Vincenti Flaminia, Montesano Camilla, Ciccola Alessandro, Serafini Ilaria, Favero Gabriele, Pallotta Matteo, Pagano Flavia, Di Francesco Gaia, Croce Martina, Leone Maria Laura, Muntoni Italo Maria, Sergi Manuel
Department of Chemistry, Sapienza University of Rome, Rome, Italy.
Department of Environmental Biology, Sapienza University of Rome, Rome, Italy.
Front Chem. 2023 Jul 26;11:1238793. doi: 10.3389/fchem.2023.1238793. eCollection 2023.
The analysis of organic residue in ancient vessels to investigate early-age civilization habits is an important archeological application that needs advanced analytical methods. However, these procedures should meet inherent requisites such as low sampling invasiveness and high sensitivity for trace analysis. This study deals with the development of advanced analytical methods for the detection of opium alkaloids in ceramic vessels and its first application to the study of Daunian pots dating back to the VIII-IV sec BC. All the stages of the analytical procedure, from sampling to analysis, were carefully optimized. Concerning sampling, the traditional scraping approach was compared with a swabbing strategy which permitted minimizing sample encroachment. Extraction was based on pressurized liquid extraction or ultrasound-assisted liquid extraction, followed by dispersive liquid-liquid microextraction, which allowed concentration enrichment. On the other hand, a UHPLC-MS/MS method was specifically developed and validated to obtain reliable data. Some Daunian pots, belonging to the Ceci-Macrini private archeological collection, were selected for sample withdrawal as their iconography could suggest opium usage. Several of the analyzed samples resulted positive to thebaine and less frequently to morphine and codeine; furthermore, 70% of the analyzed items tested positive for at least one opium alkaloid. Positive findings were common to all the samples collected in the pots, suggesting that scraping and swabbing provided comparable results and validating this unusual sampling strategy. All samples were additionally analyzed by UHPLC-HRMS to further improve the confidence level of the identified compounds. The obtained results shed new light on the hypothesis of opium usage by the ancient Daunian civilization. Furthermore, this study provided suitable analytical tools for further investigations on the same topic, with a good level of confidence in the quality of the results.
通过分析古代容器中的有机残留物来研究早期文明习惯是一项重要的考古应用，需要先进的分析方法。然而，这些方法应满足一些内在要求，如低采样侵入性和对痕量分析的高灵敏度。本研究致力于开发用于检测陶瓷容器中鸦片生物碱的先进分析方法，并首次将其应用于对可追溯至公元前8至4世纪的道年陶壶的研究。从采样到分析，分析过程的所有阶段都经过了精心优化。在采样方面，将传统的刮擦方法与擦拭策略进行了比较，后者可将样品侵蚀降至最低。提取基于加压液体萃取或超声辅助液体萃取，随后进行分散液液微萃取，以实现浓缩富集。另一方面，专门开发并验证了一种超高效液相色谱-串联质谱法以获取可靠数据。选择了一些属于切奇-马克里尼私人考古收藏的道年陶壶进行样品采集，因为其图像可能暗示了鸦片的使用。几个分析样品对蒂巴因呈阳性反应，对吗啡和可待因呈阳性反应的频率较低；此外，70%的分析物品至少对一种鸦片生物碱检测呈阳性。所有从陶壶中采集的样品均有阳性发现，这表明刮擦和擦拭提供了可比的结果，并验证了这种不同寻常的采样策略。所有样品还通过超高效液相色谱-高分辨质谱进行了额外分析，以进一步提高所鉴定化合物的可信度。所得结果为古代道年文明使用鸦片的假设提供了新的线索。此外，本研究为同一主题的进一步研究提供了合适的分析工具，对结果的质量有较高的可信度。
