Application of HPLC-HRMS to Archaeological Second Iron Age Gray Wares: Identifying Wine-Related Markers at Bostel di Rotzo (VI, Italy)

The Bostel di Rotzo site (Sette Comuni Vicentini Plateau, Vicenza) is a key Magrè group settlement from the Second Iron Age (5th-2nd century BCE). Archaeological excavations unearthed gray fine ware carinated beakers, traditionally associated with rituals and banquets. During this period, the Fritzens-Sanzeno culture spread winemaking to the prealpine regions, with Rhaetic wine later becoming a high-end product across the Roman world. Archaeobotanical evidence of Vitis vinifera grape pips also suggests a possible local wine-related activity, which is currently under investigation [1][2]. This study therefore examined the intended use of these ceramic vessels through untargeted High-Performance Liquid Chromatography-High Resolution quadrupole-Orbitrap Exploris 120 Mass Spectrometry (HPLC-HRMS, Thermo Scientific), focusing on wine-related markers. Preliminary characterization of markers was performed on modern ceramics immersed in wine and thermally treated, leading to a water/MeOH extraction method later applied to the archaeological samples. Soil control samples were also analyzed to exclude potential contamination from the surrounding environment. Several compounds were identified; in particular, the co-occurrence of tartaric and syringic acids strongly indicates the presence of red wine in some of the archaeological samples. Additionally, chromatograms were processed and statistically analyzed via Compound Discoverer, reducing the dataset complexity and aiding the identification of additional molecular markers. The employed HPLC-HRMS method avoided complex extraction/derivatization steps, limiting contamination and analyte loss. Its high sensitivity and specificity confirm its suitability for detecting molecular markers in archaeological pottery, highlighting its potential for future organic residue analyses. References [1] L. Zamboni, 2014, LANX. Rivista Della Scuola Di Specializzazione in Beni Archeologici - Università Degli Studi Di Milano, https://doi.org/10.13130/2035-4797/3736. [2] A. E. Fiorentin, F. Pieragostini and M. Marchesini, Il faggio e la capra: Il paleoambiente del Bostel alla luce degli studi archeobotanici e archeo-zoologici. Traces of complexity: Studi in onore di Armando de Guio, SAP, Mantova, Italy, 2021, 313-323.