Fate of multi-residue insecticides and their metabolites in the process of vinification: Analytical method validation, dissipation kinetics, processing factor, and risk assessment.

In viticulture, the use of synthetic chemical formulations introduces insecticide residues into harvested grapes and further into processed grape products, posing a safety concern to consumers. This study investigated the fate of ten insecticide residues and their metabolites from vine to wine. A rapid validated multi-residue approach using QuEChERS extraction and LC-MS/MS configuration was employed for targeted analysis in grape, pomace, and wine. The targeted insecticides showed satisfactory mean recoveries (76.03-111.95%) and precision (RSD = 0.75-7.90%) across the three matrices, with a matrix effect ranging from -16.88 to 35.18%, particularly higher in pomace. Preliminary grape washing effectively removed 15.52-61.31% of insecticide residues based on water solubility and systemic nature. Residue dissipation during fermentation ranged from 73.19% to 87.15% with a half-life spanning from 1 to 5.5 days. The mitigation rate was observed at 12.85-26.81% for wine and 17.76-51.55% for pomace, with the highest transfer rate for buprofezin (51.55%) to pomace and fipronil (25.72%) to wine. Calculated processing factors (PF) for final wine ranged from 0.16 to 0.44, correlating strongly with the octanol-water partition ratio of targeted insecticides. The reported PF, calculated hazard quotient (HQ) (0.003-5.800%), and chronic hazard index (cHI) (2.041-10.387%) indicate reduced residue concentrations in wine and no potential chronic risk to consumers, ensuring a lower dietary risk to wine consumers.

Application of Fourier-Transform Infrared Spectroscopy for the Assessment of Wine Spoilage Indicators: A Feasibility Study.

Wine aroma is one of the most frequently used and explored quality indicators. Typically, its assessment involves estimating the volatile composition of wine or highly trained assessors conducting sensory analysis. However, current methodologies rely on slow, expensive and complicated analytical procedures. Additionally, sensory evaluation is inherently subjective in nature. Therefore, the aim of this work is to verify the feasibility of using FTIR spectroscopy as a fast and easy methodology for the early detection of some of the most common off-odors in wines. FTIR spectroscopy was combined with partial least squares (PLS) regression for the simultaneous measurement of isoamyl alcohol, isobutanol, 1-hexanol, butyric acid, isobutyric acid, decanoic acid, ethyl acetate, furfural and acetoin. The precision and accuracy of developed calibration models (R2P > 0.90, range error ratio > 12.1 and RPD > 3.1) proved the ability of the proposed methodology to quantify the aforementioned compounds.

Comparative assessment of Riesling wine fault development by the electronic tongue and a sensory panel.

Wine faults threaten brand recognition and consumer brand loyalty. The objective of this study was to compare the acuteness of e-tongue and human sensory evaluation of wine fault development in Riesling wine over 42 days of storage. Riesling wines uninoculated (control) or inoculated with 104 CFU/mL cultures of Wickerhamomyces anomalus, Acetobacter aceti, Lactobacillus brevis, or Pediococcus parvulus were assessed every 7 days with the e-tongue and a rate-all-that-apply (RATA) sensory panel. After 7 days of storage, the e-tongue detected differences in all four wine spoilage microorganism treatments, compared to control wine, with discrimination indices over 86%. The RATA sensory panel detected significant differences beginning on day 35 of storage, 28 days after the e-tongue detected differences. This study showed that the e-tongue was more sensitive than the human panel as a detection tool, without sensory fatigue. PRACTICAL APPLICATION: This research is useful for winemakers seeking additional instrumental methods in the early detection of wine faults. Given the results of this study, the e-tongue can be a useful tool for detecting early chemical changes in white wines that have undergone microbial spoilage, providing winemakers with time to mitigate faults before they surpass sensory thresholds.

Can Italian wines outperform European benchmarks in environmental impact? An examination through the product environmental footprint method.

