Adsorption of fluoride ions from aqueous solution by rice husk based nanocellulose

Document Type : Research Paper


Department of Environmental Science and Engineering, Guru Jambheshwar University of Science and Technology, Hisar-125001 (Haryana), India


Synthesis of nanocellulose using crop residue rice husk is an innovative method. Morphological and structural characterizations of nanocellulose were analyzed. The rice husk based nanocellulose had a particle height of 5.7 nm and a crystallinity index of 70%. Raw rice husk comprises 35% cellulose, 22% hemicellulose, 19.1% lignin, and 20% ash. Defluoridation of water samples is an imperious provocation for the advancement of society. According to World Health Organisation (WHO) guidelines, a fluoride concentration of more than 1.5 milligrams per litre leads to dental problems and bone deficiency. The appropriate defluoridation practice was selected to avoid these problems. Cost-effective nanocellulose from rice husk was used as an adsorbent to purify a fluoride-rich aqueous solution in batch experiments on a lab scale. Response of dose, temperature, time, pH, and initial ion concentration on adsorption capacity and removal efficiency were deliberated. In batch experiments, the highest removal efficiency of fluoride from aqueous solution was 74% at a 120 min time, 2 mg/l initial ion concentration, 30 ˚C temp, 0.9 g adsorbent dose at pH 2. According to WHO standards, fluoride concentrations above 1.5 mg/l cause tooth and bone insufficiency. Regeneration showed that the adsorbent was cost-effective and reusable. Two, three, and four-parameter isotherm models were applied to the experimental data. The Freundlich, Langmuir, Temkin, Redlich-Peterson, and Baudu isotherm models and the pseudo-second-order kinetic and intra-particle diffusion models best fit the data. The studied thermodynamic constraints showed the physical adsorption of fluoride.

Graphical Abstract

Adsorption of fluoride ions from aqueous solution by rice husk based nanocellulose


