Modification of Fishbone-Based Hydroxyapatite with MnFe2O4 for Efficient Adsorption of Cd(II) and Ni(II) from Aqueous Solution

Poedji Loekitowati Hariani(1), Addy Rachmat(2*), Muhammad Said(3), Salni Salni(4)

(1) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Sriwijaya, Jl. Palembang Prabumulih Km. 32, Ogan Ilir 30662, Indonesia Research Centre of Advanced Material and Nanocomposite, Faculty of Mathematics and Natural Sciences, Universitas Sriwijaya, Jl. Palembang Prabumulih Km. 32, Ogan Ilir 30662, Indonesia
(2) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Sriwijaya, Jl. Palembang Prabumulih Km. 32, Ogan Ilir 30662, Indonesia Research Centre of Advanced Material and Nanocomposite, Faculty of Mathematics and Natural Sciences, Universitas Sriwijaya, Jl. Palembang Prabumulih Km. 32, Ogan Ilir 30662, Indonesia
(3) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Sriwijaya, Jl. Palembang Prabumulih Km. 32, Ogan Ilir 30662, Indonesia Research Centre of Advanced Material and Nanocomposite, Faculty of Mathematics and Natural Sciences, Universitas Sriwijaya, Jl. Palembang Prabumulih Km. 32, Ogan Ilir 30662, Indonesia
(4) Department of Biology, Faculty of Mathematics and Natural Sciences, Jl. Palembang Prabumulih Km. 32, Ogan Ilir 30662, Indonesia
(*) Corresponding Author


Due to their toxicity, Cd(II) and Ni(II) ions in the environment are severe. The hydroxyapatite composite was improved with magnetic MnFe2O4 to remove Cd(II) and Ni(II) ions from an aqueous solution. Hydroxyapatite was extracted from Snakehead (Channa striata) fish bones via alkaline-heat treatment. The hydroxyapatite/MnFe2O4 composite performance was analyzed through XRD, FTIR, SEM-EDS, BET analysis, and VSM, and the results reveal that the hydroxyapatite/MnFe2O4 composite shows good magnetic properties of 21.95 emu/g. The kinetics evaluation confirmed that the pseudo-second-order kinetics model was more suitable to describe the adsorption of Cd(II) and Ni(II) ions by hydroxyapatite/MnFe2O4 composite from the solution. The Langmuir isotherm model was suitable to describe the adsorption process of the Cd(II) and Ni(II)  ions, where the adsorption capacities for Cd(II) and Ni(II) are 54.3 and 47.4 mg/g, respectively. Desorption of Cd(II) and Ni(II) ions from hydroxyapatite/MnFe2O4 composite using NaCl as the eluent was more effective than EDTA. The findings of this study indicate that hydroxyapatite/MnFe2O4 can reduce Cd(II) and Ni(II) ions in wastewater so that it can recover natural resources.


hydroxyapatite/MnFe2O4 composite; adsorption; Cd(II); Ni(II); desorption

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[1] Heidari, A., Younesi, H., Mehraban, Z., and Heikkinen, H., 2013, Selective adsorption of Pb(II), Cd(II), and Ni(II) ions from aqueous solution using chitosan-MAA nanoparticles, Int. J. Biol. Macromol., 61, 251–263.

[2] Li, Q., Zhao, Y., Qu, D., Wang, H., Chen, J., and Zhou, R., 2018, Preparation of Ag-MnFe2O4-bentonite magnetic composite for Pb(II)/Cd(II) adsorption removal and bacterial inactivation in wastewater, Chem. Res. Chin. Univ., 34 (5), 808–816.

[3] Torres-Caban, R., Vega-Olivencia, C.A., and Mina-Camilde, N., 2019, Adsorption of Ni2+ and Cd2+ from water by calcium alginate/spent coffee grounds composite beads, Appl. Sci., 9 (21), 4531.

[4] Liao, V.H.C., Chien, M.T., Tseng, Y.Y., and Qu, K.L., 2006, Assessment of heavy metal bioavailability in contaminated sediments and soils green fluorescent protein-based bacterial biosensors, Environ. Pollut., 142 (1), 17–23.

[5] Soylak, M., Kars, A., and Narin, I., 2008, Coprecitation of Ni2+, Cd2+ and Pb2+ for preconcentration in environmental samples prior to flame atomic absorption spectrometric determination, J. Hazard. Mater., 159 (2-3), 435–439.

[6] Kasprzak, K.S., Sunderman Jr., F.W., and Salnikow, K., 2003, Nickel carcinogenesis, Mutat. Res., Fundam. Mol. Mech. Mutagen., 533 (1-2), 67–97.

[7] Sobhanardakani, S., and Zandipak, R., 2015, Adsorption of Ni(II) and Cd(II) from aqueous solutions using modified rice husk, Iran. J. Health Sci., 3 (1), 1–9.

