Macrowine 2021
IVES 9 IVES Conference Series 9 Wine archeochemistry: a multiplatform analytical approach to chemically profile shipwreck wines

Wine archeochemistry: a multiplatform analytical approach to chemically profile shipwreck wines

Abstract

AIM: The Cape of Storms (also known as Cape of Good Hope) is renowned for harbouring a multitude of shipwrecks due to the inherent treacherous coastline and blistering storms. One such shipwreck is the English East Indiaman Colebrooke, wrecked in False Bay, South Africa, in 1778. A discovery on the shipwreck was a shipment of wine of unknown origin and style, possibly Madeira as it was known that the English East India Company often purchased wine from there but this was not mentioned in the ship’s log. As the wreck was exploited by treasure hunters, very little contextual information is known. To further expand the sample pool with more examples of old wine, we have included another sample recovered from the wreck of the SS Maori sunk in 1909. Additionally, three samples of (old) wines stored in vinotheque conditions were included: a Château d’Yquem (1918 vintage) and two Château Margaux (1984).

METHODS: A minimal volume of wine (<50 mL) was analysed using untargeted analyses (GC-MS, LC-HRMS and NMR spectroscopy), metals (ICP-MS/OES), and sugars and organic acids (HPLC-DAD-RID). Important volatile aroma compounds were identified by HS-SPME-GCMS and their identification confirmed using Wiley/NIST libraries and RI. A screening exercise was performed by experienced researchers to sensorially evaluate the possible wine-like aromas.

RESULTS: Unexpected chemical characteristics regarding the metal concentrations, sugar and acid composition as well as the aroma profile were found. Compared to current export regulations, the levels of heavy metals were considerably higher, possibly due to the bottle glass composition and leaching over time. The untargeted analyses showed various compounds including fermentation-derived products (esters, alcohols, aldehydes and fatty acids), terpenoids (linalool, fenchone) and “woody” compounds (furfural and guaiacol). Incredibly, some of the samples still presented wine-like features related to aroma both in the chemical and the sensory evaluation. 

CONCLUSIONS

Unlike other work where the source and/or type of beverage recovered from shipwrecks were known, and with a limited volume of sample, we could still obtain results providing interesting “chemical snapshots” of old wines using advanced analytical and spectroscopic techniques. Combining new technology platforms in analytical chemistry can provide valuable insight into the composition of wines recovered from shipwrecks with the help of maritime archaeologists. Including analyses such as X-ray diffraction on the bottles can assist in tracing more information about the sources of heavy metal content and possibly even the origin of the wines.

DOI:

Publication date: September 13, 2021

Issue: Macrowine 2021

Type: Article

Authors

Astrid Buica

South African Grape and Wine Research Institute, Department of Viticulture and Oenology, Stellenbosch University, South Africa,Cody, WILLIAMS, Department of Viticulture and Oenology, Stellenbosch University, South Africa Jaco, BOSHOFF, Iziko Museums of South Africa, Maritime Archaeology Unit, Research and Exhibitions, Cape Town, South Africa Wendy, BLACK, Iziko Museums of South Africa, Archaeology Unit, Research & Exhibitions Department, Cape Town, South Africa Valeria, PANZERI, Department of Viticulture and Oenology, Stellenbosch University, South Africa

Contact the author

Keywords

marine archeology, shipwreck, untargeted analyses, metals, sugars and organic acids, sensory screening

Citation

Related articles…

Sustainable fertilisation of the vineyard in Galicia (Spain)

Excessive fertilization of the vineyard leads to low quality grapes, increased costs and a negative impact on the environment. In order to establish an integrated management system aimed at a sustainable fertilization of the vineyards, nutritional reference levels were established. For this purpose, 30 representative vineyards of the Albariño variety were studied, in which soil and petiole analyses were carried out for two years and grape yield and quality at harvest were measured. In both years of study, soil pH, calcium, sodium and cation exchange capacity were positively correlated with calcium content and negatively correlated with manganese in grapes. Irrigated vineyards had higher levels of aluminium in soil and lower levels of calcium in petiole. Climatic conditions were very different in the years of the study. The year 2019 was colder than usual, in 2020 there was a marked water stress with high summer temperatures. This resulted in medium-high acidity in grapes in 2019 and low acidity in 2020, with sugar levels being similar both years. A very marked decrease in must amino nitrogen was observed in 2020, with ammonia nitrogen remaining stable. The correlation of acidity and sugar values in grapes with soil and petiole analysis data made it possible to establish reference levels for the nutritional diagnosis of the Albariño variety in this region. Based on these results, an easy-to-use TIC application is currently being created for grapegrowers, aimed at improving the sustainability of the vineyard through reasoned fertilization. This study has now been extended to other Galician vine varieties.

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.

