agricultural practices (GAP), following the recommended pre-harvest interval, and the second one under critical agricultural practices (CAP) that involves treating the same field just before the harvest. The residue levels were determined by gas and liquid chromatography coupled to mass detectors (GC-MS and LC-MS). The antioxidant activity was determined in the wines obtained from the thirteen trials including one control, six from treated grapes obeying the pre-harvest interval, and six from grapes treated at the day of harvest or at most unfavorable conditions. Elimination of 40–100% of the initial fungicide residues present in grapes was observed during the wine-making process. It can be inferred from the results that the use of these fungicides did not produce any decrease of the antioxidant activity in the wines (7.19 ± 0.22 mmol Trolox/L for the blank wine versus a range of 6.45 ± 0.82 mmol Trolox/L to 10.06 ± 0.59 mmol Trolox/L for the treated wines) at the pre-harvest interval and most unfavorable conditions. Nevertheless, the presence of famoxadone, kresoxim-methyl and quinoxyfen increased the antioxidant activity and this was directly related to their residue levels in the grapes. Also, the wine phenolic composition was altered in variable intensity by the presence of the fungicide residues.

Disappearance of six pesticides in fresh and processed zucchini, bioavailability and health risk assessment

A field study was carried out on the dissipation of three insecticides and three fungicides during the freezing of zucchini. A simultaneous residue analysis method is validated using QuEChERS extraction with acetonitrile and CG-MS and LC-MS analysis. The residues detected after field application never exceeded the established maximum residue limits. The processing factors calculated (fresh product/frozen product) are lower than 1, indicating a clear influence of the stages of the freezing process, especially the washing and blanching. The in vitro study of bioavailability establishes a low percentage of stomach absorption capacity. The level of residues detected in fresh zucchini and the Estimated Daily Intake calculated for Spain suggest that there is no risk of acute toxicity due to dietary exposure.

Persistence of the mixture of chlorfenvinphos and cypermethrin (Survan) in citrus fruits

The Survan (a mixture of the insecticides chlorfenvinphos and cypermethrin) persistence in lemon citrus fruits, verna variety, is studied. In all the cases, residues of both compounds have been detected in the juices of the fruits treated. When the mixture of the insecticides is used at a concentration of 0.20%, the levels of chlorfenvinphos after 14 days is not higher than 0.14 ppm; however, when it is used at a 0.15% concentration, this value is overpassed in all the samples. The residues of the cypermethrin component are not higher than 0.35 ppm throughout the whole experiment.

Degradation catalytique du chlorfenvinphos et du methidathion deposes sur kaolinite et bentonite saturees par differents cations

Abstract The catalytic degradation of chlorfenvinphos and methidathion on H+, Ca+2, Na+ and ?+ monoionic kaolinite and bentonite was investigated. The results showed that the decomposition of chlorfenvinphos was greater than methidathion in both clays. The extent of degradation was influenced by the nature of the exchange cations and its degree hydration, in the following sequence: K+ >Na+ >Ca+2 >H+/A1+3. In both clays the process of hydrolysis occurred in two stages involving first‐order kinetics of differents hydrolysis rates. The first stage consisted a high hydrolysis rate of short duration and the second had a slow rate but involved a continuous hydrolysis.

Adsorption du chlorfenvinphos et du methidathion sur argiles saturees par differents cations

Summary Adsorption of chlorfenvinphos and methidathion from dissolutions on H+, Ca++, Na+ and K+ are studied. In all cases the saturating cation distinctly influenced the Freundlich‐type adsorption, with adsorption decreasing in the following sequence: H+> Ca++> Na+ > K+. Chlorfenvinphos adsorption was slightly greater than methidathion in two clays, and the adsorption extent for them in kaolinite is slower that bentonite.

Effect of processing on the disappearance of pesticide residues in fresh-cut lettuce: Bioavailability and dietary risk

ABSTRACT The aim of this research is to establish the processing factors of six pesticides durong the preparation of fresh-cut lettuce and to assess the risk of ingestion of pesticide residues associated with the consumption of the same. A field study was carried out on the dissipation of three insecticides (imidacloprid, tebufenozide, cypermethrin) and three fungicides (metalaxyl, tebuconazole, azoxystrobin) during treatment conditions simulating those used for commercial fresh-cut lettuce. A simultaneous residue analysis method is validated using QuEChERS extraction with acetonitrile and CG-MS and LC-MS/MS analysis. The residues detected after field application never exceed the established Maximum Residue Limits. The processing factors were generally less than 1 (between 0.34 for tebufenozide and 0.53 for imidacloprid), indicating that the process, as a whole, considerably reduces residue levels in processed lettuce compared to fresh lettuce. It is confirmed that cutting, followed by washing and drying, considerably reduces the residues. A matrix effect in the dialyzation of the pesticides is observed and the in vitro study of bioavailability establishes a low percentage of stomach absorption capacity (<15%). The EDI/ADI ratios found in all cases were well below their ADI values, and the dietary exposure assessed (EDI) in fresh-cut lettuce showed no concerns for consumer health.