Abstract
Heavy metal pollution is hazardous for the environment and human health. However, there are few studies of heavy metal pollution caused by historic metallurgical activity. The Laoniupo site in the Bahe River valley, Guanzhong Basin, China, was an important settlement of the Shang Culture (1600`-1046 BCE). We studied two stratigraphic profiles at the Laoniupo site, which were used for measurements of magnetic susceptibility, heavy metal concentrations, and AMS 14C ages to provide evidence of copper smelting activity at the site during the Shang Dynasty. The Nemerow Pollution Index and Geoaccumulation Index were calculated to assess the heavy metals record (Cu, Zn, Ni, Pb, Cr, and As) in the topsoil on the loess tableland. According to the Single Pollution Index, the topsoil was slightly polluted by As and unpolluted by Cu, Zn, Ni, Pb and Cr; according to the Nemerow Composite Pollution Index the topsoil was mildly polluted; and according to the Geoaccumulation Index, the topsoil was moderately polluted by As, slightly polluted by Cu, and unpolluted by Zn, Ni, Pb and Cr. The main cause of the heavy metal pollution in the topsoil is the presence of copper slag in the cultural layers that was disturbed by modern farming activity.
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
References
Alloway B J, 1995. Heavy Metals in Soils. London: Blackie Academic and Professional.
An Z S, Kukla G J, Porter S C et al., 1991. Magnetic susceptibility evidence of monsoon variation on the Loess Plateau of central China during the last 130,000 years. Quaternary Research, 36(1): 29–36.
Asami T, 1988. Soil pollution by metals from mining and smelting activities. In: Salomons W, Förstner U (eds.), Chemistry and Biology of Solid Waste: Dredged Materials and Mine Tailings. Berlin, Heidelberg: Springer, 143–169.
Beaver M B, Beaver J R, Mendenhall W, 2012. Introduction to Probability and Statistics. New Delhi: Cengage Learning.
Breitenlechner E, Goldenberg G, Lutz J et al., 2013. The impact of prehistoric mining activities on the environment: A multidisciplinary study at the fen Schwarzenbergmoos (Brixlegg, Tyrol, Austria). Vegetation History and Archaeobotany, 22(4): 351–366.
Breitenlechner E, Hilber M, Lutz J et al., 2010. The impact of mining activities on the environment reflected by pollen, charcoal and geochemical analyses. Journal of Archaeological Science, 37(7): 1458–1467.
CNEPA (China National Environmental Protection Agency), 2018. Environmental Quality Standard for Soils, Report No.GB 15618-2018. Beijing: China National Environmental Protection Agency. (in Chinese)
Chen K L, Rehren T, Mei J J et al., 2009. Special alloys from remote frontiers of the Shang Kingdom: Scientific study of the Hanzhong bronzes from southwest Shaanxi, China. Journal of Archaeological Science, 36(10): 2108–2118.
CNEMC (China National Environmental Monitoring Centre), 1990. Background Value of Soil Elements in China. Beijing: China Environmental Science Press. (in Chinese)
Chen K L, Liu S R, Li Y X et al., 2017b. Evidence of arsenical copper smelting in Bronze Age China: A study of metallurgical slag from the Laoniupo site, central Shaanxi. Journal of Archaeological Science, 82: 31–39.
Chen Y F, Ma J H, Liu D X et al., 2017a. Heavy metal enrichment and pollution of historical cultural layers in Kaifeng City, Henan Province. Acta Geographica Sinica, 72(5): 892–905. (in Chinese)
Conroy N, Hawley K, Keller W et al., 1976. Influences of the atmosphere on lakes in the Sudbury Area. Journal of Great Lakes Research, 2: 146–165.
Cui J F, Wu X H, Tong W H et al., 2009. A study of copper vessels unearthed in the Yuanqu Shang Dynasty city, Shanxi province. Archaeology and Cultural Relics, (6): 86–90. (in Chinese)
De Ryck I, Adriaens A, Adams F, 2005. An overview of Mesopotamian bronze metallurgy during the 3rd millennium BC. Journal of Cultural Heritage, 6(3): 261–268.
Dodson J, Li X Q, Ji M et al., 2009. Early bronze in two Holocene archaeological sites in Gansu, NW China. Quaternary Research, 72(3): 309–314.
Du Y, 2019. Research review of Sanxingdui bronze ware. Collection World, (5): 112–113. (in Chinese)
Duruibe J O, Ogwuegbu M O C, Egwurugwu J N, 2007. Heavy metal pollution and human biotoxic effects. International Journal of Physical Sciences, 2(5): 112–118.
