Synthesis and characterization of aluminum-based adsorbent and application in fluoride removal from aqueous solution


  • Jihane Assaoui Chouaïb Doukkali University, Faculty of Science, Water and Environment Team, Laboratory “Biomaterials and Electrochemistry”,El Jadida, Morocco
  • Zineb Hatim Chouaïb Doukkali University, Faculty of Science, Water and Environment Team, Laboratory “Biomaterials and Electrochemistry”,El Jadida, Morocco
  • Abdelmoula Kheribeche Chouaïb Doukkali University, Faculty of Science, Water and Environment Team, Laboratory “Biomaterials and Electrochemistry”,El Jadida, Morocco



A novel adsorbent was obtained by a facile precipitation method and was used for fluoride removal from aqueous solution. Mineralogical and physicochemical characterization of the adsorbent was carried out by X-Ray Diffraction (XRD), X-Ray Fluorescence (XRF), Energy Dispersive X-Ray attached to Scanning Electron Microscopy (SEM-EDX), BET Specific Surface Area(SSAN2BET) analysis and Fourier-Transform Infrared Spectrometry (FTIR). The effect of various operational parameters such as contact time, initial fluoride concentration, (20-160 mg L-1) adsorbent dose (1-6 g L-1) and initial pH solution (3-11) was evaluated in batch procedures at room temperature (25±2°C). The results of the batch adsorption experiments proved that 24 h of contact time was sufficient for attaining equilibrium. The maximum wastewater defluoridation (84.91%) was obtained for 40 mg L-1 and 3 g L-1 of initial fluoride concentration and adsorbent dose, respectively. It appears that there was no significant effect on the F- removal over a wide range of pH 3-11. Kinetic studies revealed that fluoride adsorption fitted well to pseudo-second-order. The adsorption isotherm of fluoride sorption indicated that the maximum adsorption capacity was noted to be 43.29 mg g-1. Batch adsorption data was better described by Langmuir isotherm confirming monolayer adsorption with homogenous distribution of active sites and without interaction between adsorbed molecules. The obtained results indicated that the ion exchange is probably the main mechanism involved in the F- adsorption by the aluminium-based adsorbent.

Author Biographies

Jihane Assaoui, Chouaïb Doukkali University, Faculty of Science, Water and Environment Team, Laboratory “Biomaterials and Electrochemistry”,El Jadida, Morocco

Dr in departement chemistry and application, Water and Environment Team, Laboratory “Biomaterials and Electrochemistry”

Zineb Hatim, Chouaïb Doukkali University, Faculty of Science, Water and Environment Team, Laboratory “Biomaterials and Electrochemistry”,El Jadida, Morocco

Pr in departement chemistry and application, Water and Environment Team, Laboratory “Biomaterials and Electrochemistry”

Abdelmoula Kheribeche, Chouaïb Doukkali University, Faculty of Science, Water and Environment Team, Laboratory “Biomaterials and Electrochemistry”,El Jadida, Morocco

Pr in departement chemistry and application, Water and Environment Team, Laboratory “Biomaterials and Electrochemistry”


- N. Mondillo, M. Boni, G. Balassone, S. Spoleto, F. Stellato, A. Marino, L. Santoro, J. Spratt, Rareearth elements minerals in the silius fluorite vein system (sardinia, italy), Ore Geol. Rev., 2016, 74, 211-224.

- S.S. Tripathy, J.L. Bersillon, K. Gopal, Removal of fluoride from drinking water by adsorption onto alum-impregnated activated alumina, Sep. Purif. Technol., 2006, 50, 310-317.

- D.E. Yerien, S. Bonesi, A. Postigo, Fluorination methods in drug discovery, Org. Biomol. Chem., 2016, 14, 8398-8427.

- Y.P. Xiao, J. Zhang, Y.H. Liu, J.H. Zhang, Q.Y. Yu, Z. Huang, X.Q. Yu, Low molecular weight PEI-based fluorinated polymers for efficient gene delivery, Eur. J. Med. Chem., 2019, 162, 602-611.

