Performance of Physically and Chemically Activated Biochars in Copper Removal from Contaminated Mine Effluents

  • Flavia Lega BraghiroliEmail author
  • Hassine Bouafif
  • Carmen Mihaela Neculita
  • Ahmed Koubaa


The increasing global demand for metals and minerals justifies the intensive study of treatment options for contaminated mine effluents. The present study evaluated the conversion of wood residues into physically and chemically activated biochars and their subsequent use in the treatment of Cu in synthetic and actual contaminated mine drainage. First, wood residues were converted into biochar by fast pyrolysis. Then, physical (using steam or CO2) or chemical (using KOH) activation was carried out in a homemade pilot-scale furnace. After activation, highly microporous (KOH materials) and micro/mesoporous activated biochars (CO2 and steam materials) were obtained. Batch adsorption testing was first conducted with synthetic effluents. Results showed that CO2-activated biochar was the most Cu effective adsorbent (99% removal) at low concentrations (5–20 mg L−1). The mechanisms of Cu2+ adsorption involved physical and chemisorption for biochars and CO2-activated biochar, while chemisorption for KOH-activated biochars was probably due to the high proportion of functional groups connected to their surface. In multi-metal acid mine drainage, metal adsorption capacities deteriorated for most of the materials, probably due to the effects of ion competition. However, KOH-activated biochar decreased Cu2+ concentrations to below the authorized monthly mean allowed by Canadian law (0.3 mg L−1) and decreased Co, Pb, and Mn concentrations up to 95%. These findings indicate that high porosity and oxygenated functional groups connected to the surface of activated biochars are important properties for the enhancement of interactions between carbon materials and metals from mine effluents, as well as for their performance improvement in mine drainage treatment.


Activated biochar Adsorption Copper removal Water treatment Actual mine effluents 



This research was funded by the Québec’s Ministry of Economy, Science and Innovation (Ministère de l’Économie, de la Science et de l’Innovation du Québec), the Natural Sciences and Engineering Research Council of Canada (NSERC), the Canada Research Chairs Program, the College of Abitibi-Témiscamingue, and the Technology Centre for Industrial Waste (Centre Technologique des Résidus Industriels) through its partners on this project, Airex Energy and Iamgold Corporation. The first author, Dr. Flavia Lega Braghiroli, also sincerely acknowledges NSERC financial support via a Banting Postdoctoral Fellowship (2017–2019). The authors also thank Anne-Marie Marleau Claveau, Félicia Porqueres, Maéva Giasson, Gilles Villeneuve, Mamadou Dia, Nicolas Bergeron, and Hélie Jacob Turmel for their assistance with the experiments, analysis, and testing in the laboratory.

