Abstract
The use of industrial and biological waste to synthesize adsorbent materials for the treatment of high fluorinated geothermal water is a cost-effective way to address the fluorine pollution problem while also reusing waste resources. In this study, modified hydroxyapatite-loaded zeolite molecular sieve composites (Al(OH)3-HAP@ZMS) were synthesized using fly ash and shell as precursors, which were then cation doped and compound modified to ensure adsorption while remaining cost-effective. When the material ratio of ZMS to Al(OH)3-HAP was 1:6, the best adsorption material was obtained. Under the optimum adsorption conditions (dosage = 6 g/L, T = 50 °C), Al(OH)3-HAP@ZMS achieved a removal rate of 92.5% and an adsorption capacity of 1.56 mg/g for 10 mg/L F− solution and can reduce the F− concentration to below the national standard concentration of 1 mg/L. The fitting of kinetic, isothermal, and thermodynamic data revealed that F− adsorption by Al(OH)3-HAP@ZMS followed the pseudo-second-order kinetics and Freundlich model, confirming that the adsorption process was primarily chemisorption and multilayer adsorption. The adsorption processes included electrostatic attraction, ion exchange between -OH and F−, complexation of fluoro-aluminum, and co-precipitation of Ca2+ with F−. At the same time, Al(OH)3-HAP@ZMS demonstrated good anti-interference performance in natural waters against co-existing ions and some heat resistance. Therefore, the composite adsorbent Al(OH)3-HAP@ZMS, as an effective and environmentally friendly low-cost adsorbent, is expected to achieve the practical engineering application of geothermal water defluoridation in Guanzhong, maximizing the dual benefits of “fluoride remove” and “waste resource reuse.”
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The data that support the findings of this study are available from the corresponding author upon reasonable request.
References
Alkurdi, S. S. A., Al-Juboori, R. A., Bundschuh, J., & Hamawand, I. (2019). Bone char as a green sorbent for removing health threatening fluoride from drinking water. Environment International, 127, 704–719. https://doi.org/10.1016/j.envint.2019.03.065
Alshemary, A. Z., Akram, M., Goh, Y. F., Tariq, U., Butt, F. K., Abdolahi, A., & Hussain, R. (2015). Synthesis, characterization, in vitro bioactivity and antimicrobial activity of magnesium and nickel doped silicate hydroxyapatite. Ceramics International, 41(9), 11886–11898. https://doi.org/10.1016/j.ceramint.2015.06.003
Arokiasamy, P., Al Bakri Abdullah, M. M., Abd Rahim, S. Z., Luhar, S., Sandu, A. V., Jamil, N. H., & Nabiałek, M. (2022). Synthesis methods of hydroxyapatite from natural sources: a review. Ceramics International, 48(11), 14959–14979. https://doi.org/10.1016/j.ceramint.2022.03.064
Ayoob, S., Gupta, A. K., & Bhat, V. T. (2008). A conceptual overview on sustainable technologies for the defluoridation of drinking water. Critical Reviews in Environmental Science and Technology, 38(6), 401–470. https://doi.org/10.1080/10643380701413310
Ben Amor, T., Kassem, M., Hajjaji, W., Jamoussi, F., Ben Amor, M., & Hafiane, A. (2018). Study of defluoridation of water using natural clay minerals. Clays and Clay Minerals, 66(6), 493–499. https://doi.org/10.1346/CCMN.2018.064117
Borciani, G., Fischetti, T., Ciapetti, G., Montesissa, M., Baldini, N., & Graziani, G. (2023). Marine biological waste as a source of hydroxyapatite for bone tissue engineering applications. Ceramics International, 49(2), 1572–1584. https://doi.org/10.1016/j.ceramint.2022.10.341
Cardoso, A. M., Paprocki, A., Ferret, L. S., Azevedo, C. M. N., & Pires, M. (2015). Synthesis of zeolite Na-P1 under mild conditions using Brazilian coal fly ash and its application in wastewater treatment. Fuel, 139, 59–67. https://doi.org/10.1016/j.fuel.2014.08.016
Chen, J., Yang, R., Zhang, Z., & Wu, D. (2022). Removal of fluoride from water using aluminum hydroxide-loaded zeolite synthesized from coal fly ash. Journal of Hazardous Materials, 421, 126817. https://doi.org/10.1016/j.jhazmat.2021.126817
Chen, Y. & Yang, S. (2012). Levels of toxic elements in fish from fishing ground using geothermal water in Guanzhong basin, China, 2012 International Conference on Environment Materials and Environment Management, EMEM 2012, August 4, 2012 - August 4, 2012, Trans Tech Publications, Wuhan, China, pp. 654–658. https://doi.org/10.4028/www.scientific.net/AMR.573-574.654
Chen, Z., Liu, Y., Mao, L., Gong, L., Sun, W., & Feng, L. (2018). Effect of cation doping on the structure of hydroxyapatite and the mechanism of defluoridation. Ceramics International, 44(6), 6002–6009. https://doi.org/10.1016/j.ceramint.2017.12.191
Deng, H., Zhang, Q., & Bai, Y. (2014). Research process on the zeolite synthesis by fly ash used alkaline-activation method. Bulletin of the Chinese Ceramic Society, 33(7), 1706–1714.
