Geochemical characteristics of selenium and its correlation to other elements and minerals in selenium-enriched rocks in Ziyang County, Shaanxi Province, China

Abstract

Ziyang County, Shaanxi Province, China is a world known selenium (Se)-enriched area, and a severe selenosis incident was reported in Naore Village during the 1990s. This study investigated the geochemical characteristics of Se and its fractions in Se-enriched rocks from Ziyang. Se distribution is uneven, ranging from 0.23 to 57.00 μg/g (17.29±15.52 μg/g). Se content is higher in slate than chert, and even lower in carbonate rocks. Cd, As and V are enriched but Pb is depleted in Se-enriched strata. Se has different correlations both with TS (total sulfur) (R ²=0.59 for chert) and TC (total carbon) (R ²=0.77 for slate, R ²=0.87 for carbonate). Se has significant positive correlations with V (r=0.65), As (r=0.485), Cd (r=0.459) and Pb (r=0.405). The Se level correlates with mineral content, positively with pyrite, chlorite and illite, negatively with albite. Se associated with sulfide/selenide and elemental Se are the predominant fractions of total recovered Se, suggesting that a reducing environment and the formation of sulfides were significant to Se deposition during its geochemical cycle. Although low concentration of bio-available Se (average 5.62%±3.69%) may reduce the risk of Se poisoning in the target area, utilization of Se-rich rock as natural fertilizer should be restricted.

Keywords

selenium / Ziyang County / statistical analysis / fractions

References

[1] Barrientos E.Y., Flores C.R., Wrobel K., . Impact of Cadmium and Selenium Exposure on Trace Elements, Fatty Acids and Oxidative Stress in Lepidium Sativum. Journal of the Mexican Chemical Society, 2012, 56(1): 3-9.

[2] Bech J., Suarez M., Reverter F., . Selenium and Other Trace Elements in Phosphate Rock of Bayovar–Sechura (Peru). Journal of Geochemical Exploration, 2010, 107(2): 136-145.

[3] Chen D., Luo K. The Concentration of Se in Early Paleozonic Strata and Its Environmental Influence from Southern Shaanxi Province. Geology of Shaanxi, 1996, 3(2): 29-31.

[4] Cheng J., Mei Z. The Investigation of Selenosis in Ziyang County, Shannxi Province. Shannxi Journal of Agricultural Sciences, 1980, 06: 17-19.

[5] Fan H., Wen H., Hu R., . Selenium Speciation in Lower Cambrian Se-Enriched Strata in South China and Its Geological Implications. Geochimica et Cosmochimica Acta, 2011, 75(23): 7725-7740.

[6] Feng C., Liu S., Hu R., . Geochemistry of Lower Cambrian Se-Rich Black Series in Zunyi, Guizhou Province, Southwest China: The Petrogenesis and Enrichment Mechanism of Selenium. Earth Science—Journal of China University of Geosciences, 2010, 35(6): 947-958.

[7] Floor G.H., Román-Ross G. Selenium in Volcanic Environments: A Review. Applied Geochemistry, 2012, 27(3): 517-531.

[8] Fordyce F. Selenium Geochemistry and Health. AMBIO: AJournal of theHuman Environment, 2007, 36(1): 94-97.

[9] Fordyce F., Guangdi Z., Green K., . Soil, Grain and Water Chemistry in Relation to Human Selenium-Responsive Diseases in Enshi District, China. Applied Geochemistry, 2000, 15(1): 117-132.

[10] Ge K., Yang G. The Epidemiology of Selenium Deficiency in the Etiological Study of Endemic Diseases in China. The American Journal of Clinical Nutrition, 1993, 57(2): 259S-263S.

[11] Guo Y., Bao Z., Ma Z., . Geochemical Characteristics of Selenium in the Soil-Plants System of Enshi Area, Hubei Province. Geological Bulletin of China, 2012, 31(1): 151-155.

