Wine Residues Research Articles

Wine residues extracts modulating in vitro metabolic syndrome

Metabolic syndrome is considered a worldwide epidemic health problem. The manifestations include obesity, dyslipidemias, elevation of arterial blood pressure, and insulin resistance. The wine waste is composed mainly of skin, seed and grape pomace, and is a source of phenolic compounds. Previous studies have demonstrated that grape phenolic compounds have antioxidants and anti-inflammatory properties, acting directly in the pathogenic process of several diseases. In order to improve the bioavailability and bioactivity of these compounds, enzymatic biotransformation reactions were developed.The aimed of this work was to evaluate whether phenolic extracts produced with wine waste by biotransformation with Tannase (tannin acyl hydrolase), were able to attenuate the metabolic syndrome manifestations like oxidative stress and reduce the inflammatory parameters in vitro assays.Four different extracts were produced and the non-citotoxic concentrations of samples used (100, 200 and 500 μg/mL) were determined by MTT assay. The inflammatory response was induced in macrophages (RAW 264.7) culture using LPS (Lipopolysaccharide). The biotransformed extracts were able to reduce the TNF-α cell culture supernatant concentration by about 44%; and the IL-6 secretion was reduced by 82%. All the extracts demonstrate efficacy in reduction of intracellular reactive oxygen species (ROS) production and the same was observed for NO (nitric oxide) concentration in the cell culture supernatant after the administration of extracts. These results indicated the strong potential of employing phenolic wine waste extracts on the modulation of metabolic syndrome parameters, use that also brings environmental and socioeconomic advantages, since it brings an alternative for the use of residues.

Differences in the levels of sulphites and pesticide residues in soils and wines and under organic and conventional production methods

The surface and output of organic agriculture is growing steadily in recent years, being generally seen as a healthier, safer and more sustainable alternative to conventional agriculture. Comparisons between organic and conventional products are nonetheless scarce in the literature, especially in the case of wine. The aim of this study was to compare sulphite content and pesticide residues in both soils and wines under organic and conventional production. Fourteen samples of organic and conventional wines and vineyard soils were collected in pairs for each of the seven wine-producing islands of the Canary Islands. A QuEChERS-based method was employed to detect 218 pesticides and 49 POPs. Sulphites were measured by potentiometric titration with a double electrode. On average, higher levels of sulphites were found in conventional wines. Similarly, conventional wines presented higher numbers and concentrations of pesticide residues both in soils and wines than their organic counterparts. The overall pesticide concentrations in our sample was 4.2 µg/kg. Conventional wines presented a considerably higher average concentration than organic wines (8.2 against 0.25 µg/kg). In turn, concentrations in conventional soils averaged 8.7 against 2.8 µg/kg in organic soils, a 68.19 % lower residue concentration. The analytes most commonly found were PCB 28, p,p′-DDE, tebuconazole and the metabolite 4,4′-dichlorobenzophenone in soils and mefenoxam, tebuconazole, fluopyram and boscalid in wines. No single wine exceeded the 10 % of the MRLs established by the European Union for wine grapes. However, the presence of low levels of pesticides in organic wines should be monitored.

Pesticide residues, copper and biogenic amines in conventional and organic wines

The aim of this study was to compare pesticide residues, copper and biogenic amines concentrations in conventional and organic wines. For each type of wine production, 20 samples were collected. We used two multi-residual methods employing GC/MS (92 pesticides) and LC/MS/MS (112 pesticides) detection. Copper residues and biogenic amines were measured by standard FAAS and HPLC methods. We confirmed lower numbers and concentrations of pesticide residues in organic wines. The most frequently determined pesticide was dimethomorph, followed by boscalid, fenhexamid, metalaxyl + metalaxyl-M, iprovalicarb and pyrimethanil. Also, higher levels of copper were observed in the groups of conventional wines. For biogenic amines, we could not confirm a clear trend. It is unacceptable that some pesticide residues in organic wines were detected, which are not allowed in this type of production. Nevertheless, we can confirm the trend of added value in organic wine production in terms of reducing pesticide residues and copper in bottled wines. - Added value is in organic wine production in terms of pesticides and copper reduction. - Producers should avoid some commonly found pesticide residues in the last sprays. - No significant difference in the occurrence and concentrations of biogenic amines between both groups of wines.

