Volume 19 Issue 2
May  2026
Turn off MathJax
Article Contents
Alaa El Din Mahmoud, Rominder Suri. 2026: Fluoride and bromide removal from synthetic and real water utilizing biocompatible graphene oxide composites: Evaluating linear and nonlinear modeling. Water Science and Engineering, 19(2): 236-249. doi: 10.1016/j.wse.2026.03.002
Citation: Alaa El Din Mahmoud, Rominder Suri. 2026: Fluoride and bromide removal from synthetic and real water utilizing biocompatible graphene oxide composites: Evaluating linear and nonlinear modeling. Water Science and Engineering, 19(2): 236-249. doi: 10.1016/j.wse.2026.03.002

Fluoride and bromide removal from synthetic and real water utilizing biocompatible graphene oxide composites: Evaluating linear and nonlinear modeling

doi: 10.1016/j.wse.2026.03.002
  • Received Date: 2025-10-12
  • Accepted Date: 2026-03-11
  • Available Online: 2026-05-30
  • Access to clean water remains a critical global challenge. Accordingly, there is an urgent demand for efficient, cost-effective, and environmentally sustainable sorbents for anion removal from water. In this study, biocompatible functionalized graphene oxide (GO) composites were synthesized and evaluated for their performance in removing fluoride and bromide from water. Methionine-functionalized GO (Meth@GO) and β-cyclodextrin-functionalized GO (BCD@GO) with three different loading ratios were prepared for comparison. The influence of co-anions on the removal of both target anions was investigated, with negligible competitive effects observed in water samples. The optimal composites were selected based on application performance and further used to optimize anion removal from simulated and real water samples. Linear and nonlinear models were employed to interpret the adsorption behavior. Nonlinear pseudo-second-order models suitably described the removal of fluoride and bromide by Meth@GO and BCD@GO. The maximum adsorption capacities for fluoride and bromide were 6.57 mg/g and 4.48 mg/g for BCD@GO, and 4.73 mg/g and 3.53 mg/g for Meth@GO, respectively, as determined by nonlinear models. Model results indicated differences between linear and nonlinear findings based on error functions. Both Meth@GO and BCD@GO exhibited strong reusability over four consecutive cycles, with BCD@GO demonstrating superior performance. The removal of both anions from real water samples exceeded 97.31%, highlighting the practical potential of the sustainably synthesized biocomposites.

     

