Dissolution mechanisms of chromitite: Understanding the release and fate of chromium in the environment

Michael Schindler 1 , Aaron J. Lussier 1 , 3 , Emilia Principe 1 , 2  and Nadia Mykytczuk 2
  • 1 Department of Earth Sciences, Ontario P3E 2C6, Sudbury, Canada
  • 2 School of the Environment, Ontario P3E 2C6, Sudbury, Canada
  • 3 Canadian Museum of Nature, P.O. Box 3443, Station D, Ottawa, Canada
Michael Schindler
  • Corresponding author
  • Department of Earth Sciences, Laurentian University, Sudbury, Ontario P3E 2C6, Canada
  • Email
  • Search for other articles:
  • degruyter.comGoogle Scholar
, Aaron J. Lussier
  • Department of Earth Sciences, Laurentian University, Sudbury, Ontario P3E 2C6, Canada
  • Canadian Museum of Nature, P.O. Box 3443, Station D, Ottawa, Ontario K1P 6P4, Canada
  • Search for other articles:
  • degruyter.comGoogle Scholar
, Emilia Principe
  • Department of Earth Sciences, Laurentian University, Sudbury, Ontario P3E 2C6, Canada
  • School of the Environment, Laurentian University, Sudbury, Ontario P3E 2C6, Canada
  • Search for other articles:
  • degruyter.comGoogle Scholar
and Nadia Mykytczuk
  • School of the Environment, Laurentian University, Sudbury, Ontario P3E 2C6, Canada
  • Search for other articles:
  • degruyter.comGoogle Scholar


An understanding of the formation of toxic hexavalent chromium (Cr6+) in Cr-containing mine tailings and associated soils and sediments, requires an understanding of the underlying dissolution mechanisms of chromitite, a common chromite-bearing rock in both ophiolites suites and ultramafic intrusions. This study will examine dissolution mechanisms of chromitite in various acidic, neutral, and alkaline solutions containing cultivated bacteria, manganese oxides, sulfates, and phosphates. Dissolution of chromitite is non-stoichiometric under acidic, near-neutral, and alkaline pH conditions and involves the release of chromite nanoparticles and complex dissolution/re-precipitation reactions. Chromitite samples are obtained from the Black Thor chromite deposit in Northern Ontario, Canada; part of the “Ring of Fire” intrusive complex. The examined chromitite is composed of chromite, (Fe0.5Mg0.5) (Al0.6Cr1.4)O4 and clinochlore; Mg3[Si4O10(OH)2]·[MgAl1.33(OH)6], the latter phase contains ~3 wt% Cr in the form of chromite nanoparticles. Bulk dissolution data are collected after dissolution experiments with chromitite powders, and the chemical and mineralogical composition of treated chromitite surfaces is characterized with a combination of surface analytical techniques (X-ray photoelectron spectroscopy) and nano- to micro-analytical techniques (scanning electron microscopy, transmission electron microscopy, and focused ion beam technology). In the chromitite systems studied here, the non-stoichiometric dissolution of clinochlore is the dominant reaction, which results in the formation of a hydrous and porous silica precipitate that is depleted in chromite nanoparticles relative to untreated clinochlore. Complete replacement of clinochlore by hydrous silica on the surface of chromitite under acidic conditions promotes the release of chromite nanoparticles and results in higher Cr:Si in solutions and in higher proportions of secondary Cr species on its surface (secondary Cr species are defined as surface terminations that do not occur on an untreated chromite surface, such as -Cr3+-OH2 and -Cr6+-OH). Cultivated bacteria from a sulfide-bearing acid-mine drainage system affect neither the degree of dissolution nor the formation of secondary Cr species, whereas pyrolusite (MnO2) particles, and adsorbed or precipitated Fe- and Al-bearing hydroxide, -sulfate, and -phosphate species, affect release and re-adsorption of chromite nanoparticles and Cr-bearing species during dissolution of chromitite under acidic, neutral, and alkaline conditions. These results show that weathering of chromitite and the release of Cr into the environment are strongly controlled by factors such as dissolution rates of Cr-bearing silicates and chromite, the release of chromite nanoparticles, re-precipitation of amorphous silica, the presence of particles in solution, and the pH-dependence adsorption (or precipitation) of Fe- and Al-bearing hydroxides and sulfates.

  • Alvarez-Silva, M., Uribe-Salas, A., Mirnezami, M., and Finch, J.A. (2010) The point of zero charge of phyllosilicate minerals using the Mular–Roberts titration technique. Minerals Engineering, 23, 383–389.

  • Bartlett, R.J., and James, B.R. (1979) Behavior of chromium in soils: III. Oxidation. Journal of Environmental Quality, 8, 31–35.

  • Biesinger, M.C., Brown, C., Mycroft, J.R., Davidson, R.D., and McIntyre, N.S. (2004) X-ray photoelectron spectroscopy studies of chromium compounds Surface and Interface Analysis, 36, 1550–1563.