The Role of Biostimulants as Alleviators of Biotic and Abiotic Stresses in Grapevine: A Review.

The viticulture and wine industry contribute to the economy and reputation of many countries all over the world. With the predicted climate change, a negative impact on grapevine physiology, growth, production, and quality of berries is expected. On the other hand, the impact of these changes in phytopathogenic fungi development, survival rates, and host susceptibility is unpredictable. Grapevine fungal diseases control has been a great challenge to winegrowers worldwide. The use of chemicals in viticulture is high, which can result in the development of pathogen resistance, increasingly raising concerns regarding residues in wine and effects on human and environmental health. Promoting sustainable patterns of production is one of the overarching objectives and essential requirements for sustainable development. Alternative holistic approaches, such as those making use of biostimulants, are emerging in order to reduce the consequences of biotic and abiotic stresses in the grapevine, namely preventing grape fungal diseases, improving grapevine resistance to water stress, and increasing yield and berry quality.

An immunochromatographic assay for the rapid detection of oxadixyl in cucumber, tomato and wine samples

Oxadixyl is a systemic phenylamide fungicide, used to prevent and control disease caused by phytophthora and downy mildew in a variety of cash crops. In this study, a hapten of oxadixyl was designed and used to prepare a highly specific and sensitive anti-oxadixyl monoclonal antibody (mAb) with a 50% inhibition concentration of 3.68 ng/mL. An immunochromatographic assay (ICA) was developed for screening of oxadixyl residues in cucumber, tomato and wine. The ICA strip provided a visible limit of detection (vLOD) of 1 ng/g and a cut-off value of 20 ng/g in cucumbers and tomatoes and displayed a vLOD of 5 ng/mL and a cut-off value of 100 ng/mL in wine. The calculated limit of detection (cLOD) values of the ICA were 1.45 and 0.55 ng/g for cucumbers and tomatoes and 2.11 ng/mL for wine. The ICA gave recovery rates of 95.4–106.0% for cucumber samples, 96.4–99.5% for tomato samples and 93.0–97.4% for wine samples. Moreover, the test results provided by the ICA were highly consistent with those of LC/MS. These results and data indicated that the ICA was an effective and practical method for rapid and high-throughput detection of oxadixyl residues in cucumber, tomato, wine and other food samples.

The research of effect of diluents to the amount of pesticide residues in wine

The effect of various substances on the composition and quality of wine has been studied. Only imazalil residue was 0.35 µg/dm3, in course of use the activated coal in a dose of 300 mg/dm3 and no other pesticides were found. The pesticide residue was totally over during the next use of doses (450 & 600 mg/dm3) of the activated coal. So, the dose of activated coal of 450 mg/dm3 is sufficient to remove totally the residue of pesticide out of wine examples. The more significant dose of bentonite was 600 mg/dm3. In this case, the most affected one was imazalil. İncreasing the dose of casein from 150 mg/dm3 up to 600 mg/dm3 is observed decreasing with about 5-10 times of the different pesticide residue but these doses weren`t enough to remove the pesticide totally/ we can see show α-endosulfan (about 10 times) and pencondzolen (about 6 times) among highly affected pesticide residues. The weakest effect was PVPP and the strongest one was attributed to activated coal during the removing process of pesticides residues by diluents.

Preparation and characterization of an edible metal-organic framework/rice wine residue composite.

In this communication, using rice wine residue (RWR) as the support, an edible γ-cyclodextrin-metal–organic framework/RWR (γ-CD-MOF/RWR) composite with a macroscopic morphology was synthesized. The obtained edible composite is promising for applications in drug delivery, adsorption, food processing, and others.

