Phosphate Removal from Water and Wastewater using Sepia (Cuttlefish) Endoskeleton Powder as a Natural Adsorbent

Document Type : Research Paper


1 Assist. Prof., Dept. of Chemistry, Ahvaz Branch, Islamic Azad University, Ahvaz, Iran

2 MSc, Abadan School of Medical Sciences, Abadan, Iran

3 Assoc. Prof., Marine Pharmaceutical Science Research Center, Faculty of Pharmacy, Ahvaz Jundishapur University of Medical Sciences, Ahvaz, Iran


Wastewaters produced from various industries and their entry into surface water is one of the most important environmental problems that have harmful effects on aquatic life. Discharging phosphate from urban and industrial wastewater to the aquatic environment causes a lot of algae growth. The aim of this study was to evaluate the removal of phosphate from aqueous solutions using sepia endoskeleton (cuttlebone) powder as a natural biomass, cheap and non-toxic absorbent. This study was conducted in a batch system. Sepia endoskeleton was washed with distilled water. It was then dried at 80 °C and thoroughly powdered by milling. Physical and chemical properties of the adsorbent were determined using the Particle Sizer, atomic force microscopy, and infrared spectroscopy and X-ray fluorescence. The effects of variables affecting phosphate uptake, such as pH, adsorbent amount, contact time, initial concentration of phosphate and stirring rate were optimized. Also, the isotherm models (Langmuir, Freundlich, Tamkin and Dubbin-Radshkvich) and first-order and second-order kinetics models were used to evaluate the data. The results showed that the highest removal percentage was observed at pH 5, adsorbent content of 5 g/L and contact time of 10 min at initial phosphate concentration of 10 mg/L. Using sepia powder under optimal laboratory conditions, the phosphate ion with the concentration of 10 mg/L was removed with a yield of over 99%. The results indicated that the Freundlich isotherm model gives a better description than other models showing the adsorption of phosphate ions occurs in a heterogeneous surface. Using Langmuir model, the maximum absorption capacity for phosphate was 68.02 mg/g. The kinetic model of phosphate removal followed the pseudo-second-order model. Besides, the percentage of removal of the real samples was over 98%, indicating the great ability of this natural and inexpensive absorbent to remove this pollutant from the water solutions.


