Abstract
This study explores the possibility of developing an eco-friendly adsorbent for effective remediation of groundwater fluoride, a well-known health hazard affecting more than 25 nations on the various continents. A facile and milder approach has been adopted to synthesize chitosan-modified ZnO/ZnFe2O4 nanocomposites. The synthesized materials have been characterized by different spectroscopic, microscopic, and diffractometric techniques. X-ray photoelectron spectroscopy and X-ray diffraction studies have confirmed the formation of pure and highly crystalline ZnO/ZnFe2O4 nanocomposites. The presence of surface-adsorbed chitosan in the modified ZnO/ZnFe2O4 has been confirmed by FT-IR and thermogravimetric analysis. The results from microscopic and BET surface area analysis of ZnO/ZnFe2O4 nanocomposites indicated that chitosan plays a crucial role in modulating the surface morphology and surface properties of the nanocomposites. The nanocomposites exhibit excellent adsorption performance in the remediation of groundwater fluoride. Experimental conditions have been systematically designed to evaluate the optimum adsorption condition for fluoride, and the results have been analyzed with various non-linear models to describe the kinetics and isotherms of adsorption. The adsorption primarily follows Lagergren pseudo-first-order kinetics, and the Langmuir adsorption capacity is varied from 10.54 to 13.03 mg g−1 over the temperature range 293–323 K. The thermodynamics study reveals that the adsorption process is endothermic and spontaneous. The mechanism of adsorption has been proposed based on the spectroscopic analysis of the fluoride-loaded adsorbent. The adsorption is non-specific in nature as co-existing anion can reduce its fluoride removal capacity. The effect of the co-existing anions on adsorption of fluoride follows the trend PO43− > CO32− > SO42− > Cl−. The adsorbent can be reused successfully for the 5th consecutive cycles of adsorption-desorption study. This study offers a very promising material for remediation of groundwater fluoride of affected areas.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Abbasizadeh S, Keshtkar AR, Mousavian MA (2014) Sorption of heavy metal ions from aqueous solution by a novel cast PVA/TiO2 nanohybrid adsorbent functionalized with amine groups. J Ind Eng Chem 20:1656–1664. https://doi.org/10.1016/j.jiec.2013.08.013
Adimalla N, Qian H (2019) Hydrogeochemistry and fluoride contamination in the hard rock terrain of central Telangana, India: analyses of its spatial distribution and health risk. SN Appl Sci 1:202. https://doi.org/10.1007/s42452-019-0219-8
Alkurdi SSA, Al-Juboori RA, Bundschuh J, Bowtell L, McKnight S (2020) Effect of pyrolysis conditions on bone char characterization and its ability for arsenic and fluoride removal. Environ Pollut 262:114221. https://doi.org/10.1016/j.envpol.2020.114221
Arlappa N, Aatif Qureshi I, Srinivas R (2013) Fluorosis in India: an overview. Int J Res Dev Health 1:97–102
Borgohain X, Boruah A, Sarma GK, Rashid MH (2020) Rapid and extremely high adsorption performance of porous MgO nanostructures for fluoride removal from water. J Mol Liq 305:112799. https://doi.org/10.1016/j.molliq.2020.112799
Boyd GE, Adamson AW, Myers LS (1947) The exchange adsorption of ions from aqueous solutions by organic zeolites. II. Kinetics. J Am Chem Soc 69:2836–2848. https://doi.org/10.1021/ja01203a066
Chaudhary M, Rawat S, Jain N, Bhatnagar A, Maiti A (2019) Chitosan-Fe-Al-Mn metal oxyhydroxides composite as highly efficient fluoride scavenger for aqueous medium. Carbohydr Polym 216:140–148. https://doi.org/10.1016/j.carbpol.2019.04.028
Chen D, Shen W, Wu S, Chen C, Luo X, Guo L (2016a) Ion exchange induced removal of Pb(II) by MOF-derived magnetic inorganic sorbents. Nanoscale 8:7172–7179. https://doi.org/10.1039/c6nr00695g
Chen H, Liu W, Qin Z (2017a) ZnO/ZnFe2O4 nanocomposite as a broad-spectrum photo-Fenton-like photocatalyst with near-infrared activity. Catal Sci Technol 7:2236–2244. https://doi.org/10.1039/c7cy00308k