  • Biesinger, M.C., Paynec, B.B., Grosvenord, A.P., Laua, L.W.W., Gerson, A.R., and Smart, R.S.C. (2011) Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni. Applied Surface Science, 257, 2717–2730.

  • Brandt, F., Bosbach, D., Krawczyk-Barsch, E., Arnold, T., and Bernhard, G. (2003) Chlorite dissolution in the acid pH-range: A combined microscopic and macroscopic approach. Geochimica et Cosmochimica Acta, 67, 1451–1461.

  • Brantley, S.L. (2003) 5.03-Reaction kinetics of primary rock-forming minerals under ambient conditions. Treatise on Geochemistry, 5, 73–117.

  • Cristiano, E., Hu, Y-J., Siegfried, M., Kaplan, D., and Nitsche, H. (2011) A comparison of point of zero charge measurement methodology. Clays and Clay Minerals, 59, 107–115.

  • Eary, L.E., and Rai, D. (1987) Kinetics of chromium(III) oxidation to chromium(VI) by reaction with manganese dioxide. Environmental Science and Technology, 21, 1187–1193.

  • Fandeur, D., Juillot, F., Morin, G., Olivi, L., Cognigni, A., Ambrosi, J.P., Guyot, F., and Fritisch, E. (2009) Synchrotron-based speciation of chromium in an Oxisol from New Caledonia: Importance of secondary Fe-oxyhydroxides. American Mineralogist, 94, 710–719.

  • Faure, G. (1998) Principles and Applications of Geochemistry, 2nd ed. Prentice Hall, New Jersey.

  • Fendorf, S.E. (1995) Surface reactions of chromium in soils and waters. Geoderma, 67, 55–71.

  • Gustafsson, J.P. (2012) Visual MINTEQ, ver. 3.0. KTH Department of Land and Water Resources Engineering, Stockholm, Sweden.

  • Hellmann, R., Penisson, J-M, Hervig, R.L., Thomassin, J.H., and Abrioux, M.F. (2003) An EFTEM/HRTEM high-resolution study of the near surface of labradorite feldspar altered at acid pH: Evidence for interfacial dissolution-reprecipitation. Physics and Chemistry of Minerals, 30, 192–197.

  • Hellmann, R., Wirth, R., Daval, D., Barnes, J-P., Penisson, J-M., Tisserand, D., Epicier, T., Florin, B., and Hervig, R.L. (2012) Unifying natural and laboratory chemical weathering with interfacial dissolution-reprecipitation: A study based on the nanometer-scale chemistry of fluid-silicate interfaces. Chemical Geology, 280, 1–2.

  • Hochella, M.F. (1988) Auger electron and X-ray photoelectron spectroscopies. Reviews in Mineralogy, 18, 573–638.

  • Hotze, E.M., Phenrat, T., and Lowry, G.V. (2010) Nanoparticle aggregation: Challenges to understanding transport and reactivity in the environment. Journal of Environmental Quality, 3, 9, 1909–1924.

  • Hseu, Z.Y., and Iizuka, Y. (2013) Pedogeochemical characteristics of chromite in a paddy soils derived from serpentinites. Geoderma, 202–203, 126–133.

  • Izbicki, J.A., Ball, J.W., Bullen, T.D., and Sutley, S. (2008) Chromium, chromium isotopes and selected traced elements, western Mojave Desert, U.S.A. Applied Geochemistry, 23, 1325–1352.

  • Kamaludeen, S.P.B., Megharaj, M., Juhasz, A.L., Sethunathan, N., and Naidu, R. (2003) Chromium–microorganism interactions in soils: Remediation implications. Reviews of Environmental Contamination and Toxicology, 178, 93–164.

  • Kien, C.N., Noi, N.V., Son, L.T. Ngoc, H., Tanaka, S., Nishina, T., and Iwasaki, K. (2010) Heavy metal contamination of agricultural soils around a chromite mine in Vietnam. Soil Science and Plant Nutrition, 56, 344–356.

  • Kittrick, J.A. (1982) Solubility of two high-Mg and two high-Fe chlorites using multiple equilibria. Clays and Clay Minerals, 30, 167–179.

  • Kosmulski, M. (2009a) pH-dependent surface charging and points of sero charge. IV. Update and new approach. Journal of Colloid and Interface Science, 337, 439–448.

  • Kosmulski, M. (2009b) Surface Charging and Points of Zero Charge. CRC press, Taylor and Francis.

  • Laarman, J.E. (2013) Detailed metallogenic study of the McFaulds lake chromite deposits, Northern Ontario. Ph.D. thesis, The University of Western Ontario, pp. 494,

  • Lapham, D.M. (1958) Structural and chemical variation in chromium chlorite. American Mineralogist, 43, 921–956.

  • Morrison, J.M., Goldhaber, M.B., Mills, C.T., Breit, G.N., Hooper, R.L., Holloway, J.M., Diehl, S.F., and Ranville, J.F. (2015) Weathering and transport of chromium and nickel from serpentinite in the Coast Range ophiolite to the Sacramento Valley, California, U.S.A. Applied Geochemistry, 61, 72–86.