Akar, S. T., Tosun, I., Ozcan, A. & Gedikbey, T. 2010. Phosphate removal potential of the adsorbent material prepared from thermal decomposition of alunite ore–KCl mixture in environmental cleanup. Desalination, 260, 107-113.
Almeelbi, T. & Bezbaruah, A. 2012. Aqueous phosphate removal using nanoscale zero-valent iron. Nanotechnology for Sustainable Development. 14, 197-210.
Battistella E., Mele, S., Foltran, I., Giorgio Lesei, I., Roveri, N., Sabatino, P., et al. 2012. Cuttlefish bone scaffold for tissue engineering: a novel hydrothermal transformation, chemical-physical, and biological characterization. Journal of Applied Biomaterials and Functional Materials, 10(2),  99-106.
Almeelbi, T. & Bezbaruah, A. 2012. Aqueous phosphate removal using nanoscale zero-valent iron. Journal of Nanoparticle Research, 14, 900.
Ben Nasr, A., Walha, K., Charcosset, C. & Ben Amar, R. 2011. Removal of fluoride ions using cuttlefish bones. Journal of Fluorine Chemistry, 132, 57-62.
Berkessa, Y. W., Mereta, S. T. & Feyisa, F. F. 2019. Simultaneous removal of nitrate and phosphate from wastewater using solid waste from factory. Applied Water Science, 9(2), 28.
Banu, H., T., Karthikeyan, P. & Meenakshi, S. 2018. Lanthanum (III) encapsulated chitosan-montmorillonite composite for the adsorptive removal of phosphate ions from aqueous solution. International Journal of Biological Macromolecules, 112, 284-293.
Chen, X., Kong, H., Wu, D., Wang, X. & Lin, Y. 2009. Phosphate removal and recovery through crystallization of hydroxyapatite using xonotlite as seed crystal. Journal of Environmental Sciences, 21, 575-580.
Chiou, C. S., Lin, Y. F., Chen, H. W., Chang, C. C. & Chang, S. H. 2015. Adsorption of phosphate in aqueous solution by magnetite modified with diethylenetriamine. Journal of Nanosci Nanotechnol, 15(4), 2850-2857.
Ding, H., Zhao, Y., Duan, Q., Wang, J., Zhang, K., Ding, G., et al. 2017. Efficient removal of phosphate from aqueous solution using novel magnetic nanocomposites with Fe3O4 @SiO2 core and mesoporous CeO2 shell. Journal of Rare Earths, 35, 984-994.
He, Y., Lin, H., Dong, Y., Liu, Q. & Wang, L. 2016. Simultaneous removal of ammonium and phosphate by alkaline-activated and lanthanum-impregnated zeolite. Chemosphere, 164, 387-395.
Hong, X., Zhu, E., Ye, Z., Hui, K. S. & Hui, K. N. 2019. Enhanced phosphate removal under an electric field via multiple mechanisms on MgAl-LDHs/AC composite electrode. Journal of Electroanalytical Chemistry, 836, 16-23.
Iftekhar, S., Kucuk, M. E., Srivastava, V., Repo, E. & Sillanpaa, M. 2018. Application of zinc-aluminium layered double hydroxides for adsorptive removal of phosphate and sulfate: equilibrium, kinetic and thermodynamic. Chemosphere, 209, 470-479.
Ivankovic H., Ferrer, G. G., Tkalcec E., Orlic, S. & Ivankovic, M. 2009. Preparation of highly porous hydroxyapatite from cuttlefish bone. Journal of Materials Science: Materials in Medicine,20(5), 1039-1046.
Jia, Z., Hao, S. & Lu, X. 2018. Exfoliated Mg-Al-Fe layered double hydroxides/polyether sulfone mixed matrix membranes for adsorption of phosphate and fluoride from aqueous solutions. Journal of Environmental Sciences, China, 70, 63-73.
Jiang, H., Chen, P., Luo, S., Tu, X., Cao, Q. & Shu, M. 2013. Synthesis of novel nanocomposite Fe3O4/ZrO2/chitosan and its application for removal of nitrate and phosphate. Applied Surface Science, 284, 942-949.
Jung, K. W., Hwang, M. J., Ahn, K. H. & Ok, Y. S. 2015. Kinetic study on phosphate removal from aqueous solution by biochar derived from peanut shell as renewable adsorptive media. International Journal of Environmental Science and Technology, 12, 3363-3372.
Katz, I. & Dosoretz, C. G. 2008. Desalination of domestic wastewater effluents: phosphate removal as pretreatment. Desalination, 222(1), 230-242.
Khedri, N., Ramezani, Z. & Rahbar, N. 2016. Fast, green and effective chromium bio-speciation using Sepia pharaonis endoskeleton nano-powder. International Journal of Environmental Science and Technology, 13, 2475-2484.
Li, Y., He, X., Hu, H., Zhang, T., Qu, J. & Zhang, Q. 2018. Enhanced phosphate removal from wastewater by using in situ generated fresh trivalent Fe composition through the interaction of Fe(II) on CaCO3. Journal of Environmental Management,221, 38-44.
Li, Y. Z., Pan, H., Xu, J., Fan, X. W., Song, X. C., Zhang, Q., et al. 2010. Characterization of metal removal by os sepiae of Sepiella maindroni Rochebrune from aqueous solutions. Journal of Hazardous Materials,
179(1-3), 266-75.
Lin, Y. F., Chen, H. W., Chen, Y. C. & Chiou, C. S. 2013. Application of magnetite modified with polyacrylamide to adsorb phosphate in aqueous solution. Journal of the Taiwan Institute of Chemical Engineers, 44, 45-51.
Liu, J., Wan, L., Zhang, L. & Zhou, Q. 2011. Effect of pH, ionic strength, and temperature on the phosphate adsorption onto lanthanum-doped activated carbon fiber. Journal of Colloid and Interface Science, 364(2), 490-6.
