1. The mystery of the origin of the Shang Dynasty blue copper ore in China Since the excavation of Yin Ruins on 1928, the origin of the Shang Dynasty blue copper ore in China has been paid close attention to by academic circles. Bronzes in Shang Dynasty mainly included copper, tin and lead. From the perspective of metal composition, the academic discussion on the source of mineral substances in Shang Dynasty can be divided into two stages. In the first stage, there were three main viewpoints in academic circles: the Southern Theory, the Central Plains Theory and the Multi-source Theory. Zhao, Guo Moruo, Jian Bozan, Tong, etc. 1933, Li Ji published the article "Five Bronzes of Yin and Xu and Related Issues", saying: "The raw materials (bronzes) came from Wuxi Mine in the south and along the Yellow River valley, which is a fact that has been investigated. Therefore, the recent supply is only in the south. " [1] Like Mr. (Source: Archaeology), the scholars who advocate the "Central Plains Theory" mainly have history, Amano's introduction, and. Among them, Professor Shi analyzed the distribution of mineral resources in the past dynasties in an article published in 1955, and thought: "The source of copper deposits in the Yin Dynasty can be in the Yangtze River basin, or even in Yuanqu from Jiyuan without crossing the south of the Yellow River, but I heard that copper deposits are abundant in the mountains in the middle. [2] The advocate of "multi-source theory" is mainly Mr. Rong Geng, who said in "A General Theory of Bronzes in Yin and Zhou Dynasties": "On the one hand, the copper and tin materials of Yin people can be imported from Jianghuai, Xuchu and other places in southern China, which may be due to the exchange of materials between vassal countries and other countries, or even the plunder of war. On the other hand, in order to be self-sufficient, it is natural that they should try their best to explore and collect raw materials in their own territory. " [3] Mineral resources are the common object of the ancient political groups in the second stage, with lead as the center. The main viewpoints of academic circles are: Southwest China, Zhongtiaoshan, Qinling, Hunan, Jiangxi, Hubei and Africa. Among them, "Southwest Theory" is the most powerful, and other theories are mostly foil. Mr. Jin is the initiator of "Southwest Theory" and the first person to introduce lead isotope technology into archaeological research in China. 1In August, 984, the third international symposium on the history of Chinese science was held in Beijing Friendship Hotel. At this meeting, Jin Zhongyao, who was only 28 years old, reported an important achievement. This achievement comes from Mr. Jin's research during his master's degree under the guidance of Academician Qian and professors. 14 pieces of Yin Ruins bronzes were detected by lead isotope technique. The results show that two completely different kinds of lead are used in bronze wares in Yin Ruins. One of them is ordinary lead, and its isotope ratio is close to that of the sample of Tonglushan ancient copper mine site in Hubei Province. The other is highly radioactive lead (hereinafter referred to as "special lead") which is rare in geology, and its isotope ratio falls in the lead isotope distribution field of Yongshan Jinshachang and Luohong mines in northeast Yunnan. Based on this, Mr. Jin concluded that the mineral materials used in Yin Ruins came from northeast Yunnan. [4] Ancient copper mining and smelting map (source: China cultural relics) Mr. Jin's research has actually proved the multi-source theory of copper ore in Shang Dynasty. However, different from previous studies, Mr. Jin's research makes it possible to explore the specific causes of mineral sources because of the use of natural science and technology. After the "Southwest Theory" was put forward, the academic circles successively appeared Qinling Theory, Zhongtiaoshan Theory, Hebei Theory, Multi-source Theory, Hunan Theory, Jiangxi Theory and even Africa Theory. Professor Jin Zhongyao has analyzed these viewpoints one by one without quoting them. 2. Lead isotope detection technology, which is a tracer for tracing blue copper ore. The formation of highly radioactive lead is related to the evolution of earth geological structure, and it has the tracing ability of "fingerprint" in geological research. If carbon 14 technology solves the problem of when archaeological materials are used, then isotope