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.     

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.     

Effect of clarification process on the removal of pesticide residues in red wine and comparison with white wine

The aim of this study was to determine the potential of seven clarifying agents to remove pesticides in red wine. The presence of pesticides in wine consists a great problem for winemakers and therefore, results on pesticide removal by clarification are very useful for taking a decision on the appropriate adsorbent. The selection of an efficient adsorbent can be based on data correlating pesticide removal in red wine to pesticides' properties, given the great number and variety of pesticides used. So, this experimental work is focused on the collection of results with regard to pesticide removal by clarification using a great number of pesticides and fining agents. A Greek red wine, fortified with single solutions and mixtures of 23 or 9 pesticides was studied. The seven fining agents, used at two concentrations, were activated carbon, bentonite, polyvinylpolypyrrolidone (PVPP), gelatin, egg albumin, isinglass-fish glue, and casein. Pesticides were selected with a wide range of properties (octanol–water partition coefficient (log K_ow) 2.7–6.3 and water solubility 0.0002–142) and belong to 11 chemical groups. Solid phase extraction (SPE) followed by gas chromatography (GC) with electron capture detector (ECD) were performed to analyze pesticide residues of the clarified fortified wine. The correlation of the clarifying agents' effectiveness to pesticide's chemical structure and properties (log K_ow, water solubility) was investigated. The antagonistic and/or synergistic effects, occurring among the pesticides in the mixtures, were calculated by indices. Pesticide removal effectiveness results of the red wine were compared to those obtained from a white wine under the same experimental conditions and discussed. The order of decreasing adsorbent effectiveness (mixture of 23 pesticides) was: activated carbon 40% > gelatin 23% > egg albumin 21% > PVPP 18% > casein 12% > bentonite 7%. Isinglass showed 12% removal at the highest permitted concentration. In the case of 9 pesticides mixture, the effectiveness was quite higher but the order remained the same compared to 23 pesticides mixture. The removal of each pesticide from its single solution was generally the highest (particularly for hydrophobic pesticides). Adsorption on fining agents is increased by increasing hydrophobicity and decreasing hydrophilicity of organic pesticide molecules.     

Residue evaluation of famoxadone and trifloxystrobin in cultivated mushrooms

Dissipation of the fungicides famoxadone and trifloxystrobin in basidiocarps of Agaricus bisporus was studied in mushroom growing rooms. The mushroom samples taken at all three consecutive production flushes following single or split applications of the fungicides were extracted with solvents and the residues were determined by using a gas chromatograph equipped with an electron capture detector (GC-ECD). Recoveries from the fortified control samples ranged from 87 to 105%. Following drench applications at 0.1-1 g/m2 of culture bed area, the highest famoxadone residue determined in basidiocarps was 0.1447 mg/kg. Analysis of trifloxystrobin revealed a quantitative relationship between the application rate (0.8-1.8 g/m2) and the residue levels of both the parent compound and its acid metabolite. The maximal combined residues of trifloxystrobin and its metabolite were 0.1313 mg/kg. Short- and long-term dietary risk assessment for both fungicides was carried out using consumption data from World Health Organization and the UK Pesticide Safety Directorate's Ten Consumer Model. The potential acute and chronic residue intakes via mushroom consumption were below toxicologically significant indicators.     

Persistence and dissipation kinetics of trifloxystrobin and tebuconazole in onion and soil

The persistence and dissipation kinetics of trifloxystrobin and tebuconazole on onion were studied after application of their combination formulation at a standard and double dose of 75 + 150 and 150 + 300 g a.i. ha^?1. The fungicides were extracted with acetone, cleaned-up using activated charcoal (trifloxystrobin) and neutral alumina (tebuconazole). Analysis was carried out by gas chromatograph (GC) and confirmed by gas chromatograph mass spectrometry (GC-MS). The recovery was above 80% and limit of quantification (LOQ) 0.05 mg kg^?1 for both fungicides. Initial residue deposits of trifloxystrobin were 0.68 and 1.01 mg kg^?1 and tebuconazole 0.673 and 1.95 mg kg^?1 from standard and double dose treatments, respectively. Dissipation of the fungicides followed first-order kinetics and the half life of degradation was 6–6.6 days. Matured onion bulb (and field soil) harvested after 30 days was free from fungicide residues. These findings suggest recommended safe pre-harvest interval (PHI) of 14 and 25 days for spring onion consumption after treatment of Nativo 75 WG at the standard and double doses, respectively. Matured onion bulbs at harvest were free from fungicide residues.     

