Skip to main content Accessibility help

Cycling of As, P, Pb and Sb during weathering of mine tailings: implications for fluvial environments

  • D. Kossoff (a1) (a2), K. A. Hudson-Edwards (a1), W. E. Dubbin (a2), M. Alfredsson (a3) and T. Geraki (a4)...


The weathering and oxidation of mine tailings has the potential to contaminate water and soil with toxic elements. To understand the mechanisms, extent and products of the long-term weathering of complex Bolivian tailings from the Cerro Rico de Potosí, and their effects on As, Pb, P and Sb cycling, three-year long laboratory column experiments were carried out to model 20 years of dry- and wet-season conditions in the Pilcomayo basin. Chemical analysis of the leachate and column solids, optical mineralogy, X-ray diffraction, scanning electron microscopy, electron probe microanalysis, microscale X-ray absorption near edge structure spectroscopy, Bureau Commun de Référence sequential extraction and water-soluble chemical extractions, and speciation modelling have shown that the weathering of As-bearing pyrite and arsenopyrite, resulted in a loss of 13–29% of the original mass of As. By contrast, Pb and Sb showed much lower mass losses (0.1–1.1% and 0.6–1.9%, respectively) due to the formation of insoluble Pb- and Sb(V)-rich phases, which were stable at the low pH (~2) conditions that prevailed by the end of the experiment. The experiment also demonstrated a link between the cycling of As, Sb, and the oxidation of Fe(II)-bearing sphalerite, which acted as a nucleation point for an Fe-As-Sb-O phase. Phosphorus was relatively immobile in the tailings columns (up to 0.3% mass loss) but was more mobile in the soil-bearing columns (up to 10% mass loss), due to the formation of soluble P-bearing minerals or mobilization by organic matter. These results demonstrate the influence of mine tailings on the mobility of P from soils and on the potential contamination of ecosystems with As, and strongly suggest that these materials should be isolated from fluvial environments.