Fu F L, Wang Q, 2011. Removal of heavy metal ions from waste waters: A review. Journal of Environmental Management, 92(3): 407–418.
Fuller D Q, Van Etten J, Manning K et al., 2011. The contribution of rice agriculture and livestock pastoralism to prehistoric methane levels: An archaeological assessment. The Holocene, 21(5): 743–759.
Gao X P, 2006. The bronzes in Yin ruins are the core of bronze culture. China Cultural Heritage, (3): 46–50. (in Chinese)
Grattan J P, Gilbertson D D, Hunt C O, 2007. The local and global dimensions of metalliferous pollution derived from a reconstruction of an eight thousand year record of copper smelting and mining at a desert-mountain frontier in southern Jordan. Journal of Archaeological Science, 34(1): 83–110.
Helmisaari H, Derome J, Fritze H et al., 1995. Copper in Scots pine forests around a heavy-metal smelter in south-western Finland. Water Air and Soil Pollution, 85(3): 1727–1732.
Hillman A L, Abbott M B, Yu J Q et al., 2015. Environmental legacy of copper metallurgy and Mongol silver smelting recorded in Yunnan Lake sediments. Environmental Science & Technology, 49(6): 3349–3357.
Hong S, Candelone J, Patterson C C et al., 1996. History of ancient copper smelting pollution during Roman and Medieval Times recorded in Greenland ice. Science, 272(5259): 246–249.
Hu S, Qiu H J, Yang D D et al., 2017. Evaluation of the applicability of climate forecast system reanalysis weather data for hydrologic simulation: A case study in the Bahe River Basin of the Qinling Mountains, China. Journal of Geographical Sciences, 27(5): 546–564.
Huang C C, Pang J L, Su H X et al., 2009. The Ustic Isohumisol (Chernozem) distributed over the Chinese Loess Plateau: Modern soil or palaeosol? Geoderma, 150(3): 344–358.
Jin Z D, Li X D, Zhang B et al., 2013. Geochemical records in Holocene lake sediments of northern China: Implication for natural and anthropogenic inputs. Quaternary International, 304: 200–208.
Jin Z Y, Chase W T, Yoshimitsu H et al., 1994. Study on lead isotopic ratio of bronze wares in Shang tomb of Dayangzhou in Xingan, Jiangxi province. Archaeology, 8: 744–747, 735. (in Chinese)
Jin Z Y, Zhu B Q, Chang X Y et al., 2004. Lead istopic analysis of the bronze vessels from Jinsha near Chengdu. Cultural Relics, 7: 76–88, 1. (in Chinese)
Kicińska A, 2019a. Chemical and mineral composition of fly ashes from home furnaces, and health and environmental risk related to their presence in the environment. Chemosphere, 215: 574–585.
Kicińska A, 2019b. Environmental risk related to presence and mobility of As, Cd and Tl in soils in the vicinity of a metallurgical plant: Long-term observations. Chemosphere, 236: 124308.
Kicińska A, Mamak M, 2017. Health risks associated with municipal waste combustion on the example of Laskowa commune (Southern Poland). Human and Ecological Risk Assessment: An International Journal, 23 (8): 2087–2096.
Killick D, Fenn T, 2012. Archaeometallurgy: The study of preindustrial mining and metallurgy. Annual Review of Anthropology, 41(1): 559–575.
Kozlov M V, Haukioja E, Bakhtiarov A V et al., 1995. Heavy metals in birch leaves around a nickel-copper smelter at Monchegorsk, northwestern Russia. Environmental Pollution, 90(3): 291–299.
Kwon J C, Nejad Z D, Jung M C, 2017. Arsenic and heavy metals in paddy soil and polished rice contaminated by mining activities in Korea. Catena, 148: 92–100.
Lee C S L, Qi S H, Zhang G et al., 2008. Seven thousand years of records on the mining and utilization of metals from lake sediments in Central China. Environmental Science & Technology, 42(13): 4732–4738.