Dhand, V., Rhee, K. Y., & Park, S. J. (2014). The facile and low temperature synthesis of nanophase hydroxyapatite crystals using wet chemistry. Materials Science and Engineering C, 36, 152–159. https://doi.org/10.1016/j.msec.2013.11.049
Dupoirieux, L., Plane, L., Gard, C., & Penneau, M. (1999). Anatomical basis and results of the facial artery musculomucosal flap for oral reconstruction. British Journal of Oral and Maxillofacial Surgery, 37(1), 25–28. https://doi.org/10.1054/bjom.1998.0301
Fernando, M. S., de Silva, R. M., & de Silva, K. M. N. (2015). Synthesis, characterization, and application of nano hydroxyapatite and nanocomposite of hydroxyapatite with granular activated carbon for the removal of Pb2+ from aqueous solutions. Applied Surface Science, 351, 95–103. https://doi.org/10.1016/j.apsusc.2015.05.092
Gadore, V. & Ahmaruzzaman, M. (2021). Tailored fly ash materials: a recent progress of their properties and applications for remediation of organic and inorganic contaminants from water. Journal of Water Process Engineering, 41. https://doi.org/10.1016/j.jwpe.2020.101910.
Gao, M., Wang, W., Cao, M., Yang, H., & Li, Y. (2020). Hierarchical hollow manganese-magnesium-aluminum ternary metal oxide for fluoride elimination. Environmental Research, 188, 109735. https://doi.org/10.1016/j.envres.2020.109735
Ghorai, S., & Pant, K. K. (2004). Investigations on the column performance of fluoride adsorption by activated alumina in a fixed-bed. Chemical Engineering Journal, 98(1–2), 165–173. https://doi.org/10.1016/j.cej.2003.07.003
Gómez-Hortigüela, L., Pérez-Pariente, J., Chebude, Y. & Díaz, I. (2014). Controlled growth of hydroxyapatite on the surface of natural stilbite from Ethiopia: application in mitigation of fluorosis. RSC Advances, 4(16). https://doi.org/10.1039/c3ra46866f
Gu, D. L., & Liang, W. (2013). Adsorption of fluoride ions from drinking water using glass derived porous hydroxyapatite scaffolds. Applied Mechanics and Materials, 423–426, 1413–1417. https://doi.org/10.4028/www.scientific.net/AMM.423-426.1413
Gupta, V. K., Ali, I., & Saini, V. K. (2007). Defluoridation of wastewaters using waste carbon slurry. Water Research, 41(15), 3307–3316. https://doi.org/10.1016/j.watres.2007.04.029
Huang, P. P., Cao, C. Y., Wei, F., Sun, Y. B., & Song, W. G. (2015). MgAl layered double hydroxides with chloride and carbonate ions as interlayer anions for removal of arsenic and fluoride ions in water. RSC Advances, 5(14), 10412–10417. https://doi.org/10.1039/c4ra15160g
Huang, S., Hu, M., Li, D., Wang, L., Zhang, C., Li, K. & He, Q. (2020). Fluoride sorption from aqueous solution using Al(OH)3-modified hydroxyapatite nanosheet. Fuel, 279. https://doi.org/10.1016/j.fuel.2020.118486
Inada, M., Eguchi, Y., Enomoto, N., & Hojo, J. (2005). Synthesis of zeolite from coal fly ashes with different silica-alumina composition. Fuel, 84(2–3), 299–304. https://doi.org/10.1016/j.fuel.2004.08.012