Corresponding author


Hide All
Abollino, O., Giacomino, A., Malandrino, M. and Mentasti, E. (2008) Interaction of metal ions with montmorillonite and vermiculite. Applied Clay Science, 38, 227236.
Ake, C., Mayura, K., Huebner, H., Bratton, G. and Phillips, T. (2001) Development of porous claybased composites for the sorption of lead from water. Journal of Toxicology and Environmental Health Part A, 63, 459475.
Archer, J., Hudson-Edwards, K.A., Preston, D.A., Howarth, R.J. and Linge, K. (2005) Aqueous exposure and uptake of arsenic by riverside communities affected by mining contamination in the Rio Pilcomayo basin, Bolivia. Mineralogical Magazine, 69, 719736.
Arp, P.A. and Meyer, W.L. (1985) Formation constants for selected organo-metal (Al3+, Fe3+)-phosphate complexes. Canadian Journal of Chemistry, 63, 33573366.
Atkins, P.W. (1995) Physical Chemistry. Oxford University Press, Oxford, UK.
Benjamin, M. and Leckie, J. (1981) Multiple-site adsorption of Cd, Cu, Zn, and Pb on amorphous iron oxyhydroxide. Journal of Colloid and Interface Science, 79, 209221.
Bethke, C. (1996) Geochemical Reaction Modelling: Concepts and Applications. Oxford University Press, New York, 397 pp.
Bigham, J.M., Carlson, L. and Murad, E. (1994) Schwertmannite, a new iron oxyhydroxysulphate from Pyhäsalmi, Finland, and other localities. Mineralogical Magazine, 58, 641648.
Biver, M. and Shotyk, W. (2012) Stibnite (Sb2S3) oxidative dissolution kinetics from pH 1 to 11. Geochimica et Cosmochimica Acta, 79, 127139.
Blanchard, M., Alfredsson, M., Brodholt, J., Wright, K. and Catlow, C.R.A. (2006) Arsenic incorporation into FeS2 pyrite and its influence on dissolution: a DFT study. Geochimica et Cosmochimica Acta, 71, 624630.
Bolton, K. (1996) Corrosion. Open University, Milton Keynes, UK.
Cheng, H., Hu, Y., Luo, J., Xu, B. and Zhao, J. (2009) Geochemical processes controlling fate and transport of arsenic in acid mine drainage (AMD) and natural systems. Journal of Hazardous Materials, 165, 1326.
Craw, D., Falconer, D. and Youngson, J.H. (2003) Environmental arsenopyrite stability and dissolution: theory, experiment, and field observations. Chemical Geology, 199, 7182.
Cunningham, C., McNamee, J., Pinto, V. and Ericksen, G.E. (1991) A model of volcanic dome-hosted precious metal deposits in Bolivia. Economic Geology, 86, 415421.
Davidson, C.M., Duncan, A.L., Littlejohn, D., Ure, A.M. and Garden, L.M. (1998) A critical evaluation of the three-stage BCR sequential extraction procedure to assess the potential mobility and toxicity of heavy metals in industrially-contaminated land. Analytica Chimica Acta, 363, 4555.
Delaney, J.M. and Lundeen, S.R. (1990) The LLNL Thermodynamic Database. Lawrence Livermore National Laboratory Report UCRL-21658. Lawrence Livermore National Laboratory, Livermore, California, USA.
Diemar, G.A., Filella, M., Leverett, P. and Williams, P.A. (2009) Dispersion of antimony from oxidizing ore deposits. Pure and Applied Chemistry, 81, 15471553.
Doménech, C., de Pablo, J. and Ayora, C. (2002) Oxidative dissolution of pyritic sludge from the Aznalcó llar mine (SW Spain). Chemical Geology, 190, 339353.
Fawcett, W.E. and Jamieson, H.E. (2011) The distinction between ore processing and post-depositional transformation on the speciation of arsenic and antimony in mine waste and sediment. Chemical Geology, 283, 109118.
Filella, M., Williams, P.A. and Belzile, N. (2009a) Antimony in the environment: knowns and unknowns. Environmental Chemistry, 6, 95105.
Filella, M., Philippo, S., Belzile, N., Chen, Y. and Quentel, F. (2009b) Natural attenuation processes applying to antimony: a study in the abandoned antimony mine in Goesdorf, Luxembourg. Science of the Total Environment, 407, 62056216.
Forray, F.L., Smith, A.M.L., Drouet, C., Navrotsky, A., Wright, K., Hudson-Edwards, K.A. and Dubbin, W.E. (2010) Synthesis, characterization and thermochemistry of a Pb-jarosite. Geochimica et Cosmochimica Acta, 74, 215224.
Foster, A.L., Brown, G.E. Jr, Tingle, T.N. and Parks, G.A. (1998) Quantitative arsenic speciation in mine tailings using X-ray absorption spectroscopy. American Mineralogist, 83, 553568.
Foy, R. and Withers, P. (1995) The contribution of agricultural phosphorus to eutrophication. Proceeding of the International Fertiliser Society, no. 365, 32 pp.