Mezenner, N. Y. & Bensmaili, A. 2009. Kinetics and thermodynamic study of phosphate adsorption on iron hydroxide-eggshell waste. Chemical Engineering Journal, 147, 87-96.
Mitrogiannis D, Psychoyou, M., Baziotis, I., Inglezakis, V. J., Koukouzas, N., Tsoukalas, N., et al. 2017. Removal of phosphate from aqueous solutions by adsorption onto Ca(OH)2 treated natural clinoptilolite. Chemical Engineering Journal, 320, 510-22.
Monclus, H., Sipma, J., Ferrero, G., Rodriguez-Roda, I. & Comas, J. 2010. Biological nutrient removal in an MBR treating municipal wastewater with special focus on biological phosphorus removal. Bioresource Technology, 101(11), 3984-91.
Namasivayam, C., Sakoda, A. & Suzuki, M. 2005. Removal of phosphate by adsorption onto oyster shell powder? kinetic studies. Journal of Chemical Technology and Biotechnology, 80, 356-358.
Ogata, F., Imai, D., Toda, M., Otani, M. & Kawasaki, N. 2015. Adsorption of phosphate ion in aqueous solutions by calcined cobalt hydroxide at different temperatures. Journal of Environmental Chemical Engineering, 3, 1570-1577.
Omidinasab, M., Rahbar, N., Ahmadi, M., Kakavandi, B., Ghanbari, F., Kyzas, G. Z., et al. 2018. Removal of vanadium and palladium ions by adsorption onto magnetic chitosan nanoparticles. Environmental Science and Pollution Research, 25(34), 34262-34276.
Onar A. N., Balkaya, N. & Akyüz, T. 1996. Phosphate removal by adsorption. Environmental Technology, 17(2), 207-213.
Qiu, H., Liang, C., Yu, J., Zhang, Q., Song, M. & Chen, F. 2017. Preferable phosphate sequestration by nano-La(III) (hydr)oxides modified wheat straw with excellent properties in regeneration. Chemical Engineering Journal, 315, 345-354.
Rahbar, N., Yazdanpanah, H., Ramezani, Z., Shushizadeh, M. R., Enayat, M. & Mansourzadeh, M. 2018. Comparative and competitive adsorption of Cu(II), Cd(II) and Pb(II) onto Sepia pharaonis endoskeleton biomass from aqueous solutions. Water and Environment Journal, 32(2), 209-216.
Rahbar, N., Jahangiri, A., Boumi, S. & Khodayar, M. J. 2014. Mercury removal from aqueous solutions with chitosan-coated magnetite nanoparticles optimized using the Box-Behnken design. Jundishapur Journal of Natural Pharmaceutical Products,9(2), e15913.
Saha, B., Griffin, L. & Blunden, H. 2010. Adsorptive separation of phosphate oxyanion from aqueous solution using an inorganic adsorbent. Environmental Geochemistry and Health, 32(4), 341-7.
Sellner, B. M., Hua, G. & Ahiablame, L. M. 2019. Fixed bed column evaluation of phosphate adsorption and recovery from aqueous solutions using recycled steel byproducts. Journal of Environmetal Management, 233, 595-602.
Shushizadeh, M. R., Pour, E. M., Zare, A. & Lashkari, Z. 2015. Persian gulf β-chitin extraction from sepia pharaonis sp. cuttlebone and preparation of its derivatives. Bioactive Carbohydrates and Dietary Fibre, 6, 133-142.
Sousa, A. F. D., Braga, T. P., Gomes, E. C. C., Valentini, A. & Longhinotti, E. 2012. Adsorption of phosphate using mesoporous spheres containing iron and aluminum oxide. Chemical Engineering Journal, 210, 143-149.
Ure, D., Awada, A., Frowley, N., Munk, N., Stanger, A. & Mutus, B. 2019. Greenhouse tomato plant roots/carboxymethyl cellulose method for the efficient removal and recovery of inorganic phosphate from agricultural wastewater. Journal of Environmental Management, 233, 258-263.
Vieira, B., Coelho, L. H. G. & De Jesus, T. A. 2019. Phosphate sorption in shellfish shell (venerupis pulastra) substrates: development of green and low-cost technology for tertiary treatment of effluents. Journal of Environmental Engineering, 145, 0401-8137.
Wang, W. Y., Yue, Q. Y., Xu, X., Gao, B. Y., Zhang, J., Li, Q., et al. 2010. Optimized conditions in preparation of giant reed quaternary amino anion exchanger for phosphate removal. Chemical Engineering Journal, 157, 161-167.
Wang, W., Ma, C., Zhang, Y., Yang, S., Shao, Y. & Wang, X. 2016. Phosphate adsorption performance of a novel filter substrate made from drinking water treatment residuals. Journal of Environment Sciences, China,45, 191-9.
Xu, X., Song, W., Huang, D., Gao, B., Sun, Y., Yue, Q., et al. 2015. Performance of novel biopolymer-based activated carbon and resin on phosphate elimination from stream. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 476, 68-75.
Zarrabi, M., Noori, S. M., Shakak, M., Ebrahimzadeh, G. & Taghavi, M. 2017. Removal of phosphate from aqueous solutions by yellow and red soil from West Azerbaijan and its EDTA-modified form. Journal of Sabzevar University of Medical Sciences,244, 239-248. (In Persian)
Zhang, L., Liu, J. & Guo, X. 2018. Investigation on mechanism of phosphate removal on carbonized sludge adsorbent. Journal of Environmental Sciences, China, 64, 335-344.