Springer Nature is making Coronavirus research free. View research | View latest news | Sign up for updates

Kinetic and thermodynamic study of methylene blue adsorption onto chitosan: insights about metachromasy occurrence on wastewater remediation


Methylene blue (MB) is a dye used in the textile industry and a potential wastewater pollutant. Adsorption of MB onto the chitosan is a promising method for MB removal. Upon contact with chitosan, MB molecules can aggregate leading to the appearance of additional bands in the MB absorption spectrum. This phenomenon is called metachromasy. In this paper the kinetics and thermodynamic parameters related to the removal of MB as single molecules (Sng-MB) and aggregates (Agg-MB) species by chitosan from simulated wastewater were studied. Additionally, it was investigated means to suppress metachromasy and improve the efficiency of the removal process. For both MB species, the adsorption process followed the pseudo-second-order adsorption kinetics model. For each temperature studied, Agg-MB always presented higher rate constant than Sng-MB, indicating faster adsorption of Agg-MB in comparison with Sng-MB, whereas the highest removal percentage (around 65%) for both species was obtained at 323 K. A lower activation energy was obtained for the adsorption of Agg-MB (28 kJ/mol) than for Sng-MB (65 kJ/mol), indicating Agg-MB adsorption is favored in relation to Sng-MB. The thermodynamic studies indicated the adsorption process for both MB species is endothermic and spontaneous from 298 to 348 K. The metachromasy could be suppressed by performing the experiments at pH 3, leading to a removal percentage around 70% in comparison with 20 and 60%, for experiments at pH 7 and 12, respectively, at 298 K. Analysis of chitosan before and after adsorption process, by using X-ray diffraction, infrared spectroscopy, scanning and transmission electron microscopies, indicated that no structural changes happened to chitosan throughout the process.

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10


  1. Aich N, Flora JRV, Saleh NB (2012) Preparation and characterization of stable aqueous higher-order fullerenes. Nanotechnology 23:055705.

  2. Aich N, Boateng LK, Sabaraya IV et al (2016) Aggregation kinetics of higher-order fullerene clusters in aquatic systems. Environ Sci Technol 50:3562–3571.

  3. Alkhamis KA, Salem MS, Khanfar MS (2008) The sorption of ketotifen fumarate by chitosan. AAPS PharmSciTech 9:866–869.

  4. Allen SJ, Mckay G, Porter JF (2004) Adsorption isotherm models for basic dye adsorption by peat in single and binary component systems. J Colloid Interface Sci 280:322–333.

  5. Aranaz I, Mengíbar M, Harris R et al (2009) Functional characterization of chitin and chitosan. Curr Chem Biol 3:203–230.

  6. Awual MR (2017) Novel nanocomposite materials for efficient and selective mercury ions capturing from wastewater. Chem Eng J 307:456–465.

  7. Awual MR, Khraisheh M, Alharthi NH et al (2018) Efficient detection and adsorption of cadmium(II) ions using innovative nano-composite materials. Chem Eng J 343:118–127.

  8. Bajaj G, Van Alstine WG, Yeo Y (2012) Zwitterionic chitosan derivative, a new biocompatible pharmaceutical excipient, prevents endotoxin-mediated cytokine release. PLoS ONE 7:e30899.

  9. Bera A, Kumar T, Ojha K, Mandal A (2013) Adsorption of surfactants on sand surface in enhanced oil recovery: isotherms, kinetics and thermodynamic studies. Appl Surf Sci 284:87–99.

  10. Brienza M, Katsoyiannis IA (2017) Sulfate radical technologies as tertiary treatment for the removal of emerging contaminants from wastewater. Sustainability 9:1–18.

  11. Cenens J, Schoonheydt RA (1988) Visible spectroscopy of methylene blue on hectorite, laponite B, and barasym in aqueous suspension. Clays Clay Miner 36:214–224.

  12. Ciriminna R, Albanese L, Meneguzzo F, Pagliaro M (2017) Wastewater remediation via controlled hydrocavitation. Environ Rev 25:175–183.

  13. Crini G, Badot P-M (2008) Application of chitosan, a natural aminopolysaccharide, for dye removal from aqueous solutions by adsorption processes using batch studies: a review of recent literature. Prog Polym Sci 33:399–447.