Islam, M., & Patel, R. (2011). Thermal activation of basic oxygen furnace slag and evaluation of its fluoride removal efficiency. Chemical Engineering Journal, 169(1–3), 68–77. https://doi.org/10.1016/j.cej.2011.02.054
Jiang, N., Shang, R., Heijman, S. G. J., & Rietveld, L. C. (2018). High-silica zeolites for adsorption of organic micro-pollutants in water treatment: A review. Water Research, 144, 145–161. https://doi.org/10.1016/j.watres.2018.07.017
Kang, D., Yu, X., Ge, M., Lin, M., Yang, X., & Jing, Y. (2018). Insights into adsorption mechanism for fluoride on cactus-like amorphous alumina oxide microspheres. Chemical Engineering Journal, 345, 252–259. https://doi.org/10.1016/j.cej.2018.03.174
Kang, J., Gou, X., Hu, Y., Sun, W., Liu, R., Gao, Z., & Guan, Q. (2019). Efficient utilisation of flue gas desulfurization gypsum as a potential material for fluoride removal. Science of the Total Environment, 649, 344–352. https://doi.org/10.1016/j.scitotenv.2018.08.416
Ke, F., Luo, G., Chen, P. R., Jiang, J., Yuan, Q. Y., Cai, H. M., Peng, C. Y., & Wan, X. C. (2016). Porous metal-organic frameworks adsorbents as a potential platform for defluoridation of water. Journal of Porous Materials, 23(4), 1065–1073. https://doi.org/10.1007/s10934-016-0164-5
Kuwahara, Y., Ohmichi, T., Kamegawa, T., Mori, K. & Yamashita, H. (2009). A novel synthetic route to hydroxyapatite–zeolite composite material from steel slag: investigation of synthesis mechanism and evaluation of physicochemical properties. Journal of Materials Chemistry, 19(39). https://doi.org/10.1039/b911177h
Li, C. L., Chen, N., Zhao, Y. A., Li, R., & Feng, C. P. (2016). Polypyrrole-grafted peanut shell biological carbon as a potential sorbent for fluoride removal: Sorption capability and mechanism. Chemosphere, 163, 81–89. https://doi.org/10.1016/j.chemosphere.2016.08.016
Li, R., Tian, X., Ashraf, I., & Chen, B. (2020). Fluoride removal using a chelating resin containing phosphonic-sulfonic acid bifunctional group. Journal of Chromatography A, 1613, 460697. https://doi.org/10.1016/j.chroma.2019.460697
Li, X., Yu, X., Liu, L., Yang, J., Liu, S., & Zhang, T. (2021). Preparation, characterization serpentine-loaded hydroxyapatite and its simultaneous removal performance for fluoride, iron and manganese. RSC Advances, 11(27), 16201–16215. https://doi.org/10.1039/d1ra02028e
Lin, S., Jiang, X., Zhao, Y., & Yan, J. (2022). Zeolite greenly synthesized from fly ash and its resource utilization: a review. Science of The Total Environment, 851, 158182. https://doi.org/10.1016/j.scitotenv.2022.158182
Liu, C., Hu, W., Li, J., Jiang, C., & Chen, W. (2014). Preparation of the hydroxyapatite to remove fluorine from groundwater and its removal performance. China Environmental Science, 34(1), 58–64.