Approaches to liquid chromatography tandem mass spectrometry assessment of glyphosate residues in wine

The performance of two different analytical methodologies to investigate the presence of glyphosate (GLY) and aminomethylphosphonic acid (AMPA) residues in wine samples was evaluated. Transformation of compounds in their fluorene-9-methyloxycarbonyl derivatives permitted their separation under reversed-phase liquid chromatography with tandem mass spectrometry (LC–MS/MS) determination. Although the wine matrix severely impaired the efficiency of GLY derivatization, this drawback was solved using a molecularly imprinted sorbent for the previous, selective extraction of GLY and AMPA from wine. Alternatively, the use of a strong anionic exchange, polyvinyl alcohol-based LC column, turned to be the most effective alternative for direct determination of both compounds in diluted wine samples. The chromatographic behavior of this column and the magnitude of matrix effects observed during analysis of diluted wine samples were significantly affected by the composition of the mobile phase. Under final working conditions, this column permitted the separation of AMPA and the fungicide fosetyl (which shows common transitions in tandem MS/MS methods), it improved significantly the sample throughput versus extraction-derivatization-purification method, and it allowed the use of solvent-based calibration standards. Both analytical procedures provided similar limits of quantification (LOQs) for GLY (0.5–1.0 ng mL−1), while the multistep method was 8 times more sensitive to AMPA than the direct procedure. GLY residues stayed above method LOQs in 70% of the processed wines; however, concentrations measured in 95% of positive samples remained 100 times below the maximum residue limit (MRL) set for GLY in vinification grapes.Graphical abstract

Utilizing a Rapid Multi-Plug Filtration Cleanup Method for 72 Pesticide Residues in Grape Wines Followed by Detection with Gas Chromatography Tandem Mass Spectrometry

A convenient and fast multi-residue method for the efficient identification and quantification of 72 pesticides belonging to different chemical classes in red and white grape wines has been developed. The analysis was based on gas chromatography tandem quadrupole mass spectrometric determination (GC–MS/MS). The optimization strategy involved the selection of the amount of multi-walled carbon nanotubes (MWCNTs) and the number of cleanup procedure cycles for multi-plug filtration cleanup (m-PFC) to achieve ideal recoveries and reduce the sample matrix compounds in the final extracts. The optimized procedure obtained consistent recoveries between 70.2 and 108.8% (70.2 and 108.8% for white wine, and 72.3 and 108.4% for red wine), with relative standard deviations (RSDs) that were generally lower than 9.2% at the three spiking levels of 0.01, 0.05 and 0.1 mg/kg. The linearity was studied in the range between 0.002 and 0.1 mg/kg using pesticide standards prepared both in pure solvent and in the presence of the matrix, showing coefficients of determination (R2) higher than 0.9495 for all the pesticides. To improve accuracy, matrix-matched calibration curves were used for calculating the quantification results. Finally, the method was used successfully for detecting pesticide residues in commercial grape wines.

Determination of pesticide residues in wine by solid-phase extraction on-line combined with liquid chromatography tandem mass spectrometry

Liquid chromatography tandem mass spectrometry (LCMS/MS) has been combined with different sample preparation strategies to determine potential pesticide residues existing in wine. Herein, we propose the on-line coupling between solid-phase extraction (SPE), based on a reversed-phase polystyrene-divinyl benzene (PS-DVB) sorbent, and LCMS/MS for the automated monitoring of a selection of 48 pesticides (37 fungicides and 11 insecticides) in this beverage. Parameters affecting the sensitivity, selectivity, accuracy and robustness of the method are evaluated as function of sample volume, clean-up conditions, and number of extraction-desorption cycles performed with the same SPE cartridge. Considering a sample volume of 3 μL, the on-line SPE LCMS/MS method was free of MEs, attaining LOQs below 2.5 μg L−1, and providing recoveries in the range from 70 to 120 % for 90 % of investigated compounds. Increasing the volume of sample loaded in the on-line SPE cartridge to 25 μL permitted a further reduction of LOQs, with a linear response range (0.1–25 μg L −1), covering the analysis of low residue samples. Twelve out of 48 investigated compounds were noticed at individual concentrations above 10 μg L−1 in at least one out of 30 processed wines. In white wines, the sum of concentrations for iprovalicarb, fenhexamide and metalaxyl represented more than 50 % of total residues. As regards red wines, tebuconazole, cyprodinil and metalaxyl were the predominant species.