detection technology can solve the problem of where cultural relics are used. (1) Tracing principle of lead isotope To understand the tracing principle of lead isotope, it is necessary to understand the tracing theory of radioactive isotope system and the evolution of ore lead isotope system. The Theory and Application of Isotope System in Earth Science written by Zhu Bingquan, a researcher of Chinese Academy of Sciences, has a detailed introduction to this, which can be used for reference. [5] Professor Jin has introduced the principle of lead isotope tracing for many times. The following is an introduction: the formation of lead isotopes is related to the evolution of the earth. The basic principle of applying lead isotope tracing method to bronze archaeological research is that the lead isotopic compositions of copper, tin and lead metal deposits on the earth are different because of their different geological ages and different enrichment conditions of uranium and thorium in environmental materials when they were formed, that is, four lead isotopes (204pb, 206pb and 206 Pb). Compared with trace elements, four stable isotopes can better retain the origin information, because they will not fractionate during the heating process of smelting and casting in ancient bronze industry. Therefore, the source of bronze raw materials can be studied by comparing the lead isotope analysis data of bronze samples and mineral deposits. [6] The ratio of 207 Pb to 206 Pb of highly radioactive lead is generally less than 0.82, which is lower than that of ordinary lead, so this special lead is generally called "low ratio lead". (II) Cases of Using Lead Isotopes in Foreign Archaeological Research The following year, three scholars, including Peng Zicheng of the Chinese University of Science and Technology, published articles in Archaeology, introducing the application of lead isotope ratio method in archaeological research abroad. [7] The following are two cases mentioned in this paper: fish-shaped glass bottle (unearthed in Begram, Afghanistan) 1962, and Brill of Corning Glass Museum published the first paper on lead isotope archaeology technology. After more than ten years, Brill and his collaborators have done a lot of research on lead isotopes of ancient glasses, bronzes, coins, pigments, gold and silver. 1983, Brill published a paper at the Beijing International Glass Conference, summarized hundreds of lead isotope data he obtained, and plotted them. As can be seen from the figure, the ancient glass he studied in China is divided into two areas, which shows that the lead content in ancient glass in China is completely different from that in Greece (L), the United States, Italy and Turkey (E), Spain, Wales, Sardinia (S) and ancient Egypt, which proves that China has its own glass manufacturing system in ancient times. Brill's determination of lead isotope ratio of ancient artifacts in different regions is 198 1. Professor Xiong of Nagoya University and other scholars published a report on bronze mirrors. This report reports the test results of Japanese scholars on bronze mirrors imported from China and unearthed in Japan, and confirms that the mineral sources of bronze mirrors in the Eastern Han Dynasty and the Western Han Dynasty in China are quite different. At the same time, the research results show that the lead isotope ratio of triangular prism animal mirrors imported from China or copied from Japan is in the same distribution area as that of ancient Eastern Han mirrors made in China, which is completely different from the views of some Japanese scholars in the past. Japanese scholars' determination results of lead isotope ratio of bronze mirrors III. China bronze age special lead Mr. Jin's research results quickly attracted academic attention. 