Chen L, Zhang K, He J, Cai X-G, Xu W, Liu J-H (2016b) Performance and mechanism of hierarchically porous Ce–Zr oxide nanospheres encapsulated calcium alginate beads for fluoride removal from water. RSC Adv 6:36296–36306. https://doi.org/10.1039/c6ra01337f
Chen M, Liu D, Deng Y, Fu W, Zou H, Liang F (2017b) Tailoring the porosity of ZnO/ZnFe2O4 composites for photocatalytic applications. Ceram Int 43:16027–16031. https://doi.org/10.1016/j.ceramint.2017.08.148
Chigondo M, Paumo HK, Bhaumik M, Pillay K, Maity A (2018) Rapid high adsorption performance of hydrous cerium-magnesium oxides for removal of fluoride from water. J Mol Liq 265:496–509. https://doi.org/10.1016/j.molliq.2018.06.015
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. https://doi.org/10.1016/j.chemosphere.2017.11.021
Falak P, Hassanzadeh-Tabrizi SA, Saffar-Teluri A (2017) Synthesis, characterization, and magnetic properties of ZnO-ZnFe2O4 nanoparticles with high photocatalytic activity. J Magn Magn Mater 441:98–104. https://doi.org/10.1016/j.jmmm.2017.05.044
Fan K et al (2018) Towards enhanced tribological performance as water-based lubricant additive: selective fluorination of graphene oxide at mild temperature. J Colloid Interface Sci 531:138–147. https://doi.org/10.1016/j.jcis.2018.07.059
Feng J et al (2015) Synthesis of magnetic ZnO/ZnFe2O4 by a microwave combustion method, and its high rate of adsorption of methylene blue. J Colloid Interface Sci 438:318–322. https://doi.org/10.1016/j.jcis.2014.10.009
Foo KY, Hameed BH (2010) Insights into the modeling of adsorption isotherm systems. Chem Eng J 156:2–10. https://doi.org/10.1016/j.cej.2009.09.013
Gan Y, Wang X, Zhang L, Wu B, Zhang G, Zhang S (2019) Coagulation removal of fluoride by zirconium tetrachloride: performance evaluation and mechanism analysis. Chemosphere 218:860–868. https://doi.org/10.1016/j.chemosphere.2018.11.192
Gao Q, Xu J, Bu X-H (2019) Recent advances about metal-organic frameworks in the removal of pollutants from wastewater. Coord Chem Rev 378:17–31. https://doi.org/10.1016/j.ccr.2018.03.015
Gawas UB, Verenkar VMS, Barman SR, Meena SS, Bhatt P (2013) Synthesis of nanosize and sintered Mn0.3Ni0.3Zn0.4Fe2O4 ferrite and their structural and dielectric studies. J Alloys Compd 555:225–231. https://doi.org/10.1016/j.jallcom.2012.12.054
Ghanbarian M, Ghanbarian M, Mahvi AH, Tabatabaie T (2020) Enhanced fluoride removal over MgFe2O4–chitosan–CaAl nanohybrid: response surface optimization, kinetic and isotherm study. Int J Biol Macromol 148:574–590. https://doi.org/10.1016/j.ijbiomac.2020.01.143
Hameed BH, El-Khaiary MI (2008a) Equilibrium, kinetics and mechanism of malachite green adsorption on activated carbon prepared from bamboo by K2CO3 activation and subsequent gasification with CO2. J Hazard Mater 157:344–351. https://doi.org/10.1016/j.jhazmat.2007.12.105
Hameed BH, El-Khaiary MI (2008b) Kinetics and equilibrium studies of malachite green adsorption on rice straw-derived char. J Hazard Mater 153:701–708. https://doi.org/10.1016/j.jhazmat.2007.09.019
Hou L, Lian L, Zhang L, Pang G, Yuan C, Zhang X (2015) Self-sacrifice template fabrication of hierarchical mesoporous bi-component-active ZnO/ZnFe2O4 sub-microcubes as superior anode towards high-performance lithium-ion battery. Adv Funct Mater 25:238–246. https://doi.org/10.1002/adfm.201402827
Huang H, Liu J, Zhang P, Zhang D, Gao F (2017) Investigation on the simultaneous removal of fluoride, ammonia nitrogen and phosphate from semiconductor wastewater using chemical precipitation. Chem Eng J 307:696–706. https://doi.org/10.1016/j.cej.2016.08.134
Huang Y-H, Shih Y-J, Chang C-C (2011) Adsorption of fluoride by waste iron oxide: the effects of solution pH, major coexisting anions, and adsorbent calcination temperature. J Hazard Mater 186:1355–1359. https://doi.org/10.1016/j.jhazmat.2010.12.025
Jagtap S, Yenkie MK, Labhsetwar N, Rayalu S (2012) Fluoride in drinking water and defluoridation of water. Chem Rev 112:2454–2466. https://doi.org/10.1021/cr2002855