Combination of polyvinylpolypyrrolidone extraction and standard addition strategy for the accurate determination of multiple allergen residues in red wine by UPLC-MS/MS

During the winemaking process, fining materials derived from milk and egg products are traditionally used to remove undesirable substances to reduce bitterness and astringency. The possible residues of allergens in treated wine may pose a potential risk for allergy patients. In this study, we developed a method for the simultaneous quantification of eight allergens (αS1-casein, αS2-casein, β-casein, κ-casein, β-lactoglobulin, lysozyme, ovalbumin and ovotransferrin) in red wine by ultrahigh-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS). The sample was extracted with polyvinylpolypyrrolidone (PVPP) solution, following trypsin digestion and peptide-level purification by solid-phase extraction (SPE). A strategy based on standard addition was used for the accurate quantification of the target allergens in wine products. The limits of detection (LODs) were shown to be 0.003–0.015 μg/mL for milk allergens and 0.1 μg/mL for egg allergens. This economical and reliable method would be appropriate for routine analysis and further allergen label management for red wine.

Plant Fibers in Comparison with Other Fining Agents for the Reduction of Pesticide Residues and the Effect on the Volatile Profile of Austrian White and Red Wines

Pesticide residues in Austrian wines have so far been poorly documented. In 250 wines, 33 grape musts and 45 musts in fermentation, no limit values were exceeded, but in some cases high levels (>0.100 mg/L) of single residues were found, meaning that a reduction of these levels before bottling could make sense. In the course of this study, a white and a red wine were spiked with a mix of 23 pesticide residues from the group of fungicides (including botryticides), herbicides and insecticides. The influence of the following treatments on residue concentrations and volatile profiles were investigated: two activated charcoal products, a bentonite clay, two commercial mixed fining agents made of bentonite and charcoal, two yeast cell wall products, and a plant fiber-based novel filter additive. The results of this study show that all the agents tested reduced both residues and volatile compounds in wine, with activated charcoal having the strongest effect and bentonite the weakest. The mixed agents and yeast wall products showed less aroma losses than charcoal products, but also lower residue reduction. Plant fibers showed good reduction of pesticides with moderate aroma damage, but these results need to be confirmed under practical conditions.

Physical, chemical, and biological evaluation of nanoparticles containing phenolic compounds from wine production residues

The objective of the study was to perform the nanoencapsulation of phenolic compounds from wine residues and to evaluate the in vitro antioxidant activity and simulated gastrointestinal digestion of the particles, as well as the in vivo influence on oxidative stress and longevity in Caenorhabditis elegans. Nanoparticles were formulated and produced using spray drying, freeze drying, and low-energy emulsion. The content of anthocyanins, phenolic compounds, and total flavonoids; as well as in vitro antioxidant activity, particle size and morphology of the nanoparticles were assessed. The highest bioactivity was observed for nanoparticles formulated using Shiraz and Merlot extracts, being confirmed in the simulated gastrointestinal digestion. The in vivo assays revealed that Shiraz nanoparticles acted as pro-oxidants with no resistance to oxidative stress and caused decreased longevity. Conversely, Merlot nanoparticles showed high resistance to oxidative stress and increased the longevity of C. elegans, to a maximum survival of 37 days. Practical applications The nanoparticles of phenolic winemaking residues were evaluated. They presented antioxidant activity and showed a good gastrointestinal performance. In addition, the nanoparticles of wine residues would influence positively lifespan of Caenorhabditis elegans. In this way, this study can contribute for the utilization of this type of residue in food applications.

Accurate mass screening of pesticide residues in wine by modified QuEChERS and LC-hybrid LTQ/Orbitrap-MS

In this research, a quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction procedure and Ultra-High Performance Liquid Chromatography-Orbitrap-Mass Spectrometry (UHPLC-Orbitrap-MS), were combined to obtain a sensitive and rapid method for the determination of multiclass pesticides in white and red wines. The optimization strategy involved the selection of buffering conditions, by applying different QuEChERS procedures and sorbents for the cleanup step in order to achieve acceptably high recoveries and low co-extractives in the final extracts. Identification was based on both accurate mass and retention time, while further confirmation was achieved by MS fragmentation. The method was evaluated in terms of linearity, recovery, precision, limit of detection (LOD) and quantification (LOQ), matrix effects (ME) and expanded uncertainty. The validated method was successfully applied to real samples (home-made and commercial) revealing the presence of two selected fungicides, in relatively low levels compared to the MRLs defined by the EU for vinification grapes.

