Environmental Geochemistry and Health

, Volume 40, Issue 6, pp 2421–2439 | Cite as

Geochemical fractionation of metals and metalloids in tailings and appraisal of environmental pollution in the abandoned Musina Copper Mine, South Africa

  • M. W. Gitari
  • S. A. Akinyemi
  • L. Ramugondo
  • M. Matidza
  • S. E. Mhlongo
Original Paper


The economic benefits of mining industry have often overshadowed the serious challenges posed to the environments through huge volume of tailings generated and disposed in tailings dumps. Some of these challenges include the surface and groundwater contamination, dust, and inability to utilize the land for developmental purposes. The abandoned copper mine tailings in Musina (Limpopo province, South Africa) was investigated for particle size distribution, mineralogy, physicochemical properties using arrays of granulometric, X-ray diffraction, and X-ray fluorescence analyses. A modified Community Bureau of Reference (BCR) sequential chemical extraction method followed by inductively coupled plasma mass spectrometry/atomic emission spectrometry (ICP-MS/AES) technique was employed to assess bioavailability of metals. Principal component analysis was performed on the sequential extraction data to reveal different loadings and mobilities of metals in samples collected at various depths. The pH ranged between 7.5 and 8.5 (average ≈ 8.0) indicating alkaline medium. Samples composed mostly of poorly grated sands (i.e. 50% fine sand) with an average permeability of about 387.6 m/s. Samples have SiO2/Al2O3 and Na2O/(Al2O3 + SiO2) ratios and low plastic index (i.e. PI ≈ 2.79) suggesting non-plastic and very low dry strength. Major minerals were comprised of quartz, epidote, and chlorite while the order of relative abundance of minerals in minor quantities is plagioclase > muscovite > hornblende > calcite > haematite. The largest percentage of elements such as As, Cd and Cr was strongly bound to less extractable fractions. Results showed high concentration and easily extractable Cu in the Musina Copper Mine tailings, which indicates bioavailability and poses environmental risk and potential health risk of human exposure. Principal component analysis revealed Fe-oxide/hydroxides, carbonate and clay components, and copper ore process are controlling the elements distribution.


Geochemical fractions Heavy metals Mineralogy Principal component analysis 



The authors would want to acknowledge the support from ESKOM Foundation, NRF, and THRIP for funding this study through student bursaries and consumables.