  • loading
  • [1]
    Al-Ghouti, M.A., Da'ana, D.A., 2020. Guidelines for the use and interpretation of adsorption isotherm models: A review. J. Hazard Mater. 393, 122383. https://doi.org/10.1016/j.jhazmat.2020.122383.
    [2]
    Al Hawash, M., Kumar, R., Barakat, M.A., 2022. Fabrication of polyaniline/graphene oxide nanosheet@tea waste granules adsorbent for groundwater purification. Nanomaterials 12(21), 3840. https://doi.org/10.3390/nano12213840.
    [3]
    Ali, I., Alothman, Z.A., Sanagi, M.M., 2015. Green synthesis of iron nano-impregnated adsorbent for fast removal of fluoride from water. J. Mol. Liq. 211, 457-465. https://doi.org/10.1016/j.molliq.2015.07.034.
    [4]
    Avornyo, A., Chrysikopoulos, C.V., 2024. Applications of graphene oxide (GO) in oily wastewater treatment: Recent developments, challenges, and opportunities. J. Environ. Manag. 353, 120178. https://doi.org/10.1016/j.jenvman.2024.120178.
    [5]
    Batool, F., Akbar, J., Iqbal, S., Noreen, S., Bukhari, S.N.A., 2018. Study of isothermal, kinetic, and thermodynamic parameters for adsorption of cadmium: An overview of linear and nonlinear approach and error analysis. Bioinorgan. Chem. Appl. 2018, 3463724. https://doi.org/10.1155/2018/3463724.
    [6]
    Belachew, N., Meshesha, D.S., Basavaiah, K., 2019. Green syntheses of silver nanoparticle decorated reduced graphene oxide using l-methionine as a reducing and stabilizing agent for enhanced catalytic hydrogenation of 4-nitrophenol and antibacterial activity. RSC Adv. 9, 39264-39271. https://doi.org/10.1039/C9RA08536J.
    [7]
    Bhattacharjee, T., Rahman, S., Deka, D., Purkait, M.K., Chowdhury, D., Majumdar, G., 2022. Synthesis and characterization of exfoliated beta-cyclodextrin functionalized graphene oxide for adsorptive removal of atenolol. Mater. Chem. Phys. 288, 126413. https://doi.org/10.1016/j.matchemphys.2022.126413.
    [8]
    Chubar, N.I., Samanidou, V.F., Kouts, V.S., Gallios, G.G., Kanibolotsky, V.A., Strelko, V.V., Zhuravlev, I.Z., 2005. Adsorption of fluoride, chloride, bromide, and bromate ions on a novel ion exchanger. J. Colloid Interface Sci. 291(1), 67-74. https://doi.org/10.1016/j.jcis.2005.04.086.
    [9]
    Chufa, B.M., Gonfa, B.A., Anshebo, T.Y., 2022. Graphene oxide nanoadsorbent for the removal of fluoride ion from groundwater: Adsorbent performance and adsorption mechanism. J. Nanotechnol. 2022, 7371227. https://doi.org/10.1155/2022/7371227.
    [10]
    Deng, M., Huang, Y., Zhang, X., Feng, Z., Gou, J., Sun, B., 2016. Preparation of a novel chelating resin bearing amidinothiourea moieties and its removal properties for Hg(II) ions in aqueous solution. Separ. Sci. Technol. 51, 1499-1508. https://doi.org/10.1080/01496395.2016.1166135.
    [11]
    Dhillon, A., Sharma, S., Singh, N., Kumar, D., 2022. Use of core-shell nanomaterials as potential adsorbents for fluoride remediation: Toward a sustainable ecosystem. Groundw. Sustain. Dev. 18, 100785. https://doi.org/10.1016/j.gsd.2022.100785.
    [12]
    Gangani, N., Joshi, V.C., Sharma, S., Bhattacharya, A., 2022. Fluoride contamination in water: Remediation strategies through membranes. Groundw. Sustain. Dev. 17, 100751. https://doi.org/10.1016/j.gsd.2022.100751.
    [13]
    Gao, Y., Jiao, T., Ma, K., Xing, R., Zhang, L., Zhou, J., Peng, Q., 2017. Variable self-assembly and in situ host-guest reaction of beta-cyclodextrin-modified graphene oxide composite Langmuir films with azobenzene compounds. RSC Adv. 7, 41043-41051. https://doi.org/10.1039/C7RA07109D.
    [14]