Liu, W. K., Liaw, B. S., Chang, H. K., Wang, Y. F., & Chen, P. Y. (2017). From waste to health: Synthesis of hydroxyapatite scaffolds from fish scales for lead ion removal. JOM Journal of the Minerals Metals and Materials Society, 69(4), 713–718. https://doi.org/10.1007/s11837-017-2270-5
Liu, X. W., & Cao, J. L. (2019). The synthesis of magnetic X zeolites and their uptake of fluoride ion and lead ion. International Journal of Environmental Science and Technology, 16(2), 1111–1118. https://doi.org/10.1007/s13762-018-1732-9
Lue, H., Wang, B., & Ban, Q. (2010). Defluoridation of drinking water by zeolite NaP1 synthesized from coal fly ash. Energy Sources, Part a: Recovery, Utilization, and Environmental Effects, 32(16), 1509–1516. https://doi.org/10.1080/15567030902780352
Mahramanlioglu, M., Kizilcikli, I., & Bicer, I. O. (2002). Adsorption of fluoride from aqueous solution by acid treated spent bleaching earth. Journal of Fluorine Chemistry, 115(1), 41–47. https://doi.org/10.1016/S0022-1139(02)00003-9
Meenakshi, S., Sundaram, C. S., & Sukumar, R. (2008). Enhanced fluoride sorption by mechanochemically activated kaolinites. Journal of Hazardous Materials, 153(1), 164–172. https://doi.org/10.1016/j.jhazmat.2007.08.031
Meenakshi, S., & Viswanathan, N. (2007). Identification of selective ion-exchange resin for fluoride sorption. Journal of Colloid and Interface Science, 308(2), 438–450. https://doi.org/10.1016/j.jcis.2006.12.032
Meski, S., Tazibt, N., Khireddine, H., Ziani, S., Biba, W., Yala, S., Sidane, D., Boudjouan, F., & Moussaoui, N. (2019). Synthesis of hydroxyapatite from mussel shells for effective adsorption of aqueous Cd(II). Water Science and Technology, 80(7), 1226–1237. https://doi.org/10.2166/wst.2019.366
Mullick, A., & Neogi, S. (2019). Ultrasound assisted synthesis of Mg-Mn-Zr impregnated activated carbon for effective fluoride adsorption from water. Ultrasonics Sonochemistry, 50, 126–137. https://doi.org/10.1016/j.ultsonch.2018.09.010
Nie, Y., Hu, C., & Kong, C. (2012). Enhanced fluoride adsorption using Al (III) modified calcium hydroxyapatite. Journal of Hazardous Materials, 233–234, 194–199. https://doi.org/10.1016/j.jhazmat.2012.07.020
Ouyang, P., & Fan, H. (2014). Research progress of fly ash adsorbent in wastewater disposal. New Chemical Materials, 42(8), 199–201.
Pandi, K., Viswanathan, N., & Meenakshi, S. (2019). Hydrothermal synthesis of magnetic iron oxide encrusted hydrocalumite-chitosan composite for defluoridation studies. International Journal of Biological Macromolecules, 132, 600–605. https://doi.org/10.1016/j.ijbiomac.2019.03.115
Piccirillo, C., & Castro, P. M. L. (2017). Calcium hydroxyapatite-based photocatalysts for environment remediation: Characteristics, performances and future perspectives. Journal of Environmental Management, 193, 79–91. https://doi.org/10.1016/j.jenvman.2017.01.071
Piri, F., Mollahosseini, A., khadir, A. & Milani Hosseini, M. (2019). Enhanced adsorption of dyes on microwave-assisted synthesized magnetic zeolite-hydroxyapatite nanocomposite. Journal of Environmental Chemical Engineering, 7(5). https://doi.org/10.1016/j.jece.2019.103338.
