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Optimization of fluoride removal by activated clays using response surface methodology: Box–Behnken design, kinetic and isotherm studies

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Abstract

In numerous regions globally, particularly in Tunisia, the fluoride concentration in industrial wastewater surpasses regulatory thresholds, which posing environmental challenges. Therefore, this research investigates the efficacy of two clays sourced from Jebel Haidoudi Gabes–Tunisia (east longitude 9° 42′ 51.5″ (9.7143°); north latitude 34° 2′ 9.7″ (34.036°)) and Douiret–Tunisia (east longitude 10° 17′ 18.28 (10.28°); north latitude 32° 51′ 24.36″ (32.85°) as adsorbents and compared their performance in removing fluoride. These clays were used as adsorbents after activation with acid for 3.5 and 4.5 h, respectively. The design of Box–Behnken was applied to enhance the influence of initial fluoride concentration (50–300 mg/g), pH (2–6), and contact time (2–5 h). The results highlight the following order of significance for these factors: initial fluoride concentration > contact time > pH. The empirical model predicted that a maximum amounts adsorbed of fluoride with activated clays were obtained at fluoride concentration of 300 mg/L at a contact time of 5 h and pH = 2. A comparative analysis of activated clays from Jebel Haidoudi (142.56 mg/g) and Douiret (136.24 mg/g) elucidates their differential performance in fluoride removal. Results show that the experimental data fit well the pseudo-second-order equation, with R2 close to 1 (0.999) and χ2 low (1 ≥); the isotherm studies illustrate that the most excellent liner fits were obtained use the Langmuir model with highest R2 (0.986 and 0.983) and lowest χ2 (41.07 ad 43.56). These results demonstrate that fluoride removal might be mostly a chemisorption and a monolayer process. Finally, both activated clays could be used as efficient and inexpensive adsorbents. This work offers practical insights for optimizing treatment processes in regions grappling with elevated fluoride concentrations in industrial effluents.

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References

  • Aguilar J, Almeida-Naranjo C, Aldás MB, Guerrero Víctor H (2020) Acid activation of bentonite clay for recycled automotive oil purification. E3S Web Conf 191:03002

    CAS  Google Scholar 

  • Aliyu A (2019) Synthesis, electron microscopy properties and adsorption studies of zinc (II) ions (Zn2+) onto as-prepared carbon nanotubes (CNTs) using Box-Behnken design (BBD). Sci African 3:e00069

    Google Scholar 

  • Amor TB, Kassem M, Hajjaji W, Jamoussi F, Amor MB, Hafiane A (2018) Study of defluoridation of water using natural clay minerals. Clays Clay Miner 66(6):493–499

    CAS  Google Scholar 

  • Ba M, Ezzeddine A (2016) Optimization studies for industrial wastewater defluoridation by adsorption: application of a design of experiments. Int J Eng Res 2:2395–6992

    Google Scholar 

  • Balti S, Boudenne A, Hamdi N (2023) Characterization and optimization of eco-friendly gypsum materials using response surface methodology. J Build Eng 69:106219

    Google Scholar 

  • Baskan MB, BIyikli AR (2021) The adsorption of fluoride from aqueous solutions by Fe, Mn and Fe/Mn modified natural clinoptilolite and optimization using response surface methodology. Water Environ Res 93(4):620–635

    Google Scholar 

  • BenMessaoud I, Hamdi N, Srasra E (2018) Physicochemical characterization of geopolymer binders and foams made from Tunisian clay. Adv Mater Sci Eng 2018:1–8

    Google Scholar 

  • Bennour A, Mahmoudi S, Srasra E (2017) Physico-chemical and geotechnical characterization of Bargou clays (Northwestern Tunisia): application on traditional ceramics. J Aust Ceram Soc 54(1):149–159

    Google Scholar 

  • Berrama T, Benaouag N, Kaouah F, Bendjama Z (2013) Application of full factorial design to study the simultaneous removal of copper and zinc from aqueous solution by liquid–liquid extraction. Desalin Water Treat 51(10–12):2135–2145

    CAS  Google Scholar 

  • Bhatnagar A, Kumar E, Sillanpää M (2011) Fluoride removal from water by adsorption—a review. Chem Eng J 171(3):811–840

    CAS  Google Scholar 

  • Bhaumik R, Mondal NK (2016) Optimizing adsorption of fluoride from water by modified banana peel dust using response surface modelling approach. Appl Water Sci 6:115–135

    CAS  Google Scholar 

  • Biswas G, Kumari M, Adhikari K, Dutta S (2017) Application of response surface methodology for optimization of biosorption of fluoride from groundwater using Shorea robusta flower petal. Appl Water Sci 7:4673–4690

