Hostname: page-component-78c5997874-dh8gc Total loading time: 0 Render date: 2024-11-08T05:31:55.188Z Has data issue: false hasContentIssue false
  • English
  • Français

Selective precipitation of schwertmannite in a stratified acidic pit lake of Iberian Pyrite Belt

Published online by Cambridge University Press:  02 January 2018

E. Santofimia ,
E. López-Pamo  and
E. Montero
E. Santofimia*
Affiliation:
Instituto Geológico y Minero de Espan˜a (IGME), Ríos Rosas, 23, 28003, Madrid, Spain
E. López-Pamo
Affiliation:
Instituto Geológico y Minero de Espan˜a (IGME), Ríos Rosas, 23, 28003, Madrid, Spain
E. Montero
Affiliation:
Departamento de Geodinámica, Facultad de Ciencias Geológicas, Universidad Complutense de Madrid, José A. Novais, 2, 28040 Madrid, Spain
*
*E-mail: [email protected]
Get access Rights & Permissions [Opens in a new window]

Abstract

Selective precipitation of schwertmannite was identified in the water column of a chemically stratified acidic lake (pH 2.0 2.5). A set of analytical techniques was used to identify accurately the mineral phase (X-ray diffraction, X-ray fluorescence spectrometry, scanning electron microscopy coupled with energy dispersive spectroscopy). The lake has two clearly differentiated layers: a thin superficial layer that extends to ∼2 m in depth with less dissolved solid content and, therefore, lower density, which contrasts with a thicker lower layer that extends to 34 m in depth. The upper layer is strongly influenced by climatic factors, triggering dilution (rainfall), concentration (dry season) and intense seasonal thermal fluctuations, while the lower layer is more compositionally and thermally stable.

Schwertmannite precipitate was initially observed only in the upper layer, adhered to a plastic buoy and the anchor line. The latter was confirmed through a test involving a precipitation device that consisted of maintaining a series of plastic plates at different depths over a period of several months. Only the plates located in the upper layer became covered with precipitate, whereas the plates that were submerged in the lower layer remained clean. These observations clearly differed from the saturation indices of schwertmannite (SIsch) calculated using PHREEQC and using Bigham et al. (1996) or Kawano and Tomita (2001) solubility products. Schwertmannite would not precipitate in the lake with the former but would precipitate in both layers with the latter. It is the constant provided by Yu et al. (1999) that makes SIsch in both layers approach the observed behaviour: SIsch>0 displays oversaturation in the upper layer while SIsch<0 displays undersaturation in the lower layer. The value of the product of solubility that better adjusts to this situation is log Ksch = 9.5 10. Using the method by Yu et al. (1999) to establish the apparent solubility, a range of log Ksch values was defined between 10.5 and 11.5 for the system studied.

Keywords

schwertmannitesolubility product constantacid PIT lakeIberian Pyrite Belt
Type
Research Article
Information
Mineralogical Magazine , Volume 79 , Issue 2 , April 2015 , pp. 497 - 513
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2015

