Evaluation of Influence of Nano-Hydroxyapatite Application on the Cadmium Immobilization in Contaminated Calcareous Soil

Document Type : Complete scientific research article


1 Soil Science, Agriculture, Ferdowsi University, Mashhad, Iran

2 Associate professor of soil science. Department of Soil Science, Ferdowsi University of Mashhad. Iran.

3 Professor of Soil Science. Department of Soil Science, Ferdowsi University of Mashhad. Iran.

4 Professor of Soil Science. Department of Soil Science, Isfahan University of Technology


Background and Objective: Cadmium (Cd) is one of the most common soil pollutants that can adversely affect all living organisms Therefore, proper remediation is necessary to reduce metal availability in soil. Owing to nano-material with higher reactivity and adsorption capacity than ordinary-sized materials, with the development of various nanotechnology applications in human life, the evaluation of the effectiveness of nanoparticles in remediation of polluted soils has been considered by researchers. However up to now it has been not reported information about heavy metal immobilization by nHAP in calcareous soils. This experiment was conducted to investigate efficiency of nHAP on stabilization of Cd in polluted soil.
Materials and Methods: This experiment was conducted in a completely randomized design with factorial arrangement and three replications. First the soils were contaminated with Cd at three levels (0, 20 and 40 mg kg-1 using CdCl2) and then were incubated for one month in 70% field capacity. Then nHAP was applied to soils at three levels (0, 0.25 and 1%). After 30 days incubation, Cd was fractionated by sequential extraction and analyzed for DTPA extractable form. To quantify the effect of nHAP in binding intensity and mobility of loaded Cd, the reduced partition index (IR) and mobility factor were used.
Results: The results of sequential extraction showed that nHAP application significantly reduced concentration of Cd in the exchangeable and organic fraction and increased in the carbonate fraction. But there was no change for Cd in the residual fraction. The results of extraction with DTPA experiment indicated that at 40 mg kg-1 of Cd both of the levels of nHAP decreased DTPA-extractable Cd, but at 20 mg kg-1 of Cd, addition of nHAP at 0.25 % level did not significantly reduced concentration of DTPA extractable Cd. It was also found that efficiency of nHAP increased when Cd loading quantities to soils increased. However the role of nHAP in the reducing of bioavailability was not very large. The results also illustrated that the IR value increased when Cd and nHAP loading quantities to soils increased, demonstrating a decrease in the mobility of Cd in mobile fractions. Application of nHAP caused reduction of the mobility factor of Cd indicating decreasing availability and environmental risk of Cd.
Conclusion: On the basis of results obtained in this study, it can be stated that although the nHAP addition has somewhat stabilized and reduced the mobility of Cd in the soil, it seems that the effect of nHAP on decreasing of Cd was not considerable. Therefore, further studies should be carried out more on the feasibility of application of nHAP at the widespread level and the economic status of its application.