    CAS  Google Scholar 

  • Bouguerra NS, Trabelsi M, Frikha MH (2009) Activation d’une argile smectite tunisienne à l’acide sulfurique : rôle catalytique de l’acide adsorbé par l’argile. Journal De La Société Chimique De Tunisie 11:191–203

    Google Scholar 

  • Boussen S, Sghaier D, Chaabani F, Jamoussi B, Messaoud SB, Bennour A (2015) The rheological, mineralogical and chemical characteristic of the original and the Na2CO3activated Tunisian swelling clay (Aleg Formation) and their utilization as drilling mud. Appl Clay Sci 118:344–353

    CAS  Google Scholar 

  • Box GEP, Behnken DW (1960) Some new three level designs for the study of quantitative variables. Technometrics 2(4):455–475

    Google Scholar 

  • Chakroun I, Fakhfakh E, Medhioub M, Lopez-Galindo A, Viseras IC, Jamoussi F (2013) Characterization of some Tunisian clays to be used as antidiarrhoeic agents. Period Mineral 82(1):89–100

  • Chan YT, Tan MC, Chin NL (2019) Application of Box-Behnken design in optimization of ultrasound effect on apple pectin as sugar replacer. Food Sci Technol 115:108449

    CAS  Google Scholar 

  • El Hajam M, Kandri NI, Plavan G-I, Harrath AH, Mansour L, Boufahja F, Zerouale A (2020) Pb2+ ions adsorption onto raw and chemically activated Dibetou sawdust: application of experimental designs. J King Saud Univ-Sci 32(3):2176–2189

    Google Scholar 

  • Gammoudi S, Srasra E (2017) Characterization of Tunisian clay suitable for pharmaceutical and cosmetic applications. Appl Clay Sci 146:162–166

    Google Scholar 

  • Gammoudi S, Frini-Srasra N, Srasra E (2013) Preparation, characterization of organosmectites and fluoride ion removal. Int J Miner Process 125:10–17

    CAS  Google Scholar 

  • Gharbi M, Masrouhi A, Espurt N, Bellier O, Amari EA, Youssef MB, Ghanmi M (2013) New tectono-sedimentary evidences for Aptian to Santonian extension of the Cretaceous rifting in the northern Chotts range (southern Tunisia). J Afr Earth Sci 79:58–73

    Google Scholar 

  • Gogoi PK, Baruah R (2008) Fluoride removal from water by adsorption on acid activated kaolinite clay. Indian J Chem Technol 15:500–503

    CAS  Google Scholar 

  • Guiza S, Brouers F, Bagane M (2021) Fluoride removal from aqueous solution by montmorillonite clay: kinetics and equilibrium modeling using new generalized fractal equation. Environ Technol 21:101187

  • Guiza S, Hajji H, Bagane M (2019) External mass transport process during the adsorption of fluoride from aqueous solution by activated clay. Comptes Rendus Chimie 22(2-3):161–168

  • Guo Q, Reardon EJ (2012) Fluoride removal from water by meixnerite and its calcination product. Appl Clay Sci 56:7–15

    CAS  Google Scholar 

  • Habuda-Stanić M, Ergović Ravančić M, & Flanagan A (2014) A review on adsorption of fluoride from aqueous solution. Materials 7(9):6317–6366

  • Hajam ME, El Hajam M, Kandri NI, Plavan GI, Harrath AH, Mansour L, Boufahja F, Zerouale A (2020) Pb2+ ions adsorption onto raw and chemically activated Dibetou sawdust: application of experimental designs. J King Saud Univ-Sci 32(3):2176–2189

    Google Scholar 

  • Hamdi N, Srasra E (2012) Removal of phosphate ions from aqueous solution using Tunisian clays minerals and synthetic zeolite. J Environ Sci 24:617

    CAS  Google Scholar 

  • Hamed Y, Demdoum A, Al-Gamal SA, Bouri S, Ben Dhia H (2012) Groundwater recharge areas of the continental intercalaire aquifer-hydrogeochemical and environmental isotopes: Southern Tunisia and Algeria. Quater Int. https://doi.org/10.1016/j.quaint.2012.11.011

  • Islem C, Sana A, Kamel J (2017) Treatment of Tannery Effluent by Tunisian Clay. Colloid Surf Sci 2(4):130–136

    Google Scholar 

  • Jamoussi F, Bédir M, Boukadi N, Kharbachi S, Zargouni F, López-Galindo A, Paquet H (2003) Répartition des minéraux argileux et contrôle tectono-eustatique dans les bassins de la marge tunisienne. CR Geosci 335(2):175–183

    Google Scholar 

  • Jayarathna L, Bandara A, Ng WJ, Weerasooriya R (2015) Fluoride adsorption on γ− Fe2O3 nanoparticles. J Environ Health Sci Eng 13:1–10

