Sulfur Dioxide In Wine Research Articles

A modified pararosaniline hydrochloride method for determination of total and bound sulfur dioxide in wine

An improved pararosaniline hydrochloride (PRA) method for rapid and accurate determination of total and bound sulfur dioxide (SO2) in wine was established. The determination conditions for total SO2 were optimized in model wine systems. The pH of the acidified PRA reagent had a significant effect on the color and the maximum absorption wavelength (λmax) of the reaction system, with its optimum pH 0.48 and a λmax at 549 nm. The addition of ethylene diamine tetraacetic acid (EDTA) could effectively shield the interference of coexisting metal ions present in wine, and a novel approach to double background subtraction was confirmed to remove the matrices interference of red wine color. Under the optimum conditions, the linear range for total SO2 in wine was within 1.00–8.00 mg L−1 (R = 0.9975), with the detection and quantification limits (MDL and MQL) found as 0.02 and 0.06 mg L−1, respectively. The recovery of SO2 ranged from 85.73 % to 105.70 % with the relative standard deviations (RSD) of 0.21 % - 7.78 %, suggesting high sensitivity and accuracy of the method. Combining with the optimized Monier-Williams method, the determination of bound SO2 in wine was also achieved. Sulfite determination can be performed in wine using the rapid, accurate and sensitive method without any pretreatment, and the results were comparable with those of the standard methods.

The use of chitosan and an inactivated yeast to reduce the amount of sulfur dioxide in wine

This study aims to evaluate the sulfur dioxide dynamics in two wines, dry white wine Fetească albă and dry red wine Fetească neagră made in Târnave vineyard, and to observe their evolution after application of Bactiless and Longevity to lower the level of SO2. The wines from 2020 harvest were produced using traditional winemaking techniques. The experimental variants were: Control, Longevity (20, 30, 40, 0, and 40 g/hL) with Bactiless (20, 35, 50, 50 and 0 g/hL). For all the samples studied in this work, it was determined a decrease concentration of free and total sulfur dioxide. The best results obtained for the Fetească albă wine was the decrease of free SO2 from 35.00 mg/L to 25.33±0.60 mg/L and total SO2 from 120.50 mg/L to 117.50 mg/L by using 50 g/hL of Bactiless (CFAV4). For the Fetească neagră wine, the best results obtained were the decrease of free SO2 from 32.50±0.29 mg/L to 14.83±0.18 mg/L and total SO2 from 85.00±0.87 mg/L to 75.00±0.86 mg/L by adding 40 g/hL of Longevity and 50 g/hL of Bactiless (CFNV3). With an allowed SO2 concentration, the evaluated wines maintained their varietal characteristics and organoleptic properties.

Validation of a fast automated photometric method for the analysis of sulfur dioxide in wines

In this work a simple and rapid automated analytical method for the determination of sulfur dioxide in wines by employing a sequential automatic analyser was validated. The methodology is based on the reaction of sulfur dioxide with 5,5′-dithiobis-(2-nitrobenzoic acid) in an alkaline medium followed by photometric detection. The linearity of the calibration curve was excellent (R2 = 1.000) and the LOQ (2.00 mg L−1) was well suited for the monitoring of regulatory limits. The accuracy and precision were evaluated with reference materials, providing highly successful results (RSD% < 3.8 for precision and R2 = 0.99 of correlation between the obtained and declared values). The method was applied to the analysis of commercial samples of wines ensuring compliance with legislation. The results found were compared to those obtained with the spectrophotometric method recommended for beers, implemented in a flow system, showing that there are no statistical differences between them (α ≤ 0.05). When compared with conventional methods, the proposed methodology showed to be fast, with minimum handling of the sample and small sample and reagents volume requirement, which together with a minimum maintenance, involves a considerable reduction in laboratory costs.

An Interference-Free Voltammetric Method for the Detection of Sulfur Dioxide in Wine Based on a Boron-Doped Diamond Electrode and Reaction Electrochemistry.

