Origin and mobility of thallium in the Iberian Pyrite Belt
DOI:
https://doi.org/10.3989/egeol.45699.1126Keywords:
acid mine drainage, massive sulfides, Ría de Huelva estuary, Tinto River, Odiel River, thalliumAbstract
Thallium (Tl) is a non-essential element for living beings and is a ubiquitous metal in the Earth’s crust, with an average concentration of approximately 0.5 mg/kg. This metal is commonly recovered as a byproduct during the processing of pyrite concentrates and polymetallic sulfides (Cu-Pb-Zn). Tl may exhibit a high potential for cytotoxicity and genotoxicity to humans in its two major oxidation states (I and III). The Tl content of soils and surface waters is strongly conditioned by the geological substrate. Although surface concentrations of Tl in soils range between 0.1 and 2 mg/kg, elevated concentrations of Tl found in the Earth’s crust are associated with sulfides or potassium-rich minerals. The weathering of rocks rich in these minerals leads to increasing levels of this metal in soils, waters and sediments. The present study examines the origin, mobility and ultimate fate of Tl in areas affected by acid mine drainage in the Iberian Pyrite Belt, one of the most significant polymetallic massive sulfide districts globally.
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Alonso, F.M., Garcia Navarro, E. & Camacho, M.A. (1999). Deformación progresiva de la Zona Sudportuguesa: Plegamiento y cizallamiento de secuencias multicapa. Geogaceta, 25.
Alpers, C. N., Jambor, J. L., & Nordstrom, D. (Eds.). (2018). Sulfate minerals: crystallography, geochemistry, and environmental significance (Vol. 40). Walter de Gruyter GmbH & Co KG.
Álvarez-Ayuso, E., Otones, V., Murciego, A., García-Sánchez, A. & Santa Regina, I. (2013). Zinc, cadmium and thallium distribution in soils and plants of an area impacted by sphalerite-bearing mine wastes. Geoderma, 207, 25-34.
Armstrong, T. N., Iannuzzi, T. J., Thelen, J. B., Ludwig, D. F. & Firstenberg, C. E. (2005). Characterization of chemical contamination in shallow-water estuarine habitats of an industrialized river. Part II. metals. Soil & Sediment Contamination, 14(1), 35-52.
Ayora, C., Caraballo, M. A., Macias, F., Rötting, T. S., Carrera, J. & Nieto, J. M. (2013). Acid mine
drainage in the Iberian Pyrite Belt: 2. Lessons learned from recent passive remediation experiences. Environmental Science and Pollution Research, 20, 7837-7853.
Ayora, C., Macías, F., Torres, E., Lozano, A., Carrero, S., Nieto, J. M., Pérez-López, R., Fernández-Martínez, A. & Castillo-Michel, H. (2016). Recovery of rare earth elements and yttrium from passive-remediation systems of acid mine drainage. Environmental Science and Technology, 50(15), 8255-8262.
Barrón, V., Torrent, J. & Greenwood, J. P. (2006). Transformation of jarosite to hematite in simulated Martian brines. Earth and Planetary Science Letters, 251(3-4), 380-385.
Basallote, M.D., Zarco, V., Macías, F., Cánovas, C.R., Hidalgo, P.J (2023). Metal bioaccumulation in spontaneously grown aquatic macrophytes in Fe-rich substrates of a passive treatment plant for acid mine drainage. Journal of Environmental Management 345, 118495.
Belzile, N. & Chen, Y. W. (2017). Thallium in the environment: a critical review focused on natural waters, soils, sediments and airborne particles. Applied Geochemistry, 84, 218-243.
Cánovas, C. R., Olías, M., Nieto, J. M., Sarmiento, A. M. & Cerón, J. C. (2007). Hydrogeochemical characteristics of the Tinto and Odiel Rivers (SW Spain). Factors controlling metal contents. Science of the Total Environment, 373(1), 363-382.
Cánovas, C. R., Olías, M., Nieto, J. M. & Galván, L. (2010). Wash-out processes of evaporitic sulfate salts in the Tinto river: hydrogeochemical evolution and environmental impact. Applied Geochemistry, 25(2), 288-301.