    Google Scholar 

  • Karthikeyan G, Pius A, Alagumuthu G (2005) Fluoride adsorption studies of montmorillonite clay. Indian J Chem Technol 10:263

    Google Scholar 

  • Kausar A, Iqbal M, Javed A, Aftab K, Nazli Z-H, Bhatti HN, Nouren S (2018) Dyes adsorption using clay and modified clay: a review. J Mol Liq 256:395–407

    CAS  Google Scholar 

  • Khiari I, Mefteh S, Sánchez-Espejo R, Cerezo P, Aguzzi C, López-Galindo A, Iborra CV (2014) Study of traditional Tunisian medina clays used in therapeutic and cosmetic mud-packs. Appl Clay Sci 101:141–148

    CAS  Google Scholar 

  • Khoshnamvand N, Jafari A, Kamarehie B, Faraji M (2019) Optimization of adsorption and sonocatalytic degradation of fluoride by zeolitic imidazole framework-8 (ZIF-8) using RSM-CCD. Desalin Water Treat 171:270–280

    CAS  Google Scholar 

  • Khuri AI, Mukhopadhyay S (2010) Response surface methodology Response surface methodology. Wiley Interdiscip Rev Comput Stat 2(2):128–149

    Google Scholar 

  • Kumari U, Behera SK, Meikap BC (2019) Defluoridation of synthetic and industrial wastewater by using acidic activated alumina adsorbent: characterization and optimization by response surface methodology. J Environ Sci Health A 54(1):79–88

    CAS  Google Scholar 

  • Mahmoudi S, Bennour A, Srasra E, Zargouni F (2016) Characterization, firing behavior and ceramic application of clays from the Gabes region in South Tunisia. Appl Clay Sci 135:215–225

    Google Scholar 

  • Meenakshi S, Sundaram CS, Sukumar R (2008) Enhanced fluoride sorption by mechanochemically activated kaolinites. J Hazard Mater 153(1–2):164–172

    CAS  Google Scholar 

  • Mefteh S, Khiari I, Sanchez-Espejo R, Aguzzi C, Jamoussi F, Viseras C (2014) Characterisation of Tunisian layered clay materials to be used in semisolid health care products. Mater Technol 29(s3):B88–B95

    Google Scholar 

  • Mohapatra M, Anand S, Mishra BK, Giles DE, Singh P (2009) Review of fluoride removal from drinking water. J Environ Manage 91(1):67–77

    CAS  Google Scholar 

  • Mosbahi M, Tlili A, Khlifi M, Jeddoui Y (2008) Activation acido-basique des argiles de la formation el haria du bassin maknassy - mezzouna et essais de clarification des huiles neutres de soja. Congrès national de 3èmes journée de l’Association Tunisienne de Géologie Appliquée (ATGA)

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

    CAS  Google Scholar 

  • Mourabet M, El Rhilassi A, El Boujaady H, Bennani-Ziatni M, El Hamri R, Taitai A (2015) Removal of fluoride from aqueous solution by adsorption on hydroxyapatite (HAp) using response surface methodology. J Saudi Chem Soc 19:603–615

    Google Scholar 

  • Moussa KB, Eturki S, Van Poucke R, Bodé S, De Grave J, Van Ranst E, Tack FM, Moussa M (2022) Evaluating the adsorptive capacity of three Tunisian clays deposits for several potentially toxic metals in phosphogypsum waste. Arab J Geosci 15(9):911

    CAS  Google Scholar 

  • Mudzielwana R, Gitari MW, Akinyemi SA, Msagati TAM (2018) Performance of Mn2+-modified bentonite clay for the removal of fluoride from aqueous solution. Afr J Chem 71:15–23

    Google Scholar 

  • Myers RH, Montgomery DC, Anderson-Cook CM (2002) Process and product optimization using designed experiments. Response Surf Methodol 2:328–335

    Google Scholar 

  • Nabbou N, Belhachemi M, Boumelik M, Merzougui T, Lahcene D, Harek Y, Jeguirim M (2019) Removal of fluoride from groundwater using natural clay (kaolinite): optimization of adsorption conditions. C R Chim 22(2–3):105–112

    CAS  Google Scholar 

  • Nmiri A, Duc M, Hamdi N, Yazoghli-Marzouk O, Srasra E (2019) Replacement of alkali silicate solution with silica fume in metakaolin-based geopolymers. Int J Min Met Mater 26:555–564

    CAS  Google Scholar 

  • Ouaja M, Barale G, Philippe M, Ferry S (2011) Occurrence of an in situ fern grove in the Aptian Douiret formation, Tataouine area. South-Tunisia Geobios 44(5):473–479

    Google Scholar 

  • Ravanipour M, Kafaei R, Keshtkar M, Tajalli S, Mirzaei N, Ramavandi B (2017) Fluoride ion adsorption onto palm stone: optimization through response surface methodology, isotherm, and adsorbent characteristics data. Data Brief 12:471–479