Fu, Z., Wu, F., Amarasiriwardena, D., Mo, C., Liu, B., Zhu, J., Deng, Q. and Liao, H. (2010) Antimony, arsenic and mercury in the aquatic environment and fish in a large antimony mining area in Hunan, China. Science of the Total Environment, 408, 34033410.
Gaboreau, S., Beaufort, D., Vieillard, P., Patrier, P. and Bruneton, P. (2005) Aluminum phosphate-sulfate minerals associated with Proterozoic unconformitytype uranium deposits in the East Alligator River uranium field, Northern Territories, Australia. The Canadian Mineralogist, 43, 813827.
He, M. (2007) Distribution and phytoavailability of antimony at an antimony mining and smelting area, Hunan, China. Environmental Geochemistry and Health, 29, 209219.
Hochella, M.F. Jr, Moore, J.N., Golla, U. and Putnis, A. (1999) A TEM study of samples from acid mine drainage systems: metal-mineral association with implications for transport. Geochimica et Cosmochimica Acta, 63, 33953406.
Hudson-Edwards, K.A., Macklin, M.G., Miller, J.R. and Lechler, P.J. (2001) Sources, distribution and storage of heavy metals in the Río Pilcomayo, Bolivia. Journal of Geochemical Exploration, 72, 229250.
Hudson-Edwards, K.A., Macklin, M.G., Jamieson, H.E., Brewer, P.A., Coulthard, T.J., Howard, A.J. and Turner, J. (2003) The impact of tailings dam spills and clean-up operations on sediment and water quality in river systems: the Ríos Agrio-Guadiamar, Aznalcó llar, Spain. Applied Geochemistry, 18, 221239.
Hudson-Edwards, K.A., Jamieson, H.E., Charnock, J.M. and Macklin, M.G. (2005) Arsenic speciation in waters and sediment of ephemeral floodplain pools, Ríos Agrio-Guadiamar, Aznalcó llar, Spain. Chemical Geology, 219, 175192.
Jambor, J.L., Nordstrom, D.K. and Alpers, A.N. (2000) Metal-sulfate salts from sulfide mineral oxidation. Pp. 303350 in: Sulfate Minerals. Crystallography, Geochemistry and Environmental Significance (C.N. Alpers J.L. Jambor and D.K. Nordstrom, editors). Reviews in Mineralogy and Geochemistry, 40. Mineralogical Society of America, Washington DC and the Geochemical Society, St Louis, Missouri. USA.
Jamieson, H.E., Robinson, C., Alpers, A.N., McCleskey, R.B., Nordstrom, D.K. and Peterson, R.C. (2005) Major and trace element composition of copiapitegroup minerals and coexisting water from the Richmond mine, Iron Mountain, California. Chemical Geology, 215, 387405.
Jimnez-Cáceles, F.J. and Á varez-Rógel, J. (2008) Phosphorus fractionation and distribution in salt marsh soils affected by mine wastes, and eutrophicated water: a case study in SE Spain. Geoderma, 144, 299309.
Kossoff, D., Hudson-Edwards, K.A., Dubbin, W.E. and Alfredsson, M.A. (2011) Incongruent weathering of Cd and Zn from mine tailings: a column leaching study. Chemical Geology, 281, 5271.
Kossoff, D., Hudson-Edwards, K.A., Dubbin, W.E. and Alfredsson, M. (2012) Major and trace metal mobility during weathering of mine tailings: implications for floodplain soils. Applied Geochemistry, 27, 562576.
Leverett, P., Reynolds, J.K., Roper, A.J. and Williams, P.A. (2012) Tripuhyite and schafarzikite: two of the ultimate sinks for antimony in the natural environment. Mineralogical Magazine, 76, 891902.
Macklin, M., Payne, I., Preston, D. and Sedgwick, C. (1996) Review of the Porco Mine Tailings Dam Burst and Associated Mining Waste Problems, Pilcomayo Basin, Bolivia. Report to UK Overseas Development Administration. University of Wales, Aberystwyth, UK.
Majzlan, J., Lalinská, B., Chovan, M., Bläb, U., Brecht, B., Gö ttlicher, J., Steininger, R., Hug, K., Ziegler, S. and Gescher, J. (2011) A mineralogical, geochemical, and microbiological assessment of the antimony- and arsenic-rich neutral mine drainage tailings near Pezinok, Slovakia. American Mineralogist, 96, 113.
Mihaljevic, M., Ettler, V., Sebek, O., Drahota, P., Strnad, L., Procházka, R., Zeman, J. and Sracek, O. (2009) Alteration of arsenopyrite in soils under different vegetation covers. Science of the Total Environment, 408, 12861294.
Miller, J.R. and Orbock Miller, S.M. (2007) Contaminated Rivers: A Geomorphological- Geochemical Approach to Site Assessment and Remediation. Springer, London.
Miller, J.R., Hudson-Edwards, K.A., Lechler, P.J., Preston, D. and Macklin, M.G. (2004) Heavy metal contamination of water, soil and produce within riverine communities of the Río Pilcomayo basin, Bolivia. Science of the Total Environment, 320, 189209.
