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Low-crystallinity products of trace-metal precipitation in neutralized pit-lake waters without ferric and aluminous adsorbent: Geochemical modelling and mineralogical analysis

Published online by Cambridge University Press:  02 January 2018

Javier Sánchez-España  and
Iñaki Yusta
Javier Sánchez-España*
Affiliation:
Unidad de Mineralogía e Hidrogeoquímica Ambiental (UMHA), Instituto Geológico y Minero de España, C/ Calera 1, 28760, Tres Cantos, Madrid, Spain
Iñaki Yusta
Affiliation:
Unidad de Mineralogía e Hidrogeoquímica Ambiental (UMHA), Departamento de Mineralogía y Petrología, Universidad del País Vasco UPV/EHU, Apdo 644, 48080, Bilbao, Spain
*
*E-mail: [email protected]
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Abstract

The removal of dissolved trace metals during neutralization of acid mine drainage has usually been described and modelled as a progressive, pH-dependent sorption onto standard ferric or aluminous adsorbent. In the absence of adsorbent mineral surfaces, trace metals tend to form amorphous to low-crystallinity compounds which are often difficult to characterize. Here, we study the behaviour of the more soluble metals (Cu2+, Zn2+, Mn2+, Co2+, Ni2+, Cd2+) in the absence of ferric and aluminous adsorbent by neutralization experiments with waters from two acidic pit lakes. The objectives of our study were to identify the mineral products formed by trace-metal precipitation and the pH ranges at which these metals are removed from the solutions. Both geochemical modelling and detailed mineralogical and chemical analyses (XRD, SEM, TEM, XRF, ICP-AES) were undertaken to characterize the products. The schwertmannite and hydrobasaluminite colloids formed in the initial neutralization stages were removed from the waters at pH 3.5 and 5.1, respectively. These two minerals had previously adsorbed the Cr3+ and Pb2+ initially present in the solutions. The Cu precipitates were amorphous to X-rays, though chemical and modelling data suggest that Cu probably precipitated as a precursor of brochantite (Cu4(SO4)(OH)6·2H2O) at pH >6.0, together with minor quantities of other Cu hydroxysulfates (langite, antlerite) and Cu(OH)2. At higher pH, other divalent metals (Zn2+, Mn2+) precipitated as silicates, carbonates and/or (possibly) minor oxides and (oxy)hydroxides. The high concentration of aqueous SiO2 in the solutions allowed Zn to precipitate as willemite (Zn2SiO4) at pH >7.0. Similarly, the presence of inorganic carbon (originally as CO2 (aq.)) greatly influenced the nature of the corresponding precipitate of Mn. This metal was initially present as Mn2+ and experienced a partly oxidative precipitation forming, in combination with Mg2+, the hydroxyl carbonate desautelsite (Mg6Mn2(CO3)(OH)16·4H2O) at pH 9.0–10.0. The formation of Mn3+/Mn4+ oxides and hydroxides (hausmannite, manganite, birnessite) could not be demonstrated, although geochemical calculations support their subordinate formation. Other metallic cations such as Co2+, Ni2+ and Cd2+ did not form discrete mineral phases but were totally removed by sorption onto and/or incorporation into the cited Zn and Mn compounds. The discrepancies between theoretical and demonstrated mineralogy and the significance of these minerals for future pit-lake remediation initiatives are discussed.

Keywords

low-crystallinity productsgeochemical modellingpit-lake waterstrace-metal precipitation
Type
Research Article
Information
Mineralogical Magazine , Volume 79 , Issue 3 , June 2015 , pp. 781 - 798
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2015