Li J H, 1985. Some views on early copper smelting technology and related issues in the Central China. Cultural Relics, 12: 75–78. (in Chinese)
Li S C, 2005. Regional characteristics and interaction of early smelting copper industry in Northwest China and Central China. Acta Archaeologica Sinica, 3: 239–275, 278. (in Chinese)
Li S C, Shui T, 2000. On the bronzes of the Siba Culture. Cultural Relics, (3): 36–44. (in Chinese)
Li X Q, Sun N, Dodson J et al., 2011. The impact of early smelting on the environment of Huoshiliang in Hexi Corridor, NW China, as recorded by fossil charcoal and chemical elements. Palaeogeography, Palaeoclimatology, Palaeoecology, 305: 329–336.
Li Y X, Chen G K, Qian W et al., 2015. Study on smelting and casting relics of Xichengyi Site in Zhangye. Archaeology and Cultural Relics, 2: 119–128. (in Chinese)
Liu J, Wang J, Chen Y H et al., 2016. Thallium transformation and partitioning during Pb-Zn smelting and environmental implications. Environmental Pollution, 212: 77–89.
Liu S E, 2002. Laoniupo. Xi’an: Shaanxi People’s Publishing House. (in Chinese)
Liu S E, 2004. Discussion on the Shang dynasty rammed earth foundation building of Laoniupo in Xi’an. Papers on Chinese Archaeology, 2: 289–295. (in Chinese)
Liu S E, Yue L J, 1991. The main harvest of the second stage excavation of Laonipo site in Xi’an. Journal of Northwest University (Philosophy and Social Sciences Edition), 3: 43–47. (in Chinese)
Liu T S, 1985. Loess and the Environment. Beijing: China Ocean Press. (in Chinese)
Liu T S, Ding Z L, 1998. Chinese loess and the paleomonsoon. Annual Review of Earth and Planetary Sciences, 26(1): 111–145.
Liu X T, 2012. Origin and Dissemination of Early Bronze Wares in China. Cultural Relics of Central China, (4): 51–57. (in Chinese)
Liu Y, 2018. Discussion of the casting technology of bronze wares in Yinxu. Cultural Relics of Central China, (5): 82–89. (in Chinese)
Longman J, Veres D, Finsinger W et al., 2018. Exceptionally high levels of lead pollution in the Balkans from the early Bronze Age to the Industrial Revolution. Proceedings of the National Academy of Sciences, 115(25): E5661–E5668.
Maher B A, 1998. Magnetic properties of modern soils and Quaternary loessic paleosols: paleoclimatic implications. Palaeogeography, Palaeoclimatology, Palaeoecology, 137: 25–54.
Maher B A, Thompson R, 1995. Paleorainfall reconstructions from pedogenic magnetic susceptibility variations in the Chinese loess and paleosols. Quaternary Research, 44(3): 383–391.
Mao P N, Pang J L, Huang C C et al., 2017. Loess deposits of the upper Hanjiang River valley, south of Qinling Mountains, China: Implication for the pedogenic dynamics controlled by paleomonsoon climate evolution. Aeolian Research, 25: 63–77.
Mei J J, Chen K L, Cao W, 2009. Scientific examination of Shang-Dynasty bronzes from Hanzhong, Shaanxi Province, China. Journal of Archaeological Science, 36(9): 1881–1891.
Mei J J, Shell C, 1999. The existence of Andronovo cultural influence in Xinjiang during the 2nd millennium BC. Antiquity, 73(281): 570–578.
Mei J J, Wang P, Chen K L et al., 2015. Archaeometallurgical studies in China: some recent developments and challenging issues. Journal of Archaeological Science, 56: 221–232.
Mighall T M, Timberlake S, Foster I D L et al., 2009. Ancient copper and lead pollution records from a raised bog complex in Central Wales, UK. Journal of Archaeological Science, 36(7): 1504–1515.
Mo S H, Li Z L, Gou K et al., 2018. Quantifying the effects of climate variability and direct human activities on the change in mean annual runoff for the Bahe River (Northwest China). Journal of Coastal Research, 341(1): 81–89.
Müller G, 1969. Index of geoaccumulation in sediments of the Rhine River. Geomicrobiology Journal, 2(3): 108–118.
Nemerow N L, 1974. Scientific Stream Pollution Analysis. New York: McGraw-Hill Book Company.
Nikolic D, Milosevic N, Mihajlovic I et al., 2010. Multi-criteria analysis of air pollution with SO2 and PM10 in urban area around the copper smelter in Bor, Serbia. Water Air and Soil Pollution, 206: 369–383.
Nocete F, Álex E, Nieto J M et al., 2005. An archaeological approach to regional environmental pollution in the south-western Iberian Peninsula related to third millennium BC mining and metallurgy. Journal of Archaeological Science, 32(10): 1566–1576.
