OENO IVAS 2019 banner
IVES 9 IVES Conference Series 9 OENO IVAS 9 OENO IVAS 2019 9 Analysis and composition of grapes, wines, wine spirits 9 Identification of cis-2-methyl-4-propyl-1,3-oxathiane as a new volatile sulfur compound (VSC) in wine

Identification of cis-2-methyl-4-propyl-1,3-oxathiane as a new volatile sulfur compound (VSC) in wine

Abstract

Despite their trace concentrations, volatile sulfur compounds (VSCs) are an important category of flavour-active compounds that significantly contribute to desirable or undesirable aromas of many foods and beverages. In wines, VSCs in the form of polyfunctional thiols, notably 3-sulfanylhexan-1-ol (3-SH), 3-sulfanylhexyl acetate (3-SHA), and 4-sulfanyl-4-methyl-pentan-2-one (4-MSP), possess extremely low olfactory thresholds (≈ ng/L) and pleasant “tropical aroma” notes. They have received much attention with respect to their sensory contributions, quantitative occurrences, biogenesis, and thiol management through viticulture and winemaking. However, the fate of these potent volatiles are still not fully understood.

In this work [1], the fate of 3-SH in wine was probed based on the potential sensory and chemistry interactions between 3-SH and acetaldehyde, which led to the identification of cis-2-methyl-4-propyl- 1,3-oxathiane (cis-1) in wine for the first time. Subsequently, a stable isotope dilution assay (SIDA) using headspace–solid-phase microextraction with gas chromatography and mass spectrometry (HS–SPME GC– MS) was developed. A range of parameters was optimised, a deuterated internal standard was synthesised, and the method was fully validated and applied to the quantitation of cis-1 in wines. The aroma detection threshold of 1 was also determined.

The existence of cis-1 in Sauvignon blanc wines from a laboratory-scale fermentation trial was revealed by mass spectral comparison to an authentic standard, linear retention indices of naturally present cis- 1 on two GC columns, and co-injection experiments. Challenges were faced when analysing commercial wine samples due to unknown co-eluting interferences in some wines. After employing d4-1 as the internal standard and evaluating additional capillary column phases, a sensitive SIDA HS–SPME GC–MS method was developed and applied to a survey of commercial wines. Interestingly, trans-1 was not detected whereas cis-1 ranged from undetectable to 460 ng/L, which highly correlated (r = 0.72) to the concentrations of 3-SH, determined in the same wines by HPLC–MS/MS after derivatisation. The aroma detection threshold of 1* in a neutral Australian white wine was found to be 7.1 μg/L. Although cis-1 concentrations in the studied wines were below the odour detection threshold of 1, our results suggest a potential link from cis-1 to the potent VSC 3-SH, and more research is required to gain a better understanding of the importance of cis-1 in wine, from both chemistry and sensory perspectives. The identification and method development work will be presented along with additional experiments involving cis-1 in wine.

references:

[1]. Chen, L., D.L. Capone, and D.W. Jeffery, Identification and Quantitative Analysis of 2-Methyl-4-propyl-1,3-oxathiane in Wine. Journal of Agricultural and Food Chemistry, 2018, 66 (41), 10808–10815.

* Using a commercial standard consisting of 85% cis-1 and 15% trans-1.

DOI:

Publication date: June 23, 2020

Issue: OENO IVAS 2019

Type: Article

Authors

Liang Chen, Dimitra Capone, David Jeffery

The ARC Training Centre for Innovative Wine Production, The University of Adelaide, PMB 1, Glen Osmond, South Australia 5064, Australia 

Contact the author

 

Keywords

wine aroma, tropical fruit, 3-sulfanylhexan-1-ol, stable isotope dilution assay

Tags

IVES Conference Series | OENO IVAS 2019

Citation

Related articles…

Vineyards and clay minerals: multi-technique analytical approach and correlations with soil properties

Purpose of this research is to quantitatively assess the mineral component of vineyard soils, with particular attention to the mineralogical analysis of clays, which represent an element of high importance in the vineyard culture as well as in general agriculture. An X-ray diffraction (XRD) / thermogravimetric (TG) multi-technique analytical approach was developed, tested on soil samples taken from vineyards around the world. This codified analytical procedure was necessary to obtain precise qualitative and quantitative mineralogical data, globally comparable to distinguish the geopedological identity of the vineyards. Soil samples from vineyards of various locations were analysed, in very different geological conditions. The bulk-rock quantitative phase analysis (QPA) was obtained by the Rietveld method while the detailed composition of the clay-sized fraction was determined by modelling of the oriented X-ray diffraction patterns. The research provided a precise classification of the mineral component of soils, distinguishing the mineral phases of the clays and the so-called mixed-layer clay minerals. We found that the content in mixed layers can be directly correlated with the water retention and the cation exchange capacity ​​of the soil, while the presence of other clayey minerals and phyllosilicates in this research did not affect this CEC parameter, which codes the fertility level of the soils. The study demonstrates that terroir, in particular soils formed in complex or very different geological conditions, can only be effectively interpreted by properly analysing its mineral phases, in particular the mixed-layer clay component. These are characteristic abiotic ecological indicators, which may have specific eco-physiological influences on the plant.

Use of a new, miniaturized, low-cost spectral sensor to estimate and map the vineyard water status from a mobile 

Optimizing the use of water and improving irrigation strategies has become increasingly important in most winegrowing countries due to the consequences of climate change, which are leading to more frequent droughts, heat waves, or alteration of precipitation patterns. Optimized irrigation scheduling can only be based on a reliable knowledge of the vineyard water status.