[12] Herbel M. J., Blum J. S., Oremland R. S., . Reduction of Elemental Selenium to Selenide: Experiments with Anoxic Sediments and Bacteria that Respire Se-Oxyanions. Geomicrobiology Journal, 2003, 20(6): 587-602.

[13] Huang K., Xu H., Liu Q., . Selenium: Its Chemistry, Biochemistry and Application in Life Science, 2009 Wuhan, China: Huazhong University of Science and Technology-Publishing Inc., 2.

[14] Ježek P., Hlušek J., Lošák T. A., . Effect of Foliar Application of Selenium on the Content of Selected Amino Acids in Potato Tubers (Solanum tuberosum L.). Plant, Soil and Environmen., 2011, 57: 315-320.

[15] Kolawole Sunday E., Obueh Henrietta O. Relationship between Soil Contents and Plasma Levels of Selenium, Chromium and Manganese in Healthy Adult Nigerians. African Journal of Biotechnology, 2013, 12(34): 5339-5346.

[16] Koller L., Exon J. The Two Faces of Selenium- Deficiency and Toxicity—Are Similar in Animals and Man. Canadian Journal of Veterinary Research, 1986, 50(3): 297-306.

[17] Kulp T.R., Pratt L.M. Speciation and Weathering of Selenium in Upper Cretaceous Chalk and Shale from South Dakota and Wyoming, USA. Geochimica et Cosmochimica Acta, 2004, 68(18): 3687-3701.

[18] Lehmann B., Nägler T.F., Holland H.D., . Highly Metalliferous Carbonaceous Shale and Early Cambrian Seawater. Geology, 2007, 35(5): 403-406.

[19] Lei L., Zhu J., Qin H., . Progress in Microbial Geochemistry of Selenium in the Environment. Earth and Environment, 2011, 39(1): 97-104.

[20] Lenz M., Lens P.N. The Essential Toxin: The Changing Perception of Selenium in Environmental Sciences. Science of the Total Environment, 2009, 407(12): 3620-3633.

[21] Li D. The Microelement Feature and a Sugggestion of Selenium-Rich Crops to be Developed in Ziyang Area. Geology of Shaanxi, 1999, 17(1): 67-73.

[22] Li Y., Wang W., Luo K., . Environmental Behaviors of Selenium in Soil of Typical Selenosis Area, China. Journal of Environmental Sciences, 2008, 20(7): 859-864.

[23] Liang L., He B., Jiang G. Determination of Total Selenium in Coals by Hydride Generation Atomic Fluorescence Spectrometry. Rock and Mineral Analysis, 2001, 20(1): 31-33.

[24] Luo K. The Age of Rock Distribustion in the Selenosis Region, South Shaanxi Province. Geological Review, 2003, 49(4): 383-388.

[25] Luo K. The Lujiaping Formtion of Northern Daba Mountain. Journal of Stratigraphy, 2006, 30(2): 149-156.

[26] Luo K., Jiang J. Selenium Content and Enrichment Pattern in Lower Cambrian Strata in Ziyang and Rugao Areas, Shaanxi Province. Geology-Geochemistry, 1995, 1: 68-71.

[27] Luo K., Pan Y., Wang W., . Selenium Content and Distribution Pattern in the Palaeozoic Strata in the Southern Qinling Mountains. Geologocal Review, 2001, 47(2): 211-217.

[28] Luo K., Tan J., Wang W., . Chemical Mobility of Selenium in Early Paleozoic Rock and Stone Coal in Daba Mountain, South Qinling. Acta Scientiae Circumstantiae, 2002, 22(1): 86-91.

[29] Luo K., Xu L., Xiang L. Selenium Content in the Water of the River, Springs and Wells in the Daba Mountain Area of the South Qinling Mountains and Its Distribution Pattern. Acta Geologica Sinica, 2002, 76(3): 389-394.

[30] Luo K. L., Xu L. R., Tan J. A., . Selenium Source in the Selenosis Area of the Daba Region, South Qinling Mountain, China. Environmental Geology, 2004, 45(3): 426-432.