Nowadays, there is a pressing demand for precise tools to quantify sustainability and assess the contributions of products and processes to sustainable development. This requirement extends to the wine industry as well. In 2013, the European Commission introduced the Product Environmental Footprint (PEF), providing a standardized methodology grounded in life cycle thinking for evaluating the environmental impacts of products across various industries. Despite its potential and the availability of specific guidelines for wine, the application of PEF remains unexplored in the sector. This study contributes to the knowledge by applying PEF to assess environmental impacts of Italian still and sparkling wines production, identifying variations from European benchmarks. Additionally, it aims to pinpoint pivotal hotspots and provide guidance for effective mitigation strategies. Average data from 27 wines certified as sustainable under Italian VIVA program, were collected and used to perform a life cycle assessment in accordance with PEF protocol. Results revealed that Italian still wines exhibited a greater environmental impact than the European reference value, while sparkling wines displayed a slightly more favourable environmental performance compared to the European average. Notably, specific impact categories remained consistent across different wines and countries, with climate change, resource utilization, land use, and particulate matter harmful for human health accounting for nearly 80 % of the overall environmental footprint. Hotspot analysis identified the plantation/destruction of vines, energy usage in the winery, and packaging as significant factors influencing the environmental footprint of Italian wines. Addressing these elements could enhance the environmental competitiveness of the Italian wine sector relative to its European counterparts. However, to validate these findings, further studies are necessary, both within Italy and in other European wine-producing regions. Such research initiatives will improve and strengthen PEF methodology, bolstering its adoption as the primary tool for environmental impact assessment of wine at the community level.

Semi-industrial ultrasound-assisted extraction of grape-seed proteins.

BACKGROUND: To manage industrial waste in accordance with the circular bioeconomy concept it is sometimes necessary to handle grape seeds, an abundant by-product of the wine-making process. This study presents a process based on ultrasound technology for the extraction of grape-seed proteins, due to their nutritional and techno-functional properties. The protein content of extracts obtained under silent and lab-scale conditions was compared with that obtained under semi-industrial ultrasound conditions, and the chemical composition (carbohydrates, total phenols, and lipids) and the elemental profiles of the final, up-scaled downstream extracts were characterized. RESULTS: This work found that the maximum amount of protein in the final product was 378.31 g.kg-1 of the extract. Chemical characterization revealed that each 1 kg of extract had an average content of 326.19 g gallic acid equivalent as total phenols, 162.57 g glucose equivalent as carbohydrates, and 382.76 g of lipophilic compounds. Furthermore, when the extract was checked for hazardous elements, none were found in levels that could be considered a risk for human health. CONCLUSION: The proposed semi-industrial strategy has the potential to contribute greatly to the valorization of grape seeds through the preparation of a protein-rich extract that can be used as an alternative to synthetic wine stabilizers and for the development of novel food and nutraceutical products. © 2024 Society of Chemical Industry.

Chemical and Electrochemical Assessment of Wine Lees Extracts Tested as Novel Antioxidant Additives in Model Wine.

Yeast derivatives are used in winemaking for a variety of purposes, including the protection of wines from oxidation. In this work, by the application of an autoclave extraction method, different fractions were obtained from red wine lees and a lab-grown culture of the same yeast strain. Each extract was characterized for their protein, polysaccharide, glutathione, thiol, and polyphenol contents. The antioxidant activity was tested by adding each extract in a model wine enriched with catechin and saturated with oxygen. The presence of both wine lees and lab-grown yeast extracts delayed oxygen consumption when compared to the untreated control. This delay was confirmed by the development of a yellow color, which was lower in 5 out of 6 of the samples added with yeast/lees extracts. The electrochemical behavior of the samples also showed a greater resistance to oxidation, thus suggesting a protective role of the wine lees extracts against wine oxidative phenomena.

Removal of ochratoxin A in wine by Cryptococcus albidus and safety assessment of degradation products.

BACKGROUND: Ochratoxin A (OTA) is a mycotoxin that contaminates grape-based products and is extremely harmful to the health of the host. It is effectively removed by yeast during the fermentation of wine, whereas the removal mechanism of OTA remains unclear. Therefore, the present study aimed to investigate the removal mechanism of ochratoxin A by yeast and to evaluate the safety of its degradation products. RESULTS: Cryptococcus albidus (20-G) with better effect on ochratoxin A (OTA) was screened out in the main fermentation stage of wine. The results showed that 20-G removed OTA through biosorption and biodegradation. Intracellular enzymes played the main role (18.44%) and yeast cell walls adsorbed a small amount of OTA (8.44%). Furthermore, the identification of proteins in 20-G revealed that the decrease in OTA content was mainly a result of the action of peroxidase, and validation tests were carried out. By analyzing the degradation products of OTA, OTα and phenylalanine with lower toxicity were obtained. Animal experiments showed that the intervention of yeast 20-G reduced the damage and adverse effects caused by OTA toxicity to the mice. CONCLUSION: The present study demonstrates the mechanism of OTA removal by 20-G and the toxicity of OTA was reduced by peroxidase in 20-G. © 2023 Society of Chemical Industry.

Assessment of the volatile and non-volatile profile of Savatiano PGI wines as affected by various terroirs in Attica, Greece.