Cánovas, C. R., Basallote, M. D., Macías, F., Freydier, R., Parviainen, A. & Pérez-López, R. (2022). Thallium distribution in an estuary affected by acid mine drainage (AMD): The Ría de Huelva estuary (SW Spain). Environmental Pollution, 306, 119448.
Capitán, M.A., (2006). Mineralogía y geoquímica de la alteración superficial de sulfuros masivos en la Faja Pirítica Ibérica [Doctoral dissertation, Universidad de Huelva]. http://rabida.uhu.es/dspace/handle/10272/7627
Casiot, C., Egal, M., Bruneel, O., Verma, N., Parmentier, M. & Elbaz-Poulichet, F. (2011). Predominance of aqueous Tl (I) species in the river system downstream from the abandoned Carnoulès mine (Southern France). Environmental Science & Technology, 45(6), 2056-2064.
Chen, Y., Wang, C., Liu, J., Wang, J., Qi, J. & Wu, Y. (2013). Environmental exposure and flux of thallium by industrial activities utilizing thallium-bearing pyrite. Science China Earth Sciences, 56, 1502-1509.
Codeço, M. S., Mateus, A., Figueiras, J., Rodrigues, P. & Gonçalves, L. (2018). Development of the Ervidel-Roxo and Figueirinha-Albernoa volcanic sequences in the Iberian pyrite Belt, Portugal: Metallogenic and geodynamic implications. Ore Geology Reviews, 98, 80-108.
Comisión Europea, (2000). Directive 2000/60/EC of the European Parliament and the Council of
10.2000. A framework for community action in the field of water policy. EU Official Journal, 327, 1-73. http://data.europa.eu/eli/dir/2000/60/oj
Dill, H. G. (2010). The “chessboard” classification scheme of mineral deposits: Mineralogy and geology from aluminum to zirconium. Earth-Science Reviews, 100(1-4), 1-420.
Dutrizac, J. E., Chen, T. T. & Beauchemin, S. (2005). The behaviour of thallium (III) during jarosite precipitation. Hydrometallurgy, 79(3-4), 138-153.
Garrido, F., Garcia-Guinea, J., Lopez-Arce, P., Voegelin, A., Göttlicher, J., Mangold, S., & Almendros, G. (2020). Thallium and co-genetic trace elements in hydrothermal Fe-Mn deposits of Central Spain. Science of the Total Environment, 717, 137162.
Gómez-González, M. A., García-Guinea, J., Laborda, F. & Garrido, F. (2015). Thallium occurrence and partitioning in soils and sediments affected by mining activities in Madrid province (Spain). Science of the Total Environment, 536, 268-278.
Grande, J. A. (Ed.) (2016). Drenaje Ácido de Mina en la Faja Pirítica Ibérica: Técnicas de estudio e inventario de explotaciones (Vol. 15). Servicio de Publicaciones de la Universidad de Huelva.
Grimalt, J. O., Ferrer, M. & Macpherson, E. (1999). The mine tailing accident in Aznalcollar. Science of the Total Environment, 242(1-3), 3-11.
Hunt, J., Lottermoser, B. G., Parbhakar-Fox, A., Van Veen, E. & Goemann, K. (2016). Precious metals in gossanous waste rocks from the Iberian Pyrite Belt. Minerals Engineering, 87, 45-53.
Iannuzzi, T. J., Armstrong, T. N., Long, E. R., Iannuzzi, J. & Ludwig, D. F. (2008). Sediment quality triad assessment of an industrialized estuary of the northeastern USA. Environmental Monitoring and Assessment, 139(1), 257-275.
ITGE (1999). Investigación geológica y cartografía básica en la Faja Pirítica y áreas aledañas a escala 1:50000. Consultado en junio de 2022.
Johnson, D. B. & Hallberg, K. B. (2005). Acid mine drainage remediation options: a review. Science of the Total Environment, 338(1-2), 3-14.
Karbowska, B. (2016). Presence of thallium in the environment: sources of contaminations, distribution and monitoring methods. Environmental Monitoring and Assessment, 188, 1-19.
Karbowska, B., Zembrzuski, W., Jakubowska, M., Wojtkowiak, T., Pasieczna, A. & Lukaszewski, Z. (2014). Translocation and mobility of thallium from zinc–lead ores. Journal of Geochemical Exploration, 143, 127-135.