NY/T 1377, 2007. Determination of pH in Soil. (in Chinese)
Peng M H, 2005. The view on the 30-year culture research about Wucheng. Yindu Journal, (4): 16–24. (in Chinese)
Pompeani D P, Abbott M B, Bain D J et al., 2014. Copper mining on Isle Royale 6500-5400 years ago identified using sediment geochemistry from McCargoe Cove, Lake Superior. The Holocene, 25(2): 253–262.
Pongratz J, Reick C H, Raddatz T et al., 2008. A reconstruction of global agricultural areas and land cover for the last millennium. Global Biogeochemical Cycles, 22(3): GB3018.
Pope C A, Rodermund D L, Gee M M, 2007. Mortality effects of a copper smelter strike and reduced ambient sulfate particulate matter air pollution. Environmental Health Perspectives, 115(5): 679–683.
Pyatt F B, Amos D, Grattan J P et al., 2002. Invertebrates of ancient heavy metal spoil and smelting tip sites in southern Jordan: Their distribution and use as bioindicators of metalliferous pollution derived from ancient sources. Journal of Arid Environments, 52(1): 53–62.
Qiu L P, Zhuang X Y, Huang X J et al., 2019. Study on heavy metals’ influence on buried cultural relics in soil of an archaeological site. Environmental Technology, 11(4): 1–12.
Radivojevic M, Rehren T, Pernicka E et al., 2010. On the origins of extractive metallurgy: New evidence from Europe. Journal of Archaeological Science, 37(11): 2775–2787.
Rebele F, Surma A, Kuznik C et al., 1993. Heavy metal contamination of spontaneous vegetation and soil around the copper smelter “Legnica”. Acta Societatis Botanicorum Poloniae, 62: 53–57.
Reimer P J, Bard E, Bayliss A et al., 2013. IntCal13 and Marine13 radiocarbon age calibration curves 0-50000 years cal BP. Radiocarbon, 55(4): 1869–1887.
Roberts B W, Thornton C P, Pigott V C, 2009. Development of metallurgy in Eurasia. Antiquity, 83(322): 1012–1022.
Rouhani A, Shahivand R, 2020. Potential ecological risk assessment of heavy metals in archaeology on an example of the Tappe Rivi (Iran). SN Applied Sciences, 2: 1277.
Ruddiman W F, Ellis E C, 2009. Effect of per-capita land use changes on Holocene forest clearance and CO2 emissions. Quaternary Science Reviews, 28(27/28): 3011–3015.
Ruddiman W F, Guo Z T, Zhou X et al., 2008. Early rice farming and anomalous methane trends. Quaternary Science Reviews, 27(13/14): 1291–1295.
Shi J S, 2017. Rethinking of Sanxingdui Culture. Sichuan Cultural Relics, (4): 39–43. (in Chinese)
Song X C, 1992. Discussion on the stage and characteristics of Laoniupo’s Shang Culture. Relics and Museolgy, (2): 12–18, 41. (in Chinese)
Steffen W, Grinevald J, Crutzen P J et al., 2011. The Anthropocene: Conceptual and historical perspectives. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 369: 842–867.
Sun S Y, Han R B, 1997. Studies of early bronze objects from Gansu in terms of their casting and manufacturing techniques. Cultural Relics, (7): 75–84. (in Chinese)
Tian X S, Zhu C, Shui T et al., 2013a. An evaluation of heavy metal pollution within historic cultural strata at Liangwangcheng site in the north of Jiangsu Province. Chinese Journal of Soil Science, 44(5): 1253–1258. (in Chinese)
Tian X S, Zhu C, Sun Z B et al., 2013b. An evaluation of heavy metal pollution within historic cultural strata at a specialized salt production site at Zhongba in the Three Gorges Reservoir region of the Yangtze River, China. Environmental Earth Sciences, 69(7): 2129–2138.
Urrutia-Goyes R, Argyraki A, Ornelas-Soto N, 2017. Assessing lead, nickel, and zinc pollution in topsoil from a historic shooting range rehabilitated into a public urban park. International Journal of Environmental Research and Public Health, 14(7): 698.
US EPA, 1996. Method 3052 (SW-846): Microwave Assisted Acid Digestion of Siliceous and Organically Based Matrices. Washington, DC.
US EPA, 2014. “Method 6010D (SW-846): Inductively Coupled Plasma-Atomic Emission Spectrometry” Revision 4. Washington, DC.