    Google Scholar 

  • Sarkar B, Rusmin R, Ugochukwu UC, Mukhopadhyay R, Manjaiah KM (2019) Modified clay minerals for environmental applications. Modified clay and zeolite nanocomposite materials. Elsevier, pp 113–127

    Google Scholar 

  • Sdiri A, Khairy M, Bouaziz S, El-Safty S (2016) A natural clayey adsorbent for selective removal of lead from aqueous solutions. Appl Clay Sci 126:89–97

    CAS  Google Scholar 

  • Shen F, Chen X, Gao P, Chen G (2003) Electrochemical removal of uoride ions from industrial wastewater. Chem Eng Sci 58(3–6):987–993

    CAS  Google Scholar 

  • Singh NB, Nagpal G, Agrawal S (2018) Water purification by using adsorbents: a review. Environ Technol & Innovat 11:187–240

    Google Scholar 

  • Suneetha M, Sundar BS, Ravindhranath K (2015) Studies on defluoridation techniques: a critical review. Int J Chem Tech Res 8(8):295–309

    CAS  Google Scholar 

  • Tan KL, Hameed BH (2017) Insight into the adsorption kinetics models for the removal of contaminants from aqueous solutions. J Taiwan Inst Chem Eng 74:25–48

    CAS  Google Scholar 

  • Trabelsi W, Tlili A (2017) Phosphoric acid purification through different raw and activated clay materials (Southern Tunisia). Afr Earth Sci 129:647–658

    CAS  Google Scholar 

  • Turner BD, Binning P, Stipp SLS (2005) Fluoride removal by calcite: evidence for fluorite precipitation and surface adsorption. Environ Sci Technol 39(24):9561–9568

    CAS  Google Scholar 

  • Vinati A, Mahanty B, Behera SK (2015) Clay and clay minerals for fluoride removal from water: a state-of-the-art review. Appl Clay Sci 114:340–348

    CAS  Google Scholar 

  • Vitorette PJ, Zaccaron A, Müller TG, de Oliveira CM, Peterson M, Raupp-Pereira F (2022) Analysis of solid waste discharged from water treatment plant as a fluoride-absorbing functional material. Groundwater Sustain Dev 17:100765

  • Wambu EW, Onindo CO, Ambusso W, Muthakia GK (2013) Removal of fluoride from aqueous solutions by adsorption using a siliceous mineral of a Kenyan origin. Clean–soil Air Water 41(4):340–348

    CAS  Google Scholar 

  • World Health Organization (2011) Guidelines for drinking-water quality

  • Yahya K, Msadok I, Mlayah A, Srasra E, Hamdi N (2021) Retention and selectivity of phosphate and fluoride from single and industrial aqueous solutions using purified and surfactant modified Tunisian clay. Desalin Water Treat 216:199–210

    CAS  Google Scholar 

  • Yahya K, Hamdi W, Hamdi N (2022) Organoclay nano-adsorbent: preparation, characterization and applications. IntechOpen

    Google Scholar 

  • Yahya K, Ba M, Msadok I, Mlayah A, Srasra E, Hamdi N (2022) Removal of phosphate from synthetic wastewater: a comparative study between both activated clays using an experimental design methodology. Water Environ Res 94(11):e10800

    CAS  Google Scholar 

  • Zendehdel M, Shoshtari-Yeganeh B, Khanmohamadi H, Cruciani G (2017) Removal of fluoride from aqueous solution by adsorption on NaP:HAp nanocomposite using response surface methodology. Process Saf Environ Prot 109:172–191

    CAS  Google Scholar 

  • Zhang S, Lyu Y, Su X, Bian Y, Yu B, Zhang Y (2016) Removal of fluoride ion from groundwater by adsorption on lanthanum and aluminum loaded clay adsorbent. Env Earth Sci 75(5):1–9

    Google Scholar 

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Acknowledgements

The authors wish to thank the technical staff of the High Institute of Sciences and Technologies of Water of Gabes.

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KY performed all the experiments; analyzed the data; and wrote the manuscript. MB contributed to the statistical analyses. IM contributed to the X-ray diffraction (XRD) analysis and reviewed the manuscript. KBM contributed to the review and validation. AKH contributed to the review. AM contributed the materials and equipment. ES contributed to the materials. NH supervised the work and reviewed the paper.

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Correspondence to K. Yahya.

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Yahya, K., Msadok, I., Moussa, K.B. et al. Optimization of fluoride removal by activated clays using response surface methodology: Box–Behnken design, kinetic and isotherm studies. Int. J. Environ. Sci. Technol. 21, 7923–7940 (2024). https://doi.org/10.1007/s13762-024-05535-6

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