[31] Luo T., Ning X., Luo Y., . Super-Enrichment of Se in the Bottom Black Shales Lower Cambrian at Zunyi, Guizhou Province, China. Acta Mineralogica Sinica, 2005, 25(3): 275-282.

[32] Lyons G.H., Judson G.J., Ortiz-Monasterio I., . Selenium in Australia: Selenium Status and Biofortification of Wheat for Better Health. Journal of Trace Elements in Medicine and Biology, 2005, 19(1): 75-82.

[33] Mackay W. Selenium Concentrations in the Tissues of Fish from the Upper McLeod and Upper Smoky River Systems, 2006 Alberta: Alberta Environment, 39.

[34] Mao D., Su H. The Migration of Selenium in Stone Coal in Aqueous Medium and Its Environmental Capacity. Endemic Diseases Bulletin, 1997, 12(3): 58-59.

[35] Martens D., Suarez D. Selenium Speciation of Marine Shales, Alluvial Soils, and Evaporation Basin Soils of California. Journal of Environmental Quality, 1997, 26(2): 424-432.

[36] Mei Z. The Second High-Se Area in China—Shuang’an Countryside, Ziyang County, Shaanxi Province. Journal of Agro-Environment Science, 1986, 3: 36-37.

[37] Meseck S., Cutter G. Selenium Behavior in San Francisco Bay Sediments. Estuaries and Coasts, 2011, 35(2): 646-657.

[38] Ni S., Zhang C., Xu Z., . Geochemical Characteristics of Selenium in Wanyuan Area, Sichuan Province. J. Mineral. Petrol., 2007, 37(4): 39-44.

[39] Park M., Chon H.T., Marton L. Mobility and Accumulation of Selenium and Its Relationship with Other Heavy Metals in the System Rocks/Soils-Crops in Areas Covered by Black Shale in Korea. Journal of Geochemical Exploration, 2010, 107(2): 161-168.

[40] Plant J., Kinniburgh D., Smedley P., . Arsenic and Selenium. Treatise on geochemistry, 2003, 9: 17-66.

[41] Qin H. B., Zhu J. M., Su H. Selenium Fractions in Organic Matter from Se-Rich Soils and Weathered Stone Coal in Selenosis Areas of China. Chemosphere, 2012, 86(6): 626-633.

[42] Qin H.B., Zhu J.M., Liang L., . The Bioavailability of Selenium and Risk Assessment for Human Selenium Poisoning in High-Se Areas, China. Environment International, 2013, 52: 66-74.

[43] Qu J., Xu B., Gong S. Selenium Extraction Techniques for Determination of Selenium Speciation in Soils and Sediments. Environmental Chemistry, 1997, 16(3): 277-283.

[44] Rowell D.L. Soil Science: Methods and Applications, 1994, 350.

[45] Song C. A Brief Description of the Yutangba Sedimentary Type Selenium Mineralized Area in Southwestern Hubei. Mineral Deposits, 1989, 8(3): 83-89.

[46] Strachan S., Wyncoll D. Selenium in Critically Ill Patients. Journal of the Intensive Care Society, 2009, 10: 38-43.

[47] Sunde R.A. Bowman B.A., Russell R.M. Selenium. Present Knowledge in Nutrition, 2006 Washington, D.C.: ILSI Press, 480-497.

[48] Tan J., Zhu W., Wang W., . Selenium in Soil and Endemic Diseases in China. Science of the Total Environment, 2002, 284(1): 227-235.

[49] Thomson C.D. Assessment of Requirements for Selenium and Adequacy of Selenium Status: AReview. European Journal of Clinical Nutrition, 2004, 58(3): 391-402.

[50] Tinggi U. Essentiality and Toxicity of Selenium and Its Status in Australia: AReview. Toxicology Letters, 2003, 137(1): 103-110.

[51] Wang S., Liang D., Wang D., . Selenium Fractionation and Speciation in Agriculture Soils and Accumulation in Corn (Zea mays L.) under Field Conditions in Shaanxi Province, China. Science of the Total Environment, 2012, 427–428: 159-164.