1.Abollino, O., Giacomino, A., Malandrino, M., and Mentasti, E. 2005. The use of sequential extraction procedures for the characterization and management of contaminated soils. Analytical, Environmental and Cultural Heritage Chemistry. 95: 527-538.
2.Basta, N.T., Gradwohl, R., Snethen, K.L., and Schroder, L. 2001. Chemical Immobilization of Lead, Zinc and Cadmium in Smelter-Contaminated Soils Using Biosolids and Rock Phosphate. Environmental Quality. 30: 1222-1230.
3.Boparai, H.K., Joseph, M., and O’Carroll, D.M. 2011. Kinetics and thermodynamics of cadmium ion removal by adsorption onto nano zerovalent iron particles. J. Hazard. Mater. 186: 458-65.
4.Buekers, J., Van Laer, L., Amery, F., Van Buggenhout, S., Maes, A., and Smolders, E. 2007. Role of soil constituents in fixation of soluble Zn, Cu, Ni and Cd added to soils. Europ. J. Soil Sci. 58: 1514-1524.
5.Cao, X.D., Ma, L.Q., Rhue, D.R., and Appel, C.S. 2004. Mechanisms of lead, copper and zinc retention by phosphate rock. Environmental Pollution. 131: 435-444.
6.Chen, J.H., Wang, Y.J., Wang, H.W., Zhou, D.M., and Yang, J.H. 2009. Assessment of remediation of soil heavy metals with nano-particle hydroxyapatite by toxicity characteristic leaching procedure. J. Agro-Environ. Sci. 28: 645-648.
7.Chen, S.B., MA, Y.B., Chen, L., and Xian, K. 2010. Adsorption of aqueous Cd2+, Pb2+, Cu2+ ions by nano-hydroxyapatite: Single- and multi-metal competitive adsorption study. Geochemical. 44: 233-239.
8.Cui, H., Zhou, J., Zhao, Q., Shi, Y., Mao, J., Fang, G., and Liang, J. 2013. Fractions of Cu, Cd and enzyme activities in a contaminated soil as affected by applications of micro-and nanohydroxyapatite. J. Soil Sed. 13: 742-752.
9.Ding, L., Li, J., Liu, W., Zuo, Q., and Liang, S.X. 2017. Influence of Nano-Hydroxyapatite on the Metal Bioavailability, Plant Metal Accumulation and Root Exudates of Ryegrass for Phytoremediation in Lead-Polluted Soil. Inter. J. Environ. Res. Pub. Health. 14: 532-540.
10.Eriksson, J.E. 1989. The influence of pH, soil type and time on adsorption and uptake by plants of Cd added to the soil. Water, Air and Soil Pollution. 48: 317-335.
11.Filgueiras, A.V., Lavilla, I., and Bendicho, C. 2002. Chemical sequential extraction for metal partitioning in environmental solid samples. J. Environ. Monitor. 4: 823-857.
12.Fu, H., Zhang, B., Yang, J., Liu, H., Yang, S., and Zhao, P. 2018. Cadmium and Lead Speciation as Affected by Soil Amendments in Calcareous Soil. Environmental Engineering Science.
13.Gee, G.W., and Bauder., J.W. 1982. Hydrometer Method. P 383-314, In: Klute, A. (ed), Methods of Soil Analysis: Physical Properties, Part 1, second ed. Agron Monogr, No 9, Madison WI: ASA and SSSA.
14.Han, F.X., Banin, A., Kingery, W.L., Triplett, G.B., Zhou, L.X., and Zheng, S.J. 2003. New approach to studies of heavy metal redistribution in soil. Advances in Environmental Research. 8: 113-120.
15.He, M., Shi, H., Zhao, X., Yu, Y., and Qu, B. 2013. Immobilization of Pb and Cd in contaminated soil using nanocrystallite hydroxyapatite. Procedia Environmental Sciences. 18: 657-665.
16.Hoodji, M., and Afyuni, M. 2009. The Effect of Sewage Sludge and CdCl2 Application on Cadmium Transport in Soil and Plant Uptake', J. Environ. Sci. Technol. 11: 2. 47-58.
(In Persian)
17.Jalali, M., and Arfania, H. 2011. Distribution and fractionation of cadmium, copper, lead, nickel and zinc in a calcareous sandy soil receiving municipal solid waste. Environmental Monitoring and Assessment. 173: 241-250.
18.Jalali, M., and Khanboluki, G. 2008. Redistribution of zinc, cadmium and lead among soil fractions in a sandy calcareous soil due to application of poultry litter. Environmental Monitoring and Assessment. 136: 327-335.
19.Kabala, C., and Singh, B.R. 2001. Fractionation and mobility of copper, lead and zinc in soil profiles in the vicinity of a copper smelter. J. Environ. Qual. 30: 485-492.
20.Kabata-Pendias A., and Pendias H. 2010. Trace elements in soils and plants. CRC Press. Boca Ratton. Florida. 548p.
21.Khadivi Borujeni, E., Nourbakhsh, F., Afyuni, M., and Shariatmadari, H. 2007. Forms of Pb, Ni and Cd in a Sewage Sludge - treated Calcareous Soil. J. Water Soil. 11: 1. 41-54.
(In Persian)
22.Khanmirzaee, A., Bazargan, K., Moezzi, A., and Shahbazi, K. 2011. The relationship between the chemical forms of Cd concentration in wheat grain in some soils of Golestan province. J. Soil Sci. (Soil and Water). 26: 347-357.
23.Li, Zh., Zhou, M.M., and Lin, W. 2014. The research of nano particle and micro particle hydroxyapatite amendment in multiple heavy metals contaminated soil remediation.
J. Nanomater. 2014.
24.Lindsay, W.L., and Norvell, W.A. 1978. Development of a DTPA soil test for zinc, iron, manganese and copper. Soil Science Society American. 42: 421-428.
25.Loeppert, R.H., and Suarez, L. 1996. Carbonate and gypsum. In ‘Methods of soil
