Archaeobotanical and chemical investigations on wine amphorae from San Felice Circeo (Italy) shed light on grape beverages at the Roman time.

We hereby investigate the pitch used for coating three Roman amphorae from San Felice Circeo (Italy) through a multidisciplinary study. The identification of molecular biomarkers by gas chromatography-mass spectrometry is combined with archaeobotanical evidence of pollen and plant tissues of Vitis flowers. Diterpenic chemical markers together with Pinus pollen and wood revealed Pinaceae tar coating. Aporate 3-zonocolpate pollen, identified as Vitis, together with tartaric, malic and pyruvic acids elucidate the grape-fermented nature of the content. Our conclusions open new consideration on the use of grape derivatives that cannot be supported by traditional analytical methods. Based on the finds of aporate Vitis pollen, found also in local modern and Middle Pleistocene samples, we hypothesize the use of autochthonous vines. The presence of a medicinal wine (historically reported as oenanthium) is also considered. We interrogate Vitis pollen capacity to target grapevine domestication, thereby providing innovative tools to understand such an important process. We anticipate our study to encourage a more systematic multidisciplinary approach regarding the analyses of wine amphorae.

The concentration and origins of carboxylic acid groups in oil paint.

Although the concentration of carboxylic acid (COOH) groups is crucial to understand oil paint chemistry, analytical challenges hindered COOH quantification in complex polymerised oil samples thus far. The concentration of COOH groups is important in understanding oil paint degradation because it drives the breakdown of reactive inorganic pigments to dissolve in the oil network and form metal carboxylates. The metal ions in such an ionomeric polymer network can exchange with saturated fatty acids to form crystalline metal soaps (metal complexes of saturated fatty acids), leading to serious problems in many paintings worldwide. We developed two methods based on ATR-FTIR spectroscopy to accurately estimate the COOH concentration in artificially aged oil paint models. Using tailored model systems composed of linseed oil, ZnO and inert filler pigments, these dried oil paints were found to contain one COOH group per triacylglycerol unit. Model systems based on a mixture of long chain alcohols showed that the calculated COOH concentration originates from side chain autoxidation at low relative humidity (RH). The influence of increasing RH and ZnO concentration on COOH formation was studied and high relative humidity conditions were shown to promote the formation of COOH groups. No significant ester hydrolysis was found under the conditions studied. Our results show the potential of quantitative analysis of oil paint model systems for aiding careful (re)evaluation of conservation strategies.