Piri, F., Mollahosseini, A., Khadir, A., & Milani Hosseini, M. (2020). Synthesis of a novel magnetic zeolite–hydroxyapatite adsorbent via microwave-assisted method for protein adsorption via magnetic solid-phase extraction. Journal of the Iranian Chemical Society, 17(7), 1635–1648. https://doi.org/10.1007/s13738-020-01883-5
Qi, L. Q., Wang, X., Wang, W., Li, J. X., & Huang, Y. (2022). Mercury removal from coal combustion flue gas by pyrite-modified fly ash adsorbent. Environmental Science and Pollution Research, 29(26), 39228–39238. https://doi.org/10.1007/s11356-022-18963-z
Qian, Y., Zhang, H., Li, L., & Duan, Y. (2020). Optimization of crystal growth of hierarchical porosity ZSM-5 zeolite based on coal fly ash “waste utilization.” Materialwissenschaft Und Werkstofftechnik, 51(9), 1295–1303. https://doi.org/10.1002/mawe.201900217
Rojas-Mayorga, C. K., Bonilla-Petriciolet, A., Silvestre-Albero, J., Aguayo-Villarreal, I. A., & Mendoza-Castillo, D. I. (2015). Physico-chemical characterization of metal-doped bone chars and their adsorption behavior for water defluoridation. Applied Surface Science, 355, 748–760. https://doi.org/10.1016/j.apsusc.2015.07.163
Ryu, G. U., Khalid, H. R., Lee, N., Wang, Z. & Lee, H. K. (2020). The effects of NaOH concentration on the hydrothermal synthesis of a hydroxyapatite–zeolite composite using blast furnace slag. Minerals, 11(1). https://doi.org/10.3390/min11010021.
Srivastav, A. L., Singh, P. K., Srivastava, V., & Sharma, Y. C. (2013). Application of a new adsorbent for fluoride removal from aqueous solutions. Journal of Hazardous Materials, 263(Pt 2), 342–352. https://doi.org/10.1016/j.jhazmat.2013.04.017
Tchomgui-Kamga, E., Alonzo, V., Nanseu-Njiki, C. P., Audebrand, N., Ngameni, E., & Darchen, A. (2010). Preparation and characterization of charcoals that contain dispersed aluminum oxide as adsorbents for removal of fluoride from drinking water. Carbon, 48(2), 333–343. https://doi.org/10.1016/j.carbon.2009.09.034
Velazquez-Jimenez, L. H., Vences-Alvarez, E., Flores-Arciniega, J. L., Flores-Zuñiga, H., & Rangel-Mendez, J. R. (2015). Water defluoridation with special emphasis on adsorbents-containing metal oxides and/or hydroxides: A review. Separation and Purification Technology, 150, 292–307. https://doi.org/10.1016/j.seppur.2015.07.006
Wang, H., Yan, K. & Chen, J. (2021a). Preparation of hydroxyapatite microspheres by hydrothermal self-assembly of marine shell for effective adsorption of Congo Red. Materials Letters, 304. https://doi.org/10.1016/j.matlet.2021.130573
Wang, H. B., Yan, K. Q., Xing, H. R., Chen, J. D. & Lu, R. (2021b). Effective removal of Cu2+ from aqueous solution by synthetic abalone shell hydroxyapatite microspheres adsorbent. Environmental Technology & Innovation, 23. https://doi.org/10.1016/j.eti.2021.101663
Wang, X., Pfeiffer, H., Wei, J., Dan, J., Wang, J., & Zhang, J. (2022). 3D porous Ca-modified Mg-Zr mixed metal oxide for fluoride adsorption. Chemical Engineering Journal, 428, 131371. https://doi.org/10.1016/j.cej.2021.131371
Wang, Y., Chen, N. P., Wei, W., Cui, J., & Wei, Z. G. (2011). Enhanced adsorption of fluoride from aqueous solution onto nanosized hydroxyapatite by low-molecular-weight organic acids. Desalination, 276(1–3), 161–168. https://doi.org/10.1016/j.desal.2011.03.033
Wu, S. C., Hsu, H. C., Wu, Y. N., & Ho, W. F. (2011). Hydroxyapatite synthesized from oyster shell powders by ball milling and heat treatment. Materials Characterization, 62(12), 1180–1187. https://doi.org/10.1016/j.matchar.2011.09.009