This paper describes a new, simple, and highly selective analytical technique for the detection of sulfur dioxide in wine, as a real sample with a relatively complicated matrix. The detection of the above analyte was based on the electrogeneration of iodine from iodide on a boron-doped diamond electrode, without modifications, in the presence of 0.1 mol dm-3 HClO4 as a supporting electrolyte. The electrogenerated iodine reacted with sulfur dioxide, forming iodide ions and sulfuric acid (i.e., a Bunsen reaction). The product of this reaction, the iodide ion, diffused back to the surface of the boron-doped diamond electrode and oxidized itself again. This chemical redox cycling enhanced the voltammetric response of the boron-doped diamond electrode. The selectivity of the determination was assured using NaOH and formaldehyde during sample preparation, and a blank was also measured and taken into account. The detection limit was estimated to be 10-6-10-7 mol dm-3. However, the content of sulfur dioxide in wine is significantly higher, which can lead to more accurate and reliable results.

Rapid determination of free sulfur dioxide in wine and cider by capillary electrophoresis

A novel method for the determination of “true” free sulfur dioxide (SO2) in wine and cider was developed using capillary electrophoresis with direct ultraviolet-visible spectrophotometric detection (CE-UV/vis). Free SO2 was measured in model solutions with different SO2-binding agents present (α-ketoglutarate, pyruvate, acetaldehyde, glucose, fructose, and malvidin-3-glucoside) as well as a variety of white and red wines and ciders. The CE method was compared to three conventional methods for measuring free SO2, the Ripper method, Aeration-Oxidation (AO), and pararosaniline by discrete analyzer (DA). While some statistically significant differences (p<0.05) were found between the four methods in unpigmented model solutions and samples, the values generally agreed. In the presence of anthocyanins in model solution and red wines, free SO2 values found by CE were significantly lower than the other three methods (p<0.05). The difference in values found by Ripper and CE correlated strongly with anthocyanin content (R2 = 0.8854) and even more strongly when accounting for polymeric pigments (R2 = 0.9251). The results in red ciders differed from those in red wines, while the CE measured significantly lower free SO2 values than the other three methods, the difference in free SO2 values measured by CE and Ripper correlated more closely with anthocyanin concentration (R2 = 0.8802) than absorbance due to bleachable pigment (R2 = 0.7770). The CE method was found to be rapid (4 min/injection), sensitive (LOD=0.5 mg/L, LOQ=1.6 mg/L free SO2 in wine, 0.8 and 2.8 mg/L, respectively, in cider), robust, and repeatable (average RSD = 4.9%) and did not suffer from the issue of over-reporting free SO2 in pigmented samples often observed with currently accepted methods.

Validation of a new method for the rapid determination of free sulfur dioxide in wine

Sulfur dioxide is widely used in most wines around the world. The determination of free SO2 is probably the most frequently conducted analysis in the wine industry used to assure wine conservation. The most frequently used methods of analysis are the aeration-oxidation method and the Ripper method. Both methods are relatively long and require specialized technicians. A new methodology based on voltammetry has been developed. It is based on a specialized hand-held automatic and fast analyzer that uses analytical stripes. This study compared this new method with the traditional aeration-oxidation and Ripper methods in a wide range of red and white wines. The results showed a good correlation of the voltametric method with the aeration-oxidation method as a standard and very similar results were observed with the Ripper method. Variability and precision were also high, validating the use of the proposed method for daily use in cellar work.

Microanalytical flow system for the simultaneous determination of acetic acid and free sulfur dioxide in wines

Free sulfur dioxide and volatile acidity are parameters related to the quality of wines. Traditional methods for their determination are tedious, time consuming and require analysis in decentralized laboratories, therefore corrective actions cannot be applied on time. This may be more complex in aging wine cellars, where hundreds of individual barrels containing almost finished wines should be monitored. To achieve this aim, a portable microanalytical flow system for the simultaneous detection of free SO2 and acetic acid during the ageing of wines is proposed in this work. The miniaturized system is based on the use of a gas-diffusion membrane and a pH-ISFET, and can be easily installed in barrels. The system was optimized in the range of 5–60 mg L−1 and 0.15–1.40 g L−1 for SO2 and acetic acid, respectively. It was validated with different sets of wine samples by comparing the results with standard methods, demonstrating a good agreement between methods.

Biotechnological Approach Based on Selected Saccharomyces cerevisiae Starters for Reducing the Use of Sulfur Dioxide in Wine.

