Clean technology for synchronous sequestration of charged organic micro-pollutant onto microwave-assisted hybrid clay materials

  • 33 Accesses


The Sustainable Development Goal 6 (SDG #6) of the United Nations (UN) is hinged on the provision, availability, and sustainability of water for the global populace by 2030. In a bid to achieve this goal, the quest to seek for ubiquitous and low-cost adsorbents to treat effluents laden with industrial dyes, such as methylene blue (MB), is on the increase in recent years. Acute exposure of humans to (MB) dye causes cyanosis, necrosis, and jaundice and even leads to death. In this research, zinc-modified hybrid clay composite adsorbent (materials from kaolinite and biomass (crushed Carica papaya seeds and/or plantain peel)) was developed via microwave route. This adsorbent was characterized using field emission scanning electron microscopy (FE-SEM), Fourier transform infrared (FTIR) spectroscopy, energy-dispersive X-ray (EDX), and high-resolution transmission electron microscopy (HR-TEM). These characterization techniques confirmed the success achieved in doping hybrid clay with Zn. These adsorbents were used to sequester cationic dye (MB) from aqueous solutions and textile effluent under various experimental conditions. The adsorption and desorption data obtained were analyzed using various kinetic models, which are two-step kinetics, pseudo-first order, pseudo-second order, fractal kinetics, first-order desorption, second-order desorption, and modified statistical rate theory (MSRT) desorption models. Results showed that the adsorption of the dye occurred via several chemical interactions, while the latter models (for desorption) indicated that desorption occurred in two different desorption sites on the adsorbent surfaces, which showed that the adsorption of MB dye onto the adsorbents was stable without the emergence of any secondary pollution. Adsorption of MB was achieved within 15 min for aqueous solutions and 900 min for textile effluent, which is an improvement on previous results from other studies. The three adsorption-desorption cycles for MB uptake by the adsorbents showed that it is pragmatically applicable to treat textile effluents. Hence, low-cost composite adsorbents have a potential for the effective remediation of MB dye from textile effluents as this study confirmed.

This is a preview of subscription content, log in to check access.

Access options

Buy single article

Instant unlimited access to the full article PDF.

US$ 39.95

Price includes VAT for USA

Subscribe to journal

Immediate online access to all issues from 2019. Subscription will auto renew annually.

US$ 99

This is the net price. Taxes to be calculated in checkout.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5


  1. Abdellaoui K, Pavlovic I, Bouhent M, Benhamou A, Barriga C (2017) A comparative study of the amaranth azo dye adsorption/desorption from aqueous solutions by layered double hydroxides. Appl Clay Sci 143:142–150

  2. Adeyemo AA, Adeoye IO, Bello OS (2017) Adsorption of dyes using different types of clay: a review. Appl Water Sci 7:543–568

  3. Akpotu SO, Moodley B (2016) Synthesis and characterization of citric acid grafted MCM-41 and its adsorption of cationic dyes. J Environ Chem Eng 4:4503–4513

  4. Al-Degs Y, Khraisheh M, Allen S, Ahmad M (2009) Adsorption characteristics of reactive dyes in columns of activated carbon. J Hazard Mater 165:944–949

  5. Armah FA, Ekumah B, Yawson DO, Odoi JO, Afitiri A-R, Nyieku FE (2018) Access to improved water and sanitation in sub-Saharan Africa in a quarter century. Heliyon 4:e00931

  6. Azizian S, Bashiri H (2008) Description of desorption kinetics at the solid/solution interface based on the statistical rate theory. Langmuir 24:13013–13018

  7. Babalola JO, Olowoyo JO, Durojaiye AO, Olatunde AM, Unuabonah EI, Omorogie MO (2016) Understanding the removal and regeneration potentials of biogenic wastes for toxic metals and organic dyes. J Taiwan Inst Chem Eng 58:490–499

  8. Barragán BE, Costa C, Marquez MC (2007) Biodegradation of azo dyes by bacteria inoculated on solid media. Dyes Pigments 75:73–81

