Lee, Chan-Ki;Kim, Hae-Suk;Kwon, Jae-Hyuk

  • Published : 2005.10.31


The study was conducted to investigate the removal of heavy metals by using Hydroxyapatite(HAp) made from waste oyster shells and wastewater with high concentration of phosphorus. The maximum calcium concentration for the production of HAp in this study was released up to 361 mg/L at pH of 3 by elution experiments. When the pH was at adjusted 6, the maximum calcium released concentration was 41 mg/L. During the elution experiment, most of the calcium was released within 60 minutes. This reaction occurred at both pH levels of 3 and 6. The result of the XRD analysis for the HAp product used in this study shows the main constituent was HAp, as well as OCP. The pH was 8.6. As the temperature increased, the main constituent did not vary, however its structure was crystallized. When the pH was maintained at 3, the removal efficiency decreased as the heavy metal concentration increased. The order of removal efficiency was as follows: $Fe^{2+}$(92%), $Pb^{2+}$(92%) > $Cu^{2+}$(20%) > $Cd^{2+}$(0%). Most of these products were dissolved and did not produce sludge in the course of heavy metals removal. As the heavy metal concentration increased at pH of 6, the removal efficiency increased. The removal efficiencies in all heavy metals were over 80%. From the analysis of the sludge after reaction with heavy metals, the HAp was detected and the OCP peak was not observed. Moreover, lead ion was observed at the peaks of lead-Apatite and lead oxidant. In the case of cadmium, copper and iron ions, hydroxide forms of each ion were also detected.


Oyster shells;HAp(Hydroxyapatite);XRD;OCP(Octa-Calcium Phosphate);heavy metals removal


  1. Makhloufi L, Saidani B, and Hammache H., 'Removal of lead from acidic aqueous solutions by cementation on iron,' Water Res., 34(9), 2517-2524 (2000)
  2. Lopez-Delgado A, Perez C, and Lopez FA, 'Sorption of heavy metals on blast furnace sludge,' Water Res., 32(4), 989-996 (1998)
  3. Goh, E. O., Lee, J. O., Cho, W. J., Hyun, J. H., Kang, C. H., Chun, K. S., 'Adsorption characteristics of copper ion onto a bentonite,' J. of KSEE, 22(1), 83-89 (2000)
  4. J. R. Conner, 'Fixation of Metals. Chemical Fixation and Solidification of Hazardous Waste,' 58-171, Van Nostrand Reinhood, New York (1990)
  5. H. Monma and T. Kanazawa, 'Wet-Process Formation of Nonstoichiometric Hydroxyapatite from Tricalcium Phosphate,' Yogyo-Kyokai-Shi, 86(2), 72-79 (1978)
  6. Lee, M. S., Kim, O. B., and Kim, M. Y., 'A Study on Synthesis and Properties of Porous Hydroxyapatite,' J. of the Korean Mining and Mineral resource, 32, 192-203 (1995)
  7. SUZUKI, T. and HATSUSHIKA, T., 'Latticeion Reaction Characteristics of Hydroxyapatite for Fe, Fe and Pb Ions in Acidic Aqueous Solutions,' Gypsum & Lime, 224, 15-20 (1990)
  8. SUZUKI, T., HATSUSHIKA, T., and HAYAKAWA, Y., 'Synthetic Hydroxyapatites Employed as Inorganic Cation-exchangers,' J. Chem. Soc. Faraday Trans. I., 77, 1059-1062 (1981)
  9. Standard Method for examination of water and wastewater, 18th edition, American Public Health Association, Washington D.C (1992)
  10. Kanazawa, T., 'Calcium orthophosphate,' in Inorganic Phosphate Materials, 79-102, Elsevier Amsterdam (1989)
  11. Ronald, M., Verbeek, H., Steyaer, H., Thun, H. P., and Veerbeek, F., 'Solubility of Synthetic Calcium Hydroxyapatite,' J. Chem. Soc. Faraday I, 76, 209-219 (1980)
  12. An, H-K., Park, B-Y., and Kim, D-S., 'The removal of heavy metals by crab shell in aqueous solution,' J. of KESS, 9(5), 40-414 (2000)
  13. An, H-K., No, H. K., and Kim, D. S., 'Comparison of heavy metal ions($Pb^{2+},Cd^{2+},Mn^{2-},Cu^{2+}$) removal by several materials, Environ. Eng. Res., 6(3), 117-122 (2001)
  14. SUZUKI, T., ISHIGAKI, K., and MIYAKE, M., 'Synthetic Hydorxyapatites as Inorganic Cation Exchangers, Part 3.-Exchange Characteristics of Lead Ions,' J. Chem. Soc. Faraday Trans. I, 80, 3157-3165 (1984)
  15. Kim, C. E., Lee, H. S., Park, H., and Lee, S. H., 'Fixation of Pb, Cd ions by the Hydroxyapatite,' JKSWES, 11(2), 147-160 (1994)
  16. Panda, A., Sahu, B., Patel, P. N., and Mishra, B., 'Calcium lead-copper and calcium-lead- cadmium hydroxyapatite solid solution: preparation,' infrared and lattice constant measurements. Transition Met. Chem., 16, 476-477 (1991)
  17. Venkataramani, B., Venkates varlu, K. S., and Shankar, J., 'Colloid Interface Sci.,' 67(2), 187-194 (1978)
  18. Walton, A. G., Bodin, W. J., Furedi, H., and Schwartz, 'Nucleation of calcium phosphate from solution,' Canadian Journal of Chemistry, 45, 2695-2701 (1967)
  19. Lee, M. S., Na, C. K., Lee, M. S., Kim, O. B., and Kim, M. Y., 'The heavy metal adsorption properties of Hydroxyapatite powder synthesized by precipitation reaction Method and its application for the removal agents of noxious metallic ions in wastewater,' Eco. Environ. Geol., 28(3), 231-241 (1995)
  20. Kang, J-T. and Jeong, G-H., 'The Removal of Heavy Metals in Aqueous Solution by Hydroxyapatite,' J. of KESS, 9(4), 325-330 (2000)
  21. Poon, C. S., Clark, A. I., Peters, C. J., and Perry, R., 'Mechanisms of Metal Fixation and Leaching by Cement based Fixation Process,' Waste Management & Research, 3, 127-142 (1985)
  22. Blumenthal, N. C., Betts, F., and Posner, A. S., 'Formation and Structure of Ca-deficient hydroxyapatite,' Calcif, Tissue Int., 33, 111-117 (1981)

Cited by

  1. Removal of Cu(II) with hydroxyapatite (animal bone) as an inorganic ion exchanger vol.4, pp.1-3, 2009,
  2. Adsorptive removal of Pb(II) from aqueous solution using nano-sized hydroxyapatite vol.3, pp.1, 2013,
  3. Ability of Hydroxyapatite Synthesized from Waste Oyster Shells to Remove Fluoride Ions vol.56, pp.9, 2015,
  4. ) ions vol.42, pp.6, 2018,
  5. Volcanoes, medicine, and monasticism: Investigating mercury exposure in medieval Iceland pp.1047482X, 2018,