199 1 year, researchers from China Academy of Social Sciences, Freer Art Museum of the United States and Tokyo National Institute of Culture and Finance started a research project on lead isotopes of Shang and Zhou bronzes unearthed in China. After more than three years' efforts, the program has completed the experimental determination of more than 400 Shang and Zhou bronze samples. As a result, to people's surprise, most of these bronzes contain highly radioactive lead! [8] Now, let's take a look at the relevant test results (all from lead isotope archaeology in Jin Zhongguo): (1) Sanxingdui culture. The researchers obtained 53 data of Sanxingdui bronzes, and the results showed that these bronzes all contained special lead. (Lead Isotope Archaeology in China, p. 104) Portrait of Dragon Face (in Sanxingdui Museum) (2) Panlongcheng Culture. Three groups of scholars detected lead isotopes in bronze wares in Panlongcheng. Among them, Professor Sun of University of Science and Technology Beijing tested 30 pieces, and the results showed that 18 pieces contained special lead; Professor Peng Zicheng of China University of Science and Technology tested 9 pieces, and 6 pieces contained special lead; [9] Another 5 pieces were tested by Professor Jin, and 4 pieces contained special lead. (China Lead Isotope Archaeology, page 27) Panlongcheng Mask (3) Newly developed Oceania culture. There are two batches of lead isotope detection data of bronze wares in Xing 'an Tomb. Among them, 1 1 tested by Professor Jin and others all contain special lead. (Lead Isotope Archaeology in China, p. 15 1) In addition, scholars such as Peng Zicheng released a batch of data in 1997, including four data from Xing 'an Tomb, all of which are special lead. [10] Double-tailed bronze statue of Fu Bird (Source: Shang Dynasty Heritage) (4) Yanshi Mall and Zhengzhou Mall. Seven bronzes and 1 malachite from Yanshi Shopping Mall, Zhengzhou Shopping Mall and Erligang were tested for lead isotopes. The results showed that except a coffin in Yanshi Mall and a plate in Erligang, all the others contained special lead. (Lead Isotope Archaeology in China, page 26) Zhengzhou Mall hoards bronzes (Source: Popular Archaeology) (5) Chengyang Bronzes Group. Chengyang Bronze Group is the abbreviation of Chenggu and Yangxian Bronze Group, which is located in Hanzhong Basin. Professor Jin and others examined 27 bronzes in Chengyang Bronze Group, of which 24 contained special lead. (Lead Isotope Archaeology in China, page 143) Baoshan Bronze Animal Mask (collected by Shaanxi Museum) (6) Yin Ruins Culture. Professor Jin and others * * * tested the bronze wares of Yin Ruins 178 pieces and got the data 179. Among them, 18 pieces were tested in the first stage, and 14 pieces contained special lead; In the second stage, 64 pieces were tested, and 52 pieces contained special lead; In the third phase, 6 1 piece was tested, and 23 pieces contained special lead; In the fourth phase, 32 pieces were tested, and 2 pieces contained special lead. (Lead Isotope Archaeology in China, p. 159- 160) The roof of Simuwu in Yin Ruins (National Museum) (7) Jinsha Culture. In 2004, researchers published the results of lead isotope detection of bronzes in Jinsha site. The results show that the Ge-shaped utensils, hoe-shaped utensils, shape-shaped utensils and more than half of the living decorations in Jinsha site, which have the characteristics of local bronze civilization, contain special lead completely consistent with Sanxingdui bronzes. (Lead Isotope Archaeology in China, p. 120) Dragon Head Sculpture (collected by Jinsha Museum) (8) Bronzes of Shang and Zhou Dynasties in northern Shaanxi. The Shang and Zhou bronzes in northern Shaanxi are represented by Lijiaya culture, and the bronzes in northern Shaanxi are tested by University of Science and Technology Beijing. Among them, 17 bronzes in the late Shang Dynasty were detected, 10 bronzes contained special lead (page 74), while1/kloc-0 bronzes in the Western Zhou Dynasty and 30 bronzes in the Eastern Zhou Dynasty were all common lead. [1 1] bronze horse of Lijiaya culture (unearthed in Yanjiagou, Ganquan, northern Shaanxi) (9) bronze wares of Shang and Zhou Dynasties in Ningxiang. The bronze ware group of Shang and Zhou Dynasties in Ningxiang is represented by the ancient city culture of Tanzheli. The lead isotopes of 26 bronzes in the ancient city of Tanheli were detected by researchers, and it was found that 6 bronzes contained special lead. [12] Fang Zun of Siyang (unearthed from Tanheli site) (10) Jinguo Cemetery in Qucun, Shanxi Province. The researchers examined 7 1 bronze wares from the Jin State Cemetery in Qucun, Shanxi Province, and found that 3 of them contained special lead. (Lead Isotope Archaeology of China, p. 185) It should be pointed out that there is no bronze ware containing this special lead in Erlitou culture (Lead Isotope Archaeology of China, p. 25). After the collapse of Erlitou culture, minerals containing this special lead began to be widely used in the study of ancient cultures such as Sanxingdui, Panlongcheng, Yanshi Mall, Zhengzhou Mall, Xing 'an Tomb, Hanzhong Basin and Anyang Yin Ruins, until the third phase of Yin Ruins suddenly declined. According to the above information, we can draw the following table: the main archaeological culture of bronzes containing extra lead in Shang and Zhou Dynasties. 