[8] Qdais, H.A., and Moussa, H., 2004, Removal of heavy metals from wastewater by membrane processes: A comparative study, Desalination, 164 (2), 105–110.

[9] Igiri, B.E., Okoduwa, S.I.R., Idoko, G.O., Akabuogu, E.P., Adeyi, A.O., and Ejiogu, I.K., 2018, Toxicity and bioremediation of heavy metals contaminated ecosystem from tannery wastewater: A review, J Toxicol., 2018, 2568038.

[10] Thaçi, B.S., and Gashi, S.T., 2019, Reverse osmosis removal of heavy metals from wastewater effluents using biowaste materials pretreatment, Pol. J. Environ. Stud., 28 (1), 337–341.

[11] Zewail, T.M., and Yousef, N.S., 2015, Kinetic study of heavy metal ions removal by ion exchange in batch conical air spouted bed, Alexandria Eng. J., 54 (1), 83–90.

[12] Torab-Mostaedi, M., Ghassabzadeh, H., Ghannadi-Maragheh, M., Ahmadi, S.J., and Taheri, H, 2010, Removal of cadmium and nickel from aqueous solution using expanded perlite, Braz. J. Chem. Eng., 27 (2), 299–308.

[13] Wijesinghe, W.P.S.L., Mantilaka, M.M.M.G.P.G., Peiris, T.A.N., Rajapakse, R.M.G., Wijayantha, K.G.U., Pitawala, H.M.T.G.A., Premachandra, T.N., Herath, H.M.T.U., and Rajapakse, R.P.V.J., 2018, Preparation and characterization of mesoporous hydroxyapatite with non cytotoxicity and heavy metal adsorption capacity, New J. Chem., 42 (12), 10271–10278.

[14] Guo, X., Tang, S., Song, Y., and Nan, J., 2018, Adsorptive removal of Ni2+ and Cd2+ from wastewater using a green longan hull adsorbent, Adsorpt. Sci. Technol., 36 (1-2), 762–773.

[15] Lin, P., Wu, J., Ahn, J., and Lee, J., 2019, Adsorption characteristic of Cd(II) and Ni(II) from aqueous solution using succinylated hay, Int. J. Miner. Metall. Mater., 26 (10), 1239–1246.

[16] Roy, S., and Das, P., 2016, Thermodynamic and kinetics study of de-fluoridation in wastewater using hydroxyapatite (Hap) as adsorbent: optimization using response surface methodology, Front. Nanosci. Nanotechnol., 2 (3), 121–128.

[17] Hamzah, S., Yatim, N.I., Alias, M., Ali, A., Rasit, N., and Abuhabib, A., 2019. Extraction of hydroxyapatite from fish scales and its integration with rice husk for ammonia removal in aquaculture wastewater, Indones. J. Chem.,19 (4), 1019–1030.

[18] Iconaru, S.L., Heino, M.M., Guegan, R., Beuran, M., Costecu, A., and Predoi, D., 2018, Adsorption of Pb(II) ions onto hydroxyapatite nanopowders in aqueous solution, Materials, 11 (11), 2204.

[19] Le, D.T., Le, T.P.T., Do, H.T., Vo, H.T., Pham, N.T., Nguyen, T.T., CaO, H.T., Nguyen, P.T., Dinh, T.M.T., Le, H.V., and Tran, D.L., 2019, Fabrication of porous hydroxyapatite granules as an effective adsorbent for the removal of aqueous Pb(II) ions, J. Chem., 2019, 8620181.

[20] Dabiri, S.M.H., Rezaie, A.A., Moghimi, M., and Rezaie, H., 2018, Extraction of hydroxyapatite from fishbone and its application, BioNanoScience, 8 (3), 823–834.

[21] Idea, P., Degli Esposti, L., Miguel, C.C., Adamiano, A., Iafisco, M., and Castilho, P.C., 2021, Extraction and characterization of hydroxyapatite-based materials from grey triggerfish skin and black scabbardfish bones, Int. J. Appl. Ceram. Technol., 18 (1), 235–243.

[22] Zairin, D.A., and Phang, S.W., 2018, Calcination time and temperature effect on natural hydroxyapatite obtained from fish bones for bone tissue engineering, Int. J. Eng. Sci. Technol., Special issue August, 39–51.

[23] Hariani, P.L., Muryati, M., and Said, M.,2019, Kinetic and thermodynamic adsorption of nickel(II) onto hydroxyapatite prepared from Snakehead (Channa striata) fish bone, Mediterr. J. Chem., 9 (2), 85–94

[24] Hariani, P.L., Muryati, M., Said, M., and Salni, S., 2020, Synthesis of nano-hydroxyapatite from Snakehead (Channa striata) fish bone and its antibacterial properties, Key Eng. Mater., 840, 293–299.

[25] Dong, L., Zhu, Z., Qiu, Y., and Zhao, Z., 2010, Removal of lead from aqueous solution by hydroxyapatite/magnetite composite adsorbent, Chem. Eng. J., 165 (3), 827–834.