Sulfites are considered the main additives in winemaking for their antimicrobial, antioxidant and anti-oxidasic activities. The current concern about the potential negative effects of sulfur dioxide (SO2) on consumer health has focused the interest on replacing or reducing SO2 use. Our work aims to develop a strategy based on the use of selected starter culture, able to perform wine fermentation without SO2 addition. Four selected Saccharomyces cerevisiae indigenous strains were tested as mixed starter cultures in laboratory scale fermentations. The starter culture, characterized by a similar percentage of dominance of both strains composing the mixed starter and able to produce a wine characterized by the best combination of chemical and aromatic characteristics, was chosen. This mixed culture was tested as a starter at pilot scale with and without SO2 addition, by using a higher inoculum level in the vinification without SO2. The selected starter confirmed higher dominance ability in vinification without SO2 addition than in SO2-added fermentation, demonstrating that sulfite addition is not a guarantee to reach an absolute dominance of starter culture on indigenous microflora. The proposed biotechnological tool allowed to produce good quality wines possessing also “functional properties”, as NO-SO2 added wines were characterized by high polyphenol content and antioxidant activity.

Direct quantification of sulfur dioxide in wine by Surface Enhanced Raman Spectroscopy

A rapid Surface Enhanced Raman Spectroscopy (SERS) method to detect SO2 in wine is presented, exploiting the preferential binding of silver nanoparticles (AgNPs) with sulfur-containing species. This interaction promotes the agglomeration of the AgNPs and inducing the formation of SERS “hot spots” responsible for SO2 signals enhancement. For increasing SO2 concentrations from 0 to100 mg/l in wine simulant, SERS intensity showed an increasing trend, following a Langmuir absorption function (R2 = 0.94). Due to the wine matrix variability, a standard additions method was then employed for quantitative analysis in red and white wines. This method does not require the SO2 separation but only a matrix pre-cleaning by solid phase extraction. The limit of detection (LOD) was defined for each wine tested, ranging from 0.6 mg/l to 9.6 mg/l. The results obtained were validated by comparison with the International Organization of Vine and Wine method (OIV-MA-AS323-04A).

Determination of Molecular and “Truly” Free Sulfur Dioxide in Wine: A Comparison of Headspace and Conventional Methods

Conventional methods such as Ripper titration and aeration-oxidation (A-O) are widely used for the analysis of sulfur dioxide (SO2) in wine. However, the free SO2 reported by these procedures is overestimated due to dissociation of weakly bound SO2 forms during the analysis, particularly from anthocyanin-bisulfite complexes. “Truly” free SO2 in wine can be determined from the headspace SO2 concentration of an equilibrated wine sample. A headspace SO2 method based on gas detection tubes (HS-GDT) was recently described but is not readily automated. While solid phase microextraction (SPME) yielded poor precision in our experiments, our new method, based on static headspace gas chromatography and sulfur chemiluminescence detection (HS-GC-SCD), is readily automated and achieves high precision (

In Vitro Toxicity Assessment of Stilbene Extract for Its Potential Use as Antioxidant in the Wine Industry.

The reduction of sulfur dioxide in wine is a consumer’s demand, considering the allergic effects that may occur in people who are sensitive to it. Stilbenes are candidates of great interest for this purpose because of their antioxidant/antimicrobial activities and health properties, and also because they are naturally found in the grapevine. In the present study, the in vitro toxicity of an extract from grapevine shoots (with a stilbene richness of 45.4%) was assessed in two human cell lines. Significant damage was observed from 30 μg/mL after 24 h, and 40 µg/mL after 48 h of exposure. Similarly, the ultrastructural study revealed a significant impairment of cell growing. The extract was able to protect cells against an induced oxidative stress at all concentrations studied. In view of the promising results, a more exhaustive toxicological assessment of the extract is needed to confirm the safety of its further use as additive in wine.

Headspace-Sampling Paper-Based Analytical Device for Colorimetric/Surface-Enhanced Raman Scattering Dual Sensing of Sulfur Dioxide in Wine.