Supplementary material

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  1. Adebisi, G. A., Chowdhury, Z. Z., & Alaba, P. A. (2017a). Equilibrium, kinetic, and thermodynamic studies of lead ion and zinc ion adsorption from aqueous solution onto activated carbon prepared from palm oil mill effluent. Journal of Cleaner Production, 148, 958–968. Scholar
  2. Adebisi, G. A., Chowdhury, Z. Z., Hamid, S. B. A., & Ali, E. (2017b). Equilibrium isotherm, kinetic, and thermodynamic studies of divalent cation adsorption onto Calamus Gracilis sawdust-based activated carbon. BioResources, 12(2), 2872–2898.CrossRefGoogle Scholar
  3. Aharoni, C., & Tompkins, F. C. (1970). Kinetics of adsorption and desorption and the Elovich equation. Advances in Catalysis, 21, 1–49. Scholar
  4. Akar, S. T., Akar, T., Kaynak, Z., Anilan, B., Cabuk, A., Tabak, Ö., et al. (2009). Removal of copper(II) ions from synthetic solution and real wastewater by the combined action of dried Trametes versicolor cells and montmorillonite. Hydrometallurgy, 97(1–2), 98–104. Scholar
  5. Baccar, R., Bouzid, J., Feki, M., & Montiel, A. (2009). Preparation of activated carbon from Tunisian olive-waste cakes and its application for adsorption of heavy metal ions. Journal of Hazardous Materials, 162(2–3), 1522–1529. Scholar
  6. Banerjee, S., Mukherjee, S., LaminKa-ot, A., Joshi, S. R., Mandal, T., & Halder, G. (2016). Biosorptive uptake of Fe2+, Cu2+ and As5+ by activated biochar derived from Colocasia esculenta: isotherm, kinetics, thermodynamics, and cost estimation. Journal of Advanced Research, 7(5), 597–610. Scholar
  7. Bilal, M., Shah, J. A., Ashfaq, T., Gardazi, S. M. H., Tahir, A. A., Pervez, A., et al. (2013). Waste biomass adsorbents for copper removal from industrial wastewater—a review. Journal of Hazardous Materials, 263, 322–333. Scholar
  8. Bouchelta, C., Medjram, M. S., Zoubida, M., Chekkat, F. A., Ramdane, N., & Bellat, J.-P. (2012). Effects of pyrolysis conditions on the porous structure development of date pits activated carbon. Journal of Analytical and Applied Pyrolysis, 94, 215–222. Scholar
  9. Braghiroli, F. L., Bouafif, H., Hamza, N., Bouslimi, B., Neculita, C. M., & Koubaa, A. (2018a). The influence of pilot-scale pyro-gasification and activation conditions on porosity development in activated biochars. Biomass and Bioenergy, 118, 105–114. Scholar
  10. Braghiroli, F. L., Bouafif, H., Neculita, C. M., & Koubaa, A. (2018b). Activated biochar as an effective sorbent for organic and inorganic contaminants in water. Water, Air, and Soil Pollution, 229(7).
  11. Brunauer, S., Emmett, P. H., & Teller, E. (1938). Adsorption of gases in multimolecular layers. Journal of the American Chemical Society, 60(2), 309–319. Scholar
  12. Calo, J. M., & Perkins, M. T. (1987). A heterogeneous surface model for the “steady-state” kinetics of the Boudouard reaction. Carbon, 25(3), 395–407. Scholar
  13. Chowdhury, Z. Z., Zain, S. M., Khan, R. A., Rafique, R. F., & Khalid, K. (2012). Batch and fixed bed adsorption studies of lead (II) cations from aqueous solutions onto granular activated carbon derived from Mangostana garcinia shell. BioResources, 7(3), 2895–2915.Google Scholar
  14. Chowdhury, Z. Z., Hasan, M. R., Abd Hamid, S. B., Marlina Samsudin, E., Zain, S. M., & Khalid, K. (2015). Catalytic pretreatment of biochar residues derived from lignocellulosic feedstock for equilibrium studies of manganese, Mn(II) cations from aqueous solution. RSC Advances, 5(9), 6345–6356. Scholar
  15. Cuppett, J. D. (2006). Evaluation of copper speciation and water quality factors that affect aqueous copper tasting response. Chemical Senses, 31(7), 689–697. Scholar
  16. Ding, Z., Hu, X., Wan, Y., Wang, S., & Gao, B. (2016). Removal of lead, copper, cadmium, zinc, and nickel from aqueous solutions by alkali-modified biochar: batch and column tests. Journal of Industrial and Engineering Chemistry, 33, 239–245. Scholar
  17. Dubinin, M. M. (1989). Fundamentals of the theory of adsorption in micropores of carbon adsorbents: characteristics of their adsorption properties and microporous structures. Carbon, 27(3), 457–467. Scholar
  18. Dudka, S., & Adriano, D. C. (1997). Environmental impacts of metal ore mining and processing: a review. Journal of Environmental Quality, 26(3), 590. Scholar
  19. Environment and Climate Change Canada. (1999). Environmental Code of Practice for Base Metals Smelters and Refineries: Code of Practice, Canadian Environmental Protection Act. Available at Accessed 15 June 2018.
  20. Freundlich, H. M. F. (1906). Over the adsorption in solution. The Journal of Physical Chemistry, 57, 385–471.Google Scholar
  21. Gregg, S. J., & Sing, K. S. W. (1991). Adsorption, surface area, and porosity. London: Academic Press.Google Scholar
  22. Hamid, S. B. A., Chowdhury, Z. Z., & Zain, S. M. (2014). Base catalytic approach: a promising technique for the activation of biochar for equilibrium sorption studies of copper, Cu(II) ions in single solute system. Materials, 7(4), 2815–2832. Scholar
  23. Health Canada. (1992). Guidelines for Canadian drinking water quality: guideline technical document – copper. Available at Accessed 15 June 2018.
  24. Kołodyńska, D., Krukowska, J., & Thomas, P. (2017). Comparison of sorption and desorption studies of heavy metal ions from biochar and commercial active carbon. Chemical Engineering Journal, 307, 353–363. Scholar
  25. Lagergren, S. (1898). About the theory of so-called adsorption of soluble substances. Kungl. Svenska vetenskapsakademiens handlingar, 24(4), 1–39.Google Scholar