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References

Allison, J.D., Brown, D.S. and Novo-Gradac, J. (1999) MINTEQA2/PRODEAFA2, A Geochemical Assessment Model for Environmental Systems: User Manual Supplement for Version 4.0. United States Environmental Protection Agency, National Exposure Research Laboratory, Athens, Georgia, USA. Alpers, C.N. and Nordstrom, D.K. (1999) Geochemical modelling of water-rock interactions in mining environments. Pp. 289–323. in: The Environmental Geochemistry of Mineral Deposits, Part A. Processes, Techniques, and Health Issues (G.S. Plumlee, M.J. Logsdon and L.F. Filipek, editors). Reviews in Economic Geology, Vol. 6A. Society of Economic Geologists, Littleton, Colorado, USA.Google Scholar
Asta, M.P., Ayora, C., Acero, P. and Cama, J. (2010) Field rates for natural attenuation of arsenic in Tinto Santa Rosa acid mine drainage (SW Spain). Journal of Hazardous Materials, 177, 1102–1111.CrossRefGoogle Scholar
Bigham, J.M. and Nordstrom, D.K. (2000) Iron and aluminium hydroxysulfates from acid sulphate waters. Pp. 351–403. in: Sulfate Minerals: Crystallography, Geochemistry, and Environmental Significance (C.N. Alpers, J.L. Jambor and D.K. Nordstrom, editors). Reviews in Mineralogy & Geochemistry, 40. Mineralogical Society of America and the Geochemical Society, Chantilly, Virginia, USA.Google Scholar
Bowell, R.J. and Parshley, J.V. (2005) Control of pitlake water chemistry by secondary minerals, Summer Camp pit, Getchell mine, Nevada. Chemical Geology, 215, 373–385.CrossRefGoogle Scholar
Brugam, R.B. and Stahl, J.B. (2000) The potential of organic matter additions for neutralizing surface mine lakes. Transactions of the Illinois State Academy of Science, 93, 127–144.Google Scholar
Castro, J.M. and Moore, J.N. (2000) Pit lakes: their characteristics and the potential for their remediation. Environmental Geology, 244, 56–73.Google Scholar
Davis, C.C., Chen, H.W. and Edwards, M. (2002) Modelling silica sorption to iron hydroxide. Environmental Science & Technology, 36, 582–587.CrossRefGoogle Scholar
Davis, J.A. and Kent, D.B. (1990) Surface complexation modelling in aqueous geochemistry. Pp. 177–260. in: Mineral-Water Interface Geochemistry (M.F. Hochella and A.F. White, editors). Reviews in Mineralogy, 23. Mineralogical Society of America, Washington, DC.Google Scholar
Davies, C.W. (1962) Ion Association. Butterworths, London, pp. 37–53.Google Scholar
Diez-Ercilla, M., Pamo, E.L. and Sánchez-España, J. (2009) Photoreduction of Fe(III) in the acidic mine pit lake of San Telmo (Iberian Pyrite Belt): field and experimental work. Aquatic Geochemistry, 15, 391–419.CrossRefGoogle Scholar
Diez-Ercilla, M., Sánchez-España, J., Yusta, I., Wendt-Potthoff, K. and Koschorreck, M. (2014) Formation of biogenic sulphides in the water column of an acidic pit lake: Biogeochemical controls and effects on trace metal dynamics. Biogeochemistry, 121, 519–536.CrossRefGoogle Scholar
Dzombak, D.A. and Morel, F.M.M. (1990) Surface Complexation Modeling: Hydrous Ferric Oxide. John Wiley and Sons, New Jersey, USA, pp. 393.Google Scholar
Eary, L.E. (1999) Geochemical and equilibrium trends in mine pit lakes. Applied Geochemistry, 14, 963–987.CrossRefGoogle Scholar
Eary, L.E. and Castendyk, D.N. (2013) Hardrock metal mine pit lakes: Occurrence and geochemical characteristics. Pp. 75–106. in: Acidic Pit Lakes: The Legacy of Coal and Metal Surface Mines (Geller, W., Schultze, M., Kleinmann, B. and Wolkersdorfer, C., editors). Springer-Verlag, Berlin-Heidelberg.Google Scholar
Egal, M., Casiot, C., Morin, G., Parmentier, M., Bruneel, O., Lebrun, S. and Elbaz-Poulichet, F. (2009) Kinetic control on the formation of tooeleite, schwertmannite and jarosite by Acidithiobacillus ferrooxidans strains in an As(III)-rich acid mine water. Chemical Geology, 265, 432–441.CrossRefGoogle Scholar
Gammons, C.H. (2006) Geochemistry of perched water in an abandoned underground mine, Butte, Montana. Mine Water and the Environment, 25, 114–123.CrossRefGoogle Scholar
Geller, W. and Schultze, M. (2013) Remediation and management of acidified pit lakes and outflowing waters. Pp. 225–264. in: Acidic Pit Lakes: The Legacy of Coal and Metal Surface Mines (Geller, W., Schultze, M., Kleinmann, B. and Wolkersdorfer, C.|Geller, W., Schultze, M., Kleinmann, B. and Wolkersdorfer, C.|Geller, W., Schultze, M., Kleinmann, B. and Wolkersdorfer, C., editors). Springer-Verlag, Berlin-Heidelberg.Google Scholar