  14. Csoka L, Appel TR, Eitner A et al (2013) Polarization optical-histochemical characterization and supramolecular structure of carbohydrate fibrils. Acta Histochem 115:22–31.

  15. D’mello AXP, Sylvester TV, Ramya V et al (2016) Metachromasia and metachromatic dyes: a review. Int J Adv Health Sci 2:12–17

  16. Dobritoiu R, Patachia S (2013) A study of dyes sorption on biobased cryogels. Appl Surf Sci 285:56–64.

  17. Doǧan M, Alkan M, Türkyilmaz A, Özdemir Y (2004) Kinetics and mechanism of removal of methylene blue by adsorption onto perlite. J Hazard Mater 109:141–148.

  18. Du Q, Sun J, Li Y et al (2014) Highly enhanced adsorption of congo red onto graphene oxide/chitosan fibers by wet-chemical etching off silica nanoparticles. Chem Eng J 245:99–106.

  19. Fagerlund G (1973) Determination of specific surface by the BET method. Matér Constr 6:239–245.

  20. Foo KY, Hameed BH (2010) Insights into the modeling of adsorption isotherm systems. Chem Eng J 156:2–10.

  21. Forgacs E, Cserháti T, Oros G (2004) Removal of synthetic dyes from wastewaters: a review. Environ Int 30:953–971.

  22. Gupta VK, Suhas (2009) Application of low-cost adsorbents for dye removal—a review. J Environ Manag 90:2313–2342.

  23. Haghseresht F, Lu GQ (1998) Adsorption characteristics of phenolic compounds onto coal-reject-derived adsorbents. Energy Fuels 12:1100–1107.

  24. Haubner K, Murawski J, Olk P et al (2010) The route to functional graphene oxide. ChemPhysChem 11:2131–2139.

  25. Heyne B (2016) Self-assembly of organic dyes in supramolecular aggregates. Photochem Photobiol Sci 15:1103–1114.

  26. Hirano S, Kinugawa J, Nishioka A, Tino H (1987) Transformation of triplet induced cotton effects of the methylene blue complexes of some sulphate derivatives of chitosan. Int J Biol Macromol 9:11–14.

  27. Ho YS, Mckay G (1998) A comparison of chemisorption kinetic models applied to pollutant removal on various sorbents. Process Saf Environ Prot 76:332–340.

  28. Iqbal MJ, Ashiq MN (2007) Adsorption of dyes from aqueous solutions on activated charcoal. J Hazard Mater 139:57–66.

  29. Kim Y, Kim C, Choi I et al (2004) Arsenic removal using mesoporous alumina prepared via a templating method. Environ Sci Technol 38:924–931.

  30. Kluczka J, Gnus M, Kazek-Kęsik A, Dudek G (2018) Zirconium-chitosan hydrogel beads for removal of boron from aqueous solutions. Polymer (Guildf) 150:109–118.

  31. Kumar V, Kumar R, Nayak A et al (2013) Adsorptive removal of dyes from aqueous solution onto carbon nanotubes: a review. Adv Colloid Interface Sci 194:24–34.

  32. Kumar MS, Sonawane SH, Pandit AB (2017) Degradation of methylene blue dye in aqueous solution using hydrodynamic cavitation based hybrid advanced oxidation processes. Chem Eng Process Process Intensif 122:288–295.

  33. Kumar Dutta P, Dutta J, Tripathi VS (2004) Chitin and chitosan: chemistry, properties and applications. J Sci Ind Res 63:20–31.

  34. Matafonova G, Batoev V (2018) Recent advances in application of UV light-emitting diodes for degrading organic pollutants in water through advanced oxidation processes: a review. Water Res 132:177–189.

  35. McKay RB (1966) Red forms of methylene blue. Nature 210:296–297.

  36. Mills A, Hazafy D, Parkinson J et al (2011) Effect of alkali on methylene blue (C.I. Basic Blue 9) and other thiazine dyes. Dye Pigment 88:149–155.

  37. Moreno-Villoslada I, Torres-Gallegos C, Araya-Hermosilla R, Nishide H (2010) Influence of the linear aromatic density on methylene blue aggregation around polyanions containing sulfonate groups. J Phys Chem B 114:4151–4158.

  38. Murthy ASN, Bhardwaj AP (1980) Electronic absorption spectroscopic studies on the red form of methylene blue ion. Proc Indian Acad Sci (Chem Sci) 89:463–468.