The impact of sustainable management regimes on amino acid profiles in grape juice, grape skin flavonoids, and hydroxycinnamic acids

One of the biggest challenges of agriculture today is maintaining food safety and food quality while providing ecosystem services such as biodiversity conservation, pest and disease control, ensuring water quality and supply, and climate regulation. Organic farming was shown to promote biodiversity and carbon sequestration, and is therefore seen as one possibility of environmentally friendly production. Consumers expect organically grown crops to be free from chemical pesticides and mineral fertilizers and often presume that the quality of organically grown crops is different or higher compared to conventionally grown crops. Integrated, organic, and biodynamic viticulture were compared in a replicated field trial in Geisenheim, Germany (Vitis vinifera L. cv. Riesling). Amino acid profiles in juice, grape skin flavonoids, and hydroxycinnamic acids were monitored over three consecutive seasons beginning 7 years after conversion to organic and biodynamic viticulture, respectively. In addition, parameters such as soil nutrient status, yield, vigor, canopy temperature, and water stress were monitored to draw conclusions on reasons for the observed changes. Results revealed that the different sustainable management regimes highly differed in their amino acid profiles in juice and also in their skin flavonol content, whereas differences in the flavanol and hydroxycinnamic acid content were less pronounced. It is very likely that differences in nutrient status and yield determined amino acid profiles in juice, although all three systems showed similar amounts of mineralized nitrogen in the soil. Canopy structure and temperature in the bunch zone did not differ among treatments and therefore cannot account for the observed differences in favonols. A different light exposure of the bunches in the respective systems due to differences in vigor together with differences in berry size and a different water status of the vines might rather be responsible for the increase in flavonol content under organic and biodynamic viticulture.

Using δ13C and hydroscapes as a tool for discriminating cultivar specific drought response

Measurement of carbon isotope discrimination in berry juice sugars at maturity (δ13C) provides an integrated assessment of water use efficiency (WUE) during the period of berry ripening, and when collected over multiple seasons can be used as an indication of drought stress response. Berry juice δ13C measurements were carried out on 48 different varieties planted in a common garden experiment in Bordeaux, France from 2014 through 2021 and were paired with midday and predawn leaf water potential measurements on the same vines in a subset of six varieties. The aim was to discriminate a large panel of varieties based on their stomatal behaviour and potentially identify hydraulic traits characterizing drought tolerance by comparing δ13C and hydroscapes (the visualisation of plant stomatal behaviour as a response to predawn water potential). Cluster analysis found that δ13C values are likely affected by the differing phenology of each variety, resulting in berry ripening of different varieties taking place under different stress conditions within the same year. We accounted for these phenological differences and found that cluster analysis based on specific δ13C metrics created a classification of varieties that corresponds well to our current empirical understanding of their relative drought tolerances. In addition, we analysed the water potential regulation of the subset of six varieties (using the hydroscape approach) and found that it was well correlated with some δ13C metrics. Surprisingly, a variety’s water potential regulation (specifically its minimum critical leaf water potential under water deficit) was strongly correlated to δ13C values under well-watered conditions, suggesting that base WUE may have a stronger impact on drought tolerance than WUE under water deficit. These results give strong insights on the innate WUE of a very large panel of varieties and suggest that studies of drought tolerance should include traits expressed under non-limiting conditions.

Water deficit differentially impacts the performances and the accumulation of grape metabolites of new varieties tolerant to fungi

The use of resistant varieties is a long-term but promising solution to reduce chemical input in viticulture. Several important breeding programs in Europe and abroad are now releasing a range of new hybrids performing well regarding fungi susceptibility and producing good quality wines. Unfortunately, insufficient attention is paid by the breeders to the adaptation of these varieties to climatic changes, notably to the increased climatic demand and water deficit (WD). Thus, prior to the adoption of such varieties by the wine industry in Mediterranean regions, there is a need to consider their suitability to WD. This study aimed to characterize the different drought-strategies adopted by 6 new resistant varieties selected by INRAE in comparison to Syrah. To allow the assessment of long-term impacts of WD, field-grown vines were exposed to contrasted WD from 2018 to 2021 under a semi-arid Mediterranean climate. A gradient of WD was applied in the field and controlled through plant measurements at the single plant level. Grape development was non-destructively monitored to determine the arrest of berry phloem unloading. The impacts of WD on berry composition, including water, primary metabolites (sugars, organic acids), secondary metabolites (anthocyanins, thiols precursors) and main cations contents, were assessed at this specific stage. Results showed different varietal responses during the year and inter-annual acclimation in terms of plant water use efficiency, biomass accumulation, as well as yield components and berry composition. WD differentially reduced the accumulation of primary metabolites at plant and berry levels, but it little changed their concentrations in the fruits at the ripe stage. Moreover, WD differentially impacted the accumulation of secondary metabolites and major cations between the varieties. In the talk, we’ll present the main results regarding the WD impacts on fruit metabolites and enlarge the reflection about the practical assessment of the grapevine acclimation to WD.