Ultrasound-Assisted Enzymatic Extraction of Anthocyanins from Raspberry Wine Residues: Process Optimization, Isolation, Purification, and Bioactivity Determination

Raspberry wine residues (RWR) contain abundant anthocyanins. The extraction conditions for the ultrasound-assisted enzymatic extraction (UAEE) of anthocyanins from RWR were optimized using response surface methodology coupled with genetic algorithm. The optimum extraction parameters were extraction temperature of 44 °C, ultrasound power of 290 W, pectinase dosage of 0.16%, and extraction time of 30 min. Results showed that UAEE exhibited the highest anthocyanin yield (0.853 ± 0.009) mg/g and extraction efficiency (84.75 ± 2.11)% when compared with the other three conventional extraction methods (hot water-, acidified ethanol-, and enzymatic-assisted extractions). UAEE method was available for realizing high activities of DPPH (417.15 ± 11.83) Trolox equivalents/g extract and ABTS (520.07 ± 8.29) Trolox equivalents/g extract, and reducing power (412.79 ± 9.11) Trolox equivalents/g extract. AB-8 macroporous resin, Sephadex LH-20 column chromatography, and high-speed countercurrent chromatography (HSCCC) were used to separate and purify anthocyanins in turn. The main anthocyanins were identified by using HPLC-MS/MS and NMR. The two main anthocyanins (cyanidin-3-glucoside with the purity of 93.46% and cyanidin-3-rutinoside with the purity of 94.16%) were obtained from RWR. Ultimately, we further evaluated the anti-tumor activity of the main anthocyanins on lung cancer. Results showed that the anti-tumor effect of cyanidin-3-rutinoside on A549 cells was better than that of cyanidin-3-glucoside. In addition, cyanidin-3-rutinoside could memorably increase intracellular ROS levels and apoptosis of MCF-7 cells. The UAEE is an effective and rapid method. This method has a broad application prospect in the extraction of bioactive substances from natural plant resources.

Hydrophobic deep eutectic solvent-based ultrasonic-assisted dispersive liquid-liquid microextraction for preconcentration and determination of trace cadmium and arsenic in wine samples

In present study, DL-lactic acid/trioctylmethylammonium chloride-based deep eutectic solvent (DES), which was considered as an environmental friendly extraction solvent to replace traditional organic reagent, was firstly presented for monitoring of trace cadmium (Cd) and arsenic (As) in wine samples by ultrasonic-assisted dispersive liquid-liquid microextraction (UA-DLLME) method. Moreover, different extraction conditions, including the type and volume of DES and dispersive solvent, pH of the solution, salt amount, time of vortex and sonication, were systematically evaluated. At the optimized extraction conditions, good linear relationships (0.50–8.0 μg·L−1 for Cd, 2.0–50 μg·L−1 for As) were obtained and limits of detection of Cd and As were 0.080 and 0.30 μg·L−1, respectively. In addition, the accuracy (as recoveries %), and intra-/inter-day precision (as relative standard deviation %) were in the ranges of 90.6–103.6% and 2.9–4.5%, respectively. Finally, the proposed method was applied to analyze 6 kinds of wine samples, which possessed wide practical application value in monitoring heavy metal residues in wine and even complex food matrices.