Wang L X, Li Y X, Li B et al., 2016. Resurvey and initial analysis of two copper smelting sites in Jianping county, Liaoning province. Research of China’s Frontier Archaeology, 1: 47–59. (in Chinese)
Wei C Y, Wang C, Yang L S et al., 2009. Characterizing spatial distribution and sources of heavy metals in the soils from mining-smelting activities in Shuikoushan, Hunan Province, China. Journal of Environmental Sciences, 21(9): 1230–1236.
Wertime T A, 1973. The Beginnings of Metallurgy: A New Look: Arguments over diffusion and independent invention ignore the complex metallurgic crafts leading to iron. Science, 182(4115): 875–887.
Wuana R A, Okieimen F E, 2011. Heavy metals in contaminated soils: A review of sources, chemistry, risks and best available strategies for remediation. International Scholarly Research Notices Ecology, 2011: 402647.
Xu L B, Sun L G, You K H et al., 2010. Geochemical characteristics of Pb in cultural layers of Yuchisi site and source tracing of primitive metallurgy in China. Acta Pedologica Sinica, 47(2): 193–205. (in Chinese)
Yang F G, Zhang G L, Gong Z T et al., 2004. Distribution of heavy metals in cultural layers of urban soils in Nanjing. Quaternary Science, 2: 203–212. (in Chinese)
Yang Y B, Sun G Q, 1994. Discovery and research of bronze wares in Shang Dynasty. Cultural Relics in Southern China, (1): 35–41. (in Chinese)
Yang Y S, Dong G H, Zhang S J et al., 2016. Copper content in anthropogenic sediments a tracer for detecting smelting activities and its impact on environment during prehistoric period in Hexi Corridor, Northwest China. The Holocene, 27(2): 282–291.
Yu Y B, Wang K, Chen J L et al., 2015. New harvest of early copper smelting technology in the southern Anhui. Archaeology, 5: 103–113. (in Chinese)
Zhang G L, Yang F G, Zhao W J et al., 2007. Historical change of soil Pb content and Pb isotope signatures of the cultural layers in urban Nanjing. Catena, 69: 51–56.
Zhang G L, Yang F G, Zhao Y G et al., 2005. Historical change of heavy metals in urban soils of Nanjing, China during the past 20 centuries. Environment International, 31(6): 913–919.
Zhang S J, Yang Y S, Storozum M J et al., 2017. Copper smelting and sediment pollution in Bronze Age China: A case study in the Hexi corridor, Northwest China. Catena, 156: 92–101.
Zhang Y, 2016. Discussion on the discovery and dissemination of arsenical copper in ancient China. World Antiquity, 2: 20–23. (in Chinese)
Zhao C Y, Li C L, Gong G Q, 2017. Measurement and evaluation on content of heavy metal pollution of soil at the Tang Daming Palace site. Quaternary Science, 37(6): 1456–1463. (in Chinese)
Zhao Y, 2020. Vegetation coverage dynamics and its response to climate factors in the Guanzhong basin. Journal of Yangtze River Scientific Research Institute, 37(6): 49–54. (in Chinese)
Zhuang Y J, Kidder T R, 2014. Archaeology of the Anthropocene in the Yellow River region, China, 8000-2000 cal. BP. The Holocene, 24(11): 1602–1623.
Acknowledgments
We thank Dr. Jan Bloemendal for polishing our English language and the editor and two anonymous reviewers for their helpful comments and suggestions for improvement.
Author information
Authors and Affiliations
Corresponding authors
Additional information
Foundation
National Natural Science Foundation of China, No.41801060; The Strategic Priority Research Program of the Chinese Academy of Sciences, No.XDA20060201; The Open Foundation of the Key Laboratory of Cultural Heritage Research and Conservation of the Education Ministry in Northwest University of China, No. GXYDFA2018XBD003, No. WYSYS201909
Author
Wu Menglei (1989-), Engineer, specialized in environmental archaeology and cultural relic analysis. E-mail: wmlnwu@nwu.edu.cn
Rights and permissions
About this article
Cite this article
Wu, M., Jia, Y., Zhang, Y. et al. Heavy metal pollution from copper smelting during the Shang Dynasty at the Laoniupo site in the Bahe River valley, Guanzhong Basin, China. J. Geogr. Sci. 31, 1675–1693 (2021). https://doi.org/10.1007/s11442-021-1917-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11442-021-1917-x