Hansen, H.C.B. and Taylor, R.M. (1991) Formation of synthetic analogues of double metal-hydroxy carbonate minerals under controlled pH conditions: II. The synthesis of desaultelsite. Clay Minerals, 26, 507–525.CrossRefGoogle Scholar
Kinniburgh, D.G. and Jackson, M.L. (1981) Cation adsorption by hydrous metal oxides and clay. Pp. 91–160. in: Adsorption of Inorganic at Solid-Liquid Interfaces (M.A. Anderson and A.J. Rubin, editors). Ann Arbor Science, Ann Arbor, Michigan, USA.Google Scholar
Kinniburgh, D.G., Jackson, M.L. and Syers, J.K. (1976) Adsorption of alkaline earth, transition, and heavy metal cations by hydrous oxide gels of iron and aluminum. Soil Science Society of America Journal, 40, 796–799.CrossRefGoogle Scholar
Lee, G., Bigham, J.M. and Faure, G. (2002) Removal of trace metals by coprecipitation with Fe, Al and Mn from natural waters contaminated with acid mine drainage in the Ducktown Mining District, Tennessee. Applied Geochemistry, 17, 569–581.CrossRefGoogle Scholar
McNee, J., Crusius, J., Martin, A.J., Whittle, P., Pieters, R. and Pedersen, T.F. (2003) The physical, chemical and biological dynamics in two contrasting pit lakes: implications for pit lake bioremediation. Pp. 550–564. in: Sudbury 2003 Mining and the Environment (G. Spiers, P. Beckett and H. Conroy, editors). Laurentian University, Sudbury, Canada.Google Scholar
Moncur, M.C., Ptacek, C.J., Blowes, D.W. and Jambor, J.L. (2006) Spatial variations in water composition at a northern Canadian lake impacted by mine drainage. Applied Geochemistry, 21, 1799–1817.CrossRefGoogle Scholar
Nordstrom, D.K. (2004) Modelling low-temperature geochemical processes. Pp. 37–72. in: Surface and Ground Water, Weathering, and Soils (H.D. Holland and K.K. Turekian, series editors, J.I. Drever, vol. editor). Treatise on Geochemistry, Vol. 5. Elsevier, Amsterdam.Google Scholar
Nordstrom, D.K. (2008) Questa baseline and pre-mining ground-water quality investigation, 25. Summary of results and baseline and pre-mining ground-water geochemistry, Red River Valley, Taos County, New Mexico, 2001-2005. US Geological Survey Professional Paper 1728.Google Scholar
Nordstrom, D.K. and Alpers, C.N. (1999) Geochemistry of acid mine waters. Pp. 133–156. in: The Environmental Geochemistry of Mineral Deposits, Part A. Processes, Techniques, and Health Issues, (G.S. Plumlee, M.J. Logsdon and L.F. Filipek, editors). Reviews in Economic Geology, Vol. 6A. Society of Economic Geologists, Littleton, Colorado, USA.Google Scholar
Nordstrom, D.K. and Munoz, J.L. (1994) Geochemical Thermodynamics, 2nd edition. The Blackburn Press, Caldwell, New Jersey, USA. Palmqvist, U., Ahlberg, E., Lövgren, L. and Sjöberg, S. (1997) In situ voltammetric determinations of metal ions in goethite suspensions: Single metal ion systems. Journal of Colloid Interface Science, 196, 254–266.Google Scholar
Parkhurst, D.L. and Appelo, C.A.J. (2013) Description of input and examples for PHREEQC (Version 3)-A computer program for speciation, batch-reactions, one-dimensional transport, and inverse geochemical calculations. US Geological Survey Techniques and Methods, Book 6, Chapter A43. Denver, Colorado, USA.Google Scholar
Pelletier, C.A., Wen, M.E. and Poling, G.W. (2009) Flooding pit lakes with surface water. Pp. 239–248. in: Mine Pit Lakes-Characteristics, Predictive Modeling and Sustainability (D.N. Castendyk and L.E. Eary, editors). Society for Mining, Metallurgy and Exploration, Littleton, Colorado, USA.Google Scholar
Regenspurg, S. and Peiffer, S. (2005) Arsenate and chromate incorporation in schwertmannite. Applied Geochemistry, 20, 1226–1239.CrossRefGoogle Scholar
Sánchez-España, J. (2007) The behavior of iron and aluminum in acid mine drainage: Speciation, Mineralogy, and Environmental Significance. Pp. 137–149. in: Thermodynamics, Solubility and Environmental Issues (T.M. Letcher, editor). Elsevier B.V., The Netherlands.Google Scholar
Sánchez-España, J., López-Pamo, E., Santofimia, E., Reyes, J. and Martín Rubí, J.A. (2006) The removal of dissolved metals by hydroxysulfate precipitates during oxidation and neutralization of acid mine waters, Iberian Pyrite Belt. Aquatic Geochemistry, 12, 269–298.CrossRefGoogle Scholar