Modeling the Methane Production Kinetics of Anaerobic Co-Digestion of Agricultural Wastes Using Sigmoidal Functions

The modified sigmoidal bacteria growth functions (the modified Gompertz, logistic, and Richards) were used to evaluate the methane production process kinetics of agricultural wastes. The mesophilic anaerobic co-digestion experiments were conducted with various agricultural wastes as feedstocks, including cow manure, corn straw, grape leaves, vines, wine residue, strawberry leaves, and tomato leaves. The results showed that anaerobic co-digestion of cow manure and other agricultural wastes increased the methane yields while it prolonged the lag phase time. Compared with the modified Gompertz and logistic models, the modified Richards model obtained higher correlation coefficients and was able to fit experimental data better. The results of this study were expected to determine a suitable model to simulate and study the kinetic process of anaerobic co-digestion with mixed agricultural wastes as feedstocks.

Metodi za določanje ostankov fitofarmacevtskih sredstev v vinu s sorpcijsko ekstrakcijo z mešalom ter študija slovenskih vin s trgovskih polic

New analytical methods for the determination of pesticide residues in wine were introduced and validated. Extraction was performed with sorption of the active substances on the stir bar and determination by gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry. The methods were applied in practice. A total of 77 active substances were searched for in 42 wine samples from all 3 wine-growing regions of Slovenia. The fungicides dimethomorph, fludioxonil and pyraclostrobin were found in 78.6% of all analysed samples. The risk assessment concluded that the analysed wine samples do not pose an unacceptable risk to consumers. The results were compared with previous studies.

Study of Tetrahydroxylated Anthraquinones-Potential Tool to Assess Degradation of Anthocyanins Rich Food.

Degradation of anthocyanins involves scission of the flavonoid skeleton yielding 2,4,6-trihydroxybenzaldehyde (phloroglucinaldehyde, PGA) and a phenolic acid. However, the process is not finished with the formation of PGA, as the consequent condensation of two PGA molecules providing colored hydroxylated anthraquinones was observed for the first time. This process was studied using a combination of preparative column chromatography, nuclear magnetic resonance, liquid chromatography/high resolution tandem mass spectrometry (LC/HRMS2), and quantum calculations using density functional theory. 1,3,5,7-tetrahydroxyanthraquinone (anthrachrysone) and its isomers were found to rise during heating (95 °C) in a buffered PGA model solution (phosphate buffer, pH 7). These compounds were detected in heated red wine after an increase of its pH value. The concentration of the identified anthrachrysone in the red wine reached 0.01 mg·L−1. Presence of those compounds could therefore indicate involvement of certain steps in the processing of plant materials rich in anthocyanins (e.g., utilization of a higher temperature and/or reduction of acidity) or long-term transformation of anthocyanins (potentially, for instance, in archaeological findings such as wine or fruit residues). Additionally, measurement of wine–soil suspensions proved an increase of their pH to the values suitable for anthocyanin cleavage (neutral to slightly alkaline; reached using soil from archaeologically well-known Bull Rock Cave). Although not found in artificially prepared samples (imitations) or authentic materials so far, according to our results the above mentioned conditions are suitable for the formation of tetrahydroxylated anthraquinone derivatives and their monitoring would be beneficial.

English

The aim of this study was to assess the level of pesticide residues in locally produced grape wine in Tanzania. Fifty samples of grape wine from different locations in Dodoma urban and Bahi district were analyzed to determine the presence of 49 pesticides using the quick, easy, cheap, effective, rugged and safe (QuEChERS) multi-residue extraction, followed by gas chromatography-tandem mass spectrometry (GC-MS/MS). Twenty-two pesticides were detected among the 49 pesticides analyzed. The selected 49 pesticides was based on its use in grape cultivation which were reported by grape farmers in the study location which includes fungicides, insecticides and herbicides. The pesticides whose concentrations exceeded the maximum residue levels (MRL) were: Pyroquilon, ethofumasate, chlorobeb, azobenzene and cycloate in 38, 33, 46, 14 and 1 wine samples, respectively. Of the samples analyzed 9 (18%) contained one pesticide, 8 (16%) contained two different pesticides, 23 (46%) contained three different pesticides 8 (16%). The results indicated the occurrence of pesticide residues in grape wine produced in Dodoma urban and Bahi districts, Tanzania, and pointed to an urgent need to develop comprehensive intervention measures to reduce potential health risk to consumers. Key words: Pesticides residues, grape wine, food safety, maximum residue levels (MRL).