Kazantzis, G. (2000). Thallium in the environment and health effects. Environmental Geochemistry and Health, 22, 275-280.
Kersten, M., Xiao, T., Kreissig, K., Brett, A., Coles, B. J. & Rehkämper, M. (2014). Tracing anthropogenic thallium in soil using stable isotope compositions. Environmental Science & Technology, 48(16), 9030-9036.
Krasnodębska-Ostręga, B., Sadowska, M. & Ostrowska, S. (2012). Thallium speciation in plant tissues—Tl (III) found in Sinapis alba L. grown in soil polluted with tailing sediment containing
thallium minerals. Talanta, 93, 326-329.
Law, S. & Turner, A. (2011). Thallium in the hydrosphere of south west England. Environmental Pollution, 159(12), 3484-3489.
Lin, T. S., & Nriagu, J. (1999). Thallium speciation in the Great Lakes. Environmental Science & Technology, 33(19), 3394-3397.
Lindsay, M. B., Moncur, M. C., Bain, J. G., Jambor, J. L., Ptacek, C. J. & Blowes, D. W. (2015). Geochemical and mineralogical aspects of sulfide mine tailings. Applied Geochemistry, 57, 157-177.
Lis, J., Pasieczna, A., Karbowska, B., Zembrzuski, W. & Lukaszewski, Z. (2003). Thallium in soils and stream sediments of a Zn− Pb mining and smelting area. Environmental Science & Technology, 37(20), 4569-4572.
Liu, J., Wang, J., Chen, Y., Lippold, H., Xiao, T., Li, H., Shen, C., Xie, L., Xie, X. & Yang, H. (2017). Geochemical transfer and preliminary health risk assessment of thallium in a riverine system in the Pearl River Basin, South China. Journal of Geochemical Exploration, 176, 64-75.
Liu, J., Li, N., Zhang, W., Wei, X., Tsang, D. C., Sun, Y., Luo, X., Bao, Z., Zheng, W., Wang, J., Xu, G., Hou, L., Chen, Y. & Feng, Y. (2019). Thallium contamination in farmlands and common vegetables in a pyrite mining city and potential health risks. Environmental Pollution, 248, 906-915.
Lopez-Arce, P., Garcia-Guinea, J. & Garrido, F. (2017). Chemistry and phase evolution during roasting of toxic thallium-bearing pyrite. Chemosphere, 181, 447-460.
López-Arce, P., Garrido, F., García-Guinea, J., Voegelin, A., Göttlicher, J. & Nieto, J. M. (2019). Historical roasting of thallium-and arsenic-bearing pyrite: Current Tl pollution in the Riotinto mine area. Science of the Total Environment, 648, 1263-1274.
Lottermoser, B.G., 2010. Mine Wastes: Characterization, Treatment, Environmental Impacts (2nd edition). Springer.
Macias, F., Caraballo, M. A., Nieto, J. M., Rötting, T. S. & Ayora, C. (2012). Natural pretreatment and passive remediation of highly polluted acid mine drainage. Journal Of Environmental Management, 104, 93-100.
Madejón, P., Murillo, J. M., Marañón, T. & Lepp, N. W. (2007). Factors affecting accumulation of thallium and other trace elements in two wild Brassicaceae spontaneously growing on soils contaminated by tailings dam waste. Chemosphere, 67(1), 20-28.
Martin, F., Garcia, I., Dorronsoro, C., Simón, M., Aguilar, J., Ortiz, I., Fernández, E. & Fernández, J. (2004). Thallium behavior in soils polluted by pyrite tailings (Aznalcollar, Spain). Soil & Sediment Contamination, 13(1), 25-36.
Migaszewski, Z. M. & Gałuszka, A. (2021). Abundance and fate of thallium and its stable isotopes in the environment. Reviews in Environmental Science and Bio/Technology, 20, 5-30.
Moreno, C. (1993). Postvolcanic Paleozoic of the Iberian pyrite belt; an example of basin morphologic control on sediment distribution in a turbidite basin. Journal of Sedimentary Research, 63(6), 1118-1128.
Moreno, C., Sierra, S. & Sáez, R. (1996). Evidence for catastrophism at the Famennian Dinantian boundary in the Iberian Pyrite Belt. Geological Society Special Publications, 107(1), 153-162.