- I. Kaur, B.N. Misra, A. Kohli, Synthesis of Teflon-FEP grafted membranes for use in water desalination, Desalination, 2001, 139, 357-365.

- K.S. Oh, W. Bae, H. Kim, Dispersion polymerization of N-vinylcarbazole using siloxane-based and fluorine-based surfactants in compressed liquid dimethyl ether, Polymer, 2007, 48, 1450-1454.

- S. Sasamoto, H. Suzuki, Fluorine-based surfactant, and coating composition and resist composition each using the same, US20130172476A1, 2013.

- M. Mohapatra, K. Rout, P. Singh, S. Anand, S. Layek, H.C. Verma, B.K. Mishra, Fluoride adsorption studies on mixed-phase nano iron oxides prepared by surfactant mediation-precipitation technique, J. Hazard. Mater., 2011, 186, 1751-1757.

- J. Dai, Stable electrolytes for high voltage batteries and the batteries derived therefrom, US20110200864A1, 2011.

- A. Ghosh, K. Mukherjee, S.K. Ghosh, B. Saha, Sources and toxicity of fluoride in the environment, Res. Chem. Intermed., 2013, 39, 2881-2915.

- L. Deng, Y. Liu, T. Huang, T. Sun, Fluoride removal by induced crystallization using fluorapatite/calcite seed crystals, Chem. Eng. J., 2016, 287, 83-91.

- D.L. Ozsvath, Fluoride and environmental health: a review, Rev. Environ. Sci. Biotechnol., 2009, 8, 59-79.

- S. Raghav, D. Kumar, Adsorption equilibrium, kinetics, and thermodynamic studies of fluoride adsorbed by tetrametallic oxide adsorbent, J. Chem. Eng. Data., 2018, 63, 1682-1697.

- C.Y. Hu, S.L. Lo, W.H. Kuan, Y.D. Lee, Removal of fluoride from semiconductor wastewater by electrocoagulation–flotation, Water Res., 2005, 39, 895-901.

- H. Huang, J. Liu, P. Zhang, D. Zhang, F. Gao, Investigation on the simultaneous removal of fluoride, ammonia nitrogen and phosphate from semiconductor wastewater using chemical precipitation, Chem. Eng. J., 2017, 307, 696-706.

- K. Van den Broeck, N. Van Hoornick, J. Van Hoeymissen, R. de Boer, A. Giesen, D. Wilms, Sustainable treatment of HF wastewaters from semiconductor industry with a fluidized bed reactor, IEEE Trans. Semicond. Manuf., 2003, 16, 423-428.

- N. Zhang, X. Xiao, H. Pang, Transition metal (Fe, Co, Ni) fluoride-based materials for electrochemical energy storage, Nanoscale Horiz., 2019, 4, 99-116.

- C.-X. Zu, H. Li, Thermodynamic analysis on energy densities of batteries, Energy Environ. Sci., 2011, 4, 2614.

- A.M.H.R. Hasan, S.K. Sidhu, J.W. Nicholson, Fluoride release and uptake in enhanced bioactivity glass ionomer cement (“glass carbomerTM”) compared with conventional and resin-modified glass ionomer cements, J. Appl. Oral Sci., 2019, 27.

- R.S. Quimby, M. Saad, Pathways to a 4 μm Dy3+ Fluoride Glass Fiber Laser, in: Lasers Congr. 2016 ASSL LSC LAC, OSA, Boston, Massachusetts, 2016, 2A-34.

- J.A. Camargo, Fluoride toxicity to aquatic organisms: a review, Chemosphere, 2003, 50, 251-264.

- M.A. Karami, Y. Fakhri, S. Rezania, A.A. Alinejad, A.A. Mohammadi, M. Yousefi, M. Ghaderpoori, M.H. Saghi, M. Ahmadpour, Non-carcinogenic health risk assessment due to fluoride exposure from tea consumption in iran using monte carlo simulation, Int. J. Environ. Res. Public Health, 2019, 16, 4261.

