Fractionation of toxic trace elements in soils around Mo-Ni black shale-hosted mines, Zunyi region, southern China: Environmental implications.


Authors: Poňavič M, Pašava J, Vymazalová A, Kříbek B, Hailin Deng, Taiji Luo, Chaoyang Li, Mingguo Zeng

Published in: Bulletin of Geosciences, volume 81, issue 3; pages: 197 - 206; Received 10 April 2006; Accepted in revised form 15 September 2006;

Keywords: metals in soils, extraction analyses, metal-rich black shales, environmental implications, south China,

full text (PDF, 0.24 MB)

Export to RIS



This paper examines the influence of Lower Cambrian metal-rich black shales and locally mined black shale-hosted Ni-Mo ore layers of southern China on the concentrations of selected toxic trace elements in soils. In order to better understand the mobility of toxic trace elements, and to evaluate the potential risk of environmental contamination, a sequential extraction analysis from soil horizons A, B, C1 and C2 in the area of the Jiepo-Ling Mo-Ni mine (Zunyi region) was carried out. Geochemical analyses confirmed significant enrichments of As, Mo, V and slightly lower proportions of Pb and Ni in the A-horizon relative to a local reference sample of uncontaminated soil. This contamination is anthropogenic, probably caused by the release of metal-rich black shale particles during mining operations. Conversely, the distribution of V and Cr in soils is controlled by the host rock. The results of sequential extraction analyses from individual soil horizons showed that almost all As, Ni, V, Cr and Zn are bound to the residual fraction. Some of the Mo (15.13-39.75%) was found to be associated with the organic matter/sulphide fraction. The distribution of Pb and Hg is erratic, indicating considerable mobility of these elements in the soil profile. In Hg-enriched horizons (B and C1) most Hg (78.21-78.95% of the total content) occurs in the organic matter/sulphide fraction. The concentrations of Mo, Ni, Cr, V, Zn and Hg found in different parts of selected agricultural plants (e.g., tobacco leaves, corn grains, corn leaves, and corn stalks) exceed normal values given by Kabata-Pendias & Pendias (1984). We emphasise that long-term consumption of these products could result in serious health problems for the human population and domestic animals. Arsenic and lead concentrations were found to be within the range of normal values given for agricultural plants.


Adriano, D.C. 1986. Trace elements in the terrestrial environment. 533 pp. Springer-Verlag, New York.View article

Bencko, V., Cikert, M. & Lener, J. 1995. Toxické kovy v životním a pracovním prostředí člověka. 288 pp. Grada, Prague (in Czech).

Borovec, Z. 1994. Distribution of toxic metals in stream sediment. Acta Universitatis Carolinae, Geologica 38, 91–103.

Bowen, H.J.M. 1979. Environmental chemistry of the elements. 316 pp. Academic Press, London.

Coveney, R.M., Grauch, R.I. & Murowchick, J.B. 1993. Ore mineralogy of nickel-molybdenum beds hosted by black shales of south China, 369–375. In Reddy, R.G. & Weizenbach, R.N. (eds) The minerals, metals and materials society, Proceedings of the Paul E. Queneau International Symposium “Extractive Metallurgy of Copper, Nickel and Cobalt”.

Chon, H.T., Cho, C.H., Kim, K.W. &Moon, H.S. 1996. The occurrence and dispersion of potentially toxic elements in areas covered by black shales and slates in Korea. Applied Geochemistry 11, 69–76.View article

Davies, R., Beckett, P.H.T. & Wollan, E. 1978. Critical levels of twenty potentially toxic elements in young spring barley. Plant Soil 49, 395–408.View article

Domingo, L.E. & Kyuma, K. 1983. Trace elements in tropical Asian paddy soils. Soil Science Plant Nutrition 29, 439–452.View article

Fan, D. 1983. Polyelements in the Lower Cambrian black shale series in southern China, 447–474. InAugustithis, S.S. (ed.) The significance of trace metals in solving petrogenetic problems and controversies. Theophrastus Publications S.A., Athens.

Fergusson, J.E. 1990. The heavy elements: Chemistry, environmental impact and health effects. 614 pp. Pergamon Press, Oxford.

Gupta, U.C. & Lipsett, J. 1981. Molybdenum in soils, plants and animals. Advances in Agronomy 34, 73–115.View article

Horan, M.F., Morgan, J.B., Grauch, R.I., Coveney, R.M. Jr., Murowchick, J.B. & Hulbert, L.J. 1994. Rhenium and osmium isotopes in black shales and Ni-Mo-PGE-rich sulfide layers, Yukon Territory, Canada, and Hunan and Guizhou Provinces, China. Geochimica et Cosmochimica Acta 58, 257–265.View article

Kabata-Pendias, A. & Pendias, H. 1984. Trace elements in soils and plants. 315 pp. CRC Press, Boca Raton, Florida.