4. Is the "Southwest Theory" the terminator of the mysterious mineral source? As mentioned above, "Southwest Theory" is the most powerful theory to study the source of special lead ore in academic circles. So, what are the evidence and defects of the "Southwest Theory"? Next, let's talk about this problem. (1) The main evidence of the "Southwest Theory" First of all, from the geochemical point of view, special lead ores are most likely to exist in the southwest region. In 2002 and 2003, China Academy of Sciences researcher Zhu Bingquan and other scholars published articles twice, pointing out that according to the geological environment conditions, there are four areas in Chinese mainland that are most likely to form this kind of high-level radioactive lead mine: northeast Yunnan, Xiaoqinling, Qingchengzi in Liaodong Peninsula and the middle and lower reaches of the Yangtze River. Among them, the preferred area is northeast Yunnan. In addition, Zhu Bingquan's research particularly emphasizes that the possibility that this special lead is related to extraterrestrial resources (referring to meteorites) cannot be ruled out. [13] It is a common phenomenon that meteorites contain high radioactive lead (source: Sina). Secondly, from the perspective of archaeological culture, after the third phase of Yin Ruins, the number of bronzes containing this special lead in other areas of China has decreased rapidly, while the Jinsha culture in Chengdu Plain still uses this special lead material in large quantities. Thirdly, according to the literature, there are only three places where tin is produced, namely Shikongshan in Gao Lu (now Luliang) county of Yizhou county, Caishan and Wushan in Bengu (Mengzi) county, while the Central Plains lacks tin mines. Another book, Biography of Southern Qi, records that under Mengshan (Zhuti Mountain) in Nanguang County, there is a city called Mengcheng, which covers an area of two hectares. There are four stoves, one foot high and one foot and five feet wide. Hundreds of steps from Mengcheng to the south, the ground dug two feet deep to get copper, and there was an ancient copper pit, two feet deep, which still exists in the middle of the people. (2) The main defects of the "Southwest Theory" There is no doubt that from the published academic materials, the "Southwest Theory" is the most likely answer. However, the Southwest Theory also faces two major challenges. First, there is no archaeological culture like Tonglushan ancient copper mine in Hubei and Tongling ancient copper mine in southwest Jiangxi. Secondly, there are obvious differences between the special lead data found in southwest China and the lead data contained in bronzes. What's going on here? Professor Jin pointed out in 1993 and 1994 that the special lead data found in archaeological materials have the same isochronal age relationship of about 2.45 billion years, while the known high-level radioactive lead deposits on the earth were generally formed after1600 million years. [14] That is to say, the special lead used in ancient bronzes discovered now is not the same as that known in the deposits in northeast Yunnan. Comparison between the distribution area of lead isotope ratio in bronzes and the distribution area of lead isotope ratio in major deposits: Is this special lead really a whisper? On the one hand, it is not excluded that it is extraterrestrial resources. At the same time, researcher Zhu Bingquan explained this phenomenon: it should be noted that the crustal activity is much stronger than that in the ancient block, and the U/Pb ratio will be more differentiated. These areas are called craton boundaries, that is, geochemical boundaries. When the mineralization occurs on the geochemical boundary and the ore-forming materials come from the mixing of blocks formed in two different eras, it is possible to produce a 2.5 billion-year isochron trend of highly radioactive lead ore. [13] 5. The mystery of lead has been solved. The unexpected answer lies in the time when the "Southwest Theory" became the most likely answer but could not be the final conclusion. The time came to 20 17. This year, the cultural relics department of Nanyang City, Henan