Establishing the concept of terroir in wines, combined with the exploitation of native grape varieties, is considered a viable alternative to produce quality wines for increasing interest in the wine market. The aim of this study is the characterization of Protected Geographical Indication (PGI) Savatiano white wines from different regions of Attica (Greece), through the chemical and sensory description of the aroma of wines and the determination of their phenolic profiles. The wines produced with the same vinification protocol were evaluated using the descriptive sensory analysis method while they underwent profiling of volatile and phenolic compounds by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) respectively. The presence of regional differences within the wines was also explored, elaborated with variables that contribute to their differentiation, such as soil type, monthly average temperature, and rainfall. Volatile and sensory profiles of the wines separated the regions and confirmed that sub-regional differences attributed mainly to soil characteristics affect wine aroma. The wines from the east part of Attica were higher in esters, terpenes and higher alcohols with high scores in fruity and blossoms attributes while wines from the north part of Attica presented higher intensity of mineral, nutty and herbaceous attributes. The separations based solely on the phenolic compounds concentration were less clear but a relationship was found between the content of phenolic acids and flavonoids and the studied regions. To our knowledge this is the first characterization of Savatiano PGI wines of Attica generating a fingerprint including chemical composition and sensory aroma characteristics to differentiate wines, combining this pattern with particular sub-regions.

Paper chromatography approach for the assessment of interaction between red wine and whole saliva.

In-mouth interaction of red wine compounds with salivary proteins is a primary event allegedly responsible for eliciting the mouth-feel sensation of astringency. Those interactions have been currently associated with precipitation of salivary protein/polyphenol complexes. However, such single physicochemical evidence for interaction does not account for the complexity of astringency. This study aimed to develop a paper chromatography method to assess interactions between red wine and the salivary protein fraction using stepwise series of red wine/saliva binary mixtures from 100% wine to 100% saliva ("Alpha and Omega series"). Aliquots of each one of the mixtures were spotted on a cellulose membrane to scrutinize independently the distribution areas of wine components (naturally pink-colored) and salivary protein (stained blue in Coomassie Brilliant R-250). This double target detection revealed interactions between saliva and red wine components along most of the quantitative Alpha and Omega series, a point of equivalence corresponding to maximum interactivity for both complex reactants and a non-diffusible sub-fraction of saliva displaying the highest interactivity. The results indicate a novel way to assess quantitatively physicochemical interactions between red wines and human saliva but also provide new lights to approach the identification of molecular salivary structures involved in triggering astringency.

Development of a Novel Magnetic-Bead-Based Automated Strategy for Efficient and Low-Cost Sample Preparation for Ochratoxin A Detection Using Mycotoxin-Albumin Interaction.

The mycotoxin ochratoxin A (OTA) is toxic to humans and frequently contaminates wine and beer. Antibodies are essential recognition probes for the detection of OTA. However, they have several drawbacks, such as high costs and difficulty in preparation. In this study, a novel magnetic-bead-based automated strategy for efficient and low-cost OTA sample preparation was developed. Human serum albumin, which is an economical and stable receptor based on the mycotoxin-albumin interaction, was adapted and validated to replace conventional antibodies to capture OTA in the sample. Ultra-performance liquid chromatography-fluorescence detection was used in combination with this preparation method for efficient detection. The effects of different conditions on this method were investigated. The recovery of OTA samples spiked at three different concentrations ranged from 91.2% to 102.1%, and the relative standard deviations (RSDs) were 1.2%-8.2% in wine and beer. For red wine and beer samples, the LODs were 0.37 and 0.15 µg/L, respectively. This reliable method overcomes the drawbacks of conventional methods and offers significant application prospects.

Redox Biomarkers Assessment after Oral Administration of Wine Extract and Grape Stem Extract in Rats and Mice.

Wine and by-products of the winemaking process, such as grape stems, are rich in bioactive polyphenolic compounds that might be beneficial for animal and human health. In recent years, the administration of dietary polyphenols with strong antioxidant and cytoprotective properties has constituted an emerging line of research interest toward disease prevention. However, in scientific literature, only a limited number of studies have investigated the safety and the toxicological risks of polyphenolic compounds in vivo. Based on the above, the purpose of the present study was two-fold: first, to examine the effects of oral administration of a grape stem extract, derived from the Greek red wine Mavrodaphne, on mice redox biomarkers; and second, to investigate the biological effects of oral administration of a wine extract, derived from the emblematic Greek red wine Xinomavro, on rats. Toward this purpose, body weight, growth rate, hematological, biochemical, and histopathological parameters, as well as a panel of redox biomarkers, were examined. According to our results, the administration of Mavrodaphne grape stem extract in mice induced alterations in redox homeostasis, preventing mice from the adverse effects of lipid peroxidation. Contrariwise, the administration of Xinomavro wine extract induced both beneficial and harmful outcomes on rat redox status determined by the examined tissue. Collectively, our study reports that the Mavrodaphne grape stem extract, a serious pollutant when disposed in environmental matrices, is an important source of bioactive polyphenolic compounds that could protect from oxidative damage and improve animal and human health. Finally, the Xinomavro wine extract exerts tissue-specific changes in redox balance, which are indicative of the complexity that characterizes the biological systems.