Cyprodinil retention on mixtures of soil and solid wastes from wineries. Effects of waste dose and ageing

In spite of its wide-world economic relevance, wine production generates a huge amount of waste that threatens the environment. A batch experiment was designed to assess the effect of the amendment of an agricultural soil with two winery wastes (perlite and bentonite wastes) in the immobilization of cyprodinil. Waste addition (0, 10, 20, 40, and 80 Mg ha^?1) and different times of incubation of soil-waste mixtures (1, 30, and 120 days) were tested. The addition of wastes improved the soil’s ability to immobilize cyprodinil, which was significantly correlated to total C content in soil-waste mixtures. Longer incubation times decreased the cyprodinil sorption possibly due to the mineralization of organic matter but also as a consequence of the high pH values reached after bentonite waste addition (up to 10.0). Cyprodinil desorption increased as the amount of waste added to soil, and the incubation time increased. The use of these winery wastes contributes to a more sustainable agriculture preventing fungicide mobilization to groundwater.     

Herbicide residues in grapes and wine

Abstract

The persistence of several common herbicides from grapes to wine has been studied. Shiraz, Tarrango and Doradillo grapes were separately sprayed with either norflurazon, oxyfluorfen, oxadiazon or trifluralin ‐ persistent herbicides commonly used for weed control in vineyards. The dissipation of the herbicides from the grapes was followed for 28 days following treatment. Results showed that norflurazon was the most persist herbicide although there were detectable residues of all the herbicides on both red and white grapes at the end of the study period. The penetration of herbicides into the flesh of the grapes was found to be significantly greater for white grapes than for red grapes. Small‐lot winemaking experiments showed that norflurazon persisted at levels close to the initial concentration through vinification and into the finished wine. The other herbicides degraded, essentially via first‐order kinetics, within the period of “ first fermentation”; and had largely disappeared after 28 days. The use of charcoal together with filter pads, or with diatomaceous earth was shown to be very effective in removing herbicide residues from the wine. A 5% charcoal filter removed more than 96% of the norflurazon persisting in the treated wine.     

Behaviour and redox sensitivity of pharmaceutical residues during bank filtration - Investigation of residues of phenazone-type analgesics

The behaviour of residues of phenazone-type pharmaceuticals during bank filtration was investigated at a field site in Berlin, Germany, where bank-filtered water is used for drinking water production. The concentrations of the pharmaceutical residues in the shallow, young bank filtrate (travel times相似文献   

Residues of EBDC fungicides and ETU in experimental and commercial beverages (beer and wine)

Residues of EBDC (ethylenebisdithiocarbamate) fungicides and ETU (ethylenethiourea; 2-imidazolidinethione) were monitored in beers and wines from different locations. No EBDC residues were detected in any of the samples examined. Concerning the ETU residues, the residue levels higher than the limit of method detection (0.01 ppm) were 22.6% and 7.3% in the commercial beer and wine samples respectively, but the number of samples containing more than 0.1 ppm of ETU was practically negligeable.     

Simultaneous detection and degradation patterns of kresoxim-methyl and trifloxystrobin residues in citrus fruits by HPLC combined with QuEChERS

This study aimed to investigate the residues, kinetics and dissipation patterns of kresoxim-methyl, (E)-methoxyimino[α-(o-tolyloxy)-o-tolyl]acetate, and trifloxystrobin, methyl(E)-methoxyimino-{(E)-α[1-(α,α,α-trifluoro-m-tolyl)ethylideneaminooxy]-o-tolyl}acetate”. A simple and sensitive liquid chromatography-ultraviolet detection (LC-UV) method combined with the ‘Quick Easy Cheap Effective Rugged and Safe' (QuEChERS) protocol was developed to quantify the levels of kresoxim-methyl and trifloxystrobin residues in citrus. More than 97% of the kresoxim-methyl and trifloxystrobin deposists gradually dissipated from the citrus peels within 15 days. The half-lives of kresoxim-methyl and trifloxystrobin in the peels were in the ranges of 2.63–2.66 d and 3.12–3.15 d, respectively, and the pattern of decline in the peels followed first-order kinetics. The kresoxim-methyl and trifloxystrobin residues in the pulp dissipated below the detectable level of 0.01 mg kg^?1 after 9 days. Kresoxim-methyl and trifloxystrobin were easily decomposed (T_1/2 < 30 d), and the observed dissipation patterns could support the application of these two fungicides in the postharvest storage of citrus fruits.     

