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Mineralogy and Weathering of Smelter-Derived Spherical Particles in Soils: Implications for the Mobility of Ni and Cu in the Surficial Environment

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Abstract

Spherical particles have been sampled from soils and silica-rich rock coatings close to major smelter centers at Coppercliff, Coniston, and Falconbridge in the Sudbury area, Canada. Detailed analyses employing optical microscopy, scanning electron microscopy, transmission electron microscopy, micro-Raman spectroscopy, and Mössbauer spectroscopy have been conducted to elucidate their nature, origin and potential alteration. The spherical particles are on the nano- to millimeter-size range and are composed principally of magnetite, hematite, Fe-silicates (olivine, pyroxenes), heazlewoodite, bornite, pyrrhotite, spinels (including trevorite and cuprospinel), delafossite, and cuprite or tenorite. The spinels present have variable Cu and Ni contents, whereas delafossite and cuprite are Ni free. Texturally, the spherical particles are composed of a Fe-oxide–Fe-silicate matrix with sulfide inclusions. The matrix displays growth features of a Fe-rich phase that commonly form during rapid cooling and transformation processes within smelter and converter facilities. Examination of weathered spherical particles indicates that some sulfide inclusions have dissolved prior to the alteration of the Fe-silicates and oxides and that the weathering of Fe-silicates occurs simultaneously with the transformation of magnetite into hematite. A higher proportion of Cu vs. Ni in the clay and organic fraction noted in the Sudbury soils is explained by (1) the formation of stronger adsorption complexes between Cu and the corresponding surface species and (2) the preferential release of Cu vs. Ni by smelter-derived particles. The latter mechanism is based on the observations that (a) cuprospinels have higher dissolution rates than Ni spinels, (b) a larger proportion of Cu occurs in the nanometer-size (and thus more soluble) fraction of the emitted particles, and (c) Ni spinels of relatively low solubility form in the alteration zone of heazlewoodite inclusions.

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Acknowledgments

This work was supported by NSERC Discovery grants to MS, AMcD, and FCH; NSERC summer student scholarships to SL and KS; and an Ontario Graduate Scholarship to NM. MH acknowledges NSF and EPA under NSF Cooperative Agreement EF-0830093. Any opinions, findings, conclusions, or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the NSF or the EPA. This work has not been subjected to EPA review and no official endorsement should be inferred. We would like to thank the technical staff members at the Central Analytical Facility, Laurentian University and at the Nanoscale Characterization and Fabrication Laboratory, ICTAS, Virginia Tech, for their assistance.

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  1. Department of Earth Sciences, Laurentian University, Sudbury, ON, P3E 2C6, Canada

    Sonia Lanteigne, Michael Schindler, Andrew M. McDonald & Nathalie M. Mantha

  2. Department of Geological Sciences and Geological Engineering, Queen’s University, Kingston, ON, Canada

    Kristina Skeries

  3. Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba, Canada

    Yassir Abdu & Frank C. Hawthorne

  4. Department of Materials Science and Engineering, Virginia Tech, Blacksburg, VA, 24061, USA

    Mitsuhiro Murayama

  5. Center for NanoBioEarth, Department of Geosciences, Virginia Tech, Blacksburg, VA, 24061-0420, USA

    Michael F. Hochella Jr.

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Lanteigne, S., Schindler, M., McDonald, A.M. et al. Mineralogy and Weathering of Smelter-Derived Spherical Particles in Soils: Implications for the Mobility of Ni and Cu in the Surficial Environment. Water Air Soil Pollut 223, 3619–3641 (2012). https://doi.org/10.1007/s11270-012-1135-3

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