Low-cost and portable colorimetric platform for simultaneous detection of Fe, methanol, and total phenols in wine.

A multi-channel colorimetric device was developed for the low-cost and simultaneous determination of three important parameters in wine safety and quality- total iron (Fe), methanol (MeOH), and total phenols. The detection was performed by assembling light-dependent resistors and light-emitting diodes in a 3D printed chamber, which measured colorimetric signals horizontally transmitting through the microwells of an 8-well strip. This device demonstrated linear relationships (R2 greater than 0.99) for all analytes with detection limits of 0.04 mg/L, 2.26 mg/L, and 3.40 mg/L for Fe, MeOH, and total phenols, respectively. Wine sample measurements showed that the multi-channel device was as accurate as the professional spectrophotometer and could simultaneously provide the three target concentrations to facilitate the analysis. With the merits of low fabrication cost and ease of use, this device could be used as a general platform for multiple-target detection, demonstrating great potential for application in food analysis.

Bioactive Amines in Wines. The Assessment of Quality Descriptors by Flow Injection Analysis with Tandem Mass Spectrometry.

Biogenic amines (BAs) occur in a wide variety of foodstuffs, mainly from the decomposition of proteins by the action of microorganisms. They are involved in several cellular functions but may become toxic when ingested in high amounts through the diet. In the case of oenological products, BAs are already present in low concentrations in must, and their levels rise dramatically during the fermentation processes. This paper proposes a rapid method for the determination of BAs in wines and related samples based on precolumn derivatization with dansyl chloride and further detection by flow injection analysis with tandem mass spectrometry. Some remarkable analytes such as putrescine, ethanolamine, histamine, and tyramine have been quantified in the samples. Concentrations obtained have shown interesting patterns, pointing out the role of BAs as quality descriptors. Furthermore, it has been found that the BA content also depends on the vinification practices, with malolactic fermentation being a significant step in the formation of BAs. From the point of view of health, concentrations found in the samples are, in general, below 10 mg L-1, so the consumption of these products does not represent any special concern. In conclusion, the proposed method results in a suitable approach for a fast screening of this family of bioactive compounds in wines to evaluate quality and health issues.

Multivariate Statistical Analysis for Mutual Dependence Assessment of Selected Polyphenols, Organic Acids and Metals in Cool-Climate Wines.

Polyphenols, organic acids and metal ions are an important group of compounds that affect the human health and quality of food and beverage products, including wines. It is known that a specific correlation between these groups exist. While wines coming from the New World and the Old World countries are extensively studied, wines coming from cool-climate countries are rarely discussed in the literature. One of the goals of this study was to determine the elemental composition of the wine samples, which later on, together as polyphenols and organic acids content, was used as input data for chemometric analysis. The multivariate statistical approach was applied in order to find specific correlations between the selected group of compounds in the cool-climate wines and the features that distinguish the most and differ between red and white wines and rosé wines. Moreover, special attention was paid to resveratrol and its correlation with selected wine constituents.

Correlating Sensory Assessment of Smoke-Tainted Wines with Inter-Laboratory Study Consensus Values for Volatile Phenols.

Vineyard exposure to wildfire smoke can taint grapes and wine. To understand the impact of this taint, it is imperative that the analytical methods used are accurate and precise. This study compared the variance across nine commercial and research laboratories following quantitative analysis of the same set of smoke-tainted wines. In parallel, correlations between the interlaboratory consensus values for smoke-taint markers and sensory analyses of the same smoke-tainted wines were evaluated. For free guaiacol, the mean accuracy was 94 ± 11% in model wine, while the free cresols and 4-methylguaiacol showed a negative bias and/or decreased precision relative to guaiacol. Similar trends were observed in smoke-tainted wines, with the cresols and glycosidically bound markers demonstrating high variance. Collectively, the interlaboratory results show that data from a single laboratory can be used quantitatively to understand smoke-taint. Results from different laboratories, however, should not be directly compared due to the high variance between study participants. Correlations between consensus compositional data and sensory evaluations suggest the risk of perceivable smoke-taint can be predicted from free cresol concentrations, overcoming limitations associated with the occurrence of some volatile phenols, guaiacol in particular, as natural constituents of some grape cultivars and of the oak used for barrel maturation.