Kao, L.S., Peacor, D.R., Coveney, R.M. Jr., Zhao, G., Dungey, K.E., Curtis, M.D. & Penner-Hahn, J.E. 2001. A C/MoS2 mixed-layer phase (MoSC) occurring in metalliferous black shales from southern China, and new data on jordisite. American Mineralogist 86, 852–861.View article

Kim, K.K., Kim, K.W., Kim, J.Y., Kim, I.S., Cheong, Y.W. & Min, J.S. 2001. Characteristics of tailings from the closed metal mines as potential contamination source in South Korea. Environmental Geology 41, 358–364.View article

Lott, D.A., Coveney, R.M. Jr.,Murowchick, J.B. & Grauch, R.I. 1999. Sedimentary exhalative nickel molybdenum ores in south China. Economic Geology 94, 1051–1066.View article

Loukola-Ruskeeniemi, K., Kantola, M., Henttonen, P. & Halonen, T. 1999. Migration of elements from black shales to aquatic ecosystems and local residents: a pilot study in Finland, 30–31. In Pašava, J. (ed.) Organics in major environmental issues, Proceedings of the IGCP 429 Inaugural Meeting. Czech Geological Survey, Special Publication, Prague.

Lumsdon, D.G., Meeussem, J.C.L., Paterson, E., Garden, L.M. &Anderson, P. 2001. Use of solid phase characterisation and chemical modelling for assessing the behaviour of arsenic in contaminated soils. Applied Geochemistry 16, 571–581.View article

Mao, J., Lehmann, B., Andao, D., Guangdi, Z., Dongsheng, M., Yitian, W., Mingguo, Z. & Kerrich, R. 2002. Re-Os dating of polymetallic Ni-Mo-PGE-Au mineralization in Lower Cambrian black shales of South China and its geological significance. Economic Geology 17, 1535–1547.View article

Mihaljevič, M., Poňavič, M., Ettler, V. & Šebek, O. 2003. A comparison of sequential extraction techniques for determining arsenic fractionation in synthetic mineral mixtures. Analytical and Bioanalytical Chemistry 377, 723–729.View article

Pašava, J., Gabriel, Z. & Kovalová, M. 1993. Proterozoic normal and metal-rich black shales from the Bohemian Massif, Czech Republic: industrial and environmental aspects, 209–212. In Fenoll Hach-Ali, P., Torres-Ruiz, J. & Gervilla, F. (eds) Current Research in Geology Applied to Ore Deposits. University of Granada, Granada.

Pašava, J.,Kříbek, B., Žák, K., Li, C.,Deng, H., Liu, J.,Gao, Z., Luo, T. & Zeng,M. 2003. Environmental impacts of mining of Ni-Mo black shale-hosted deposits in the Zunyi region, southern China: Preliminary results of the study of toxic metals in the system rock-soil-plant. Bulletin of Geosciences 78(3), 251–260.

Presser, T.S. & Swain, W.C. 1990. Geochemical evidence for Se mobilization by weathering of pyritic shales, San Joaquin Valley, California, USA. Applied Geochemistry 5, 703–717.View article

Quantin, C., Becquer, T., Rouiller, J.H. & Berthelin, J. 2002. Redistribution of metals in a New Caledonia ferrasol after microbial weathering. Soil Science Society of America Journal 66(6), 1797–1804.View article

Reichenbach, I. 1992. Black shales as an environmental hazard: a database on black shales in Canada. Internal Report, Geological Survey of Canada, Ottawa, 1–69.

Shacklette, H.T., Erdman, J.A. & Harms, T.F. 1978. Trace elements in foodstuffs, 25. In Oehme, F.W. (ed.) Toxicity of heavy metals in environment, Part I. Marcel Decker, New York.

Steiner, M.,Wallis, E., Erdtmann, B.D., Zhao, Y. & Yang, R. 2001. Submarine-hydrothermal exhalative ore layers in black shales from South China and associated fossils – insight into a Lower Cambrian facies and bio-evolution. Palaeogeography, Palaeoclimatology, Palaeoecology 169(3–4), 165–191.View article

Temple, P.J. & Linzon, S.N. 1977. Contamination of vegetation, soil, snow and garden crops by atmospheric deposition of mercury from a chlor-alkali plant, 389–398. In Hemphill, D.D. (ed.) 11th Annual Conference on Trace substances in environmental health. University of Missouri Press, Columbia, Mo.

Tessier, A., Campbell, P.G.C. & Bosson, M. 1979. Sequential extraction procedure for speciation of particulate trace metals. Analytical Chemistry 51, 844–851.View article

Zeng, M. 1998. Geological feature of the Huangjiawan Ni-Mo deposit in Zunyi of Guizhou and its prospect for development. Guizhou Geology 15, 305–310 (in Chinese with English abstract).

Yudovich, Y.E. & Ketris, M.P. 1997. Geochemistry of black shales. 211 pp. Prolog Publisher, Syktyvkar.