    Gao, Y., Zeng, X., Zhang, W., Zhou, L., Xue, W., Tang, M., Sun, S., 2022. The aggregation behaviour and mechanism of commercial graphene oxide in surface aquatic environments. Sci. Total Environ. 806, 150942. https://doi.org/10.1016/j.scitotenv.2021.150942.
    [15]
    Guan, C., Lv, X., Han, Z., Chen, C., Xu, Z., Liu, Q., 2020. The adsorption enhancement of graphene for fluorine and chlorine from water. Appl. Surf. Sci. 516, 146157. https://doi.org/10.1016/j.apsusc.2020.146157.
    [16]
    Hashemi, S.Y., Azari, A., Raeesi, M., Yaghmaeian, K., 2021. Application of response surface methodology (RSM) in optimisation of fluoride removal by magnetic chitosan/graphene oxide composite: Kinetics and isotherm study. Int. J. Environ. Anal. Chem. 103(7), 5368-5386. https://doi.org/10.1080/03067319.2021.1938021.
    [17]
    Heydari, A., Sheibani, H., 2016. Facile polymerization of β-cyclodextrin functionalized graphene or graphene oxide nanosheets using citric acid crosslinker by In situ melt polycondensation for enhanced electrochemical performance. RSC Adv. 6, 9760-9771. https://doi.org/10.1039/C5RA24685G.
    [18]
    Heydari, A., Sheibani, H., Hronsky, V., Janigova, I., Slouf, M., Siffalovic, P., Chodak, I., 2018. β-cyclodextrin-epichlorohydrin polymer/graphene oxide nanocomposite: Preparation and characterization. Chem. Pap. 72, 1299-1313. https://doi.org/10.1007/s11696-017-0371-9.
    [19]
    Hussain, A., Wang, H., Fu, R., Afsar, N.U., Wang, B., Jiang, C., Wang, Y., Xu, T., 2022. Ion transport behavior in bipolar membrane electrodialysis: Role of anions. Ind. Eng. Chem. Res. 62(1), 698-707. https://doi.org/10.1021/acs.iecr.2c03812.
    [20]
    Ihaddaden, S., Aberkane, D., Boukerroui, A., Robert, D., 2022. Removal of methylene blue (basic dye) by coagulation-flocculation with biomaterials (bentonite and Opuntia ficus indica). J. Water Process Eng. 49, 102952. https://doi.org/10.1016/j.jwpe.2022.102952.
    [21]
    Januario, E.F.D., Fachina, Y.J., Wernke, G., Demiti, G.M.M., Beltran, L.B., Bergamasco, R., Vieira, A.M.S., 2022. Application of activated carbon functionalized with graphene oxide for efficient removal of COVID-19 treatment-related pharmaceuticals from water. Chemosphere 289, 133213. https://doi.org/10.1016/j.chemosphere.2021.133213.
    [22]
    Jeyaseelan, A., Katubi, K.M.M., Alsaiari, N.S., Naushad, M., Viswanathan, N., 2021. Design and fabrication of sulfonic acid functionalized graphene oxide for enriched fluoride adsorption. Diam. Relat. Mater. 117, 108446. https://doi.org/10.1016/j.diamond.2021.108446.
    [23]
    Kathi, S., Mahmoud, A.E.D., 2024. Trends in effective removal of emerging contaminants from wastewater: A comprehensive review. Desalination Water Treat. 317, 100258. https://doi.org/10.1016/j.dwt.2024.100258.
    [24]
    Kavisri, M., Abraham, M., Moovendhan, M., 2023. Effective removal of fluoride ions from aqueous solution by marine microalgae as natural biosorbent. Chemosphere 313, 137312. https://doi.org/10.1016/j.chemosphere.2022.137312.
    [25]
    Kocot, K., Pytlakowska, K., Talik, E., Krafft, C., Sitko, R., 2022. Sensitive determination of uranium using β-cyclodextrin modified graphene oxide and X-ray fluorescence techniques: EDXRF and TXRF. Talanta 246, 123501. https://doi.org/10.1016/j.talanta.2022.123501.
    [26]
    Li, K., Yan, J., Zhou, Y., Li, B., Li, X., 2021. β-cyclodextrin and magnetic graphene oxide modified porous composite hydrogel as a superabsorbent for adsorption cationic dyes: Adsorption performance, adsorption mechanism and hydrogel column process investigates. J. Mol. Liq. 335, 116291. https://doi.org/10.1016/j.molliq.2021.116291.
    [27]