- S. Raghava, D. Kumara, Comparative kinetics and thermodynamic studies of fluoride adsorption by two novel synthesized biopolymer composites, Carboh Poly., 2019, 203, 430–440.

- M. Yousefi, S. Ghalehaskar, F.B. Asghari, A. Ghaderpoury, M.H. Dehghani, M. Ghaderpoori, A.A. Mohammadi, Distribution of fluoride contamination in drinking water resources and health risk assessment using geographic information system, northwest Iran, J. Reg. Toxicol. Pharm., 2019, 107, 104408.

- S. Gupta, A.N. Poddar, Sodium fluoride toxicity in the fresh water cat fish clarias batrachus (linn.): effects on the erythrocyte morphology and antioxidant enzymes, Res. J. Environ. Toxicol., 2014, 8, 68-76.

- A. Dhillon, S. Nehra, D. Kumar, Dual adsorption behaviour of fluoride from drinking water on Ca-Zn(OH)2CO3 adsorbent, J. Surf. In., 2017, 6, 154-161.

- M. Ghaderpoori, M. Paydar, A. Zarei, H. Alidadi, A.A. Najafpoor, A.H. Gohary, M. Shams, Health risk assessment of fluoride in water distribution network of Mashhad, Iran, Human and Ecological Risk Assessment: An International Journal, 2019, 25, 851-862.

- M. Radfard, M. Rahmatinia, H. Akbari, B. Hashemzadeh, H. Akbari, A. Adibzadeh, Data on health risk assessment of fluoride in water distribution network of Iranshahr, Iran, J. Data. Brief., 2018, 20, 1446–1452.

- B.L. Riggs, S.F. Hodgson, W.M. O’Fallon, E.Y.S. Chao, H.W. Wahner, J.M. Muhs, S.L. Cedel, L.J. Melon, Effect of fluoride treatment on the fracture rate in postmenopausal women with osteoporosis, N. Engl. J. Med., 1990, 322, 802-809.

- J. Li, Q. Zhao, Y. Li, Y. Bao, B. Li, H. Yan, S. Huo, Y. Fan, Y. Yang, Y. Gao, Effects of embryonic exposure to fluoride on bone development of zebrafish, Chin. J. Endem., 2018, 37, 24-29.

- P.T.C. Harrison, Fluoride in water: A UK perspective, J. Fluor. Chem., 2005, 126, 1448-1456.

- Y. Zhou, C. Yu, Y. Shan, Adsorption of fluoride from aqueous solution on La3+ impregnated cross-linked gelatin, Sep. Purif. Technol., 2004, 36, 89-94.

- J. Fawell, K. Bailey, J.Chilton, E. Dahi, Y. Magara, Fluoride in drinking- water the first edition, London, UK, IWA publishing, 2006, 97-126.

-H. Rezaei, A. Jafari, B. Kamarehie, Y. Fakhri, Af. Ghaderpoury, M.A. Karami, M.Ghaderpoori, M. Shams, F. Bidarpoor, M. Salimi, Health-risk assessment related to the fluoride, nitrate, and nitrite in the drinking water in the Sanandaj, Kurdistan County, Iran." Human and ecological risk assessment: an international journal, 2018, 25, 1242-1250.

- G.C. dos Santos Bazanella, G.F. da Silva, A.M.S. Vieira, R. Bergamasco, Fluoride removal from water using combined Moringa Oleifera/ultrafiltration process, Water. Air. Soil Pollut., 2012, 233, 6083-6093.

- M. Suneetha, B.S. Sundar, K. Ravindhranath, Removal of fluoride from polluted waters using active carbon derived from barks of Vitex negundo plant, J. Anal. Sci. Technol., 2015, 6, 15.

