An Ag+ SPE method combined with Deans’ switch heart-cutting MDGC–MS/Olfactometry approach for identifying unknown volatile thiols in wine

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Agriculture, natural resource management and the production and sale of products such as wine are increasingly data-driven activities. Thus, the use of remote and proximal crop and soil sensors to aid management decisions is becoming commonplace and ‘Agtech’ is proliferating commercially; mapping, underpinned by geographical information systems and complex methods of spatial analysis, is widely used. Likewise, the chemical and sensory analysis of wines draws on multivariate statistics; the efficient winery intake of grapes, subsequent production of wines and their delivery to markets relies on logistics; whilst the sales and marketing of wines is increasingly driven by artificial intelligence linked to the recorded purchasing behaviour of consumers. In brief, there is data everywhere!

Opinions will vary on whether these developments are a good thing. Those concerned with the ‘mystique’ of wine, or the historical aspects of terroir and its preservation, may find them confronting. In contrast, they offer an opportunity to those interested in the biophysical elements of terroir, and efforts aimed at better understanding how these impact on vineyard performance and the sensory attributes of resultant wines. At the previous Terroir Congress, we demonstrated the potential of analytical methods used at the within-vineyard scale in the development of Precision Viticulture, in contributing to a quantitative understanding of regional terroir. For this conference, we take this approach forward with examples from contrasting locations in both the northern and southern hemispheres. We show how, by focussing on the vineyards within winegrowing regions, as opposed to all of the land within those regions, we might move towards a more robust terroir zoning than one derived from a mixture of history, thematic mapping, heuristics and the whims of marketers. Aside from providing improved understanding by underpinning terroir with data, such methods should also promote improved management of the entire wine value chain.

Global warming is one of the biggest environmental, social, and economic threats. In the Douro Valley, change to the climate are expected in the coming years, namely an increase in average temperature and a decrease in annual precipitation. Since vine cultivation is extremely vulnerable and influenced by the climate, these changes are likely to have negative effects on the production and quality of wine.
Adaptation is a major challenge facing the viticulture sector where the choice of plant material plays an important role, particularly the rootstock as it is a driver for adaptation with a wide range of effects, the most important being phylloxera, nematode and salt, tolerance to drought and a complex set of interactions in the grafted plant.
In an experimental vineyard, established in the Douro Region in 1997, with four randomized blocs, with five varieties, Touriga Nacional, Tinta Barroca, Touriga Franca and Tinta Roriz, grafted in four rootstocks, Rupestris du Lot, R110, 196-17C, R99 and 1103P, data was collected consecutively over 20 years (2001-2020). Phenological observations were made two to three times a week, following established criteria, to determine the average dates of budbreak, flowering and veraison. During maturation, weekly berry samples were taken to study the dynamics of sugar accumulation, amongst other parameters. Climate data was collected from a weather station located near the vineyard parcel, with data classified through several climatic indices.
The results achieved show a very low coefficient of variations in the average date of the phenophases and an important contribution from the rootstock in the dynamic of the phenology, allowing a delay in the cycle of up to10-12 days for the different combinations. The Principal Component Analysis performed, evaluating trends in the physical-chemical parameters, highlighted the effect of the climate and rootstock on fruit quality by grape varieties.

The development of new generations of multispectral satellites such as Sentinel-2 opens possibilities as to vine water status assessment (Cohen et al., 2019). Based on a three years field campaign, a model of Stem Water Potential (SWP) estimation on vine using four satellite bands in Red, Red-Edge, NIR and SWIR domains was developed (Laroche-Pinel et al., 2021). The model relies on SWP field measures done using a pressure chamber (Scholander et al., 1965), which is a common, robust and precise method to assess vine water status (Acevedo-Opazo et al., 2008). The model was mainly developed from from SWP measures on Syrah N (Laroche Pinel E., 2021).

A large scale monitoring was organized in different vineyards in the Mediterranean region in 2021. 10 varieties amongst the most represented in this area were monitored (Cabernet sauvignon N, Chardonnay B, Cinsault N, Grenache N, Merlot N, Mourvèdre N, Sauvignon B, Syrah N, Vermentino B, Viognier B). The model was used to produce water status maps from Sentinel-2 images, starting from the beginning of June (fruit set) up to September (harvest). The average estimated SWP for each vine was compared to actual field SWP measures done by wine growers or technicians during usual monitoring of irrigation programs. The correlations between mean estimated SWP and mean measured SWP were at the same level than expected by the model. (Laroche Pinel, 2021) The general SWP kinetics were comparable. The estimated SWP would have led to same irrigation decisions concerning the date of first irrigation in comparison with measured SWP.

Acevedo-Opazo, C., Tisseyre, B., Ojeda, H., Ortega-Farias, S., Guillaume, S. (2008). Is it possible to assess the spatial variability of vine water status? OENO One, 42(4), 203.
Cohen, Y., Gogumalla, P., Bahat, I., Netzer, Y., Ben-Gal, A., Lenski, I., … Helman, D. (2019). Can time series of multispectral satellite images be used to estimate stem water potential in vineyards? In Precision agriculture ’19, The Netherlands: Wageningen Academic Publishers, pp. 445–451.
Laroche-Pinel, E., Duthoit, S., Albughdadi, M., Costard, A. D., Rousseau, J., Chéret, V., & Clenet, H. (2021). Towards vine water status monitoring on a large scale using sentinel-2 images. remote sensing, 13(9), 1837.
Laroche-Pinel,E. (2021). Suivi du statut hydrique de la vigne par télédétection hyper et multispectrale. Thèse INP Toulouse, France.
Scholander, P.F., Bradstreet, E.D., Hemmingsen, E.A., & Hammel, H.T. (1965). Sap pressure in vascular plants: Negative hydrostatic pressure can be measured in plants. Science, 148(3668), 339–346.

The first demonstration of the interest of carbon isotope composition of sugars in grapevine, as an integrated indicator of vineyard water status, dates back to 2000 (Gaudillère et al., 1999; Van Leeuwen et al., 2001). Thanks to the isotopic discrimination of Carbon that takes place during plant photosynthesis, under hydric stress conditions, it is possible to accurately estimate the photosynthetic activity. Ever since, δ13C has been widely applied with success to zonation, terroir studies and vine physiology research, but is still not widely used by viticulturists. This is quite astonishing by considering the impact of global warming on viticulture and the need to improve water management, that would justify a widespread use of δ13C.
The lack of private laboratories proposing the analysis, the cost of the technology, as well as the long analytical delays, have been detrimental to its development. Some laboratories tried to overcome the analytical difficulties of isotopic analysis by using fourier transformed infrared spectroscopy, as a fast and cheap alternative to the official OIV method (IRMS). These claimed FTIR models have never been published or peer reviewed and cannot be considered robust. In this work, thanks to the recent acquisition of IRMS technology, new modern and robust applications of δ13C for viticulture are proposed. This includes the use of the analysis to make parcel separations at harvesting, the possibility to increase the precision of hydric stress cartography and the potential cost reduction when compared with Scholander pressure bomb analysis.