Towards the Optimization of Microwave-Assisted Extraction and the Assessment of Chemical Profile, Antioxidant and Antimicrobial Activity of Wine Lees Extracts.

Wine lees, a sub-exploited byproduct of vinification, is considered a rich source of bioactive compounds, such as (poly)phenols, anthocyanins and tannins. Thus, the effective and rapid recovery of these biomolecules and the assessment of the bioactive properties of wine lees extracts is of utmost importance. Towards this direction, microwave-assisted extraction (MAE) factors (i.e., extraction time, microwave power and solvent/material ratio) were optimized using experimental design models in order to maximize the (poly)phenolic yield of the extracts. After optimizing the MAE process, the total phenolic content (TPC) as well as the antiradical, antioxidant and antimicrobial activity of the extracts were evaluated. Furthermore, Fourier transform infrared spectroscopy (FTIR) was employed to investigate the chemical profile of wine lees extracts. Red varieties exhibited higher biological activity than white varieties. The geographical origin and fermentation stage were also considered as critical factors. The white variety Moschofilero presented the highest antioxidant, antiradical and antimicrobial activity, while Merlot and Agiorgitiko samples showed noteworthy activities among red varieties. Moreover, IR spectra confirmed the presence of sugars, amino acids, organic acids and aromatic compounds. Thus, an efficient, rapid and eco-friendly process was proposed for further valorization of wine lees extracts.

Digital Assessment and Classification of Wine Faults Using a Low-Cost Electronic Nose, Near-Infrared Spectroscopy and Machine Learning Modelling.

The winemaking industry can benefit greatly by implementing digital technologies to avoid guesswork and the development of off-flavors and aromas in the final wines. This research presents results on the implementation of near-infrared spectroscopy (NIR) and a low-cost electronic nose (e-nose) coupled with machine learning to detect and assess wine faults. For this purpose, red and white base wines were used, and treatments consisted of spiked samples with 12 faults that are traditionally formed in wines. Results showed high accuracy in the classification models using NIR and e-nose for red wines (94-96%; 92-97%, respectively) and white wines (96-97%; 90-97%, respectively). Implementing new and emerging digital technologies could be a turning point for the winemaking industry to become more predictive in terms of decision-making and maintaining and increasing wine quality traits in a changing and challenging climate.

Isolation of a new taste-active brandy tannin A: Structural elucidation, quantitation and sensory assessment.

Enjoying a glass of spirits can be one of the delights of life. While it is well known that their taste improves during barrel aging, the molecular explanations of this phenomenon remain largely unknown. The present work aimed at searching for taste-active compounds formed in spirits during aging. An untargeted metabolomic approach using HRMS was applied on "eau-de-vie" of cognac. A fractionation protocol was then performed on brandies to isolate a targeted compound. By using HRMS and NMR, its structure was elucidated for the first time. This new ellagitannin, called brandy tannin A, considerably increased the sweetness of spirits at 2 mg/L. After development of an LC-HRMS quantitation method, it was assayed in various spirits and was detected mainly in cognacs up to 7 mg/L. These findings demonstrate the sensory contribution of this compound and more generally the relevance of combining metabolomics and separative techniques to purify new taste-active compounds.

Assessment of the lysogenic status in the lactic acid bacterium O. oeni during the spontaneous malolactic fermentation of red wines.

After alcoholic fermentation, most wines undergo malolactic fermentation (MLF), driven by the lactic acid bacterium Oenococcus oeni, which improves their organoleptic properties and microbiological stability. Prophages were recently shown to be notably diverse and widely disseminated in O. oeni genomes. Such in silico predictions confirmed previous cultivation-based approaches which showed frequent lysis of strains upon treatment with the inducing agent mitomycin C. Both strategies used to assess lysogeny in the species were so far applied to a number of strains collected from distinct countries, wineries, cepages and fermentation processes. Results may not therefore be representative of the lysogenic population in natural communities driving the MLF during winemaking. Here we report the prevalence of lysogeny during winemaking in three wineries in the Bordeaux area. The dominant LAB population was collected in 11 red wines upon completion of MLF. Using VNTR and prophage typing analyses, our data confirm the presence of lysogens in the population driving the spontaneous MLF in all tested wines, although lysogeny rates varied across wineries. Higher prevalence of lysogeny was associated to a reduced diversity in VNTR profiles, the dominance of a few prophage-types and presence of some bacterial genetic backgrounds that were particularly prone to lysogenization.

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.