Nielsen, S. G., Rehkämper, M., Porcelli, D., Andersson, P., Halliday, A. N., Swarzenski, P. W., Latkoczy, C. & Günther, D. (2005). Thallium isotope composition of the upper continental crust and rivers— an investigation of the continental sources of dissolved marine thallium. Geochimica et Cosmochimica Acta, 69(8), 2007-2019.
Nocete, F., Álex, E., Nieto, J. M., Sáez, R. & Bayona, M. R. (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.
Nordstrom, D. K., & Wilde, F. D. (2005). Chapter A6. Section 6.5. Reduction-Oxidation Potential (Electrode Method). In U.S. Geological Survey Techniques of Water-Resources Investigations, 9.
Nordstrom, D. K., Alpers, C. N., Ptacek, C. J. & Blowes, D. W. (2000). Negative pH and extremely acidic mine waters from Iron Mountain, California. Environmental Science & Technology, 34(2), 254-258.
Nriagu, JO., (1998). Thallium in the Environment. John Willey & Sons Inc.
Olías, M. & Nieto, J. M. (2015). Background conditions and mining pollution throughout history in the Río Tinto (SW Spain). Environments, 2(3), 295-316.
Olías, M., Cánovas, C. R., Basallote, M. D., Macías, F., Pérez-López, R., González, R. M., Millán-Becerro, R. & Nieto, J. M. (2019). Causes and impacts of a mine water spill from an acidic pit lake (Iberian Pyrite Belt). Environmental Pollution, 250, 127-136.
Oliveira, J. T. (1990). Stratigraphy and Synsedimentary Tectonism. In R. David Dallmeyer & E. Martinez Garcia (Eds.), Pre-Mesozoic Geology of Iberia (pp. 334–347).
Oliveira, M. L., Ward, C. R., Izquierdo, M., Sampaio, C. H., de Brum, I. A., Kautzmann, R. M., Sabedot, S., Querol, X. & Silva, L. F. (2012). Chemical composition and minerals in pyrite ash of an abandoned sulphuric acid production plant. Science of the Total Environment, 430, 34-47.
Orden, S., Macías, F., Cánovas, C. R., Nieto, J. M., Pérez-López, R. & Ayora, C. (2021). Eco-sustainable passive treatment for mine waters: Full-scale and long-term demonstration. Journal of Environmental Management, 280, 111699.
Pavoni, E., Petranich, E., Adami, G., Baracchini, E., Crosera, M., Emili, A., Lenaz, D., Higueras, P. & Covelli, S. (2017). Bioaccumulation of thallium and other trace metals in Biscutella laevigata nearby a decommissioned zinc-lead mine (Northeastern Italian Alps). Journal of Environmental Management, 186, 214-224.
Rader, S. T., Mazdab, F. K. & Barton, M. D. (2018). Mineralogical thallium geochemistry and isotope variations from igneous, metamorphic, and metasomatic systems. Geochimica et Cosmochimica Acta, 243, 42-65.
Rodríguez-Mercado, J. J., Mosqueda-Tapia, G., & Altamirano-Lozano, M. A. (2017). Genotoxicity assessment of human peripheral Lymphocytes induced by thallium (I) and thallium (III). Toxicological & Environmental Chemistry, 99(5-6), 987-998.
Romero, A., González, I., Martín, J. M., Vázquez, M. A. & Ortiz, P. (2015). Risk assessment of particle dispersion and trace element contamination from mine-waste dumps. Environmental Geochemistry and Health, 37, 273-286.
Rudnick, R.L. & Gao, S. (2003). The Composition of the Continental Crust. In: Holland, H.D., Turekian, K.K. (Eds.), Treatise on Geochemistry, Vol. 3. The Crust (pp. 1–64). Elsevier-Pergamon.
Ryu, J. G. & Kim, Y. (2022). Mineral transformation and dissolution of jarosite coprecipitated with hazardous oxyanions and their mobility changes. Journal of Hazardous Materials, 427, 128283.
Sáez, R., Pascual, E., Toscano, M. & Almodóvar, G. R. (1999). The Iberian type of volcano sedimentary massive sulphide deposits. Mineralium Deposita, 34, 549-570.