This study demonstrates a novel strategy for colorimetric/surface-enhanced Raman scattering (SERS) dual-mode sensing of sulfur dioxide (SO2) by coupling headspace sampling (HS) with paper-based analytical device (PAD). The smart and multifunctional PAD is fabricated with a vacuum filtration method in which 4-mercaptopyridine (Mpy)-modified gold nanorods (GNRs)-reduced graphene oxide (rGO) hybrids (rGO/MPy-GNRs), anhydrous methanol, and starch-iodine complex are immobilized into cellulose-based filter papers. The resultant PAD exhibits a deep-blue color with a strong absorption peak at 600 nm due to the formation of an intermolecular charge-transfer complex between starch and iodine. However, the addition of SO2 induces the Karl Fischer reaction, resulting in the decrease of color and increase of SERS signals. Therefore, the PAD can be used not only as a naked-eye indicator of SO2 changed from blue to colorless but also as a highly sensitive SERS substrates because of the SO2-triggered conversion of Mpy to pyridine methyl sulfate on the GNRs. A distinguishable change in the color was observed at a SO2 concentration of 5 μM by the naked eye, and a detection limit as low as 1.45 μM was obtained by virtue of UV-vis spectroscopy. The PAD-based SERS method is effective over a wide range of concentrations (1 μM to 2000 μM) for SO2, and the detection limit for SO2 is found to be 1 μM. The HS-PAD based colorimetric/SERS method is applied for the determination of SO2 in wine, and the detection results match well with those obtained from the traditional Monier-Williams method. This study not only offers a new method for on-site monitoring of SO2 but also provides a new strategy for designing of paper-based sensing platform for a wide range of field-test applications.

Content of endogenous sulfur dioxide in wines

Content of free and total endogenous sulfur dioxide were evaluated by classical iodometric titration in must, during winemaking processes and in bio-wine. No exogenous sulfur dioxide was added in any technological operations to simplify the evaluations. In addition, the results were corrected on the content of reductons (total content of reducing substances). The results confirmed formation of endogenous sulfur dioxide from sulfur containing substances (sulfur containing amino acids etc.) in both experiments. Microbial sulfur dioxide is preferably bound to carbonyl substances. Only minor part is present in the free (active) form of the sulfur dioxide. In addition, total content of polyphenols (TPC) and total antioxidant capacity (TAC) were determined by spectrophotometry at the same time. A procedure OIV-MA-AS323-O4B: R 2009 was used. Contents of "free" and "total" sulfur dioxide (with/without correction on contents of reductons) and total content of reductones were determined after complexing the sulfur dioxide with formaldehyde. A standard spectrophotometric method using Folin-Ciocalteu reagent was applied for determination of total content of polyphenolics (TPC) at 765 nm after 60 min incubation. The results were expressed as tannin equivalents (in mg.L-1). A standard DPPH (2,2´-difenyl-1-picrylhydrazyl dissolved in methanol) spectrophotometric method was applied for determination of total antioxidant capacity (TAC) at 515 nm. Depletion of the color intensity was measured after 60 min incubation against blank (methanol) and absorbance decrease Δ(A) = (A0 - A1)/A0 was calculated and used for construction of calibration curve. The TAC values were expressed as ascorbic acid concentrations (in mg.L-1).

Gas chromatography-mass spectrometry strategies for the accurate and sensitive speciation of sulfur dioxide in wine

Understanding the chemistry of wine oxidation requires the accurate and sensitive quantitative determination of the most important molecular species which SO2 can form. An analytical strategy based in three independent static headspace GC–MS determinations is proposed in order to obtain information about the total, nominally free and truly free levels of SO2. Nominally free forms are directly determined after sample acidulation, total forms require the previous incubation at 100°C, and truly free forms are determined after preconcentration of the headspace of the undisturbed sample in an alkaline solution. The two first determinations provide results equivalent to those reported by the aeration-oxidation (A-O) method, with lower limits of detection (1mgL−1) and better repeatabilities (<4.0%). Results from the analysis of different wines revealed that levels of nominally free are systematically in excess than those of truly free SO2, which suggests that free SO2 determined by any method using previous acidulation includes at least two different species of SO2, which may have different antioxidant behavior.

Analysis of free and total sulfur dioxide in wine by using a gas-diffusion analytical system with pH detection.

The use of sulfur dioxide as preservative in winemaking industry has a direct impact on wine quality. The standard methods to analyze this parameter require several processes and are time consuming. In this paper a simple and rapid analytical method for free and total sulfur dioxide detection is proposed. This method is based on the separation of the analyte from the sample with a permeable gas diffusion membrane and its indirect detection with a pH sensor. The system has been validated and optimized for free sulfur dioxide detection in the range of 1-60mgL-1 and for total sulfur dioxide in the range of 30-300mgL-1 with a limit of detection of 0.5mgL-1. Validation of the system has been carried out using a total of 70 samples of white and red wines and two standard methods, the Ripper and the Paul method. The obtained values have demonstrated a good agreement for both methods.

Direct quantification of total sulfur dioxide in wine using triple quadrupole ICP-MS

The unanimous ionization efficiency of various S-containing compounds indicates the great convenience for determination of total SO2in wineviaICP-QQQ.

