Comparison of Techniques for the Quantitation of Reductive Aroma Compounds in White Wine: Links to Sensory Analysis and Cu Fractions.

Multiple analytical methodologies allow quantitation of H2S and methanethiol (MeSH) in wine, but confirmation that the determined concentrations are related to perceived off-aromas, or "reductive" faults, is yet to be provided. Fifty white wines underwent sensory evaluation and measurement of free and salt-treated H2S and MeSH concentrations by gas chromatography with sulfur chemiluminescence detection and/or gas detection tubes. The determined concentrations were compared across techniques and different analysis laboratories. Sulfhydryl off-odors in the wines were best described by boiled and rotten egg and natural gas/sewerage/durian aroma attributes. The wines with the highest ratings for both aromas had high concentrations of free H2S, free MeSH, and/or salt-treated MeSH but were unrelated to salt-treated H2S. The free sulfhydryl concentrations and their associated aromas appeared to be suppressed by specific Cu fractions in the wines. This study provides evidence of the relevant measures of reductive aroma compounds and their relation to off-odors and Cu fractions.

Accurate measurement of sulfhydryls and TCEP-releasable sulfhydryls in the liquid phase of wine that contribute to 'reductive' aromas using LC-MS/MS.

Volatile sulfur compounds (VSCs) are important aroma and flavour characters in food and beverage products. The identification and quantification of these extremely reactive and volatile compounds pose analytical challenges which demand selective and sensitive methods. In this study, a novel quantification method was developed to analyse sulfhydryls as well as the total pool of sulfhydryls which can be released after tris(2-carboxyethyl)phosphine (TCEP) addition from disulfides, polysulfides, metal-bound and other yet to be identified sources naturally present in wine. The majority of methods for VSC quantification analyse VSCs in wine headspace, whereas this method measures sulfhydryls and TCEP-releasable sulfhydryl species, which likely include free and metal-bound sulfhydryl forms, in the liquid phase of wine using UHPLC-MS/MS. Sulfhydryls were derivatised with N-(2-ferroceneethyl) maleimide (FEM), subsequently, followed by differential labelling of sulfhydryls released after TCEP addition with ferrocenecarboxylic acid-(2-maleimidoyl)ethylamide (FMEA). Analysis of commercial wines revealed the presence of hydrogen sulfide, methanethiol, ethanethiol, and 2-mercaptoethanol at aroma-active concentrations. Significant positive correlations were found between MeSH and CH3-S-R TCEP-releasable species, and significant positive correlations were found between EtSH and CH3-CH2-S-R TCEP-releasable species. This method provides important information on sulfhydryls, and may also provide insights into a wine's risk of developing 'reductive' faults post-bottling from latent sources.

Surface nanoengineering technology for the removal of sulfur compounds associated with negative attributes in wines.

Volatile sulfur compounds (VSCs), such as hydrogen sulfide, methanethiol, and ethanethiol, are associated with 'reductive' aromas in wine and contribute to approximately 30% of all wine faults. These compounds can have a significant impact on wine aroma and perceived quality, and subsequently, consumer preference. In this communication, we report a method for the removal of VSC compounds based on nanoengineered surfaces that incorporate immobilized gold nanoparticles.

Mammalian exocrine secretions XIX. Chemical characterization of the interdigital secretion of the Black Wildebeest, Connochaetes gnou.

Using gas chromatography (GC) in conjunction with electron impact mass spectrometry and retention-time comparison, 94 compounds, ranging from 2-methyl-2-propenal to octadecanoic acid, were identified in the interdigital secretions of male and female black wildebeests, Connochaetes gnou (also known as the white-tailed gnu). The constituents of these secretions belong to many different compound classes, including hydrocarbons, alcohols, aromatics and aliphatic carbonyl compounds including carboxylic acids as well as carboxylic acid esters. Relatively small quantitative differences were found between the male and female interdigital secretions. It was concluded that these compounds probably do not play a significant role in territorial marking or in chemical communication between males and females of the species, but they could be involved in preserving the remarkably strong attachment between members of social subgroups in black wildebeest populations.

Changes in Metal Ion Concentrations in a Chardonnay Wine Related to Oxygen Exposure during Vinification.

The impact of oxygen exposure during winemaking on metal ion concentrations in wine were investigated throughout the winemaking process in a Chardonnay wine. The concentrations of Al, Ca, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Sn, and Zn were determined using inductively coupled plasma-mass spectrometry. Oxygen exposure significantly impacted 13 metal ions at different phases of winemaking. However, only the concentrations of Cr, Cu, and Fe were impacted by early oxygen exposure during pressing, with lower Cr and Cu concentrations in wines that were aerobically pressed and lower concentrations of Fe in wines that were inertly pressed. The sequestering of Al, Cu, Ni, and Zn by wine lees was significantly affected by oxygen treatment, with lees collected from wines that were treated oxidatively sequestering significantly greater amounts of Cu and Zn and removing these metals from the wine supernatant. The metal ion that was most affected by oxygen exposure during pressing and handling was Cu, with significantly lower Cu measured in wines that were produced under oxidative conditions. It is known that elevated Cu concentrations have negative implications for wine aroma and flavour. This study demonstrated that oxygen management during winemaking significantly impacts metal ion concentrations in lees and wine, which may decrease the risk of developing taints and faults.

Analytical strategies for the measurement of different forms of Cu and Fe in wine: Comparison between approaches in relation to wine composition.