Sánchez España, J., López Pamo, E., Santofimia, E., Aduvire, O., Reyes, J. & Barettino, D. (2005). Acid mine drainage in the Iberian Pyrite Belt (Odiel river watershed, Huelva, SW Spain): geochemistry, mineralogy and environmental implications Applied Geochemistry, 20(7), 1320-1356.
Sarmiento, A. M., Grande, J. A., Luís, A. T., Dávila, J. M., Fortes, J. C., Santisteban, M., Curiel, J., de la Torre, M.L. & da Silva, E. F. (2018). Negative pH values in an open-air radical environment affected by acid mine drainage. Characterization and proposal of a hydrogeochemical model. Science of the Total Environment, 644, 1244-1253.
Silva, J. B., Oliveira, J. T. & Ribeiro, A. (1990). Structural outline. In R. David Dallmeyer & E. Martinez Garcia (Eds.), Pre-Mesozoic Geology of Iberia (pp. 348-362).
Tornos, F. (2006). Environment of formation and styles of volcanogenic massive sulfides: The Iberian Pyrite Belt. Ore Geology Reviews, 28(3), 259-307.
Tornos, F. (2008). La geología y metalogenia de la Faja Pirítica Ibérica. Macla, 10, 13-23.
Torres, E., Lozano, A., Macías, F., Gomez-Arias, A., Castillo, J. & Ayora, C. (2018). Passive elimination of sulfate and metals from acid mine drainage using combined limestone and barium carbonate systems. Journal of Cleaner Production, 182, 114-123.
Tremel, A., Masson, P., Sterckeman, T., Baize, D. & Mench, M. (1997). Thallium in French agrosystems—I. Thallium contents in arable soils. Environmental Pollution, 95(3), 293-302.
USEPA, (2014). National Recommended Water Quality Criteria - Human Health Criteria. United States Environmental Protection Agency. https://www.epa.gov/wqc/national-recommended-water-quality-criteria-human-health-criteria-table.
USEPA, (2015). Toxic and Priority Pollutants under the Clean Water Act. Unites States Environmental Protection Agency. https://www.epa.gov/eg/toxic-and-prioritypollutants-under-clean-water-act.
USGS, (2024). Mineral commodity summaries 2022. U.S. Geological Survey.
Vaněk, A., Chrastný, V., Komárek, M., Penížek, V., Teper, L., Cabala, J. & Drábek, O. (2013). Geochemical position of thallium in soils from a smelter-impacted area. Journal of Geochemical Exploration, 124, 176-182.
Vink, B. W. (1993). The behaviour of thallium in the (sub) surface environment in terms of Eh and pH. Chemical Geology, 109(1-4), 119-123.
Wang, J., She, J., Zhou, Y., Tsang, D. C., Beiyuan, J., Xiao, T., Dong, X., Chen, Y., Liu, J., Yin, M. & Wang, L. (2020). Microbial insights into the biogeochemical features of thallium occurrence: a case study from polluted river sediments. Science of the Total Environment, 739, 139957.
Wang, J., Liu, S., Wei, X., Beiyuan, J., Wang, L., Liu, J., Sun, H., Zhang, G. & Xiao, T. (2022). Uptake, organ distribution and health risk assessment of potentially toxic elements in crops in abandoned indigenous smelting region. Chemosphere, 292, 133321.
White, W.M., (2013). Geochemistry. Wiley-Blackwell, Hoboken, NJ (USA).
Yang, C., Chen, Y., Li, C., Chang, X. & Wu, Y. (2009). Trace element transformations and partitioning during the roasting of pyrite ores in the sulfuric acid industry. Journal of Hazardous Materials, 167(1-3), 835-845.
Yin, M., Zhou, Y., Tsang, D. C., Beiyuan, J., Song, L., She, J., Wang, J., Zhu, L., Fang, F., Wang, L., Liu, J., Liu, Y., Song, G., Chen, D. & Xiao, T. (2021). Emergent thallium exposure from uranium mill tailings. Journal of Hazardous Materials, 407, 124402.
Zhuang, X., Su, S., Xiao, M., Li, J., Alastuey, A. & Querol, X. (2012). Mineralogy and geochemistry of the Late Permian coals in the Huayingshan coal-bearing area, Sichuan Province, China. International Journal of Coal Geology, 94, 271-282.
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