  1. Ahmari, S., Zhang, L., & Zhang, J. (2012). Effect of activator type/concentration and curing temperature on alkali-activated binder based on copper mine tailings. Journal of Materials Science, 47, 5933–5945.CrossRefGoogle Scholar
  2. Akinyemi, S. A., Akinlua, A., Gitari, W. M., Nyale, S. M., Akinyeye, R. O., & Petrik, L. F. (2012). An investigative study on the chemical, morphological and mineralogical alterations of dry disposed fly ash during sequential chemical extraction. Energy Science and Technology, 3(1), 28–37.Google Scholar
  3. American Society for Testing and Materials (ASTM D 2216). (1998). Standard test methods for laboratory determination of water (moisture) content of soil and rock by mass.Google Scholar
  4. American Society for Testing and Materials (ASTM D 2434-68). (2006). Standard test method for permeability of granular soils (constant head).Google Scholar
  5. Beale, C. O. (1985). Copper in South Africa-Part 11. Journal of the South African Institute of Mining and Metallurgy, 85(4), 109–124.Google Scholar
  6. Bennet, J. M., Sudhakar, M., & Natarajan, C. (2013). Development of coal ash—GGBS based geopolymer bricks. European International Journal of Science and Technology, 2(5), 133–139.Google Scholar
  7. Bock, B., McLennan, S. M., & Hanson, G. N. (1998). Geochemistry and provenance of the Middle Ordovician Austin Glen Member (Normanskill Formation) and the Taconian Orogeny in New England. Journal of Sedimentology, 45, 635–655.CrossRefGoogle Scholar
  8. Borgese, L., Federici, S., Zacco, A., Gianoncelli, A., Rizzo, L., Smith, D. R., et al. (2013). Metal fractionation in soils and assessment of environmental contamination in the Vallecamonica, Italy. Environmental Science and Pollution Research International, 20(7), 5067–5075.CrossRefGoogle Scholar
  9. Brandl, G. (1981). The geology of the Messina area. Tech. Rep. Explanation sheet 2230, Geological Survey of South Africa, Messina, Italy.Google Scholar
  10. Cao, X., Wang, X., & Zhao, G. (2000). Assessment of the bio-availability of rare earth elements in soils by chemical fractionation and multiple regression analysis. Chemo-sphere, 40, 23–28.CrossRefGoogle Scholar
  11. Ekosse, G., Van Den Heever, D. J., De Jager, L., & Totolo, O. (2004). Minerology of Tailings dump around Selebi Phikwe nickel-copper plant, Botswana. Journal of Applied Science in Environmental Management, 8(1), 37–44.Google Scholar
  12. Fadiran, A. O., Tiruneh, A. T., & Mtshali, J. S. (2014). Assessment of mobility and bioavailability of heavy metals in sewage sludge from Swaziland through speciation analysis. American Journal of Environmental Protection, 3, 198–208.CrossRefGoogle Scholar
  13. Fedo, C. M., Nesbitt, H. W., & Young, G. M. (1995). Unraveling the effects of potassium metasomatism in sedimentary rock sand paleosols, with implications for paleoweathering conditions and provenance. Geology, 23, 921–924.CrossRefGoogle Scholar
  14. Folk, R. L., & Ward, W. O. (1957). Brazos River bar: A study in the significance of grain size parameters. Journal of Sedimentary Petrology, 27, 3–26.CrossRefGoogle Scholar
  15. Rao, F., & Liu, Q. I. (2015). Geopolymerization and its potential application in mine tailings consolidation: A review. Mineral Processing and Extractive Metallurgy Review, 36, 399–409. Scholar
  16. Geotechnical Test Method-7. (2015). Test method for liquid limit, plastic limit, and plasticity index. State of New York Department of Transportation Geotechnical Engineering Bureau.Google Scholar
  17. Harnois, L. (1988). The CIW index: A new chemical index of weathering. Sedimentary Geology, 55, 319–322.CrossRefGoogle Scholar
  18. Hudson-Edwards, K. A., & Dold, B. (2015). Mine waste characterization, management and remediation. Minerals, 5, 82–85.CrossRefGoogle Scholar
  19. Hudson-Edwards, K. A., Jamieson, H. E., & Lottermoser, B. G. (2011). Mine wastes, Past, Present, Future. Elements, 7, 375–380.CrossRefGoogle Scholar