Kaloti M, Kumar A (2016) Synthesis of chitosan-mediated silver coated γ-Fe2O3 (Ag−γ-Fe2O3@Cs) superparamagnetic binary nanohybrids for multifunctional applications. J Phys Chem C 120:17627–17644. https://doi.org/10.1021/acs.jpcc.6b05851
Kameda T, Oba J, Yoshioka T (2015) Recyclable Mg–Al layered double hydroxides for fluoride removal: kinetic and equilibrium studies. J Hazard Mater 300:475–482. https://doi.org/10.1016/j.jhazmat.2015.07.023
Kuai S, Zhang Z, Nan Z (2013) Synthesis of Ce3+ doped ZnFe2O4 self-assembled clusters and adsorption of chromium(VI). J Hazard Mater 250–251:229–237. https://doi.org/10.1016/j.jhazmat.2013.01.074
Li Y et al (2011) Adsorption of fluoride from aqueous solution by graphene. J Colloid Interface Sci 363:348–354. https://doi.org/10.1016/j.jcis.2011.07.032
Lima EC, Hosseini-Bandegharaei A, Moreno-Piraján JC, Anastopoulos I (2019) A critical review of the estimation of the thermodynamic parameters on adsorption equilibria. Wrong use of equilibrium constant in the van’t Hoof equation for calculation of thermodynamic parameters of adsorption. J Mol Liq 273:425–434. https://doi.org/10.1016/j.molliq.2018.10.048
Liu J, Xie L, Yue X, Xu C, Lu X (2020) Removal of fluoride and hardness by layered double hydroxides: property and mechanism. Int J Environ Sci Technol 17:673–682. https://doi.org/10.1007/s13762-019-02457-6
Liu R, Chi L, Wang X, Sui Y, Wang Y, Arandiyan H (2018) Review of metal (hydr)oxide and other adsorptive materials for phosphate removal from water. J Environ Chem Eng 6:5269–5286. https://doi.org/10.1016/j.jece.2018.08.008
Liu Y, Liu Y-J (2008) Biosorption isotherms, kinetics and thermodynamics. Sep Purif Technol 61:229–242. https://doi.org/10.1016/j.seppur.2007.10.002
Mandal S, Mayadevi S (2008) Adsorption of fluoride ions by Zn-Al layered double hydroxides. Appl Clay Sci 40:54–62. https://doi.org/10.1016/j.clay.2007.07.004
Miretzky P, Cirelli AF (2011) Fluoride removal from water by chitosan derivatives and composites: a review. J Fluor Chem 132:231–240. https://doi.org/10.1016/j.jfluchem.2011.02.001
Mohammadi E et al (2019) Synthesis of carboxylated chitosan modified with ferromagnetic nanoparticles for adsorptive removal of fluoride, nitrate, and phosphate anions from aqueous solutions. J Mol Liq 273:116–124. https://doi.org/10.1016/j.molliq.2018.10.019
Mohseni-Bandpi A, Kakavandi B, Kalantary RR, Azari A, Keramati A (2015) Development of a novel magnetite-chitosan composite for the removal of fluoride from drinking water: adsorption modeling and optimization. RSC Adv 5:73279–73289. https://doi.org/10.1039/c5ra11294j
Mondal R, Pal S, Bhalani DV, Bhadja V, Chatterjee U, Jewrajka SK (2018) Preparation of polyvinylidene fluoride blend anion exchange membranes via non-solvent induced phase inversion for desalination and fluoride removal. Desalination 445:85–94. https://doi.org/10.1016/j.desal.2018.07.032
Nunes-Pereira J et al (2018) Highly efficient removal of fluoride from aqueous media through polymer composite membranes. Sep Purif Technol 205:1–10. https://doi.org/10.1016/j.seppur.2018.05.015
Nur T, Loganathan P, Nguyen TC, Vigneswaran S, Singh G, Kandasamy J (2014) Batch and column adsorption and desorption of fluoride using hydrous ferric oxide: solution chemistry and modeling. Chem Eng J 247:93–102. https://doi.org/10.1016/j.cej.2014.03.009
Pillai P, Lakhtaria Y, Dharaskar S, Khalid M (2019) Synthesis, characterization, and application of iron oxyhydroxide coated with rice husk for fluoride removal from aqueous media. Environ Sci Pollut Res. https://doi.org/10.1007/s11356-019-05948-8
Reichenberg D (1953) Properties of ion-exchange resins in relation to their structure. III. kinetics of exchange. J Am Chem Soc 75:589–597. https://doi.org/10.1021/ja01099a022
Roy S, Dass G (2013) Fluoride contamination in drinking water-a review. Resour Environ 3:53–58. https://doi.org/10.5923/j.re.20130303.02
Sahoo SK, Hota G (2019) Amine-functionalized GO decorated with ZnO-ZnFe2O4 nanomaterials for remediation of Cr(VI) from water. ACS Appl Nano Mater 2:983–996. https://doi.org/10.1021/acsanm.8b02286