Main Subjects

[1] Vijila, B., Gladis, E. E., Jose, J. M. A., Sharmila, T. M., Joseph, J. (2021). Removal of fluoride with rice husk derived adsorbent from agro waste materials. Materials Today: Proceedings, 45, 2125-2129.
[2] Meenakshi, Garg, V. K., Kavita, Renuka, Malik, A. (2004). Groundwater quality in some villages of Haryana, India: focus on fluoride and fluorosis. Journal of Hazardous Materials, 106(1), 85-97.
[3] World Health Organization (2001). Environmental Health Criteria (EHC).
[4] Jolly, S.S., Sing, B.M., Mathur, O.C. (1969). Endemic fluorosis in Punjab (India). The American Journal of Medicine, 47(4), 553-563.
[5] Oguz, E. (2005). Adsorption of fluoride on gas concrete materials. Journal of Hazardous Materials, 117(2-3), 227-233.
[6] Dehbandi, R., Moore, F., Keshavarzi, B. (2018). Geochemical sources, hydrogeochemical behavior, and health risk assessment of fluoride in an endemic fluorosis area, central Iran. Chemosphere, 193, 763-776.
[7] Mukherjee, I., Singh, U.K., Patra, P.K. (2019). Exploring a multi-exposure-pathway approach to assess human health risk associated with groundwater fluoride exposure in the semi-arid region of east India. Chemosphere, 233, 164-173.
[8] Miretzky, P.and Cirelli, A.F. (2011). Fluoride removal from water by chitosan deriva- tives and composites: a review. Journal of Fluorine Chemistry, 132(4), 231-240.
[9] Lahnid, S., Tahaikt, M., Elaroui, K., Idrissi, I., Hafsi, M., Laaziz, I. (2008). Eco- nomic evaluation of fluoride removal by electrodialysis. Desalination, 230(1–3), 213-219.
[10] Reardon, E.J. and Wang, Y. X. (2000). A limestone reactor for fluoride removal from wastewaters. Environmental Science and Technology, 34(15), 3247-3253.
[11] Ndiayea, P.I., Moulin, P., Dominguez, L., Millet, J.C., Charbit, F. (2005). Removal of fluoride from electronic industrial effluent by RO membrane separation. Desalination, 173(1), 25-32.
[12] Meenakshi, S. and Viswanathan, N. (2007). Identification of selective ion-exchange resin for fluoride sorption. Journal of Colloid and Interface Science, 308(2), 438–450.
[13] Ahmed, S.A. (2011). Batch and fixed-bed column techniques for removal of Cu (II) and Fe (III) using carbohydrate natural polymer modified complexing agents. Carbohydrate Polymers, 83(4), 1470-1478.
[14] Akafu, T., Chimdi, A., Gomoro, K. (2019). Removal of fluoride from drinking water by sorption using diatomite modified with aluminum hydroxide. Journal of analytical methods in chemistry, 2019.
[15] Waghmare, S., Arfin, T., Rayalu, S., Lataye, D., Dubey, S., Tiwari, S. (2015). Adsorption behavior of modified zeolite as novel adsorbents for fluoride removal from drinking water: surface phenomena, kinetics and thermodynamics studies. International Journal of Science, Engineering and Technology Research, 4(12), 4114-4124.
[16] Bhatnagar, A., Kumar, E., Sillanpaa, M. (2011). Fluoride removal from water by adsorption—a review. Chemical Engineering Journal, 171(3), 811–840.
[17] Mohapatra, M., Anand, S., Mishra, B.K., Giles, D.E., Singh, P. (2009). Review of fluoride removal from drinking water. Journal of Environmental Management, 91(1), 67-77.
[18] Yu, X., Tong, S., Ge, M., Zuo, J. (2013). Removal of fluoride from drinking water by cellulose @ hydroxyapatite nanocomposites. Carbohydrate Polymers, 92(1), 269-275.
[19] Han, R., Wang, Y., Yu, W., Zou, W., Shi, J., Liu, H. (2007). Biosorption of methylene blue from aqueous solution by rice husk in a fixed-bed column. Journal of Hazardous Materials, 141(3), 713-718.
[20] Vardhan, C. V., Karthikeyan, J. (2011, September). Removal of fluoride from water sing low-cost materials. In Fifteenth International Water Technology Conference, IWTC-15 (Vol. 1, No. 2, pp. 1-14).
[21] Goering, H. K., Van Soest, P. J. (1970). Forage fiber analyses (apparatus, reagents, procedures, and some applications) (No. 379). US Agricultural Research Service.
[22] Ananthi, A., Geetha, D., Ramesh, P.S. (2016). Preparation and characterization of silica material from rice husk ash–an economically viable method. Chemistry and Materials Research, 8(6), 1-7.
[23] Ma’ruf, A., Pramudono, B., Aryanti, N. (2017, March). Lignin isolation process from rice husk by alkaline hydrogen peroxide: Lignin and silica extracted. In AIP Conference Proceedings (Vol. 1823, No. 1). AIP Publishing.
[24] Chandra, J., George, N., Narayanankutty, S.K. (2016). Isolation and characterization of cellulose nanofibrils from arecanut husk fibre. Carbohydrate Polymers,142, 158-166.
[25] Mandal, A.andChakrabarty, D. (2011). Isolation of nanocellulose from waste sugarcane bagasse (SCB) and its characterization. Carbohydrate Polymers, 86(3), 1291-1299.