The speciation of Cu and Fe in wine was assessed by a number of methodologies and those with superior performance were utilised on 49 wines and compared to compositional data. The adopted analytical strategies were stripping potentiometry, HPLC and an extraction (solid-phase or liquid-liquid) followed by atomic absorption or optical emission spectroscopic measurement. Stripping potentiometry was specific for sulfide-bound Cu in wines, and showed that this was the predominant form of Cu. A solid phase extraction technique provided a hydrophobic fraction of Cu that was specific for sulfide-bound Cu in white wine but red wine matrix effects hindered isolation of sulfide-bound Cu. The other methods assessed either perturbed the sulfide-bound Cu or were not sufficiently sensitive. The solid phase extraction method enabled routine fractionation of Fe in red and white wines whilst the additional techniques surveyed either measured total Fe or suffered from background contamination.

Liberation of Hydrogen Sulfide from Dicysteinyl Polysulfanes in Model Wine.

Diorganopolysulfanes can be generated when hydrogen sulfide (H2S) and thiols are oxidized in the presence of Cu(II) under conditions usually aimed at removing H2S from wine. This work sought to understand if polysulfanes could act as latent sources of H2S during postbottling storage. The stability of the polysulfanes formed in situ in model wine containing cysteine, H2S, and transition metals was dependent both on the number of sulfur linking atoms (Sn) and on the presence of a reducing agent, such as sulfur dioxide or ascorbic acid. A polysulfane containing three linking sulfur atoms was the most stable, with 84% of the relative initial amount remaining in solution after six months, compared to polysulfanes containing four or more linking sulfur atoms that decomposed rapidly, with 26% remaining after six months. Importantly, sulfur dioxide was associated with the rapid degradation of polysulfanes and subsequent liberation of H2S. Three cysteine- S-sulfonates were also tentatively identified, which gives insight into the possible release mechanisms involved with H2S reappearance.

Evaluation of putative precursors of key 'reductive' compounds in wines post-bottling.

Precursors to hydrogen sulfide (H2S), methanethiol (MeSH), ethanethiol (EtSH), and dimethyl sulfide (DMS) were assessed in wines post-bottling, and the percent yield of VSCs from each precursor determined. Cysteine (Cys) and glutathione (GSH) were associated with small increases in H2S concentrations, with a maximum yield of 0.18% and 1.3%, respectively. Greater yields of H2S were obtained from the combined Cys/GSH and copper treatments in white wine. Copper, acting on unknown precursors, was associated with large increases in H2S in Shiraz wines. Dimethyl disulfide and methyl thioacetate were important precursors to MeSH, and produced maximum yields of 72% and 33%, respectively. Ethyl thioacetate was a key precursor to EtSH, with a maximum yield of 39% obtained. Copper and pH were important in modulating MeSH and EtSH accumulation in wines. A maximum yield of 23% of DMS from S-methylmethionine was obtained, with dimethyl sulfoxide producing significantly less DMS with a maximum yield of only 9.4%.

Formation of Hydrogen Sulfide in Wine: Interactions between Copper and Sulfur Dioxide.

The combined synergistic effects of copper (Cu(2+)) and sulfur dioxide (SO2) on the formation of hydrogen sulfide (H2S) in Verdelho and Shiraz wine samples post-bottling was studied over a 12-month period. The combined treatment of Cu(2+) and SO2 significantly increased H2S formation in Verdelho wines samples that were not previously treated with either Cu(2+) or SO2. The formation of H2S produced through Cu(2+) mediated reactions was likely either: (a) directly through the interaction of SO2 with either Cu(2+) or H2S; or (b) indirectly through the interaction of SO2 with other wine matrix compounds. To gain better understanding of the mechanisms responsible for the significant increases in H2S concentration in the Verdelho samples, the interaction between Cu(2+) and SO2 was studied in a model wine matrix with and without the presence of a representative thiol quenching compound (4-methylbenzoquinone, 4MBQ). In these model studies, the importance of naturally occurring wine compounds and wine additives, such as quinones, SO2, and metal ions, in modulating the formation of H2S post-bottling was demonstrated. When present in equimolar concentrations a 1:1 ratio of H2S- and SO2-catechol adducts were produced. At wine relevant concentrations, however, only SO2-adducts were produced, reinforcing that the competition reactions of sulfur nucleophiles, such as H2S and SO2, with wine matrix compounds play a critical role in modulating final H2S concentrations in wines.

The effects of pH and copper on the formation of volatile sulfur compounds in Chardonnay and Shiraz wines post-bottling.

The effects of pH and Cu(2+) treatment on the formation of volatile sulfur compounds (VSCs) were investigated in Chardonnay and Shiraz wine samples. Four VSCs were significantly affected by pH, with lower wine pH associated with decreased hydrogen sulfide (H2S), methanethiol, dimethyl sulfide, and carbon disulfide concentrations. The effects of pH and Cu(2+) on H2S formation from known precursor compounds were subsequently studied in a model wine system. In samples treated with cysteine and glutathione lower pH produced less H2S. Nanoparticle tracking analysis was used to study the effects of variable pH concentrations in a model system containing Cu(2+), tartaric acid, and H2S. Differences in Cu(2)(+)-tartrate complexes particle size and concentration were measured as a function of pH and H2S addition, suggesting the type of complexes formed may affect the binding sites of Cu(2+) available to catalyse the formation of VSCs such as H2S.