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Acero, P., Ayora, C., Torrentó, C. and Nieto, J.M. (2006) The behavior of trace elements during schwertmannite precipitation and subsequent transformation into goethite and jarosite. Geochimica et Cosmochimica Acta, 70, 4130–4139.CrossRefGoogle Scholar
Allison, J.D., Brown, D.S. and Novo-Gradac, K.L. (1990) MINTEQA2/ PRODEFA2, A Geochemical Assessment Model for Environmental Systems, Version 3.0 User’s Manual. Environmental Research Laboratory, Office of Research and Development, U.S. EPA, Athens, Georgia, USA. Ayora, C., Acero, P., Torrentó, C. and Nieto, J.M. (2006) The stability of schwertmannite and its influence on the chemistry of acid rock drainage in the Iberian Pyrite Belt. MACLA, 6, 75–76.Google Scholar
Ball, J.W. and Nordstrom, D.K. (1991) User’s manual for WATEQ4F with revised thermodynamic database and test cases for calculating speciation of major, trace and redox elements in natural waters. U.S. Geological Survey Water-Resources Investigations Report, 91–183. US Geological Survey, Reston, Virginia, USA.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 (Alpers, C.N., Jambor, J.L. and Nordstrom, D.K., editors). Reviews in Mineralogy & Geochemistry, 40. Mineralogical Society of America and the Geochemical Society, Chantilly, Virginia, USA.CrossRefGoogle Scholar
Bigham, J.M., Schwertmann, U., Carlson, L. and Murad, E. (1990) A poorly crystallized oxyhydoxysulfate of iron formed by bacterial oxidation of Fe(II) in acid mine waters. Geochimica et Cosmochimica Acta, 54, 2743–2758.CrossRefGoogle Scholar
Bigham, J.M., Carlson, L. and Murad, E. (1994) Schwermannite, a new iron oxyhydroxy-sulphate from Pyhäsalmi, Finland and other localities. Mineralogical Magazine, 58, 641–648.CrossRefGoogle Scholar
Bigham, J.M., Schwertmann, U., Traina, S.J., Winland, R.L. and Wolf, M. (1996) Schwertmannite and the chemical modeling of iron in acid sulfate waters. Geochimica et Cosmochimica Acta, 60, 2111–2121.CrossRefGoogle Scholar
Burton, E.D., Bush, R.T., Sullivan, L.A. and Mitchell, D.R.G. (2007) Reductive transformation of iron and sulfur in schwertmannite-rich accumulations associated with acidified coastal lowlands. Geochimica et Cosmochimica Acta, 71, 4456–4473.CrossRefGoogle Scholar
Caraballo, M.A., Rötting, T.S., Nieto, J.M. and Ayora, C. (2009) Sequential extraction and DXRD applicability to poorly crystalline Fe-and Al-phase characterization from an acid mine water passive remediation system. American Mineralogist, 94, 1029–1038.CrossRefGoogle Scholar
Caraballo, M.A., Santofimia, E. and Jarvis, A. (2010) Metal retention, mineralogy and design considerations of a mature Permeable Reactive Barrier (PRB) for acidic mine water drainage in Northumberland, UK. American Mineralogist, 95, 1642–1649.CrossRefGoogle Scholar
Caraballo, M.A., Rimstidt, J.D., Macías, F., Nieto, J.M. and Hochella, M.F., Jr. (2013) Metastability nanocrystallinity and pseudo-solid solution effects on the understanding of schwertmannite solubility. Chemical Geology, 360-361. 22–31.CrossRefGoogle Scholar
Dold, B. (2003) Dissolution kinetics of schwertmannite and ferrihydrite in oxidized mine samples and their detection by differential X-ray diffraction (DXRD). Applied Geochemistry, 18, 1531–1540.CrossRefGoogle Scholar
French, R.A., Caraballo, M.A., Kim, B., Rimstidt, J.D., Murayama, M. and Hochella, M.F., Jr. (2012) The enigmatic iron oxyhydroxysulfate nanomineral schwertmannite: Morphology, structure, and composition. American Mineralogist, 97, 1469–1482.CrossRefGoogle Scholar
Friese, K., Herzsprung, P. and Witter, B. (2002) Photochemical degradation of organic carbon in acidic mining lakes. Acta Hydrochimica et Hydrobiologica, 30(2-3), 141–148.3.0.CO;2-F>CrossRefGoogle Scholar
Fukushi, K., Sato, T., Yanase, N., Minato, J. and Yamada, H. (2004) Arsenate sorption on schwertmannite. American Mineralogist, 89, 1728–1734.CrossRefGoogle Scholar
Herzsprung, P., Packroff, G., Schimmele, M., Wendt-Potthoff, K., Winkler, M. and Friese, K. (1998) Vertical and annual distribution of ferric and ferrous iron in acidic mining lakes. Acta Hydrochimica et Hydrobiologica, 26, 253–262.3.0.CO;2-S>CrossRefGoogle Scholar
Jönsson, J., Persson, P., Sjöberg, S. and Lövgren, L. (2005) Schwertmannite precipitated from acid mine drainage: Phase transformation, sulfate release, and surface properties. Applied Geochemistry, 20, 179–191.CrossRefGoogle Scholar
Kawano, M. and Tomita, K. (2001) Geochemical modeling of bacterially induced mineralization of schwertmannite and jarosite in sulfuric acid spring water. American Mineralogist, 86, 1156–1165.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
Knorr, K.H. and Blodau, C. (2007) Controls on schwertmannite transformation rates and products. Applied Geochemistry, 22, 2006–2015.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