Headspace thin-film microextraction coupled with surface-enhanced Raman scattering as a facile method for reproducible and specific detection of sulfur dioxide in wine.

By coupling thin-film microextraction (TFME) with surface-enhanced Raman scattering (SERS), a facile method was developed for the determination of sulfur dioxide (SO2), the most effective food additive in winemaking technology. The TFME substrate was made by free settling of sea urchin-like ZnO nanomaterials on a glass sheet. The headspace sampling (HS) procedure for SO2 was performed in a simple homemade device, and then the SO2 was determined using SERS after uniformly dropping or spraying a SERS-active substrate (gold nanoparticles, AuNPs) onto the surface of the TFME substrate. A reproducible and strong SERS response of the SO2 absorbed onto the ZnO substrate was obtained. After condition optimization, the SERS signal intensity at a shift of 600 cm(-1) and the SO2 concentration showed a good linearity in the range of 1-200 μg/mL, and the linear correlation coefficient was 0.992. The detection limit for SO2 was found to be 0.1 μg/mL. The HS-TFME-SERS method was applied for the determination of SO2 in wine, and the results obtained agreed very well with those obtained using the traditional distillation and titration method. Analysis of variance and Student t test show that there is no significant difference between the two methods, indicating that the newly developed method is fast, convenient, sensitive and has selective characteristics in the determination of SO2 in wine.

Determination of the wine preservative sulphur dioxide with cyclic voltammetry using inkjet printed electrodes

During winemaking sulphur dioxide is added to prevent undesirable reactions. However, concerns over the harmful effects of sulphites have led to legal limits being placed upon such additives. There is thus a need for simple and selective determinations of sulphur dioxide in wine, especially during winemaking.The simultaneous detection of polyphenols and sulphur dioxide, using cyclic voltammetry at inert electrodes is challenging due to close oxidation potentials. In the present study, inkjet printed electrodes were developed with a suitable voltammetric signal on which the polyphenol oxidation is suppressed and the oxidation peak height for sulphur dioxide corresponds linearly to the concentration.Different types of working electrodes were printed. Electrodes consisting of gold nanoparticles mixed with silver showed the highest sensitivity towards sulphur dioxide.Low cost production of the sensor elements and ultra fast determination of sulphur dioxide by cyclic voltammetry makes this technique very promising for the wine industry.

Increasing the efficiency of sulfur dioxide in wine by using of saturated higher fatty acids

This work is aimed on stopping of alcoholic fermentation to leave residual sugar and the possibility of sulfur dioxide reduction in wine technology and storage. As a very good opportunity showed mixture of higher saturated fatty acids with a reduced dose of sulfur dioxide. Experiments have confirmed that the concentration of viable yeasts in 1 ml of wine for variants treated with a mixture of fatty acids is significantly lower than in variants treated with sulfur dioxide alone. Then was monitored the influence of fatty acids on stored wine with residual sugar. At this point a dramatically prolongation of interval to secondary fermentation (depreciation of wine) in the bottle was confirmed. Finally, attention was paid to influence on the organoleptic characteristics of wine treated this way. In this case, it is possible to consider the recommended concentration of fatty acid below the threshold of susceptibility.

Determination of sulfur dioxide in wine using headspace gas chromatography and electron capture detection

Sulfites are routinely added as preservatives and antioxidants in wine production. By law, the total sulfur dioxide content in wine is restricted and therefore must be monitored. Currently, the method of choice for determining the total content of sulfur dioxide in wine is the optimised Monier–Williams method, which is time consuming and laborious. The headspace gas chromatographic method described in this study offers a fast and reliable alternative method for the detection and quantification of the sulfur dioxide content in wine. The analysis was performed using an automatic headspace injection sampler, coupled with a gas chromatograph and an electron capture detector. The method is based on the formation of gaseous sulfur dioxide subsequent to acidification and heating of the sample. In addition to free sulfur dioxide, reversibly bound sulfur dioxide in carbonyl compounds, such as acetaldehyde, was also measured with this method. A total of 20 wine samples produced using diverse grape varieties and vintages of varied provenance were analysed using the new method. For reference and comparison purposes, 10 of the results obtained by the proposed method were compared with those acquired by the optimised Monier–Williams method. Overall, the results from the headspace analysis showed good correlation (R = 0.9985) when compared with the conventional method. This new method requires minimal sample preparation and is simple to perform, and the analysis can also be completed within a short period of time.