  20. International Association of Risk Compliance (IARC). (2004). Some drinking-water disinfectants and contaminants, including arsenic. IARC Monographs on the Evaluation of Carcinogenic Risks to Humans, 84, 1–477.Google Scholar
  21. Jakubick, A., & McKenna, G. (2003). Stabilisation of tailings deposits: international experience. Mining and the Environment III, Sudbury, Ontario, Canada, 25–28 May, 2003, pp 1–9.Google Scholar
  22. Keller, C., & Hammer, D. (2004). Metal availability and soil toxicity after repeated croppings of Thlaspi caerulescens in metal contaminated soils. Environmental Pollution, 131, 243–254.CrossRefGoogle Scholar
  23. Kersten, M., & Forstner, U. (1989). Speciation of trace elements in sediments. In G. E. Batley (Ed.), Trace element speciation: Analytical methods and problems (pp. 245–318). Boca Raton: CRC Press.Google Scholar
  24. Lottermoser, B. G. (2010). Mine wastes: Characterization, treatment, and environmental impacts (3rd ed., p. 400). Berlin Heidelberg: Springer.CrossRefGoogle Scholar
  25. Madrid, F., Reinoso, R., Florido, M. C., Díaz Barrientos, A., Ajmone-Marsan, F., Davidson, C. M., et al. (2007). Estimating the extractability of potentially toxic metals in urban soils: A comparison of several extracting solutions. Environmental Pollution, 147, 713–722.CrossRefGoogle Scholar
  26. Mahmood, A. A., & Mulligan, C. N. (2007). Investigation of the use of mine tailings for unpaved road base construction. In Proceedings of the annual international conference on soils, sediments, water and energy, 12, Article 11.Google Scholar
  27. Nehdi, M., & Tariq, A. (2007). Stabilization of sulphidic mine tailings for prevention of metal release and acid drainage using cementations materials: A review. Journal of Environmental Engineering and Science, 6(4), 423–436.CrossRefGoogle Scholar
  28. Nesbitt, H. W., & Young, G. M. (1982). Early Proterozoic climates and plate motions inferred from major element chemistry of lutites. Nature, 299, 715–717.CrossRefGoogle Scholar
  29. Ogola, J. S., & Sebola, A. M. (2010). Investigation of heavy metals dispersion around the Messina copper mine tailings dam, South Africa. In Proceedings of the IASTED international conference, Vol. 888, pp. 15–17Google Scholar
  30. Pacheco-Torgal, F., Castro-Gomes, J., & Jalali, S. (2007). Investigation about the effect of aggregates on strength and microstructure of geopolymeric mine waste mud binders. Cement and Concrete Research, 37, 933–941.CrossRefGoogle Scholar
  31. Pacheco-Torgal, F., Castro-Gomes, J., & Jalali, S. (2008). Properties of tungsten mine waste geopolymeric binder. Construction and Building Materials, 22, 1201–1211.CrossRefGoogle Scholar
  32. Quispe, D., Pérez-López, R., Silva, L. F. O., & Nieto, J. M. (2012). Changes in mobility of hazardous elements during coal combustion in Santa Catarina power plant (Brazil). Fuel, 94, 495–503. Scholar
  33. Rahman, M., Vahter, M., Sohel, N., Yunus, M., Wahed, M. A., Streatfield, P. K., et al. (2006a). Arsenic exposure and age and sex specific risk for skin lesions: A population-based case-referent study in Bangladesh. Environmental Health Perspectives, 114, 1847–1852.CrossRefGoogle Scholar
  34. Rahman, M., Vahter, M., Wahed, M. A., Sohel, N., Yunus, M., Streatfield, P. K., et al. (2006b). Prevalence of arsenic exposure and skin lesions. A population based survey in Matlab, Bangladesh. Journal of Epidemiology and Community Health, 60(3), 242–248.CrossRefGoogle Scholar
  35. Rao, R. M., Sahuquillo, A., & Lopez Sanchez, J. F. (2008). A review of the different methods applied in environmental geochemistry for single and sequential extraction of trace elements in soils and related materials. Water, Air, and Soil Pollution, 189, 291–333.CrossRefGoogle Scholar
  36. Rath, P., Panda, U. C., Bhatta, D., & Sahu, K. C. (2008). Use of sequential leaching, mineralogy, morphology and multivariate statistical technique for quantifying metal pollution in highly polluted aquatic sediments—A case study: Brahmani and Nandira Rivers, India. Journal of Hazardous Materials, 163(2–3), 632–644. Scholar