  9. Bashiri H (2011) Desorption kinetics at the solid/solution interface: a theoretical description by statistical rate theory for close-to-equilibrium systems. J Phys Chem C 115:5732–5739

  10. Benadjemia M, Millière L, Reinert L, Benderdouche N, Duclaux L (2011) Preparation, characterization and methylene blue adsorption of phosphoric acid activated carbons from globe artichoke leaves. Fuel Process Technol 92:1203–1212

  11. El Salam HA, Zaki T (2018) Removal of hazardous cationic organic dyes from water using nickel-based metal-organic frameworks. Inorg Chim Acta 471:203–210

  12. Fan L, Zhou Y, Yang W, Chen G, Yang F (2008) Electrochemical degradation of aqueous solution of Amaranth azo dye on ACF under potentiostatic model. Dyes Pigments 76:440–446

  13. Feddal I, Ramdani A, Taleb S, Gaigneaux EM, Batis N, Ghaffour N (2014) Adsorption capacity of methylene blue, an organic pollutant, by montmorillonite clay. Desalin Water Treat 52:2654–2661

  14. García-Montaño J, Pérez-Estrada L, Oller I, Maldonado MI, Torrades F, Peral J (2008) Pilot plant scale reactive dyes degradation by solar photo-Fenton and biological processes. J Photochem Photobiol A Chem 195:205–214

  15. Gupta V, Ali I, Mohan D (2003) Equilibrium uptake and sorption dynamics for the removal of a basic dye (basic red) using low-cost adsorbents. J Colloid Interface Sci 265:257–264

  16. Jin Y-Z, Zhang Y-F, Li W (2003) Micro-electrolysis technology for industrial wastewater treatment. J Environ Sci 15:334–338

  17. Khalili MS, Zare K, Moradi O, Sillanpää M (2018) Preparation and characterization of MWCNT–COOH–cellulose–MgO NP nanocomposite as adsorbent for removal of methylene blue from aqueous solutions: isotherm, thermodynamic and kinetic studies. J Nanostruct Chem 8:103–121

  18. Koli PB, Kapadnis KH, Deshpande UG, Patil MR (2018) Fabrication and characterization of pure and modified Co3O4 nanocatalyst and their application for photocatalytic degradation of eosine blue dye: a comparative study. J Nanostruct Chem 8:453–463

  19. Kumar A, Kumar A, Sharma G, Naushad M, Stadler FJ, Ghfar AA, Dhiman P, Saini RV (2017) Sustainable nano-hybrids of magnetic biochar supported g-C3N4/FeVO4 for solar powered degradation of noxious pollutants-synergism of adsorption, photocatalysis & photo-ozonation. J Clean Prod 165:431–451

  20. Li M, Yang Y, Yang Y, Yin J, Zhang J, Feng Y, Shao B (2013a) Biotransformation of bisphenol AF to its major glucuronide metabolite reduces estrogenic activity. PLoS One 8:e83170

  21. Li W, Zhang L-B, Peng J-H, Li N, Zhu X-Y (2008) Preparation of high surface area activated carbons from tobacco stems with K2CO3 activation using microwave radiation. Ind Crop Prod 27:341–347

  22. Li Y, Du Q, Liu T, Peng X, Wang J, Sun J, Wang Y, Wu S, Wang Z, Xia Y (2013b) Comparative study of methylene blue dye adsorption onto activated carbon, graphene oxide, and carbon nanotubes. Chem Eng Res Des 91:361–368

  23. Liu T, Li Y, Du Q, Sun J, Jiao Y, Yang G, Wang Z, Xia Y, Zhang W, Wang K (2012) Adsorption of methylene blue from aqueous solution by graphene. Colloids Surf B: Biointerfaces 90:197–203

  24. Lodha B, Chaudhari S (2007) Optimization of Fenton-biological treatment scheme for the treatment of aqueous dye solutions. J Hazard Mater 148:459–466