    Li, Y., Yang, Z., Yang, K., Wei, J., Li, Z., Ma, C., Yang, X., Wang, T., Zeng, G., Yu, G., et al., 2022. Removal of chloride from water and wastewater: Removal mechanisms and recent trends. Sci. Total Environ. 821, 153174. https://doi.org/10.1016/j.scitotenv.2022.153174.
    [28]
    Liu, D., Li, X., Zhang, Y., Bai, L., Shi, H., Qiao, Q., Li, T., Xu, W., Zhou, X., Wang, H., 2024. Industrial fluoride emissions and their spatial characteristics in the Nansi Lake Basin, Eastern China. Environ. Sci. Pollut. Control Ser. 31, 27273-27285. https://doi.org/10.1007/s11356-024-32941-7.
    [29]
    Liu, M., Zang, Z., Zhang, S., Ouyang, G., Han, R., 2021. Enhanced fluoride adsorption from aqueous solution by zirconium(IV)-impregnated magnetic chitosan graphene oxide. Int. J. Biol. Macromol. 182, 1759-1768. https://doi.org/10.1016/j.ijbiomac.2021.05.116.
    [30]
    Liu, N., Wu, Y., Sha, H., 2018a. Characterization of EDTA-cross-linked β-cyclodextrin grafted onto Fe-Al hydroxides as an efficient adsorbent for methylene blue. J. Colloid Interface Sci. 516, 98-109. https://doi.org/10.1016/j.jcis.2018.01.056.
    [31]
    Liu, Y., Huang, S., Zhao, X., Zhang, Y., 2018b. Fabrication of three-dimensional porous β-cyclodextrin/chitosan functionalized graphene oxide hydrogel for methylene blue removal from aqueous solution. Colloids Surf. A Physicochem. Eng. Asp. 539, 1-10. https://doi.org/10.1016/j.colsurfa.2017.11.066.
    [32]
    Lubojanski, A., Piesiak-Panczyszyn, D., Zakrzewski, W., Dobrzynski, W., Szymonowicz, M., Rybak, Z., Mielan, B., Wiglusz, R.J., Watras, A., Dobrzynski, M., 2023. The safety of fluoride compounds and their effect on the human body-A narrative review. Materials 16(3), 1242. https://doi.org/10.3390/ma16031242.
    [33]
    Mahmoud, A.E.D., Stolle, A., Stelter, M., 2018. Sustainable synthesis of high-surface-area graphite oxide via dry ball milling. ACS Sustain. Chem. Eng. 6(5), 6358-6369. https://doi.org/10.1021/acssuschemeng.8b00147.
    [34]
    Mahmoud, A.E.D., 2020a. Eco-friendly reduction of graphene oxide via agricultural byproducts or aquatic macrophytes. Mater. Chem. Phys. 253, 123336. https://doi.org/10.1016/j.matchemphys.2020.123336.
    [35]
    Mahmoud, A.E.D., 2020b. Graphene-based nanomaterials for the removal of organic pollutants: Insights into linear versus nonlinear mathematical models. J. Environ. Manag. 270, 110911. https://doi.org/10.1016/j.jenvman.2020.110911.
    [36]
    Mahmoud, A.E.D., Al-Qahtani, K.M., Alflaij, S.O., Al-Qahtani, S.F., Alsamhan, F.A., 2021. Green copper oxide nanoparticles for lead, nickel, and cadmium removal from contaminated water. Sci. Rep. 11, 12547. https://doi.org/10.1038/s41598-021-91093-7.
    [37]
    Mahmoud, A.E.D., Hosny, M., El-Maghrabi, N., Fawzy, M., 2022. Facile synthesis of reduced graphene oxide by Tecoma stans extracts for efficient removal of Ni(II) from water: Batch experiments and response surface methodology. Sustain. Environ. Res. 32, 22. https://doi.org/10.1186/s42834-022-00131-0.
    [38]
    Mahmoud, A.E.D., Fawzy, M., 2023. Decontamination of levofloxacin from water using a novel chitosan-walnut shells composite: Linear, nonlinear, and optimization modeling. Appl. Water Sci. 13, 244. https://doi.org/10.1007/s13201-023-02045-7.
    [39]
    Mahmoud, A.E.D., Ali, R., Fawzy, M., 2024. Insights into levofloxacin adsorption with machine learning models using nano-composite hydrochars. Chemosphere 355, 141746. https://doi.org/10.1016/j.chemosphere.2024.141746.
    [40]
    Mantovani, S., Khaliha, S., Marforio, T.D., Kovtun, A., Favaretto, L., Tunioli, F., Bianchi, A., Petrone, G., Liscio, A., Palermo, V., et al., 2022. Facile high-yield synthesis and purification of lysine-modified graphene oxide for enhanced drinking water purification. Chem. Commun. 58(70), 9766-9769. https://doi.org/10.1039/D2CC03256B.