  26. Lamb, D. T., Naidu, R., Ming, H., & Megharaj, M. (2012). Copper phytotoxicity in native and agronomical plant species. Ecotoxicology and Environmental Safety, 85, 23–29. Scholar
  27. Langmuir, I. (1918). The adsorption of gases on plane surfaces of glass, mica and platinum. Journal of the American Chemical Society, 40(9), 1361–1403. Scholar
  28. Lazzarini, A., Piovano, A., Pellegrini, R., Leofanti, G., Agostini, G., Rudić, S., et al. (2016). A comprehensive approach to investigate the structural and surface properties of activated carbons and related Pd-based catalysts. Catalysis Science & Technology, 6(13), 4910–4922. Scholar
  29. Lee, J. A., Marsden, I. D., & Glover, C. N. (2010). The influence of salinity on copper accumulation and its toxic effects in estuarine animals with differing osmoregulatory strategies. Aquatic Toxicology, 99(1), 65–72. Scholar
  30. Lehmann, J., & Joseph, S. (Eds.). (2015). Biochar for environmental management: science, technology and implementation. Abingdon: Routledge.Google Scholar
  31. Lima, I. M., Boateng, A. A., & Klasson, K. T. (2010). Physicochemical and adsorptive properties of fast-pyrolysis bio-chars and their steam activated counterparts. Journal of Chemical Technology & Biotechnology, 85, 1515–1521. Scholar
  32. Lima, I. M., Boykin, D. L., Thomas Klasson, K., & Uchimiya, M. (2014). Influence of post-treatment strategies on the properties of activated chars from broiler manure. Chemosphere, 95, 96–104. Scholar
  33. Liu, W.-J., Jiang, H., & Yu, H.-Q. (2015). Development of biochar-based functional materials: toward a sustainable platform carbon material. Chemical Reviews, 115(22), 12251–12285. Scholar
  34. Marsh, H., & Rodríguez-Reinoso, F. (2006). Activated carbon (1st ed.). Amsterdam: Elsevier.Google Scholar
  35. Mohan, D., & Chander, S. (2001). Single component and multi-component adsorption of metal ions by activated carbons. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 177(2–3), 183–196. Scholar
  36. Mohan, D., & Chander, S. (2006). Removal and recovery of metal ions from acid mine drainage using lignite—a low cost sorbent. Journal of Hazardous Materials, 137(3), 1545–1553. Scholar
  37. Nordstrom, D. K., Blowes, D. W., & Ptacek, C. J. (2015). Hydrogeochemistry and microbiology of mine drainage: an update. Environmental Geochemistry of Modern Mining, 57, 3–16. Scholar
  38. Peng, H., Gao, P., Chu, G., Pan, B., Peng, J., & Xing, B. (2017). Enhanced adsorption of Cu(II) and Cd(II) by phosphoric acid-modified biochars. Environmental Pollution, 229, 846–853. Scholar
  39. Radovic, L. R., & Rodriguez-Reinoso, F. (1997). In P. A. Thrower (Ed.), Chemistry and Physics of Carbon (Vol. 25). New York: Marcel Dekker.Google Scholar
  40. Ríos, C. A., Williams, C. D., & Roberts, C. L. (2008). Removal of heavy metals from acid mine drainage (AMD) using coal fly ash, natural clinker and synthetic zeolites. Journal of Hazardous Materials, 156(1–3), 23–35. Scholar
  41. Sekhula, M. M., Okonkwo, J. O., Zvinowanda, C. M., Agyei, N. N., & Chaudhary, A. J. (2012). Fixed bed column adsorption of Cu (II) onto maize tassel-PVA beads. Journal of Chemical Engineering & Process Technology, 03(02).
  42. Shim, T., Yoo, J., Ryu, C., Park, Y.-K., & Jung, J. (2015). Effect of steam activation of biochar produced from a giant Miscanthus on copper sorption and toxicity. Bioresource Technology, 197, 85–90. Scholar
  43. Sing, K. S. W. (1985). Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (recommendations 1984). Pure and Applied Chemistry, 57(4), 603–619. Scholar
  44. Tan, X., Liu, S., Liu, Y., Gu, Y., Zeng, G., Hu, X., et al. (2017). Biochar as potential sustainable precursors for activated carbon production: multiple applications in environmental protection and energy storage. Bioresource Technology, 227, 359–372. Scholar
  45. Tarazona, P. (1995). Solid-fluid transition and interfaces with density functional approaches. Proceedings of the 14th European Conference on Surface Science, 331, 989–994. Scholar
  46. Visual MINTEQ version 3.1. (2018). Accessed 15 Dec 2018.
  47. Wilson, K., Yang, H., Seo, C. W., & Marshall, W. E. (2006). Select metal adsorption by activated carbon made from peanut shells. Bioresource Technology, 97(18), 2266–2270. Scholar
  48. Wu, F.-C., Tseng, R.-L., & Juang, R.-S. (2009). Characteristics of Elovich equation used for the analysis of adsorption kinetics in dye-chitosan systems. Chemical Engineering Journal, 150(2–3), 366–373. Scholar
  49. Xie, R., Jin, Y., Chen, Y., & Jiang, W. (2017). The importance of surface functional groups in the adsorption of copper onto walnut shell derived activated carbon. Water Science and Technology, 76(11), 3022–3034. Scholar

Copyright information

© Springer Nature Switzerland AG 2019

Authors and Affiliations

  • Flavia Lega Braghiroli
    • 1
    • 2
    Email author
  • Hassine Bouafif
    • 2
  • Carmen Mihaela Neculita
    • 3
  • Ahmed Koubaa
    • 1
  1. 1.Research Forest Institute (Institut de recherche sur les forêts - IRF)University of Québec in Abitibi-Témiscamingue (UQAT)Rouyn-NorandaCanada
  2. 2.Centre Technologique des Résidus Industriels (CTRI, Technology Center for Industrial Waste)Cégep de l’Abitibi-Témiscamingue (College of Abitibi-Témiscamingue)Rouyn-NorandaCanada
  3. 3.Research Institute on Mines and Environment (RIME)University of Québec in Abitibi-Témiscamingue (UQAT)Rouyn-NorandaCanada

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