  25. Moradi O, Aghaie M, Zare K, Monajjemi M, Aghaie H (2009) The study of adsorption characteristics Cu2+ and Pb2+ ions onto PHEMA and P (MMA-HEMA) surfaces from aqueous single solution. J Hazard Mater 170:673–679

  26. Moradi O, Norouzi M, Fakhri A, Naddafi K (2014) Interaction of removal ethidium bromide with carbon nanotube: equilibrium and isotherm studies. J Environ Health Sci Eng 12:17

  27. Narvekar AA, Fernandes J, Tilve S (2018) Adsorption behavior of methylene blue on glycerol based carbon materials. J Environ Chem Eng 6:1714–1725

  28. Omorogie MO, Agunbiade FO, Alfred MO, Olaniyi OT, Adewumi TA, Bayode AA, Ofomaja AE, Naidoo EB, Okoli CP, Adebayo TA (2018) The sequestral capture of fluoride, nitrate and phosphate by metal-doped and surfactant-modified hybrid clay materials. Chem Pap 72:409–417

  29. Omorogie MO, Babalola JO, Unuabonah EI, Gong JR (2012) Kinetics and thermodynamics of heavy metal ions sequestration onto novel Nauclea diderrichii seed biomass. Bioresour Technol 118:576–579

  30. Organization, W.H, UNICEF, 2017, Progress on drinking water, sanitation and hygiene: 2017 update and SDG baselines

  31. Pal J, Deb MK (2014) Efficient adsorption of congo red dye from aqueous solution using green synthesized coinage nanoparticles coated activated carbon beads. Appl Nanosci 4:967–978

  32. Rajabi M, Mahanpoor K, Moradi O (2019) Preparation of PMMA/GO and PMMA/GO-Fe3O4 nanocomposites for malachite green dye adsorption: kinetic and thermodynamic studies. Compos Part B 167:544–555

  33. Remya N, Lin J-G (2011) Current status of microwave application in wastewater treatment—a review. Chem Eng J 166:797–813

  34. Robati D, Mirza B, Ghazisaeidi R, Rajabi M, Moradi O, Tyagi I, Agarwal S, Gupta VK (2016) Adsorption behavior of methylene blue dye on nanocomposite multi-walled carbon nanotube functionalized thiol (MWCNT-SH) as new adsorbent. J Mol Liq 216:830–835

  35. Rudzinski W, Panczyk T (2002) Remarks on the current state of adsorption kinetic theories for heterogeneous solid surfaces: a comparison of the ART and the SRT approaches. Langmuir 18:439–449

  36. Sarria V, Deront M, Péringer P, Pulgarin C (2003) Degradation of a biorecalcitrant dye precursor present in industrial wastewaters by a new integrated iron (III) photoassisted–biological treatment. Appl Catal B Environ 40:231–246

  37. Seow TW, Lim CK (2016) Removal of dye by adsorption: a review. Int J Appl Eng Res 11:2675–2679

  38. Stumm W, Morgan JJ, 1996, Aquatic chemistry: chemical Equilibria and rates in natural waters {environmental science and technology}. Wiley

  39. Sudarjanto G, Keller-Lehmann B, Keller J (2006) Optimization of integrated chemical–biological degradation of a reactive azo dye using response surface methodology. J Hazard Mater 138:160–168

  40. Suganya V, Anuradha V (2017) Microencapsulation and nanoencapsulation: a review. Int J Pharm Clin Res 9:233–239

  41. Torabinejad A, Nasirizadeh N, Yazdanshenas ME, Tayebi H-A (2017) Synthesis of conductive polymer-coated mesoporous MCM-41 for textile dye removal from aqueous media. J Nanostruct Chem 7:217–229

  42. Unuabonah EI, Adedapo AO, Nnamdi CO, Adewuyi A, Omorogie MO, Adebowale KO, Olu-Owolabi BI, Ofomaja AE, Taubert A (2015) Successful scale-up performance of a novel papaya-clay combo adsorbent: up-flow adsorption of a basic dye. Desalin Water Treat 56:536–551