    [41]
    Mikalauskaite, A., Kondrotas, R., Niaura, G., Jagminas, A., 2015. Gold-coated cobalt ferrite nanoparticles via methionine-induced reduction. J. Phys. Chem. C 119(30), 17398-17407. https://doi.org/10.1021/acs.jpcc.5b03528.
    [42]
    Mirzaei, B., Zarrabi, A., Noorbakhsh, A., Amini, A., Makvandi, P., 2021. A reduced graphene oxide-β-cyclodextrin nanocomposite-based electrode for electrochemical detection of curcumin. RSC Adv. 11, 7862-7872. https://doi.org/10.1039/D0RA10701H.
    [43]
    Mousazadeh, M., Alizadeh, S., Frontistis, Z., Kabdasli, I., Karamati Niaragh, E., Al Qodah, Z., Naghdali, Z., Mahmoud, A.E.D., Sandoval, M.A., Butler, E., 2021. Electrocoagulation as a promising defluoridation technology from water: A review of state of the art of removal mechanisms and performance trends. Water 13, 656. https://doi.org/10.3390/w13050656.
    [44]
    Moyle, B.D., Weaver, D.B., Gossling, S., McLennan, C.-L., Hadinejad, A., 2022. Are water-centric themes in sustainable tourism research congruent with the UN Sustainable Development Goals? J. Sustain. Tourism 30(8), 1821-1836. https://doi.org/10.1080/09669582.2021.1993233.
    [45]
    Pandi, K., Viswanathan, N., 2016. A facile synthesis of metal ion-imprinted graphene oxide/alginate hybrid biopolymeric beads for enhanced fluoride sorption. RSC Adv. 6, 75905-75915. https://doi.org/10.1039/C6RA11713A.
    [46]
    Ponikvar, M., 2008. Chapter 12 - Exposure of humans to fluorine and its assessment. In: Tressaud, A. (Ed.), Fluorine and Health. Elsevier, Amsterdam, pp. 487-549.
    [47]
    Qiao, W., Wang, L., Ye, B., Li, G., Li, J., 2015. Electrochemical behavior of palmatine and its sensitive determination based on an electrochemically reduced l-methionine functionalized graphene oxide modified electrode. Analyst 140, 7974-7983. https://doi.org/10.1039/C5AN01770J.
    [48]
    Qu, Y., Li, H., Yakub, I., He, W., Dong, W., Barawi, M.H., Wang, S., Ma, H., Zhu, Z., 2025. Synthesis and characterization of efficient adsorbents for methylene blue based on craphene oxide/β-cyclodextrin composites. Water, Air, Soil Pollut. 236, 56. https://doi.org/10.1007/s11270-024-07630-3.
    [49]
    Ragab, A.H., Gumaah, N.F., El Aziz Elfiky, A.A., Mubarak, M.F., 2024. Exploring the sustainable elimination of dye using cellulose nanofibrils- vinyl resin based nanofiltration membranes. BMC Chem. 18, 121. https://doi.org/10.1186/s13065-024-01211-5.
    [50]
    Rajabi, M., Moradi, O., Zare, K., 2017. Kinetics adsorption study of the ethidium bromide by graphene oxide as adsorbent from aqueous matrices. Int. Nano Lett. 7(1), 35-41. https://doi.org/10.1007/s40089-017-0199-x.
    [51]
    Ramezani, A., Lorestani, B., Sobhanardakani, S., Cheraghi, M., Nourmoradi, H., 2023. Fabricating modified carbon of oak fruit for adsorption of fluoride and nitrate from aqueous media: Isotherm and kinetic models. Appl. Water Sci. 13, 221. https://doi.org/10.1007/s13201-023-02023-z.
    [52]
    Rathour, R.K.S., Bhattacharya, J., Mukherjee, A., 2019. β-cyclodextrin conjugated graphene oxide: A regenerative adsorbent for cadmium and methylene blue. J. Mol. Liq. 282, 606-616. https://doi.org/10.1016/j.molliq.2019.03.020.
    [53]
    Rout, D.R., Jena, H.M., 2022. Synthesis of novel epichlorohydrin cross-linked β-cyclodextrin functionalized with reduced graphene oxide composite adsorbent for treatment of phenolic wastewater. Environ. Sci. Pollut. Control Ser. 29, 73444-73460. https://doi.org/10.1007/s11356-022-21018-y.
    [54]