Sánchez-España, J., López-Pamo, E., Santofimia, E. and Diez-Ercilla, M. (2008a) The acidic mine pit lakes of the Iberian Pyrite Belt: An approach to their physical limnology and hydrogeochemistry. Applied Geochemistry, 23, 1260–1287.CrossRefGoogle Scholar
Sánchez-España, J., González Toril, E., López Pamo, E., Amils, R., Diez, M., Santofimia, E. and San Martínriz, P. (2008b) Biogeochemistry of a hyperacidic and ultraconcentrated pyrite leachate in San Telmo mine (Iberian Pyrite Belt, Spain). Water Air and Soil Pollution, 194, 243–257.CrossRefGoogle Scholar
Sánchez-España, J., López-Pamo, E., Diez, M. and Santofimia, E. (2009) Physico-chemical gradients and meromictic stratification in Cueva de la Mora and other acidic pit lakes of the Iberian Pyrite Belt. Mine Water and the Environment, 28, 15–29.CrossRefGoogle Scholar
Sánchez-Espan˜a, J., Yusta, I. and Diez-Ercilla, M. (2011) Schwertmannite and hydrobasaluminite: A re-evaluation of their solubility and control on the iron and aluminum concentration in acidic pit lakes. Applied Geochemistry, 26, 1752–1774.CrossRefGoogle Scholar
Sánchez-España, J., Yusta, I. and López, G.A. (2012) Schwertmannite to jarosite conversion in the water column of an acidic mine pit lake. Mineralogical Magazine, 76, 2659–2682.CrossRefGoogle Scholar
Sánchez-España, J., Diez, M. and Santofimia, E. (2013) Mine pit lakes of the Iberian Pyrite Belt: Some basic limnological, hydrogeochemical and microbiological considerations. Pp. 315–342. in: Acidic Pit Lakes: The Legacy of Coal and Metal Surface Mines (Geller, W., Schultze, M., Kleinmann, B. and Wolkersdorfer, C., editors). Springer-Verlag, Berlin-Heidelberg.Google Scholar
Sánchez-España, J., Diez, M., Pérez-Cerdán, F., Yusta, I. and Boyce, A.J. (2014a) Hydrological investigation of a multi-stratified pit lake using radioactive and stable isotopes combined with hydrometric monitoring. Journal of Hydrology, 511, 494–508.CrossRefGoogle Scholar
Sánchez-España, J., Boehrer, B. and Yusta, I. (2014b) Extreme carbon dioxide concentrations in acidic pit lakes provoked by water/rock interaction. Environmental Science & Technology, 48, 4273–4281.CrossRefGoogle ScholarPubMed
Shum, M. and Lavkulich, L. (1999) Speciation and solubility relationships of Al, Cu and Fe in solutions associated with sulfuric acid leached mine waste rock. Environmental Geology, 38, 59–68.CrossRefGoogle Scholar
Smith, K.S. (1999) Metal sorption on mineral surfaces: an overview with examples relating to mineral deposits. Pp. 161–182. in: The Environmental Geochemistry of Mineral Deposits, Part A. Processes, Techniques, and Health Issues (G.S. Plumlee, M.J. Logsdon and L.F. Filipek, editors). Reviews in Economic Geology, Vol. 6A. Society of Economic Geologists, Littleton, Colorado, USA.Google Scholar
Strawn, D.G., Hickey, P., Knudsen, A. and Baker, L. (2007) Geochemistry of lead contaminated wetland soils amended with phosphorus. Environmental Geology, 52, 109–122.CrossRefGoogle Scholar
Stumm, W. and Morgan, J.J. (1996) Aquatic Chemistry, 3rd edition. John Wiley & Sons, Inc., New York, USA. Templeton, A.S., Trainor, T.P., Traina, S.J., Spormann, A.M. and Brown, G.E. (2001) Pb(II) distributions at biofilm-metal oxide interfaces. PNAS, 98, 11897–11902.Google Scholar
Twidwell, L.G., Gammons, C.H., Young, C.A. and Berg, R.B. (2006) Summary of deepwater sediment/ pore water characterization for metal-laden Berkeley pit lake in Butte, Montana. Mine Water and the Environment, 25, 86–92.CrossRefGoogle Scholar
Webster, J.G., Swedlund, P.J. and Webster, K.S. (1998) Trace metal adsorption onto acid mine drainage Fe(III) oxyhydroxysulfate. Environmental Science & Technology, 32, 1361–1368.CrossRefGoogle Scholar
Wendt-Potthoff, K., Koschorreck, M., Diez-Ercilla, M. and Sánchez-España, J. (2012) Microbial activity and biogeochemical cycling in a nutrient-rich meromictic acid pit lake. Limnologica, 42, 175–188.CrossRefGoogle Scholar
Wollast, R., Mackenzie, F.T. and Bricker, O.P. (1968) Experimental precipitation and genesis of sepiolite at earth-surface conditions. American Mineralogist, 53, 1645–1662.Google Scholar
Zhang, J., Lion, L.W., Nelson, Y.M., Shuler, M.L. and Ghiorse, W.C. (2002) Kinetics of Mn(II) oxidation by Leptothrix discophora SS1. Geochimica et Cosmochimica Acta, 66, 773–781.CrossRefGoogle Scholar
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