Saini A, Maheshwari PH, Tripathy SS, Waseem S, Dhakate SR (2020) Processing of rice straw to derive carbon with efficient de-fluoridation properties for drinking water treatment. J Water Process Eng 34:101136. https://doi.org/10.1016/j.jwpe.2020.101136
Sarma GK, Khan A, El-Toni AM, Rashid MH (2019) Shape-tunable CuO-Nd(OH)3 nanocomposites with excellent adsorption capacity in organic dye removal and regeneration of spent adsorbent to reduce secondary waste. J Hazard Mater 380:120838. https://doi.org/10.1016/j.jhazmat.2019.120838
Sarma GK, Rashid MH (2018) Synthesis of Mg/Al Layered double hydroxides for adsorptive removal of fluoride from water: a mechanistic and kinetic study. J Chem Eng Data 63:2957–2965. https://doi.org/10.1021/acs.jced.8b00242
Sattarfard R, Behnajady MA, Eskandarloo H (2018) Hydrothermal synthesis of mesoporous TiO2 nanotubes and their adsorption affinity toward Basic Violet 2. J Porous Mater 25:359–371. https://doi.org/10.1007/s10934-017-0447-5
She X, Zhang Z, Baek M, Yong K (2017) Elevated photoelectrochemical activity of FeVO4/ZnFe2O4/ZnO branch-structures via slag assisted-synthesis. RSC Adv 7:16787–16794. https://doi.org/10.1039/c7ra00812k
Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure Appl Chem 57:603–619
Specht RC (1956) Interaction of fluoride ions and ground glass. Anal Chem 28:1015–1017. https://doi.org/10.1021/ac60114a026
Tao W, Zhong H, Pan X, Wang P, Wang H, Huang L (2020) Removal of fluoride from wastewater solution using Ce-AlOOH with oxalic acid as modification. J Hazard Mater 384:121373. https://doi.org/10.1016/j.jhazmat.2019.121373
Thakur G, Singh A, Singh I (2016) Chitosan-montmorillonite polymer composites: formulation and evaluation of sustained release tablets of aceclofenac. Sci Pharm 84:603–617. https://doi.org/10.3390/scipharm84040603
Ullah R, Dutta J (2008) Photocatalytic degradation of organic dyes with manganese-doped ZnO nanoparticles. J Hazard Mater 156:194–200. https://doi.org/10.1016/j.jhazmat.2007.12.033
Wang X, Zhang S, Shao M, Huang J, Deng X, Hou P, Xu X (2017) Fabrication of ZnO/ZnFe2O4 hollow nanocages through metal organic frameworks route with enhanced gas sensing properties. Sensors Actuators B Chem 251:27–33. https://doi.org/10.1016/j.snb.2017.04.114
WHO (2017) Guidelines for drinking-water quality (2017) World Health Organization:631
Yang X, Xue H, Yang Q, Yuan R, Kang W, Lee C-S (2017) Preparation of porous ZnO/ZnFe2O4 composite from metal organic frameworks and its applications for lithium ion batteries. Chem Eng J 308:340–346. https://doi.org/10.1016/j.cej.2016.09.071
Acknowledgments
We thank Mr. Debajit Gogoi, Research Scholar, Department of Chemistry, Tezpur University, for supplying the field water sample. We also thank SAIF-GU, NEIST-Jorhat, STIC-Cochin, and CNN-JMI for extending their instrumental facilities to us.
Funding
GKS acknowledges the Science and Engineering Research Board, India, for providing the fellowship (N-PDF File No. PDF/2016/000110). Raju Sharma is grateful to IASc-INSA-NASI, India, for providing fellowship under Focus Area Science Technology Summer Fellowship to carry out the research.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
Responsible Editor: Tito Roberto Cadaval Jr
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
ESM 1
Electronic Supplementary Information provides the detail of characterization of the products; adsorption isotherm and kinetics data; water quality parameters and comparison of the performance of various adsorbent (Table S1 to S3) and Figures S1 to S8. This material is available free of cost either from the author or from the publisher at the website https//www. (PDF 1185 kb)
Rights and permissions
About this article
Cite this article
Sarma, G.K., Sharma, R., Saikia, R. et al. Facile synthesis of chitosan-modified ZnO/ZnFe2O4 nanocomposites for effective remediation of groundwater fluoride. Environ Sci Pollut Res 27, 30067–30080 (2020). https://doi.org/10.1007/s11356-020-09270-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-020-09270-6