[26] Ansari, A., Vahedi. S., Tavakoli, O., Khoobi, M., and Faramarzi, M.A., 2018, Novel Fe3O4/hydroxyapatite/β-cyclodextrin nanocomposite adsorbent: synthesis and application in heavy metal removal from aqueous solution, Appl. Organomet. Chem., 33 (1), e4634.

[27] Ragab, A., Ahmed, I., and Bader, D., 2019, The removal of brilliant green dye from aqueous solution using hydroxyapatite/chitosan composite as sorbent, Molecules, 24 (5), 847.

[28] Shao, L., Ren, Z., Zhang, G., and Chen, L., 2012, Facile synthesis, characterization of a MnFe2O4/activated carbon magnetic composite and its effectiveness in tetracycline removal, Mater. Chem. Phys., 135 (1), 16–24.

[29] Podder, M.S., and Majumder, C.B., 2016, Studies on the removal of As(III) and As(V) through their adsorption onto granular activated carbon/MnFe2O4 composite: Isotherm studies and error analysis, Compos. Interfaces, 23 (4), 327–372.

[30] Do, Q.C., Choi, S., Kim, H., and Kang, S., 2019, Adsorption of lead and nickel on to expanded graphite decorated with manganese oxide nanoparticles, Appl. Sci., 9 (24), 5375.

[31] Soejoko, D.S., and Tjia, M.O., 2002, Infrared spectroscopy and X-ray diffraction study on the morphological variations of carbonate and phosphate compounds in giant prawn (Macrobrachium rosenbergii) skeletons during its moulting period, J. Mater. Sci., 38 (9), 2087–2093.

[32] Wang, P., Li, C., Gong, H., Jiang, X., Wang, H., and Li, K., 2013, Effects of synthesis conditions on the morphology of hydroxyapatite nanoparticles produced by wet chemical process, Powder Technol., 203 (2), 315–321.

[33] Yari Moghaddam, N., Lorestani, B., Cheraghi, M., and Jamebozorgi, S, 2019, Adsorption of Cd and Ni from water by graphene oxide and graphene oxide-almond shell composite, Water Environ. Res., 91 (6), 475–482.

[34] Riyanti, F., Hariani, P.L., Purwaningrum, W., Elfita, E., Damarril, S.S., and Amelia, I., 2018, The synthesis of MnFe2O4-activated carbon composite for removal of Methyl red from aqueous solution, Molekul, 13 (2), 123–132.

[35] Danmaliki, G.I., and Saleh, T.A., 2016, Influence of conversion parameters of waste tires to activated carbon on adsorption of dibenzothiophene from models fuels, J. Cleaner Prod., 117, 50–55.

[36] Kausar, A., Naeem, K., Hussain, T., Nazli, Z.I.H., Bhatti, H.N., Jubeen, F., Nazir, A., and Iqbal, M., 2019, Preparation and characterization of chitosan/clay composite for direct rose FRN dye removal from aqueous media: Comparison of linear and non-linear regression methods, J. Mater. Res. Technol., 8 (1), 1161–1174.

[37] Hossain, M.A., Ngo, H.H., Guo, W.S., Nghiem, L.D., Hai, F.I., Vigneswaran, S., and Nguyen, T.V., 2014, Competitive adsorption of metals on cabbage waste from multi-metal solutions, Bioresour. Technol., 160, 79–88.

[38] Jodra, Y., and Mijangos, F., 2001, Ion exchange selectivities of calcium alginate gels for heavy metals, Water Sci. Technol., 43 (2), 237–244.

[39] Rao, R.A.K., and Kashifuddin, M., 2014, Kinetics and isotherm studies of Cd(II) adsorption from aqueous solution utilizing seeds of bottlebrush plant (Callistemon chisholmii), Appl. Water Sci., 4 (4), 371–383.

[40] Foroutan, R., Mohammadi, R., Farjadfard, S., Esmaeili, H., Saberi, M., Sahebi, S., Dobaradaran, S., and Ramavandi, B., 2019, Characteristic and performance of Cd, Ini, and Pb bio-adsorption using Callinectes sapidus biomass: Real wastewater treatment, Environ. Sci. Pollut. Res. Int., 26, 6336–6347.

[41] Du, X., Cui, S., Fang, X., Wang, Q., and Liu, G., 2020, Adsorption of Cd(II), Cu(II), and Zn(II) by granules prepared using sludge from a drinking water purification plant, J. Environ. Chem. Eng., 8 (6), 104530.

[42] Chella, S., Kollu, P., Komarala, E.V.P.R., Doshi, S., Saranya, M., Felix, S., Ramachandran, R., Saravanan, P., Koneru, V.L., Venugopal, V., Jeong, S.K., and Grace, A.N., 2015, Solvothermal synthesis of MnFe2O4-graphene composite—Investigation of its adsorption and antimicrobial properties, Appl. Surf. Sci., 327, 27–36.


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