Province collected several pieces of metal ingots from Yahe Industrial Zone and sent them to the Archaeological Laboratory of China University of Science and Technology. After the isotopic composition determination of Professor Jin's team, it is found that these metal ingots are very consistent with the high radioactive lead contained in Shang bronzes. Subsequently, Professor Jin immediately organized an investigation team to investigate the mines in the northern margin of Nanyang Basin. As a result, more than ten ancient mine caves were discovered and a batch of high-grade lead ore was collected. After testing, these lead ores contain high radioactive lead, which is consistent with the data of high radioactive lead in Shang Dynasty. At the same time, through the luminescence dating of environmental sediments, it is determined that the mining and smelting age of this lead mine is Shang Dynasty. At this point, the mysterious and special mystery of lead source that has plagued China's archaeological and historical circles for decades has finally been solved. Schematic diagram of the ancient mine cave (the picture has nothing to do with this article) It should be noted that the above content comes from the website of the Institute of Archaeology, Chinese Academy of Social Sciences, the science blog of researcher Zhu Bingquan and Dahe Daily. com。 [15] At present, these contents have not been seen in public academic papers and works, but they are reliable from the comparison of sources and channels and various materials. At the same time, several scholars, such as Zhang Hongfei from the Institute of Geochemistry of China Geo University, published a document in 1999 Geoscience, which confirmed that there are two basement blocks with obviously different lead isotopic compositions in Tongbai area to the east of Nanyang Basin. Among them, the basement rocks on the north side of Tongbai-Shangcheng fault have the characteristics of high radioactive lead isotope composition; The basement rocks on the south side of Tongbai-Shangcheng fault have the characteristics of low radioactive lead isotope composition. Based on the contents of this paper, the formation of high-level radioactive lead ore in Nanyang basin is the result of block mixing (North China Craton and Yangtze Craton) mentioned by researcher Zhu Bingquan. Qinling-Dabie orogenic belt is formed by mixing North China Craton and Yangtze Craton. 6. Yu Sheng: The mystery of special lead has been solved, and new challenges have just begun. Undoubtedly, this discovery of suspected special lead source is good news for historians and archaeologists in China. Now we need to wait patiently for the real hammer of this information. It should be pointed out that if the source of special lead ore is in Nanyang basin and there is Wuxi mine in Nanyang area, it means that the source of mineral substances in the Central Plains is more complicated than previously thought, and the research on the source of Shang Dynasty is not over. In addition, we should also see that since Professor Jin revealed that many archaeological cultures, such as Yin Ruins, Sanxingdui, Xing 'an Oceania, Panlongcheng, Yanshi Mall, Zhengzhou Mall and Jinsha Site, used the same special lead mine at the same time, no matter whether the lead mine is located in the southwest or Nanyang Basin, China academic circles are faced with many important questions that need to be answered. Distribution of Bronze Culture in the Period of Extra Lead (1) If this extra lead mining area is located in the northeast of Yunnan, what is the relationship between the ancient culture of Yin Ruins, Panlongcheng, Xingan and Zhengzhou Mall in the middle reaches of the Yellow River and Yangtze River and the Sanxingdui culture and Jinsha culture in Chengdu Plain? (2) If this special lead mine is located in Nanyang Basin, why did the Yin people greatly reduce the use of this mine after the third phase of Yin Ruins, and even when the fourth phase was completely unused, the Jinsha site in Chengdu Plain suddenly rose and became a large-scale user of this mine? "Sunbird" gold ornaments (collected by Jinsha Museum) (3) The lower age limit of Zhengzhou Mall and Panlongcheng is the second phase of Erligang Upper Level, which is about 1300 BC; This time coincides with the rise of Yin Ruins culture. If Zhengzhou Mall and Panlongcheng are regarded as commercial culture and the rise of Yin Ruins as the migration of Pan Geng to Yin, how