Influence of fungicide residues and in vitro gastrointestinal digestion on total antioxidant capacity and phenolic fraction of Graciano and Tempranillo red wines

Abstract

The effect of fenhexamid, mepanipyrim and cyazofamid fungicides on in vitro bioavailability of antioxidant activity and phenolic compounds of Tempranillo and Graciano red wine was studied by simulating the digestive process by dialysis in semipermeable membranes. Determination of antioxidant activity was through reaction with the DPPH ? radical and the measurement of phenolic compounds was made with liquid chromatography with diode detector (HPLC-DAD). Fenhexamid, mepanipyrim and cyazofamid reduce the total polyphenol content in both wines. During dialysis there was a large loss of total polyphenols (80–90%) and of antioxidant activity (> 90%). The bioavailability of the phenolic compounds is lower than that for non-treated wines and the highest dialization percentages were found for stilbenes > 50%. While for the remaining phenolic fraction the order is the following hydroxycinnamic derivatives?>?anthocyanins?>?flavonols.     

Herbicide residues in grapes and wine

The persistence of several common herbicides from grapes to wine has been studied. Shiraz, Tarrango and Doradillo grapes were separately sprayed with either norflurazon, oxyfluorfen, oxadiazon or trifluralin-persistent herbicides commonly used for weed control in vineyards. The dissipation of the herbicides from the grapes was followed for 28 days following treatment. Results showed that norflurazon was the most persist herbicide although there were detectable residues of all the herbicides on both red and white grapes at the end of the study period. The penetration of herbicides into the flesh of the grapes was found to be significantly greater for white grapes than for red grapes. Small-lot winemaking experiments showed that norflurazon persisted at levels close to the initial concentration through vinification and into the finished wine. The other herbicides degraded, essentially via first-order kinetics, within the period of "first fermentation" and had largely disappeared after 28 days. The use of charcoal together with filter pads, or with diatomaceous earth was shown to be very effective in removing herbicide residues from the wine. A 5% charcoal filter removed more than 96% of the norflurazon persisting in the treated wine.     

Comparison of gas chromatography and immunoassay methods in quantifying fenitrothion residues in grape juice processed into alcoholic drinks

Abstract

Wine and Arak, the national alcoholic drink in Lebanon, were prepared from grape juice fortified with fenitrothion to a concentration of 20ppm. Samples of the 11 fractions produced by the fermentation and distillation steps were analyzed for fenitrothion residues using gas chromatography (GC) and enzyme‐linked immunosorbent assay (ELISA). Results of residue analyses showed that the two techniques were highly correlated (r = 0.978) and indicated that fenitrothion was stable during the fermentation steps but not during distillation. The clarified wine 35 days later contained about 85% (15.3 ppm) of the fenitrothion concentration found in the juice as determined by GC analysis. Arak was prepared by a two‐steps distillation of the clarified wine. The alcohol distillate and undistilled fraction from the first distillation contained 2.5 ppm and 5.8 ppm of fenitrothion, respectively. No fenitrothion residues were detected by both techniques in the four fractions collected from the second distillation step.     

Comparison of gas chromatography and immunoassay methods in quantifying fenitrothion residues in grape juice processed into alcoholic drinks.

Wine and Arak, the national alcoholic drink in Lebanon, were prepared from grape juice fortified with fenitrothion to a concentration of 20ppm. Samples of the 11 fractions produced by the fermentation and distillation steps were analyzed for fenitrothion residues using gas chromatography (GC) and enzyme-linked immunosorbent assay (ELISA). Results of residue analyses showed that the two techniques were highly correlated (r = 0.978) and indicated that fenitrothion was stable during the fermentation steps but not during distillation. The clarified wine 35 days later contained about 85% (15.3 ppm) of the fenitrothion concentration found in the juice as determined by GC analysis. Arak was prepared by a two-steps distillation of the clarified wine. The alcohol distillate and undistilled fraction from the first distillation contained 2.5 ppm and 5.8 ppm of fenitrothion, respectively. No fenitrothion residues were detected by both techniques in the four fractions collected from the second distillation step.     

膨润土吸附-微波催化氧化协同处理葡萄酒废水

采用膨润土吸附-微波催化氧化技术处理葡萄酒生产废水,考察了膨润土用量、H2O2用量、微波辐照时间、微波功率、pH等5个单因素对葡萄酒生产废水处理效果的影响。确定了最终反应条件为:膨润土用量2.6 g、H2O2用量2.1mL、功率720 W、加热时间25 min、pH为3.5。在此条件下,COD去除率达到了80%以上。结果表明,该方法可快速有效地处理葡萄酒生产废水。     

Abbauverhalten von triadimefon und seinem metaboliten triadimenol in einer weizenmonokultur

Summary

In a 4‐year study, the behaviour of the residues of triadimefon and its metabolite triadimenol in different plant parts of winter wheat and in soil was investigated. The fungicide Bayleton DF (triadimefon + captafol) was applied at the beginning of earing. Triadimefon residues were quickly degraded in the great majority of the examined samples (more than 90% within the first 2 weeks after application in all aerial parts of the plant). Triadimenol residues were considerably more persistent. No residues either of triadimefon or triadimenol were found in grain at harvest time (detection limit 0.01 mg/kg).     