- L. Deng, X. Zhang, T. Huang, J. Zhou, Investigation of fluorapatite crystallization in a fluidized bed reactor for the removal of fluoride from groundwater: investigation of fluorapatite crystallization in a fluidized bed reactor for the removal, J. Chem. Technol. Biotechnol., 2019, 94, 569-581.

- N.S. Graça, A.M. Ribeiro, A.E. Rodrigues, Removal of fluoride from water by a continuous electrocoagulation process, Ind. Eng. Chem. Res., 2019, 58, 5314-5321.

- V.F. Mena, A. Betancor-Abreu, S. González, S. Delgado, R.M. Souto, J.J. Santana, Fluoride removal from natural volcanic underground water by an electrocoagulation process: parametric and cost evaluations, J. Environ. Manage., 2019, 246, 472-483.

- Y.-X. Zhang, Y. Jia, Fluoride adsorption on manganese carbonate: Ion-exchange based on the surface carbonate-like groups and hydroxyl groups, J. Colloid Interface Sci., 2018, 510, 407-417.

- N. Viswanathan, I.A. Kumar, S. Meenakshi, Development of chitosan encapsulated tricalcium phosphate biocomposite for fluoride retention, Int. J. Biol. Macromol., 2019, 133, 811-816.

- F. Shen, X. Chen, P. Gao, G. Chen, Electrochemical removal of fluoride ions from industrial wastewater, Chem. Eng. Sci., 2003, 58, 987-993.

- I. Owusu-Agyeman, M. Reinwald, A. Jeihanipour, A.I. Schäfer, Removal of fluoride and natural organic matter from natural tropical brackish waters by nanofiltration/reverse osmosis with varying water chemistry, Chemosphere, 2019, 217, 47-58.

- S. Parveen, V.N. Ratnakaram, S. Malladi, K. Kiram Kumar, Design of a Domestic Defluoridizing Unit, in: B. Subramanian, S.S. Chen, K.R. Reddy (Eds.), Emerg. Technol. Agric. Environ., Springer, Singapore, 2020, 173-183.

- X. Wang, N. Li, J. Li, J. Feng, Z. Ma, Y. Xu, Y. Sun, D. Xu, J. Wang, X. Gao, J. Gao, Fluoride removal from secondary effluent of the graphite industry using electrodialysis: Optimization with response surface methodology, Front. Environ. Sci. Eng., 2019, 13, 51.

- N. Arahman, S. Mulyati, M.R. Lubis, R. Takagi, H. Matsuyama, The removal of fluoride from water based on applied current and membrane types in electrodialysis, J. Fluor. Chem., 2016, 191, 97-102.

- G. Yan, Y. Bao, M. Tan, Q. Cui, X. Lu, Y. Zhang, Defluorination by Donnan Dialysis with seawater for seafood processing, J. Food Eng., 2018, 238, 22-29.

- S.I. Bouhadjar, H. Kopp, P. Britsch, S.A. Deowan, J. Hoinkis, J. Bundschuh, Solar-powered nanofiltration for drinking water production from fluoride-containing groundwater A pilot study towards developing a sustainable and low-cost treatment plant, J. Environ. Manage., 2019, 231, 1263-1269.

- G. Crini, E. Lichtfouse, Advantages and disadvantages of techniques used for wastewater treatment, Environ. Chem. Lett., 2019, 17, 145-155.

- L.S. Thakur, P. Mondal, Simultaneous arsenic and fluoride removal from synthetic and real groundwater by electrocoagulation process: Parametric and cost evaluation, J. Environ. Manage., 2017, 190, 102-112.

- M. Sarkar, A. Banerjee, P.P. Pramanick, A.R. Sarkar, Use of laterite for the removal of fluoride from contaminated drinking water, J. Colloid Interface Sci., 2006, 302, 432-441.

- A. Ndé-Tchoupé, R. Crane, H. Mwakabona, C. Noubactep, K. Njau, Technologies for Decentralized Fluoride Removal: Testing Metallic Iron-based Filters, Water, 2015, 7, 6750-6774.