López-Pamo, E., Sánchez España, J., Diez Ercilla, M., Santofimia Pastor, E. and Reyes Andrés, J. (2009) Cortas mineras inundadas de la Faja Pirítica: inventario e hidroquímica. Instituto Geológico y Minero de España, Serie: Medio Ambiente, 13. IGME, Madrid, pp. 279.Google Scholar
Majzlan, J., Navrotsky, A. and Schwertmann, U. (2004) Thermodynamics or iron oxides: Part III. Enthalpies of formation and stability of ferrihydrite (Fe(OH)3), schwertmannite (FeO(OH)3/4(SO4)1/8), and e-Fe2O3. Geochimica et Cosmochimica Acta, 68, 1049–1059.CrossRefGoogle Scholar
Parkhurst, D.L. and Appelo, C.A.J. (1999). User’s guide to PHREEQC (Version 2)-A computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. U.S. Geological Survey Water-Resources Investigations Report, 99–4259. US Geological Survey, Reston, Virginia, USA.Google Scholar
Pellicori, D.A., Gammons, C.H. and Poulson, S.R. (2005) Geochemistry and stable isotope composition of the Berkeley pit lake and surrounding mine waters, Butte, Montana. Applied Geochemistry, 20, 2116–2137.CrossRefGoogle Scholar
Pitzer, K.S. (1979). Theory: Ion interaction approach. Pp. 157–208. in: Activity Coefficients in Electrolyte Solutions, v. 1 (R.M. Pytkowicz, editor). CRC Press, Inc., Boca Raton, Florida, USA.Google Scholar
Pitzer, K.S. (1986). Theoretical considerations of solubility with emphasis on mixed aqueous electrolytes. Pure and Applied Chemistry, 58(12), 1599–1610.CrossRefGoogle Scholar
Pueyo, M., Mateu, J., Rigol, A., Vidal, M., López-Sánchez, J.F. and Rauret, G. (2008) Use of the modified BCR three-step sequential extraction procedure for the study of trace element dynamics in contaminated soils. Environmental Pollution, 152, 330–341.CrossRefGoogle Scholar
Ramstedt, M., Carlsson, E. and Lovgren, L. (2003) Aqueous geochemistry in the Udden pit lake, northern Sweden. Applied Geochemistry, 18, 97–108.CrossRefGoogle Scholar
Regenspurg, S. (2002) Characterisation of schwertmannite-geochemical interactions with arsenate and chromate and significance in sediments of lignite opencast lakes. PhD thesis. University of Bayreuth, Germany.Google Scholar
Regenspurg, S. and Peiffer, S. (2005) Arsenate and chromate incorporation in schwertmannite. Applied Geochemistry, 20, 1226–1239.CrossRefGoogle Scholar
Regenspurg, S., Brand, A. and Peiffer, S. (2004) Formation and stability of schwertmannite in acidic mining lakes. Geochimica et Cosmochimica Acta, 68(6), 1185–1197.CrossRefGoogle Scholar
Sánchez España, J., López Pamo, E., Santofimia, E., Adurive, O., Reyes Andrés, J. and Baretino, D. (2005) Acid mine drainage in the Iberian Pyrite Belt (Odiel river watershed, Huelva, SW Spain): Geochemistry, mineralogy and environmental implications. Applied Geochemistry, 20, 1320–1356.CrossRefGoogle Scholar
Sánchez España, J., López-Pamo, E., Santofimia, E., Reyes, J. and Martín Rubí, J.A. (2006) The removal of dissolved metals by hydroxysulphate precipitates during oxidation and neutralization of acid mine waters, Iberian Pyrite Belt. Aquatic Geochemistry, 12, 269–298.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
Santofimia, E. (2010) Evolución hidroquímica del lago minero de Aznalcóllar, Sevilla. PhD thesis. Facultad de CC. Geológicas, Universidad Complutense de Madrid, Spain.Google Scholar
Santofimia, E., López-Pamo, E. and Reyes, J. (2012) Changes in stratification and iron redox cycle of an acidic pit lake in relation with climatic factors and physical processes. Journal of Geochemical Exploration, 116–117. 40–50.CrossRefGoogle Scholar
Santofimia, E., González-Toril, E., López-Pamo, E., Gomariz, M., Amils, R. and Aguilera, A. (2013) Microbial diversity and its relationship to physicochemical characteristics of the water in two extreme acidic pit lakes from the Iberian pyrite belt (SW Spain). PlosOne, 8(6), e66746. Schwertmann, U. and Carlson, L. (2005) The pHdependent transformation of schwertmannite to goethite at 25ºC. Clay Minerals, 40, 63–66.Google Scholar
Sheals, J., Granström, M., Sjöberg, S. and Persson, P. (2003) Coadsorption of Cu(II) and glyphosate at the water-goethite (a-FeOOH) interface: molecular structures from FTIR and EXAFS measurements. Journal of Colloid and Interface Science, 262, 38–47.CrossRefGoogle Scholar
Wang, H., Bigham, J.M. and Tuovinen, O.H. (2006) Formation of schwertmannite and its transformation to jarosite in the presence of acidophilic ironoxidizing microorganisms. Materials Science and Engineering, C26, 588–592.CrossRefGoogle Scholar
Webster, J.G., Swedlund, P.J. and Webster, K.S. (1998) Trace metal adsorption onto an acid mine drainage iron(III) oxy hydroxy sulfate. Environmental Science & Technology, 32(10), 1361–1368.CrossRefGoogle Scholar
Yu, J.Y., Heo, B., Choi, I.K., Cho, J.P. and Chang, H.W. (1999) Apparent solubilities of schwertmannite and ferrihydrite in natural stream water polluted by mine drainage. Geochimica et Cosmochimica, 63, 3407–3416.CrossRefGoogle Scholar