[26] Alemdar, A. and Sain, M. (2008). Biocomposites from wheat straw nanofibres: Morphology, thermal and mechanical properties. Composites Science and Technology, 68(2), 557-565.
[27] Segal, L.G.J.M.A., Creely, J.J., Martin Jr, A.E., Conrad, C.M. (1959). An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Textile Research Journal, 29(10), 786-794.
[28] de Souza Lima, M.M.and Borsali, R. (2004). Rodlike cellulose microcrystals: structure, properties, and applications. Macromolecular Rapid Communications, 25(7), 771-787.
[29] Tang, L.G., Hon, D.N.S., Pan, S.H., Zhu, Y.Q., Wang, Z., Wang, Z.Z. (1996). Evaluation of microcrystalline cellulose. I. Changes in ultrastructural characteristics during preliminary acid hydrolysis. Journal of Applied Polymer Science, 59(3), 483-488.
[30] Azizi Samir, M.A.S., Alloin, F., Dufresne, A. (2005). Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite field. Biomacromolecules, 6(2), 612-626.
[31] Moran, J.I., Alvarez, V.A., Cyras, V.P., Vázquez, A. (2008). Extraction of cellulose and preparation of nanocellulose from sisal fibres. Cellulose, 15(1), 149-159.
[32] Silverio, H.A., Neto, W.P.F., Dantas, N.O., Pasquini, D. (2013). Extraction and characterization of cellulose nanocrystals from corncob for application as reinforcing agent in nanocomposites. Industrial Crops and Products 44, 427-436.
[33] Johar, N., Ahmad, I., Dufresne, A. (2012). Extraction, preparation and characterization of cellulose fibres and nanocrystals from rice husk. Industrial Crops and Products, 37(1), 93-99.
[34] Hornsby, P.R., Hinrichsen, E., Tarverdi, K. (1997). Preparation and properties of polypropylene composites reinforced with wheat and flax straw fibres: part I fibre characterization. Journal of Materials Science, 32(2), 443-449.
[35] Deshmukh, W.S., Attar, S.J., Waghmare, M.D. (2009). Investigation on fluoride in water using rice husk as an adsorbent. Nature, Environment and Pollution Technology, 8(2), 217-223.
[36] Tembhurkar, A.R.andDongre, S. (2006). Studies on fluoride removal using adsorption process. Journal of Environmental Science and Engineering, 48(3), 151-156.
[37] Yadav, A.K., Kaushik, C.P., Haritash, A.K., Kansal, A., Rani, N. (2006). Defluoridation of groundwater using brick powder as an adsorbent. Journal of Hazardous materials, 128(2-3), 289-293.
[38] Roy, S., Das, P., Sengupta, S. (2017). Thermodynamics and kinetics study of defluoridation using Ca-SiO2-TiO2 as adsorbent: column studies and statistical approach. Korean Journal of Chemical Engineering, 34(1), 179-188.
[39] Uddin, M.K., Ahmed, S.S., Naushad, M. (2019). A mini update on fluoride adsorption from aqueous medium using clay materials. Desalination and Water Treatment, 145, 232-248.
[40] Kir, E., Oruc, H., Kir, I., Sardohan-Koseoglu, T. (2016). Removal of fluoride from aqueous solution by natural and acid-activated diatomite and ignimbrite materials. Desalination and Water Treatment, 57(46), 21944-21956.
[41] Jamode, A.V., Sapkal, V.S., Jamode, V.S., Deshmukh, S.K. (2004). Adsorption kinetics of defluoridation using low-cost adsorbents. Adsorption Science and Technology, 22(1), 65-73.
[42] Chandra, V., Park, J., Chun, Y., Lee, J.W., Hwang, I.C., Kim, K.S. (2010). Water-dispersible magnetite-reduced graphene oxide composites for arsenic removal. ACS nano, 4(7), 3979-3986.
[43] Ho, Y.S. and McKay, G. (1999). Pseudo-second order model for sorption processes. Process Biochemistry, 34(5), 451-465.
[44] Ho, Y.S. and McKay, G. (1999). The sorption of lead (II) ions on peat. Water Research, 33(2), 578-584.
[45] Freundlich, H. (1906). Concerning adsorption in solutions.Zeitschrift Fur Physikalis- cheChemie—Stochiometrie Und Verwandtschaftslehre, 57(4), 385–470.
[46] Langmuir, I. (1918). Adsorption of gases on plain surfaces of glass, mica platinum. Journal of the American Chemical Society, 40, 1361–1403.
[47] Tian, Y., Wu, M., Lin, X., Huang, P., Huang, Y. (2011). Synthesis of magnetic wheat straw for arsenic adsorption. Journal of Hazardous Materials, 193, 10-16.
[48] Chen, Z., Ma, W., Han, M. (2008). Biosorption of nickel and copper onto treated alga (Undariapinnatifida): application of isotherm and kinetic models. Journal of Hazardous Materials, 155(1-2), 327-333.
[49] Foo, K.Y.and Hameed, B.H. (2010). Insights into the modeling of adsorption isotherm systems. Chemical Engineering Journal, 156(1), 2-10.
[50] Benhammou, A., Yaacoubi, A., Nibou, L., Tanouti, B. (2005). Adsorption of metal ions onto Moroccan stevensite: kinetic and isotherm studies. Journal of Colloid and Interface Science, 282(2), 320-326.
[51] Srivastava, V.C., Swamy, M.M., Mall, I.D., Prasad, B., Mishra, I.M. (2006). Adsorptive removal of phenol by bagasse fly ash and activated carbon: equilibrium, kinetics and thermodynamics. Colloids and Surfaces a: Physicochemical and Engineering Aspects, 272(1-2), 89-104.
