Cereal remains are common and important archaeological finds, providing crucial evidence for the origin and development of agriculture. Many previous studies have utilized one or several molecules as biomarkers to identify archaeological remains. However, there is a lack of systematic research on characteristic metabolites of common grains, especially of ancient varieties. The goal of this study was to derive a series of more species-indicative biomarkers using untargeted metabolomics as well as provide new insights into the identification of cereal remains excavated in archaeology. First, modern cereal, pottery and archeological samples were used for untargeted metabolomics to obtain plant metabolites. Then, statistical analyses were employed to screen candidate biomarkers. It was determined there are 73, 42, 138 and 58 metabolites representing broomcorn millet, foxtail millet, wheat and rice, respectively. Among the compounds mentioned above, 33 were found to be present in the archaeological samples from the Dongxiafeng site dating back around 3600 years. These 33 biomarkers would serve as characteristic elements for systematic clustering. The results indicated that among pottery sherds from the Dongxiafeng site, the most likely processed cereal is foxtail millet, and the least likely processed cereal is wheat. The theoretical calculated proportions of four grains are as follows: broomcorn millet 26%; foxtail millet 51%; wheat 18%; rice 5%. This aligns with the agricultural tradition in this region during the early Bronze Age, characterized by dryland farming with a focus on foxtail millet and broomcorn millet, while rice and wheat were also introduced.

谷物遗骸是常见且重要的考古发现，为农业的起源和发展提供了重要证据。之前的许多研究都利用一种或几种分子作为生物标志物来识别考古遗迹。然而，目前对常见谷物，尤其是古老品种的特征代谢物缺乏系统研究。这项研究的目的是利用非目标代谢组学得出一系列更具物种指示性的生物标志物，并为考古学中出土的谷物遗骸的鉴定提供新的见解。首先，利用现代谷物、陶器和考古样品进行非靶向代谢组学以获得植物代谢物。然后，采用统计分析来筛选候选生物标志物。确定了黍、谷子、小麦和水稻的代谢物分别为 73、42、138 和 58 种。在距今约3600年前的东下峰遗址考古样品中，发现了上述化合物33种。这 33 个生物标志物将作为系统聚类的特征元素。结果表明，东下峰遗址出土的陶片中，最有可能被加工的谷物是谷子，最不可能被加工的谷物是小麦。四种谷物的理论计算比例为：黍26%；谷子 51%；小麦 18%；大米5%。这与该地区青铜时代早期的农业传统相符，其特点是旱地农业，主要种植小米和黍，同时也引入了水稻和小麦。