- H. Wang, Q. Feng, K. Liu, Z. Li, X. Tang, G. Li, Highly efficient fluoride adsorption from aqueous solution by nepheline prepared from kaolinite through alkali-hydrothermal process, J. Environ. Manage., 2017, 196, 72-79.

- M.T. Hadjyoussef, M. Jendoubi, M.B. Amor, Removal of Fluoride from drinking water by an activated Bentonite: application to drinking Tunisian water, Mor. J. Chem., 2018, 6, 135-147.

- K. Kulkarni, G.M. Bhogale, R. Nalawade, Adsorptive removal of fluoride from water samples using Azospirillum biofertilizer and lignite, Korean J. Chem. Eng., 2018, 35, 153-163.

- L. Deng, Y. Liu, T. Huang, T. Sun, Fluoride removal by induced crystallization using fluorapatite/calcite seed crystals, Chem. Eng. J., 2016, 287, 83-91.

- M. Mourabet, A. El Rhilassi, H. El Boujaady, M. Bennani-Ziatni, R. El Hamri, A. Taitai, Removal of fluoride from aqueous solution by adsorption on Apatitic tricalcium phosphate using Box–Behnken design and desirability function, Appl. Surf. Sci., 2012, 258, 4402-4410.

- J.P. Maity, C.-M. Hsu, T.-J. Lin, W.-C. Lee, P. Bhattacharya, J. Bundschuh, C.-Y. Chen, Removal of fluoride from water through bacterial-surfactin mediated novel hydroxyapatite nanoparticle and its efficiency assessment: adsorption isotherm, adsorption kinetic and adsorption Thermodynamics, Environ. Nanotechnol. Monit. Manag., 2018, 9, 18-28.

- A. Vinati, E.R. Rene, K. Pakshirajan, S.K. Behera, Activated red mud as a permeable reactive barrier material for fluoride removal from groundwater: parameter optimisation and physico-chemical characterisation, Environ. Technol., 2019, 6, 1-12.

- M. Dessalegne, F. Zewge, W. Mammo, G. Woldetinsae, I. Diaz, Effective fluoride adsorption by aluminum oxide modified clays: Ethiopian bentonite vs commercial montmorillonite, Bull. Chem. Soc. Ethiop., 2018, 32, 199-211.

- S.S. Tripathy, J.-L. Bersillon, K. Gopal, Removal of fluoride from drinking water by adsorption onto alum-impregnated activated alumina, Sep. Purif. Technol., 2006, 50, 310-317.

- V.K. Gupta, Suhas, Application of low-cost adsorbents for dye removal-A review, J. Environ. Manage., 2009, 90, 2313-2342.

- U. Kumari, S.K. Behera, B.C. Meikap, A novel acid-modified alumina adsorbent with enhanced defluoridation property: Kinetics, isotherm study and applicability on industrial wastewater, J. Hazard. Mater., 2019, 365, 868-882.

- D.-C. Shin, S.S. Park, J.H. Kim, S.S. Hong, J.M. Park, S.H. Lee, D.S. Kim, G.D. Lee, Study on α-alumina precursors prepared using different ammonium salt precipitants, Journal of Industrial and Engineering Chemistry, 2014, 20, 1269-1275.

- NF T 90-004: Water quality – Determination of fluoride ion-Potentiometric method, 2002.

- A. Dhillon, S.K. Soni, D. Kumar, Enhanced fluoride removal performance by Ce-Zn binary metal oxide: Adsorption characteristics and mechanism, J. Fluo. Chem., 2017, 199, 67-76.

- K.G. Bhattacharyya, S.S. Gupta, Influence of acid activation on adsorption of Ni(II) and Cu(II) on kaolinite and montmorillonite: kinetic and thermodynamic study, Chemical Engineering Journal, 2008, 136, 1-13.