[52] Allen, S.J., Mckay, G., Porter, J.F. (2004). Adsorption isotherm models for basic dye adsorption by peat in single and binary component systems. Journal of Colloid and Interface Science, 280(2), 322-333.
[53] Tsai, W.T., Hsu, H.C., Su, T.Y., Lin, K.Y., Lin, C.M. (2006). Adsorption characteristics of bisphenol-A in aqueous solutions onto hydrophobic zeolite. Journal of Colloid and Interface Science, 299(2), 513-519.
[54] Artola, A., Martin, M., Balaguer, M., Rigola, M. (2000). Isotherm model analysis for the adsorption of Cd (II), Cu (II), Ni (II), and Zn (II) on anaerobically digested sludge. Journal of Colloid and Interface Science, 232(1), 64-70.
[55] Wu, F.C., Liu, B.L., Wu, K.T., Tseng, R. L. (2010). A new linear form analysis of Redlich–Peterson isotherm equation for the adsorptions of dyes. Chemical Engineering Journal, 162(1), 21-27.
[56] Wang, J.P., Feng, H.M., Yu, H.Q. (2007). Analysis of adsorption characteristics of 2, 4-dichlorophenol from aqueous solutions by activated carbon fibre. Journal of Hazardous Materials, 144(1-2), 200-207.
[57] Tor, A.and Cengeloglu, Y. (2006). Removal of congo red from aqueous solution by adsorption onto acid activated red mud. Journal of Hazardous Materials,138(2), 409-415.
[58] Kundu, S. and Gupta, A.K. (2007). Adsorption characteristics of As (III) from aqueous solution on iron oxide coated cement (IOCC). Journal of Hazardous Materials, 142(1-2), 97-104.
[59] Ozer, A.andDursun, G. (2007). Removal of methylene blue from aqueous solution by dehydrated wheat bran carbon. Journal of Hazardous Materials, 146(1-2), 262-269.
[60] McKay, G., Mesdaghinia, A., Nasseri, S., Hadi, M., Aminabad, M.S. (2014). Optimum isotherms of dyes sorption by activated carbon: Fractional theoretical capacity and error analysis. Chemical Engineering Journal, 251, 236-247.
[61] Ravnote, O.M.and Adsorpcizo, N.I.Z. (2013). Evaluation of equilibrium isotherm models for the adsorption of Cu and Ni from wastewater on bentonite clay. Materiali in Tehnologije, 47(4), 481-486.
[62] Van Vliet, B.M., Weber Jr, W.J., Hozumi, H. (1980). Modeling and prediction of specific compound adsorption by activated carbon and synthetic adsorbents. Water Research 14(12), 1719-1728.
[63] Hamad, B.K., Noor, A.M., Rahim, A.A. (2011). Removal of 4-chloro-2-methoxyphenol from aqueous solution by adsorption to oil palm shell
       activated carbon activated with K2CO3. Journal of Physical Science, 22(1), 39-55.
[64] Sujana, M.G., Pradhan, H.K., Anand, S. (2009). Studies on sorption of some geomaterials for fluoride removal from aqueous solutions. Journal of Hazardous Materials, 161(1), 120-125.
[65] Yu, Y., Zhuang, Y.Y., Wang, Z.H., Qiu, M.Q. (2004). Adsorption of water-soluble dyes onto modified resin. Chemosphere, 54(3), 425-430.
[66] Liu, Y.and Liu, Y.J. (2008). Biosorption isotherms, kinetics and thermodynamics. Separation and Purification Technology, 61(3), 229-242.
[67] Dzieniszewska, A., Nowicki, J., Rzepa, G., Kyziol-Komosinska, J., Semeniuk, I., Kiełkiewicz, D., Czupioł, J. (2022). Adsorptive removal of fluoride using ionic liquid-functionalized chitosan–Equilibrium and mechanism studies. International Journal of Biological Macromolecules, 210, 483-493.
[68] Tefera, N., Mulualem, Y., Fito, J. (2020). Adsorption of fluoride from aqueous solution and groundwater onto activated carbon of avocado seeds. Water Conservation Science and Engineering, 5(3), 187-197.
[69] Bibi, S., Farooqi, A., Yasmin, A., Kamran, M. A., Niazi, N. K. (2017). Arsenic and fluoride removal by potato peel and rice husk (PPRH) ash in aqueous environments. International journal of Phytoremediation, 19(11), 1029-1036.
[70] Singh, K., Lataye, D.H.,Wastewater, K.L. (2016). Removal of fluoride from aqueous solution by using low-cost sugarcane bagasse: kinetic study and equilibrium isotherm analyses. Journal of Hazardous, Toxic, and Radioactive Waste, 20(3), 04015024.
[71] Mondal, N.K. and Roy, A. (2018). Potentiality of a fruit peel (banana peel) toward abatement of fluoride from synthetic and underground water samples collected from fluoride affected villages of Birbhum district. Applied Water Science, 8(3), 1-10.
[72] Singh, N.B., Srivastava, Y.K.,Shukla, S.P. (2019). Investigating the efficacy of saw dust in fluoride removal through adsorption. Journal of The Institution of Engineers (India): Series A, 100(4), 667-674.
[73] Talat, M., Mohan, S., Dixit, V., Singh, D.K., Hasan, S.H., Srivastava, O.N. (2018). Effective removal of fluoride from water by coconut husk activated carbon in fixed bed column: Experimental and breakthrough curves analysis. Groundwater for Sustainable Development, 7, 48-55.