  37. Rauret, G., López-Sánchez, J. F., Bacon, J., Gómez, A., Muntau, H., & Quevauviller, P. (2001). Report EUR 19774 EN. European Commission; Brussels: Certification of the Contents (Mass Fractions) of Cd, Cr, Cu, Ni, Pb and Zn in an Organic-Rich Soil Following Harmonised EDTA and Acetic Acid Extraction Procedures, BCR-700, p. 61Google Scholar
  38. Saeed, A., & Zhang, L. (2012). Production of ecofriendly bricks from Cu mine tailings through geopolymerization. Construction and Building Materials, 29, 323–331.CrossRefGoogle Scholar
  39. Salomons, W. (1995). Environmental impact of metals derived from mining activities: Processes, predictions, prevention. Journal of Geochemical Exploration, 52, 5–23.CrossRefGoogle Scholar
  40. Singo, N. K. (2013). An assessment of heavy metal pollution near an old copper mine dump in Musina, South Africa. M.Sc. Thesis. The University of South Africa.Google Scholar
  41. Tokalioglu, S., Kartal, S., & Irol, G. B. (2003). Application of a three-stage sequential extraction procedure for the determination of extractable metal contents in highway soils. Turkish Journal of Chemistry, 27, 333–346.Google Scholar
  42. van Jaarsveld, J. G. S., van Deventer, J. S. J., & Schwartzman, A. (1999). The potential use of geopolymeric materials to immobilize toxic metals: part II. Material and leaching characteristics. Minerals Engineering, 12, 75–91.CrossRefGoogle Scholar
  43. Voicu, Gn, & Bardoux, M. (2002). Geochemical behaviour under tropical weathering of the Barama–Mazaruni greenstone belt at Omai gold mine, Guiana Shield. Applied Geochemistry, 17, 321–336.CrossRefGoogle Scholar
  44. Voicu, G., Bardoux, M., Harnois, L., & Grepeau, R. (1997). Lithological and geochemical environment of igneous and sedimentary rocks at Omai gold mine, Guyana, South America. Exploration and Mining Geology, 6, 153–170.Google Scholar
  45. Wilson, M. G. C. (1998). Copper. In M. G. C. Wilson & C. R. Anhaeusser (Eds.), The mineral resources of South Africa (pp. 209–227). Pretoria: Council of Geosciences.Google Scholar
  46. World Health Organisation (WHO)/International Programme Chemical Safety (IPCS). (2001). Environmental health criteria 224, arsenic and arsenic compounds (2nd ed.). Geneva: World Health Organization.Google Scholar
  47. Yang, J. S., Lee, J. Y., Baek, K., Kwon, T. S., & Choi, J. (2009). Extraction behavior of As, Pb, and Zn from mine tailings with acid and base solutions. Journal of Hazardous Materials, 171(1–3), 443–451.CrossRefGoogle Scholar
  48. Yunus, M., Sohel, N., Hore, S. K., & Rahman, M. (2011). Arsenic exposure and adverse health effects: A review of recent findings from arsenic and health studies in Matlab, Bangladesh. The Kaohsiung Journal of Medical Sciences, 27(9), 371–376.CrossRefGoogle Scholar
  49. Zhang, L. (2013). Production of bricks from waste materials—A review. Construction and Building Materials, 47, 643–655.CrossRefGoogle Scholar
  50. Zhang, L., Ahmari, S., & Zhang, J. (2011). Synthesis and characterization of fly ash modified mine-based geopolymers. Construction and Building Materials, 25, 3773–3781.CrossRefGoogle Scholar
  51. Zou, D. H., & Li, L. P. (1999). Strengthening of solidified dilute tailing slurry. Journal of Geotechnical and Geoenvironmental Engineering, 125, 11–15.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V., part of Springer Nature 2018

Authors and Affiliations

  • M. W. Gitari
    • 1
  • S. A. Akinyemi
    • 1
  • L. Ramugondo
    • 1
  • M. Matidza
    • 1
  • S. E. Mhlongo
    • 2
  1. 1.Environmental Remediation and Water Pollution Chemistry Group, Department of Ecology and Resource ManagementUniversity of VendaThohoyandouSouth Africa
  2. 2.Mining and Environmental Geology, School of Environmental SciencesUniversity of VendaThohoyandouSouth Africa

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