can we explain that Zhengzhou Mall and Panlongcheng were destroyed at the same time as the rise of Yin Ruins culture? Is this related to the special source of lead ore? (4) Sanxingdui Bronze Culture (Sanxingdui Culture Phase III) and Dayangzhou in Xing 'an were both destroyed in Yin Ruins Culture Phase I, about 1260 BC. Coincidentally, both archaeological cultures use special lead. What is the historical truth behind this? In a word, the mystery of the origin of special lead deposits may have been solved, but the real challenge to China historians may have just begun. Copyright Tip: The author of this article has signed a contract with * * * Knight, and may not reprint it without the authorization of the author Gu Shiwei and * * * Knight. Most of the pictures used in this paper come from the Internet. If there is any infringement, please contact the author to delete it. Thank you. References: [1] Li Ji: Five Bronzes in Yin Ruins and Related Issues, Collection of the Institute of History and Language,No. 1, Essay on Celebrating Mr. Cai Yuanpei's Sixty-Five Years Old (1933); This income is collected works of Li Ji, Volume 3, Shanghai People's Publishing House, 2006. [2] Stone: Copper Casting Technology in Yin Dynasty, Journal of Institute of Historical Linguistics, 26th edition, vol. 1, 1955. [3] Rong Geng: "General Theory of Bronzes in Yin and Zhou Dynasties", Cultural Relics Publishing House, 1984 edition. [4] Jin Zhongyao: Study on the Mineral Sources of Bronze in the Central Plains in the Late Shang Dynasty, published in the Proceedings of the Third International Symposium on the History of Chinese Science, Science Press, 1990. [5] Zhu Bingquan et al. Theory and application of isotope system in earth science: On the evolution of crust and mantle in Chinese mainland, Science Press, 1998. [6] Progress in the application of gold and lead isotope tracing in archaeological research, Journal of Geology, No.6, 2003. [7] Peng Zicheng et al.: Application of lead isotope ratio method in archaeological research, Archaeology1985 No. 1 1. The illustration is from lead isotope archaeology in China by Li Xiaocen and others. [8] Jin. Lead Isotope Archaeology in China, University of Science and Technology of China Press, 2008. [9] Sun et al.: Report on Determination of Lead Isotope Ratio of Bronzes Unearthed in Panlongcheng; Peng Zicheng and others. Study on lead isotope tracing of Shang bronzes in Panlongcheng. See Pan Longcheng, Cultural Relics Publishing House, 200 1 edition. [10] Peng Zicheng et al. A preliminary study on the fate of ancient mineral materials in Jiangxi, Hubei and Anhui provinces. Archaeology, No.7, 1997. [1 1] Liu: scientific analysis of bronzes unearthed in Shang and Zhou dynasties in northern Shaanxi, doctoral thesis of University of Science and Technology Beijing, 20 15. [12] Ma Jiangbo et al. Scientific Analysis of Bronzes Unearthed from Tanheli Site in Ningxiang County, Hunan Province, Archaeology, No.7, 20 16. [13] Zhu Bingquan and Chang Xiangyang: Comment on the discovery of highly radioactive lead in bronzes of Shang Dynasty, Ancient Civilization, vol. 1, 2002; Chang Xiangyang, Zhu Bingquan, Jin: Origin of Bronze Minerals in Yin and Shang Dynasties and Application of Lead Isotope Tracing, Journal of Guangzhou University, No.4, 2003. [14] Jin et al.: Study on lead isotope ratio of bronzes in Shang Tomb of Dayang Prefecture in Xingan, Jiangxi Province, Archaeology, No.8, 1994. Kim, wait. Study on lead isotope ratio of bronze wares in Sanxingdui site pit of Guanghan, cultural relics, No.2, 1995. [15] Website of Institute of Archaeology, Chinese Academy of Social Sciences: "What I can't finish reading is Yin Ruins-90th Anniversary Commemorative Meeting of Scientific Excavation of Yin Ruins and Sidelights of Forum on Development and Archaeology of Yin Ruins", see Academic Conference, 201817; Professor Jin talks about lead isotope archaeology-innovation and persistence. See Academic Trends 201May 5, 9. Zhu Bingquan's blog of Science Network: Love at the Duck Estuary in Nanyang-From Ancient Civilization to Modern Civilization, 2065438+08101October 26th. Big river. Com: Draw a new blueprint for the leap-forward economic and cultural development of Yahe Industrial Zone in Nanyang City, 20 18 12.27. [16] Zhang Hongfei et al: Pb isotopic composition characteristics of metamorphic complex and intrusive rocks in Tongbai area and its geological significance, Geological Science, No.3, 1999.