- E.I. Unuabonah, K.O. Adebowale, B.-I. Olu-Owolabi, Kinetic and thermodynamic studies of the adsorption of lead (II) ions onto phosphate-modified kaolinite clay, Journal of Hazardous Materials, 2007, 144, 386-395.

- I. Langmuir, The constitution and fundamental properties of solids and liquids, J. Ameri Chem Soci., 1916, 38, 2221-2295.

- H.M.F. Freundlich, Over the adsorption in solution, The Journal of Physical Chemistry, 1906, 57, 385-471.

- N. Drouiche, S. Aoudj, M. Hecini, N. Ghaffour, H. Lounici, N. Mameri, Study on the treatment of photovoltaic wastewater using electrocoagulation: Fluoride removal with aluminium electrodes-Characteristics of products. J. Hazard. Mat., 2009, 169, 65-69.

- L. M. Weinstock, J.M. Stevenson, S.A. Tomellin, S.H. Pan, T. Utne, R.B. Jobson, D.F. Reinhold, Characterization of the actual catalytic agent in potassium fluoride on activated alumina systems. Tetrahedron Letters, 1986, 27, 3845–3848.

- K.G. Akpomie, A.F. Dawodu, K.O. Adebowale, Mechanism on the sorption of heavy metals from binary-solution by low-cost montmorillonite and its desorption potential, Alexandria Engineering Journal, 2015, 54, 757-767.

- M. Massoudinejad, S.M. Mohsenib, M. Ghaderpoori, M. Sarkhosh, Soleyman Sahebi, Improvement of montmorillonite adsorption capacity for lead ions by modifying with hexadecyl trimethyl ammonium chloride: Characterization, modelling and optimization studies, MethodsX, 2019, 6, 2217–2229.

- K. Sakurai, Y. Ohdate, K. Kyuma, Comparison of salt titration and potentiometric titration methods for the determination of Zero Point of Charge (ZPC), Soil scien. Plant. Nutrition, 1988, 34, 171-182.

- S.H. Tan, N.A. Ismail, Isotherm and kinetic studies of L-phenylalanine adsorption onto porous nanosilica, Materials, today: Proceeding, 2018, 5, 3193-3201.

- M.S. Onyango, Y. Kojima, A. Kumar, D. Kuchar, M. Kubota, H. Matsuda Uptake of fluoride by Al3+ pretreated low-silica synthetic zeolites: Adsorption equilibrium and rate studies, Sep. Sci. Technol., 2006, 41, 683-704.

- S. Ayoob, A.K. Gupta, Insights into isotherm making in the sorptive removal of fluoride from drinking water, J. Hazard. Mater., 2008, 152, 976-985.

- R.S. Sathish, S. Sairam, V.G. Raja, G.N. Rao, C. Janardhana Defluoridation of water using zirconium impregnated coconut fiber carbon, Sep. Sci. Technol., 2008, 43, 3676-3694.

- S.K. Swain, R.K. Dey, M. Islam, R.K. Patel, U. Jha, T. Patnaik, C. Airoldi Removal of fluoride from aqueous solution using aluminum-impregnated chitosan biopolymer, Sep. Sci. Tech., 2009, 44, 2096-2116.

- E. Kumar, A. Bhatnagar, U. Kumar, M. Sillanpää, Defluoridation from aqueous solutions by nano-alumina: Characterization and sorption studies, J. Hazard. Mater., 2011, 186, 1042-1049.

- M. Barathi, A. S. K. Kumar, N. Rajesh, Aluminium hydroxide impregnated macro reticular aromatic polymeric resin as a sustainable option for defluoridation, J. Environ Chem. Eng., 2015, 3, 630-641.

- B. Meroufel, O. Benali, M. Benyahia, Y. Benmoussa, M.A. Zenasni, Adsorptive removal of anionic dye from aqueous solutions by Algerian kaolin: Characteristics, isotherm, kinetic and thermodynamic studies, J. Mater. Environ. Sci., 2013, 4, 482-491.





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