Abstract
An ancient organic residue was collected from the bottom of a Greco-Italian amphora found in the Adriatic Sea and investigated by direct GC and GC-MS analysis. The headspace composition was determined by HS-SPME using: (1) DVB/CAR/PDMS and (2) PDMS/DVB fibres. Higher percentages of benzene derivatives, monoterpenes and other low-molecular aliphatic compounds were obtained by method (1) in contrast to higher percentage of naphthalene and phenanthrene derivatives found by method (2). In comparison with the composition of pine resin, it is more likely that the found low-molecular aliphatic alcohols, acids, esters and carbonyls with 2-phenylethanol were trapped and preserved within the organic residue from stored wine – the amphora’s originally content. Semi-volatile diterpenes methyl dehydroabietate (33.6%) and retene (24.1%) were dominant in the residue CH2Cl2 solution. Other abundant compounds were 1,4-dimethoxyphenanthrene (6.8%) as well as other naphthalene and/or phenanthrene derivatives [7-(1-methylethyl)-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydronaphthalene, 7-(1-methylethyl)-1,4a-dimethyl-2,3,4,4a,9,10-hexahydrophenanthrene, 7-(1-methylethyl)-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydro-phenanthrene, 3,6-dimethylphenanthrene and 2,3,5-trimethylphenanthrene]. Possible sources and formation pathways of the major compounds in the residue were discussed.
Highlights
The amphora is one of the most characteristic products of the ancient Mediterranean area
In comparison with the composition of pine resin, it is more likely that the found low-molecular aliphatic alcohols, acids, esters and carbonyls with 2-phenylethanol were trapped and preserved within the organic residue from stored wine – the amphora’s originally content
Wine was carried in amphorae of distinctive long shape (Amphorae vinariae) that were often coated with a thin layer derived usually from pine resin or resinous wood [1]
Summary
The amphora is one of the most characteristic products of the ancient Mediterranean area. The presence or absence of methyl esters has been considered as an indicator to distinguish the material produced from wood [2,5] Concerning their nature and composition, the chemistry of natural resins exuded by trees is diverse, but most are composed of terpenes made up of isoprene units [6,7]. GC analysis of the residue polar high-molecular compounds is often performed after saponification, extraction and derivatization by silylation, methylation or alkyl chloroformate reactions [12]. Each of these techniques has some drawbacks: silylation must be performed under anhydrous conditions and requires heating of the sample and injection of reactive mixtures onto the GC column. The obtained results will be compared to the papers reporting identification of resinous deposit components of amphorae from other regions
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