Analytical methods and validation for determining trace elements in red wines

The objective of this work is to quantify As, Hg, Cd, Ni and Pb in Portuguese red wines. First, the methods for the quantification of trace elements in red wines were validated. Several pre-treatments were compared, namely a pre-digestion process with HNO₃, a pre-oxidation step with H₂O₂, and a spiking step of wine samples with a known concentration of the trace elements analyzed. Except for As, it was determined that the quantification of the trace elements does not require a pre-digestion process with HNO₃. For all of the trace elements analyzed, a pre-oxidation step with H₂O₂ may enable an accurate quantification. The techniques chosen for the quantification of trace elements were hydride generation atomic absorption spectrometry (HGAAS) for As and Hg, electrothermal atomic absorption spectrometry (ETAAS) for Cd, and flame atomic absorption spectrometry (FAAS) for Ni and Pb. In the second stage of this work, 25 Portuguese red wines spanning all of the red wine-producing regions were analyzed for all of the five trace elements referred to above. Only Cd and Pb have shown concentrations above the limit values defined by the “Organization Internationale de la Vigne et du Vin.” The Target Hazard Quotient (THQ) equation was used to determine in which wine-producing regions that wine consumption can be a problem for public health in terms of the concentrations of the five trace elements analyzed. THQ values have indicated that for the universe of the 25 red wines analyzed no region produces wines that can pose problems for public health, when the Portuguese red wine standard consumption is considered.     

Relationship between biogenic amines and free amino Acid contents of wines and musts from Alentejo (Portugal)

The concentration of biogenic amines and free amino acids was studied in 102 Portuguese wines and 18 musts from Alentejo demarcated (D.O.C.) regions. Most wines were commercial, except for 38 monovarietals obtained by micro vinification. Musts from the varieties used to produce the latter wines were also studied. Both biogenic amines and free amino acids were analyzed by HPLC using fluorescence detection for their o-phthalaldehyde/fluorenylmethyl chloroformate (OPA/FMOC) derivatives. The most significant amines (average 10.8 mg/L for histamine+tyramine in red, and 7.4 mg/L for white wines) were found to be present at low levels and, although no important relationship between each individual biogenic amine could be obtained, the total amine content depends significantly on the assimilable amino acid content in wine.     

Relationship Between Biogenic Amines and Free Amino Acid Contents of Wines and Musts from Alentejo (Portugal)

The concentration of biogenic amines and free amino acids was studied in 102 Portuguese wines and 18 musts from Alentejo demarcated (D.O.C.) regions. Most wines were commercial, except for 38 monovarietals obtained by micro vinification. Musts from the varieties used to produce the latter wines were also studied. Both biogenic amines and free amino acids were analyzed by HPLC using fluorescence detection for their o-phthalaldehyde/fluorenylmethyl chloroformate (OPA/FMOC) derivatives. The most significant amines (average 10.8 mg/L for histamine+tyramine in red, and 7.4 mg/L for white wines) were found to be present at low levels and, although no important relationship between each individual biogenic amine could be obtained, the total amine content depends significantly on the assimilable amino acid content in wine.     

4-ethylphenol and 4-ethylguaiacol in wines: estimating non-microbial sourced contributions and toxicological considerations

Analyses of commercially available wines suggested non-Brettanomyces sources of 4-ethylphenol and 4-ethylguaiacol. Grapes, enological additions, exposure to plastics, and oak-barrel aging were potential inputs considered. Investigations of whole grape bunch samples from two major red wine Vitis vinifera cultivars (L. cv. Cabernet Franc and Pinot Noir), a commercial mannoprotein additive, and three commercial enological tannin additions indicated they are not likely significant sources of these compounds. Studies on 15 commercial oak barrelled red wines from six Vitis vinifera cultivars (L. cv. Cabernet Franc, Cabernet Sauvignon, Dunkelfelder, Merlot, Pinot Meunier, and Pinot Noir), and a review of volatile phenol extraction from toasted oak wood, suggested that oak-aging may produce concentrations of up to 50 microg L(-1) 4-ethylphenol and 4-ethylguaiacol. Thus, following potential Brettanomyces-sourced aroma impacts in wine using 4-ethylphenol and/or 4-ethylguaiacol concentrations as proxies should only be considered reliable at analyte levels>100 microg L(-1). A review of worldwide 4-ethylphenol and 4-ethylguaiacol concentrations in wine, consumption patterns, and available toxicological data also suggested that levels of 4-ethylphenol being observed in wines worldwide do not warrant concerns about acute or long-term effects. While little is known about the toxicology of 4-ethylguaiacol, it is unlikely that elevated concentrations will pose any health-related concerns.