10 analysis. Part 3. Chemical methods’. (Ed. D.L. Sparks). P 437-474, Soil Science Society of 11 America: Madison, WI.
26.Ma, L.Q., and Rao, G.N. 1997. Chemical fractions of Cadmium, Copper, Nickel and Zinc contaminated soils. J. Environ. Qual. 26: 259-264.
27.Ma, Q.Y., Traina, S.J., Logan, T.J., and Ryan, J.A. 1994. Effects of aqueous Al, Cd, Cu, Fe (II), Ni and Zn on Pb immobilization by hydroxyapatite. Environmental Science & Technology, 28: 1219-1228.
28.McBride, M.B. 1995. Toxic Metal accumulation from agricultural use of sludge: Are USEPA regulations protective? J. Environ. Qual. 24: 5-18.
29.McGrath, S.P., and Segara, J. 1992. Chemical extractability of heavy metals during after and long-term applications of sewage sludge to soil. Soil Science. 43: 313-321.
30.Miretzky, P., and Rodriguez Avendano, M., Munoz, C., and Carrillo-Chavez, A. 2011. Use of partition and redistribution indexes for heavy metal soil distribution after contamination with a multi-element solution. Soils Sediments. 11: 619-627.
 31.Mobasherpour, I., Salahi, E., and Pazouki, M. 2011. Removal of divalent cadmium cations by means of synthetic nano crystallite hydroxyapatite. Desalination. 266: 142-148.
32.Paramasivam, S., Lettimore, J.M., Alva, A.K., Jayaraman, K., and Harper, L.M. 2014. Chemical fractionation of Cu, Zn, Cd, Cr and Pb in sewage sludge amended soils at the end of 65-d sorghum-sudan grass growth. Environmental Science and Health. 49: 1304-1315.
33.Rajaie, M., Karimian, N., Maftoun, M., Yasrebi, M., and Assad, M.T. 2006. Chemical forms of cadmium in two calcareous soil textural classes as affected by application of cadmium-enriched compost and incubation time. Geoderma. 136: 533-541.
34.Ramesh, S.T., Rameshbabu, N., Gandhimathi, R., Srikanth Kumar M., and Nidheesh. P.V. 2013. Adsorptive removal of Pb (II) from aqueous solution using nano-sized hydroxyapatite. Applied Water Science. 3: 105-113.
35.Rhoades, J.D. 1982. Soluble salts. P 167-179, In: Page, A.L. (ed), Methods of Soil Analysis: Chemical and microbiological properties, Part 2. 2nd Ed. Agron. Monogr. No.9, ASA and SSSA, Madison WI.
36.Shrivastava, R., Upreti, R.K., and Chaturvedi, U.C. 2003. Various cells of the immune system and intestine differ in their capacity to reduce hexavalent chromium. FEMS Immunology & Medical Microbiology. 38: 65-70.
37.Sposito, G., Lund, J., and Change, A. C. 1982. Trace metal chemistry in arid-zone field soils amended with sewage sludge: I. Fractionation of Ni, Cu, Zn, Cd and Pb in solid phases.
Soil Sci. Soc. Amer. J. 46: 260-264.
38.Stietiya, M.H., Duqqah, M., Udeigwe, T., Zubi, R., and Ammari, T. 2014. Fate and distribution of heavy metals in wastewater irrigated calcareous soils. Sci. World J. 2014.
39.Tang, X.Y., Zhu, Y.G., Cui, Y.Sh., Duan, J., and Tang, C. 2006. The effect of ageing on the bioaccessibility and fractionation of cadmium in some typical soils of China. Environment International. 32: 682-689.
40.Varasteh Khanlari, Z., and Jalali, M. 2008. Concentrations and chemical speciation of five heavy metals (Zn, Cd, Ni, Cu and Pb) in selected agricultural calcareous soils of Hamadan Province, western Iran. Archives of Agronomy and Soil Science. 54: 19-32.
41.Walkley, A., and Black, I.A. 1934. An examination of the Degtjareff method for determining soil organic matter and a proposed modification of the chromic acid titration method. Soil Science. 37: 29-38.
42.Wang, Y.J., Chen, J.H., Cui, Y.X., Wang, S.Q., and Zhou, D.M. 2009. Effect of low-molecular-weight organic acids on Cu (II) adsorption onto hydroxyapatite nanoparticles. Hazardous Materials. 162: 1135-1140.
43.Waterlot, C., Pruvot, C., Marot, F., and Douay, F. 2017. Impact of a phosphate amendment on the environmental availability and phytoavailability of Cd and Pb in moderately and highly carbonated kitchen garden soils. Pedosphere. 27: 588-605.
44.Wei, L., Wang, S., Zuo, Q., Liang, S., Shena, S., and Zhao, C. 2016. Nano-hydroxyapatite alleviates the detrimental effects of heavy metals on plant growth and soil microbes in e-waste-contaminated soil. Environmental Science: Processes & Impacts. 18: 760-767.
45.Wu, C., Yan, S., Zhang, H., and Luo, Y. 2015. Chemical forms of cadmium in a calcareous soil with different levels of phosphorus-containing acidifying agents. Soil Research.
53: 105-111.
46.Xian, X. 2003. Effect of chemical forms of Cadmium, Zinc and Lead in polluted soils on their uptake by cabbage plants. Plant and Soil. 113: 257-264.
47.Xu, Y., Schwartz, F.W., and Traina, S.J. 1994. Sorption of Zn2+ and Cd2+ on hydroxyapatite surfaces. Environmental Science Technology. 28: 1472-1480.
48.Zhang, Z.Z., Li, M.Y., Chen, W., Zhu, S.Z., Liu, N.N., and Zhu, L.Y. 2010. Immobilization of lead and cadmium from aqueous solution and contaminated sediment using nano-hydroxyapatite. Environmental Pollution. 158: 514-519.