[52] Wedepohl H.K. The Composition of the Continental Crust. Geochimica et Cosmochimica Acta, 1995, 59(7): 1217-1232.

[53] Wen H., Lu J., Yao L., . Organic Geochemistry and Biomakers of Some Lower Cambrian High-Selenium Formations in China. Geochimica, 2000, 29(1): 28-35.

[54] Wen H., Qiu T., Lin H., . Geochemistry and Genesis of Bedded Cherts in Some Typical Eopaleozoic High Selenium Black Shales, China. Acta Sedimentologica Sinica, 2003, 21(4): 619-626.

[55] Wen H., Qiu Y. Organic and Inorganic Occurrence of Se in Laerma Se-Au Deposit. Science in China Series D: Earth Sciences, 1999, 29(5): 426-432.

[56] Wen H. J., Carignan J., Qlu Y. H., . Selenium Speciation in Kerogen from Two Chinese Selenium Deposits: Environmental Implications. Environmental Science & Technology, 2006, 40(4): 1126-1132.

[57] WHO, 1996). Trace Elements in Human Nutrition and Health. [2016-09-14]. http://apps.who.int/iris/handle/10665/37931

[58] Yang G., Wang S., Zhou R., . Endemic Selenium Intoxication of Humans in China. The American Journal of Clinical Nutrition, 1983, 37(5): 872-881.

[59] Yang J., Yi F. A Study on Occurrence Modes and Enrichment Patterns of Lower Cambrian Black Shale Series in Northern Guizhou Province, China. Acta Mineralogica Sinica, 2012, 32(2): 281-287.

[60] Yu T., Yang Z. L. Y., . The Origin and Geochemical Cycle of Soil Selenium in a Se-Rich Area of China. Journal of Geochemical Exploration. 2013, 2013, 139(1): 97-108.

[61] Zhang G., Ge X., Zhang Q., . The Distribution and Controlling Factor of Selenium in Soils from Selenosis Area of Enshi, Hubei Province. Chinese Geology, 2001, 28(9): 37-40.

[62] Zheng B., Ding Z., Huang R., . Issues of Health and Disease Relating to Coal Use in Southwestern China. International Journal of Coal Geology, 1999, 40(2): 119-132.

[63] Zheng B., Hong Y., Zhao W., . The Se-Enrich Carbonaceous Siliceous Rock and Endemic Se Poisoning in Southwest Hubei, China. Chinese Science Bulletin, 1992, 37(11): 1027-1029.

[64] Zheng B., Yan L., Mao D., . The Se Resource in Southwestern Hubei Province, China, and Its Exploitation Strategy. Journal of Natural Resources, 1993, 8(3): 204-212.

[65] Zhu J. Occurrence of Native Delenium in Yutangba and Its Environmental Implications. Applied Geochemistry, 2004, 19(3): 461-467.

[66] Zhu J., Qin H., Li L., . The Method for Analyzing State of Selenium in Se-Rich Environmental Samples. Bulletin of Mineralogy, Petrology and Geochemistry, 2007, 26(3): 209-213.

[67] Zhu J., Qin H., Luo T., . A Comparative Study of Selenium Fractionation in Se-Rich Carbonaceous Rocks of Lower Cambrian and Permian in Southwest China. Geological Journal of China Universities, 2007, 13(1): 69-74.

[68] Zhu J., Wang N., Li S., . Distribution and Transport of Selenium in Yutangba, China: Impact of Human Activities. Science of the Total Environment, 2008, 392(2–3): 252-261.

[69] Zhu J., Zuo W., Qin H., . An Investigation on the Source of Soil Se in Yutangba, Enshi: Evidence from Native Selenium. Acta Mineralogica Sinica, 2008, 28(4): 397-400.

[70] Zhu J., Johnson T. M., Finkelman R. B., . The Occurrence and Origin of Selenium Minerals in Se-Rich Stone Coals, Spoils and Their Adjacent Soils in Yutangba, China. Chemical Geology, 2012, 330–331: 27-38.