In this context, this work aims at the development of a novel methodology, using a contactless, miniaturized, low-cost NIR spectral tool to monitor (on-the-go) the vineyard water status variability. On-the-go spectral measurements were acquired in the vineyard using a NIR micro spectrometer, operating in the 900–1900 nm spectral range, from a ground vehicle moving at 3 km/h. Spectral measurements were collected on the northeast side of the canopy across four different dates (July 8th, 14th, 21st and August 12th) during 2021 season in a commercial vineyard (3 ha). Grapevines of Vitis vinifera L. Graciano planted on a VSP trellis were monitored at solar noon using stem water potential (Ψs) as reference indicators of plant water status. In total, 108 measurements of Ψs were taken (27 vines per date).

Calibration and prediction models were performed using Partial Least Squares (PLS) regression. The best prediction models for grapevine water status yielded a determination coefficient of cross-validation (r2cv) of 0.67 and a root mean square error of cross-validation (RMSEcv) of 0.131 MPa. This predictive model was employed to map the spatial variability of the vineyard water status and provided useful, practical information towards the implementation of appropriate irrigation strategies. The outcomes presented in this work show the great potential of this low-cost methodology to assess the vineyard stem water potential and its spatial variability in a commercial vineyard.

Soil quality in Beaujolais vineyard. Importance of pedology and cultural practices

A pedological study was carried out from 2009 to 2017 in Beaujolais vineyard, to improve physical and chemical knowledge of soils. It was completed in 2016 and 2017 by the current study, dealing with microbial aspects, in order to build a reference frame for improved advice in soil management. Microbial biomass was measured on representative plots of the six most common soil types identified in Beaujolais and, for each soil type, on plots with different levels of the main impacting parameters: total organic carbon, pH, cation exchange capacity, extractable copper. A total of 59 soil samples were collected. Confirming the results of various trials carried out in Beaujolais over the past 20 years, the results of the present study showed that the soils were still alive, but exhibited a large variability of biological parameters, which appeared dependant on both pedological and anthropic factors. Therefore, a good interpretation of biological parameters and advice for vine growers must rely on a pedologically-based referential with differentiated main driving factors. For example, the control of pH is of primary importance in granitic soils and in no way organic matter addition can improve soil quality if pH is too low. Conversely, in calcareous soils, biological parameters are more directly affected by direct or indirect (cover crops for example) inputs of organic matter. The use of biological parameters, such as microbial biomass, is of great potential value to improve advice on agro-viticultural practices (soil management, fertilization, liming, etc.), basis of a sustainable wine production on fragile soils.

Metabolomic discrimination of grapevine water status for Chardonnay and Pinot noir

Water status impact in viticulture has been widely explored, as it strongly affects grapevine physiology and grape chemical composition. It is considered as a key component of vitivinicultural terroir. Most of the studies concerning grapevine water status have focused on either physiological traits, or berry compounds, or traits involved in wine quality. Here, the response of grapevine to water availability during the ripening period is assessed through non-targeted metabolomics analysis of grape berries by ultra-high resolution mass spectrometry. The grapevine water status has been assessed during 2 consecutive years (2019 & 2020), through carbon isotope discrimination on juices from berries collected at maturity (21.5 brix approx.) for 2 Vitis vinifera cv. Pinot noir (PN) and Chardonnay (CH). A total of 220 grape juices were collected from 5 countries worldwide (Italy; Argentina; France; Germany; Portugal). Measured δ13C (‰) varied from -28.73 to -22.6 for PN, and from -28.79 to -21.67 for CH. These results also clearly revealed higher water stress for the 2020 vintage. The same grape juices have been analysed by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) and Liquid Chromatography coupled to Mass Spectrometry (LC-qTOF-MS), leading to the detection of up to 4500 CHONS containing elemental compositions, and thus likely tens of thousands of individual compounds, which include fatty acids, organic acids, peptides, phenolics, also with high levels of glycosylation. Multivariate statistical analysis revealed that up to 160 elemental compositions, covering the whole range of detected masses (100 –1000 m/z), were significantly correlated to the observed gradients of water status. Examples of chemical markers, which are representative of these complex fingerprints, include various derivatives of the known abscisic acid (ABA), such as phaesic acid or abscisic acid glucose ester, which are significantly correlated with higher water stress, regardless of the variety. Cultivar-specific behaviours could also be identified from these fingerprints. Our results provide an unprecedented representation of the metabolic diversity, which is involved in the water status regulation at the grape level, and which could contribute to a better knowledge of the grapevine mitigation strategy in a climate change context.

Influence of a spontaneous cover crop on the vineyard and soil erosion under Mediterranean climate

Sixty five % of the agricultural area of the Basque Country located in the DO Ca Rioja corresponds to vineyards. More than 40% of it has an average slope greater than 10%, which makes it sensitive to erosive processes. Furthermore, it is foreseeable that extreme weather events (storms, hail, extreme heat and cold, etc.) will be favored due to climate change. Cover cropping can mitigate this risk, and therefore the objective of this work is to evaluate the impact that a vegetable cover has on the agronomic behavior of the vineyard, the quality of the grape and soil erosion. For this, a trial has been carried out with a Graciano variety vineyard with a slope between 10% -20% during the years 2020 and 2021. Conventional tillage management in the area has been compared (4-6 passes per year of tillage machinery) versus spontaneous vegetation cover management in the vineyard. This implies not tilling and allowing the grass of the land to colonize the range between the lines of vines, controlling their height through 1-3 mowing passes per year, always trying to affect the surface of the land as little as possible. The vegetative growth, yield and quality of the grape and wine was measured. Furthermore, erosion has been measured using Gerlasch boxes. The yield was lower in the second year of the trial in the cover crop treatment, but erosion was significantly reduced.