  • NIST X-ray Photoelectron Spectroscopy Database (2012) NIST Standard Reference Database 20, Version 4.1, https://srdata.nist.gov/xps/.

  • Oze, C., Fendorf, S., Bird, D.K., and Coleman, R.G. (2004) Chromium geochemistry in serpentinized ultramafic rocks and serpentine soils from the Franciscan complex of California. American Journal of Sciences, 304, 67–101.

  • Oze, C., Bird, D.K., and Fendorf, S. (2007) Genesis of hexavalent chromium from natural sources in soil and groundwater. Proceedings of the National Academy of Sciences, 104, 6544–6549.

  • Parthasarathy, G., Choudary, B.M., Sreedhar, B., Kunwar, A.C., and Srinivasan, R. (2003) Ferrous saponite from the Deccan Trap, India, and its application in adsorption and reduction of hexavalent chromium. American Mineralogist, 88, 1983–1988.

  • Pillay, K., von Blottnitz, H., and Petersen, J. (2003) Ageing of chromium(III)-bearing slag and its relation to the atmospheric oxidation of solid chromium(III)-oxide in the presence of calcium oxide. Chemosphere, 52, 1771–1779.

  • Putnis, C.V., and Ruiz-Aguda, E. (2013) The mineral–water interface: Where minerals react with the environment. Elements, 9, 177–182.

  • Schindler, M., and Hochella, M.F. Jr. (2017) Sequestration of Pb- Zn- Sb- and As-bearing incidental nanoparticles by mineral surface coatings and mineralized organic matter in soils. Environmental Science: Processes and Impacts, 19, 1016–1027.

  • Schindler, M., Hawthorne, F.C., Freund, M.S., and Burns, P.C. (2009a) XPS spectra of uranyl minerals and synthetic compounds I. The U 4f spectrum. Geochimica et Cosmochimica Acta, 73, 2471–2487.

  • Schindler, M. (2009b) XPS spectra of uranyl minerals and synthetic compounds II. The O1s spectrum. Geochimica et Cosmochimica Acta, 73, 2488–2509.

  • Schindler, M., Durocher, J., Abdu, Y., and Hawthorne, F.C. (2009c) Hydrous silica coatings: Occurrence, speciation of metals, and environmental significance. Environmental Science and Technology, 43, 8775–8780.

  • Schindler, M., Berti, D., and Hochella, M.F. Jr. (2017) Previously unknown mineral-nanomineral relationships with important environmental consequences: The case of chromium release from dissolving silicate minerals. American Mineralogist, 102, 2142–2145.

  • Stott, G.M., Corkery, M.T., Percival, J.A., Simard, M., and Goutier, J. (2010) A revised terrane subdivision of the Superior Province. Summary of Field Work and Other Activities 2010, Ontario Geological Survey, Open File Report 6260, p. 20-1–20-10.

  • Tiwary, R.K., Dhakate, R., Rao, V.A., and Singh, V.S. (2005) Assessment and prediction of contaminant migration in ground water from chromite waste dump. Environmental Geology, 48, 420–429.

  • Tuovinen, O.H., and Kelly, D.P. (1974) Studies on the growth of Thiobacillus ferrooxidans IV. Influence of monovalent metal cations on ferrous iron oxidation and uranium toxicity in growing cultures. Archives of Microbiology, 98, 167–174.

  • Wagner, C.D., Riggs, W.M., Davis, L.E., and Moulder, J.F. (1979) Handbook of X-ray Photoelectron Spectroscopy, 1st ed. Perkin Elemer, Waltham, Massachusetts.

  • Weaver, R.M., and Hochella, M.F. Jr. (2003) The reactivity of seven Mn-oxides with C r a q 3 + $\displaystyle \rm Cr_{aq}^{3+}$ : A comparative analysis of a complex, environmentally important redox reaction. American Mineralogist, 88, 2016–2027.

  • Weston, R., and Shinkle, D.A. (2013) Geology and stratigraphy of the Black Thor and Black Label chromite deposits, James Bay Lowlands, Ontario, Canada. 12th SGA Biennial Meeting Proceedings.

  • Wood, W.W., Clark, D., Imes, J.L., and Councell, T.B. (2010) Eolian transport of geogenic hexavalent chromium to ground water. Ground Water, 48, 19–29.

  • Zhang, B., Shi, P., and Jiang, M. (2016) Advances towards a clean hydrometallurgical process for chromite. Minerals, 6, 7; 12 p.

  • Zhao, Q., Liu, C.J., Shi, P.Y., Zhang, B., Jiang, M.F., Zhang, Q.S., and Zevenhoven, H.S.R. (2014) Sulfuric acid leaching of South African chromite. Part 1: Study on leaching behavior. International Journal of Mineral Processing, 130, 95–101.

Purchase article
Get instant unlimited access to the article.
Log in
Already have access? Please log in.

Journal + Issues