  43. Unuabonah EI, Adie GU, Onah LO, Adeyemi OG (2009) Multistage optimization of the adsorption of methylene blue dye onto defatted Carica papaya seeds. Chemical Engineering Journal 155(3):567–579

  44. Unuabonah EI, Günter C, Weber J, Lubahn S, Taubert A (2013) Hybrid clay: a new highly efficient adsorbent for water treatment. ACS Sustain Chem Eng 1:966–973

  45. Unuabonah EI, Kolawole MO, Agunbiade FO, Omorogie MO, Koko DT, Ugwuja CG, Ugege LE, Oyejide NE, Günter C, Taubert A (2017) Novel metal-doped bacteriostatic hybrid clay composites for point-of-use disinfection of water. J Environ Chem Eng 5:2128–2141

  46. Vadivelan V, Kumar KV (2005) Equilibrium, kinetics, mechanism, and process design for the sorption of methylene blue onto rice husk. J Colloid Interface Sci 286:90–100

  47. Wang S (2008) A comparative study of Fenton and Fenton-like reaction kinetics in decolourisation of wastewater. Dyes Pigments 76:714–720

  48. Weng C-H, Lin Y-T, Tzeng T-W (2009) Removal of methylene blue from aqueous solution by adsorption onto pineapple leaf powder. J Hazard Mater 170:417–424

  49. Wu J-S, Liu C-H, Chu KH, Suen S-Y (2008) Removal of cationic dye methyl violet 2B from water by cation exchange membranes. J Membr Sci 309:239–245

  50. Yari M, Norouzi M, Mahvi AH, Rajabi M, Yari A, Moradi O, Tyagi I, Gupta VK (2016) Removal of Pb (II) ion from aqueous solution by graphene oxide and functionalized graphene oxide-thiol: effect of cysteamine concentration on the bonding constant. Desalin Water Treat 57:11195–11210

  51. Yari M, Rajabi M, Moradi O, Yari A, Asif M, Agarwal S, Gupta VK (2015) Kinetics of the adsorption of Pb (II) ions from aqueous solutions by graphene oxide and thiol functionalized graphene oxide. J Mol Liq 209:50–57

  52. Yu J-X, Chi R-A, Su X-Z, He Z-Y, Qi Y-F, Zhang Y-F (2010) Desorption behavior of methylene blue on pyromellitic dianhydride modified biosorbent by a novel eluent: acid TiO2 hydrosol. J Hazard Mater 177:222–227

  53. Yu J-X, Li B-H, Sun X-M, Jun Y, Chi R-A (2009) Adsorption of methylene blue and rhodamine B on baker's yeast and photocatalytic regeneration of the biosorbent. Biochem Eng J 45:145–151

  54. Yue Q, Gao B, Wang Y, Zhang H, Sun X, Wang S, Gu RR (2008) Synthesis of polyamine flocculants and their potential use in treating dye wastewater. J Hazard Mater 152:221–227

  55. Zaghbani N, Hafiane A, Dhahbi M (2008) Removal of Safranin T from wastewater using micellar enhanced ultrafiltration. Desalination 222:348–356

  56. Zhu M-X, Lee L, Wang H-H, Wang Z (2007) Removal of an anionic dye by adsorption/precipitation processes using alkaline white mud. J Hazard Mater 149:735–741

Download references

Author information

Correspondence to Foluso O. Agunbiade.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Responsible editor: Tito Roberto Cadaval Jr

Electronic supplementary material


(DOCX 1930 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Bayode, A.A., Agunbiade, F.O., Omorogie, M.O. et al. Clean technology for synchronous sequestration of charged organic micro-pollutant onto microwave-assisted hybrid clay materials. Environ Sci Pollut Res (2020).

Download citation


  • Textile effluent
  • Dye
  • Microwave synthesis
  • Adsorption
  • Hybrid clay