    Safapour, S., Mazhar, M., Nikanfard, M., Liaghat, F., 2022. Recent advancements on the functionalized cyclodextrin-based adsorbents for dye removal from aqueous solutions. Int. J. Environ. Sci. Technol. 19, 5753-5790. https://doi.org/10.1007/s13762-021-03671-x.
    [55]
    Sappani Muthu, M., Stanly John Xavier, S., Ajith, P., Prem Anand, D., 2022. Preparation and characterization studies of nano graphene oxide. Mater. Today Proc. 66, 2449-2454. https://doi.org/10.1016/j.matpr.2022.06.367.
    [56]
    Sengupta, I., Kumar, S.S.S.S., Pal, S.K., Chakraborty, S., 2022. Investigating the effect of graphite pretreatment and contribution of the oxidizer in the synthesis of graphite oxide by hummers approach. Fullerenes, Nanotub. Carbon Nanostruct. 30(6), 626-637. https://doi.org/10.1080/1536383X.2021.1987414.
    [57]
    Song, W., Hu, J., Zhao, Y., Shao, D., Li, J., 2013. Efficient removal of cobalt from aqueous solution using β-cyclodextrin modified graphene oxide. RSC Adv. 3, 9514-9521. https://doi.org/10.1039/C3RA41434E.
    [58]
    Tahir, S., Ahmad, F., Razzaq, H., Shakoor, B., Kanwal, S., Rani, I., Imran, W.M., Saddiqua, A., Bibi, T., Noor, A., 2025. A comprehensive review on functionalized graphene oxide nanoparticles for fluorescence properties and potential in biosensing and water remediation. ChemistrySelect 10(29), e00220. https://doi.org/10.1002/slct.202500220.
    [59]
    Tan, S., Ruan, X., Ye, H., Shao, J., Shan, X., Shi, Y., Le, Y., 2025. Fabrication of aluminum-coated glucose/graphene oxide hybrid materials for the dual adsorption of fluoride and methylene blue. Sci. Rep. 15, 11492. https://doi.org/10.1038/s41598-025-95214-4.
    [60]
    Tyunina, E.Y., Tarasova, G.N., Dunaeva, V.V., 2022. Studying the interaction between L-methionine and picolinic and nicotinic acids by means of densitometry and quantum chemistry. Russ. J. Phys. Chem. A 96, 99-108. https://doi.org/10.1134/S0036024422010253.
    [61]
    Vaghela, N.R., Nath, K., 2020. Reduced graphene oxide coated graphite electrodes for treating reactive turquoise blue 21 rinse water using an indirect electro-oxidation process. SN Appl. Sci. 2, 1839. https://doi.org/10.1007/s42452-020-03719-6.
    [62]
    Winid, B., 2015. Bromine and water quality - Selected aspects and future perspectives. Appl. Geochem. 63, 413-435. https://doi.org/10.1016/j.apgeochem.2015.10.004.
    [63]
    Yadav, S., Asthana, A., Singh, A.K., Chakraborty, R., Sree Vidya, S., Singh, A., Carabineiro, S.A.J.N., 2021. Methionine-functionalized graphene oxide/sodium alginate bio-polymer nanocomposite hydrogel beads: Synthesis, isotherm and kinetic studies for an adsorptive removal of fluoroquinolone antibiotics. Nanomaterials 11(3), 568. https://doi.org/10.3390/nano11030568.
    [64]
    Zhang, Y., Wu, L., Deng, H., Qiao, N., Zhang, D., Lin, H., Chen, Y., 2021. Modified graphene oxide composite aerogels for enhanced adsorption behavior to heavy metal ions. J. Environ. Chem. Eng. 9, 106008. https://doi.org/10.1016/j.jece.2021.106008.
    [65]
    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. J. Hazard Mater. 173, 102-109. https://doi.org/10.1016/j.jhazmat.2009.08.054.
    [66]
    Zhu, M., Liang, H., Gong, X., 2024. β-cyclodextrin modified GO ultrafiltration membranes with enhanced antifouling property for water purification. Environ. Res. 258, 119472. https://doi.org/10.1016/j.envres.2024.119472.
  • 加载中

Catalog

    通讯作者: 陈斌, bchen63@163.com
    • 1. 

      沈阳化工大学材料科学与工程学院 沈阳 110142

    1. 本站搜索
    2. 百度学术搜索
    3. 万方数据库搜索
    4. CNKI搜索

    Figures(1)

    Article Metrics

    Article views (10) PDF downloads(0) Cited by()
    Proportional views
    Related

    /

    DownLoad:  Full-Size Img  PowerPoint
    Return
    Return