Xu, F. G., Jiang, C. Y., & Li, D. (2019). Defluoridation of wastewaters using HAP-coated-limestone. SEPARATION SCIENCE AND TECHNOLOGY, 54(14), 2304–2313. https://doi.org/10.1080/01496395.2018.1541470
Yadav, K. K., Kumar, S., Pham, Q. B., Gupta, N., Rezania, S., Kamyab, H., Yadav, S., Vymazal, J., Kumar, V., Tri, D. Q., Talaiekhozani, A., Prasad, S., Reece, L. M., Singh, N., Maurya, P. K. & Cho, J. (2019). Fluoride contamination, health problems and remediation methods in Asian groundwater: a comprehensive review. Ecotoxicology and Environmental Safety, 182. https://doi.org/10.1016/j.ecoenv.2019.06.045
Ye, C., Yan, B., Ji, X., Liao, B., Gong, R., Pei, X., & Liu, G. (2019). Adsorption of fluoride from aqueous solution by fly ash cenospheres modified with paper mill lime mud: Experimental and modeling. Ecotoxicology and Environmental Safety, 180, 366–373. https://doi.org/10.1016/j.ecoenv.2019.04.086
Yi, M., Wang, K., Wei, H., Wei, D., Wei, X., Wei, B., Shao, L., Fujita, T., & Cui, X. (2023). Efficient preparation of red mud-based geopolymer microspheres (RM@GMs) and adsorption of fluoride ions in wastewater. Journal of Hazardous Materials, 442, 130027. https://doi.org/10.1016/j.jhazmat.2022.130027
Zendehdel, M., Shoshtari-Yeganeh, B., & Cruciani, G. (2016). Removal of heavy metals and bacteria from aqueous solution by novel hydroxyapatite/zeolite nanocomposite, preparation, and characterization. Journal of the Iranian Chemical Society, 13(10), 1915–1930. https://doi.org/10.1007/s13738-016-0908-9
Zhan, Y., Lin, J., & Li, J. (2013). Preparation and characterization of surfactant-modified hydroxyapatite/zeolite composite and its adsorption behavior toward humic acid and copper(II). Environmental Science and Pollution Research, 20(4), 2512–2526. https://doi.org/10.1007/s11356-012-1136-1
Zhang, X. Q., Qi, Y. L., Chen, Z. H., Song, N. N., Li, X., Ren, D. J. & Zhang, S. Q. (2021). Evaluation of fluoride and cadmium adsorption modification of corn stalk by aluminum trichloride. APPLIED SURFACE SCIENCE, 543. https://doi.org/10.1016/j.apsusc.2020.148727
Zhang, Y.-X., & Jia, Y. (2016). Preparation of porous alumina hollow spheres as an adsorbent for fluoride removal from water with low aluminum residual. Ceramics International, 42(15), 17472–17481. https://doi.org/10.1016/j.ceramint.2016.08.052
Zhao, X., Wang, J., Wu, F., Wang, T., Cai, Y., Shi, Y., & Jiang, G. (2010). Removal of fluoride from aqueous media by Fe3O4@Al(OH)3 magnetic nanoparticles. Journal of Hazardous Materials, 173(1–3), 102–109. https://doi.org/10.1016/j.jhazmat.2009.08.054
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This work was supported by the National Natural Science Foundation of China (41302206); Provincial Natural Science Foundation of Shaanxi Province, China (2023-JC-YB-130); and the Fundamental Research Funds for the Central Universities, CHD (300102299205).
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Fei Wang: methodology, formal analysis, investigation, data curation, and writing—original draft preparation and revision. Yuyun Chen: conceptualization, project administration, and funding acquisition. Yanxia Dong: validation and data curation. Hongli Zhang: writing—review and editing. Rongrong Yun: writing—review and editing. Zengyu Liu: writing—review and editing.
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Wang, F., Chen, Y., Dong, Y. et al. Removal of Fluoride from Geothermal Water by Waste-Synthesized Al(OH)3-HAP@ZMS Composite Adsorbent: Sorption Capability and Mechanism. Water Air Soil Pollut 234, 411 (2023). https://doi.org/10.1007/s11270-023-06448-9
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DOI: https://doi.org/10.1007/s11270-023-06448-9