Chemical analysis of organic residues absorbed in pottery can provide valuable information on culinary practices in the past. Gas chromatography-mass spectrometry (GC-MS) is routine for identifying the organic compositions and biomarkers. In recent years, liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been increasingly applied to discern metabolites with more precision. However, the combination of these two techniques has never been reported in organic residue analysis to date. In this study, we, for the first time, introduce a new method to detect organic residues absorbed in pottery at the Peiligang site (Henan, China) during the Neolithic and Bronze Ages. The results show that compared to traditional methods (GC-MS), the metabolomic analysis (DPMA), combined with on GC-MS and UPLC-HRMS, enables rapid and comprehensive characterization of significant organic compounds in pottery. GC-MS analysis shows the lower content of lipids (0.5–40 μg/g) in all samples, including fatty acids, fatty alcohols, monoacylglycerols, while DPMA analysis indicates the presence of more lipids including fatty acyls, sterols and their derivatives, prenol lipids, polyketides among which fatty acyls are dominant. Both methods suggest that terrestrial animal and plant resources were utilized by humans, but DPMA provides more evidence on the categories of animal and plant resources. Neither method detected the cereal biomarkers (e.g. miliacin), although they were shown in archaeobotanical and dental calculus analyses. This could have been attributed to the timeline of the development of agriculture or the inertness of extraction to plant biomarkers. It is most striking that DPMA analysis finds the secondary metabolites of aromatic plants (13-tetradecanolide, tephrosol, and coumarin A, etc.), might indicating the intentional addition of herbal plants to enhance the flavour during food processing. The universal presence of organic acids in all pottery (cooking and non-cooking) in DPMA analysis supports the previously reported claim that they are not unreliable biomarkers related to alcohol-making activities. Furthermore, the discriminating analysis of metabolites among all pottery indicates the functional difference between cooking and non-cooking pottery and emphasizes the possible importance of Ding among pottery assemblages. Overall, DPMA has been proven as a novel method to look through culinary practices with highly sensitive resolution and has great potential in expanding our knowledge of ancient culinary practices. At last, the advantages and disadvantages of applying DPMA analysis are also discussed.
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