Mitsu Mineral Development Engineering Company (1999) The Study on Evaluation of Environmental Impact of Mining Sector in Potosi Prefecture of the Republic of Bolivia. Mitsu Mineral Development Engineering Co. Ltd. and Unico International Corporation.
Morris, J.C. and Stumm, W. (1967) Redox equilibria and measurements of potentials in the aquatic environment. Pp. 270285 in: Equilibrium Concepts in Natural Water Systems (W. Stumm, editor). Advances in Chemistry, 67. American Chemical Society, Washington DC.
Nordstrom, D.K. and Archer, D.G. (2003) Arsenic thermodynamic data and environmental geochemistry. Pp. 116 in: Arsenic in Ground Water (A.H. Welch and K.G. Stollenwerk, editors). Kluwer Academic Publishers, Boston, USA.
Papirer, E. (2000) Adsorption on Silica Surfaces. Marcel Dekker, New York.
Pruvot, C., Douay, F., Herve, F. and Waterlot, C. (2006) Heavy metals in soil, crops and grass as a source of human exposure in the former mining areas. Journal of Soils and Sediments, 6, 215220.
Ravel, B. and Newville, M. (2005) ATHENA, ARTEMICS, HEPHAESTUS: data analysis for Xray absorption spectroscopy using IFEFFIT. Journal of Synchrotron Radiation, 12, 537541.
Roussel, C., Néel, C. and Bril, H. (2000) Minerals controlling arsenic and lead solubility in an abandoned gold mine tailings. Science of the Total Environment, 263, 209219.
Schreiber, M., Simo, J. and Freiberg, P. (2000) Stratigraphic and geochemical controls on naturally occurring arsenic in groundwater, eastern Wisconsin, USA. Hydrogeology Journal, 8, 161176.
Shannon, R.D. (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica, A32, 751767.
Smart, L. and Gagan, M. (2002) The Third Dimension. The Open University, Milton Keynes, UK.
Smedley, P., Edmunds, W. and Pelig-Ba, K. (1996) Mobility of arsenic in groundwater in the Obuasi gold-mining area of Ghana: some implications for human health. Geological Society London Special Publication, 113, 163181.
Søvik, A.K. and Køve, B. (2005) Phosphorus retention processes in shell sand filter systems treating municipal wastewater. Ecological Engineering, 25, 168182.
Stallard, R.F. and Edmond, J.M. (1981) Geochemistry of the Amazon: 1. Precipitation chemistry and the marine contribution to the dissolved load at the time of peak discharge. Journal of Geophysical Research, 86, 98449858.
Strosnider, W.H. and Nairn, R.W. (2010) Effective passive treatment of high-strength acid mine drainage and raw municipal wastewater in Potosí, Bolivia using simple mutual incubations and limestone. Journal of Geochemical Exploration, 105, 3442.
Strosnider, W.H.J., Llanos López, F.S. and Nairn, R.W. (2011a) Acid mine drainage at Cerro Rico de Potosí I: unabated high-strength discharges reflect a five century legacy of mining. Environmental Earth Sciences, 64, 899910.
Strosnider, W.H.J., Llanos López, F.S. and Nairn, R.W. (2011b) Acid mine drainage at Cerro Rico de Potosí II: severe degradation of the upper Rio Pilcomayo watershed. Environmental Earth Sciences, 64, 911923.
Tenderholt, A., Hedman, B. and Hodgson, K.O. (2007) PySpline: a modern, cross-platform program for the processing of raw averaged XAS edge and EXAFS data. AIP Conference Proceedings (XAFS13), 882, 105107.
Tighe, M., Ashley, P., Lockwood, P. and Wilson, S. (2005) Soil, water, and pasture enrichment of antimony and arsenic within a coastal floodplain system. Science of the Total Environment, 347, 175186.
Vink, B.W. (1996) Stability relations of antimony and arsenic compounds in the light of revised and extended Eh-pH diagrams. Chemical Geology, 130, 2130.
West, A.R. (1991) Basic Solid State Chemistry. John Wiley & Sons, Chichester, UK.
Wilkie, J. and Hering, J. (1996) Adsorption of arsenic onto hydrous ferric oxide: effects of adsorbate/ adsorbent ratios and co-occurring solutes. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 107, 97110.
Wilson, S.C., Lockwood, P.V., Ashley, P.M. and Righe, M. (2010) The chemistry and behaviour of antimony in the soil environment with comparisons to arsenic: a critical review. Environmental Pollution, 158, 11691181.
Younger, P. and Wolkersdorfer, C. (2004) Mining impacts on the fresh water environment: technical and managerial guidelines for catchment scale management. Mine Water and Environment, 23, 280.



Altmetric attention score

Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed