节点文献
古代青铜器矿料来源与产地研究的新进展
【作者】 魏国锋；
【作者基本信息】 中国科学技术大学 ， 科学技术史， 2007， 博士
【摘要】 青铜器矿料来源和产地研究，是青铜时代至关重要的考古问题，也是冶金考古的重点和难点之一。对之进行研究，能反映冶金技术的起源和传承关系以及当时社会的政治、文化、方国地理、经济贸易、交通运输、生产组织、社会结构和铜、锡矿资源的获得方式等多方面、深层次的问题。微量元素示踪法是最早应用于青铜器矿料来源研究的自然科学手段，但由于对青铜冶铸过程中微量元素的变化规律认识不足，除纯铜制品外，该方法难以给出令人满意的结果。于是，自上世纪60年代开始，该方法逐渐淡出了人们的视野。青铜器矿料来源与古铜矿输出方向是同一问题的两个方面。基于此，本博士论文提出了新的研究思路，将研究青铜器的矿料来源转变为探讨古铜矿的输出方向，对微量元素示踪法进行了改进。根据这一研究思路，本文采用ICP-AES方法，对湖北铜绿山、皖南的铜陵、南陵、山西中条山、内蒙古林西大井、宁夏照壁山等先秦古铜矿冶遗址的铜矿石、炼渣、铜锭或炼渣中较大铜颗粒进行系统对比研究，了解各古代铜矿床的特征元素，深入研究铜矿冶炼过程中微量元素的化学行为和变化规律，探讨了筛选特征微量元素，并将其应用于古铜料输出方向研究中的可行性。研究发现，铜矿冶炼过程中，Au、Ag、As、Sb、Bi、Se、Te、Co、Ni等元素主要富集在金属铜中，对青铜器矿料来源具有指示意义。同时，结果表明，各矿冶遗址的铜矿和铜锭，在特征微量元素上的差异比较明显；采用微量元素示踪法，研究古铜矿的输出方向是切实可行的，尤为适用于不同铜成矿带的示踪。在此基础上，采用改进的微量元素示踪法，初步探讨了辽西地区，安徽境内的滁县何郢遗址、淮北地区、皖南沿江的铜陵、南陵、繁昌，山西侯马的上马、柳泉春秋战国墓地以及陕西扶风李家西周铸铜遗址等地青铜器样品的矿料来源。结果发现：安徽境内的青铜器所用铜矿料主要来自长江中下游的古铜矿，辽西地区的青铜器矿料主要来自大井铜矿或其周边铜矿，同时，侯马青铜器与大井铜矿微量元素特征的相似性，暗示大井铜矿有可能曾经输入到中原地区；并进一步指出，中原王都附近，作为先秦时期的青铜器铸造中心，其所用矿料可能主要来自南方的长江中下游铜矿、山西中条山铜矿以及内蒙古林西境内的大井铜锡矿床。关于青铜器的产地研究，人们长期采用考古器型学的研究方法，这种方法受研究者的主观因素影响较大。近年来，国内外学者从青铜基体的铅同位素、微量元素等多方面进行了尝试，期望利用自然科学手段判断青铜器产地。但是，青铜基体的铅同位素和微量元素数据，主要反映的是青铜器矿料来源的信息，而不是青铜器产地。本博士论文另辟蹊径，探索利用青铜器内的泥芯残留，示踪青铜器产地、即铸造地的可行性。采用偏光显微镜、XRD、XRF、NAA、ICP-AES等技术手段，测试分析了湖北九连墩楚墓青铜器内的泥芯，发现九连墩外来风格青铜器的泥芯，在物相、微观结构、化学组成（主量、微量、稀土元素）、植硅体组合等方面与本地风格青铜器的泥芯有较大差异。外来风格青铜器的泥芯，其CaO含量较高，大部分样品高达6％以上，而Na2O的含量相对较低。这一富钙、贫钠的特点，与中国黄土的典型特征极为吻合。结合泥芯中的植硅体组合特征，可以推测：九连墩楚墓中具有外来风格的青铜器，很可能来自中国北方黄土堆积地区，系当地铸造后输入到楚国的。同时，研究表明，利用青铜器内的泥芯残留，可望有效地示踪青铜器的产地。
【Abstract】 Study on ores source and casting place of bronze vessel is one of important and difficult subjects in archaeology, which can reflect the origin and spreading route of metallurgy, politics, economy, cultural intercourse, social structure, producing mode, acquiring means of copper and tin ores, etc.Trace elements analysis is one of natural science means used earliest to determine ores source of the bronze vessels. Because of unknown of variation regularity of trace elements during the copper smelting process, this means doesn’t make progress. Except for pure copper artifact, many scholars think that the application of trace elements analysis is unsatisfactory in study on copper ores source of bronze vessels. Therefore, since 1960s, this method is rarely applied. In this dissertation, trace elements analysis is improved. Study on copper ores source of bronze vessels is transformed into study on exporting rout of copper ores. According to the improved trace elements method, this dissertation firstly probes into variation regularity of trace elements during copper smelting and their potential application in the study on the exporting route of the ancient copper ores. All samples of copper ores, slag and copper ingots are from several Pre-Qin sites of mining and smelting, such as Tonglushan, Tongling, Nanling, Zhongtiaoshan, Zhaobishan and Dajing sites, and trace element analysis is conducted by Inductively Coupled Plasma Atomic Emission Spectrometer （ICP-AES）. The results reveal that trace elements Au, Ag, As, Sb, Bi, Se, Te, Co, Ni, etc. mostly enriched in the copper during copper smelting and they are indicative of copper ores source of the bronze vessels. Meanwhile, this research indicates that trace element characteristics of copper ores and copper ingots from different site of mining and smelting are obviously varied, and it is feasible to determine the exporting route of ancient copper ores using trace element tracing technology, especial for copper ores from different ore belt.Based on the above research, this dissertation also probes into the copper ores source of the bronze vessels in Shang and Zhou Dynasties from some areas in China through trace element analysis. Results show that the copper of the bronze vessels from Anhui Province comes from ancient copper ores of the middle and lower reaches of Yangtse Rive, while the copper of bronze vessels from Western Liaoning Province and Houma comes from Dajing copper ores. At the same time, this research indicates that the copper ores used for the bronze vessels in the central area in China can mostly come from copper ores of the middle and lower reaches of Yangtse Rive, Zhongtiaoshan copper ores in Shanxi Province and Dajing copper ores in Inner Mongolia Municipality.Many scholars identified the foundry area of the bronze vessels through researching into the style, decoration and inscription of the bronzes. This research method is subjected to the subjective experience and knowledge of archaeologists. Some scholars analyzed lead isotope and trace elements of bronze vessels and attempt to ascertain foundry area of the bronzes using natural science means. However, signature of lead isotope and trace elements of the bronzes provide information on ores source which metal minerals used to cast the bronzes derive from, not foundry area. The composition of casting clay core might provide clue to the foundry area of the bronze vessels. Therefore, this dissertation studies the casting place of the bronze vessels on the basis of analysis of clay core residues of the bronze vessels. Samples of the fragments of the casting clay cores were removed from the bronze vessels unearthed at Jiuliandun tombs of Chu state, in Zaoyang City, Hubei province, dated back to Warring States Period, and were analyzed by polarized light microscope, XRD, XRF, NAA and ICP-AES, etc.. The results reveal the casting clay cores of extraneous bronze vessels from Jiuliandun tombs are different from those of local bronze vessels excavated in Jiuliandun tombs 1 and 2 in phase composition, microstructure, major elements, trace elements, REE, phytolith assemblages, etc.. The contents of CaO in casting clay cores of extraneous bronze vessels are very high and the contents of Na2O are low, which are representative characteristic of loess in the northern China. Combining with the analysis of phytolith assemblages, it is possible that extraneous bronze vessels are cast in the loess area of the northern China. Meanwhile, this research indicates it is feasible to restrict the possible foundry area of the bronze vessels according to analysis of casting clay cores residues on the bronzes.