  39. Navarro R, Guzmán J, Saucedo I et al (2003) Recovery of metal ions by chitosan: sorption mechanisms and influence of metal speciation. Macromol Biosci 3:552–561.

  40. Nidheesh PV, Zhou M, Oturan MA (2018) An overview on the removal of synthetic dyes from water by electrochemical advanced oxidation processes. Chemosphere 197:210–227.

  41. O’Connor D, Hou D, Ok YS et al (2018) Sustainable in situ remediation of recalcitrant organic pollutants in groundwater with controlled release materials: a review. J Control Release 283:200–213.

  42. Qiu H, Lv L, Pan B et al (2009) Critical review in adsorption kinetic models. J Zhejiang Univ Sci A 10:716–724.

  43. Rabinowitch E, Epstein LF (1941) Polymerization of dyestuffs in solution. Thionine and methylene blue. J Am Chem Soc 63:69–78.

  44. Saratale RG, Saratale GD, Chang JS, Govindwar SP (2011) Bacterial Decolorization and degradation of azo dyes: a review. J Taiwan Inst Chem Eng 42:138–157.

  45. Sen Gupta S, Bhattacharyya KG (2011) Kinetics of adsorption of metal ions on inorganic materials: a review. Adv Colloid Interface Sci 162:39–58.

  46. Singh DK, Kumar V, Singh VK, Hasan SH (2016) Modeling of adsorption behavior of the amine-rich GOPEI aerogel for the removal of As (III) and As (V) from aqueous media. RSC Adv 6:56684–56697.

  47. Sun L, Wan S, Luo W (2013) Biochars prepared from anaerobic digestion residue, palm bark, and eucalyptus for adsorption of cationic methylene blue dye: characterization, equilibrium, and kinetic studies. Bioresour Technol 140:406–413.

  48. Tada DB, Vono LLR, Duarte EL et al (2007) Methylene blue-containing silica-coated magnetic particles: a potential magnetic carrier for photodynamic therapy. Langmuir 23:8194–8199.

  49. Tan KB, Vakili M, Horri BA et al (2015) Adsorption of dyes by nanomaterials: recent developments and adsorption mechanisms. Sep Purif Technol 150:229–242.

  50. Teng H, Suuberg EM (1993) Chemisorption of nitric oxide on char. 1. Reversible nitric oxide sorption. J Phys Chem 97:478–483.

  51. Terayama H (1949) On the nature of metachromasy. Jpn Med J (Natl Inst Health Jpn) 2:137–149.

  52. Travlou NA, Kyzas GZ, Lazaridis NK, Deliyanni EA (2013) Graphite oxide/chitosan composite for reactive dye removal. Chem Eng J 217:256–265.

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

  54. Veuthey T (2014) Dyes and stains: from molecular structure to histological application. Front Biosci 19:91–112.

  55. Walczak MM, Leavitt PK, Thiel PA (1987) Oxygenated fluorocarbons adsorbed at metal surfaces: chemisorption bond strengths and decomposition. J Am Chem Soc 109:5621–5627.

  56. Wang QZ, Chen XG, Liu N et al (2006) Protonation constants of chitosan with different molecular weight and degree of deacetylation. Carbohydr Polym 65:194–201.

  57. Wang Y, Zhu M, Li Y et al (2017) Heteroatom-doped porous carbon from methyl orange dye wastewater for oxygen reduction. Green Energy Environ 3:172–178.

  58. Yurekli K, Conley E, Krishnamoorti R (2005) Effect of laponite and a nonionic polymer on the absorption character of cationic dye solutions. Langmuir 21:5825–5830.

  59. Zanjanchi MA, Sohrabnezhad S (2005) Evaluation of methylene blue incorporated in zeolite for construction of an optical humidity sensor. Sens Actuators B Chem 105:502–507.

  60. Zhang L, Zeng Y, Cheng Z (2016) Removal of heavy metal ions using chitosan and modified chitosan: a review. J Mol Liq 214:175–191.

  61. Ziółkowska D, Kaniewska A, Lamkiewicz J, Shyichuk A (2017) Determination of carrageenan by means of photometric titration with methylene blue and toluidine blue dyes. Carbohydr Polym 165:1–6.

Download references


The authors would like to thank Prof. Akiko Fillinger (Ithaca College, Department of Chemistry) for assistance with the scanning electron microscopy images collection and also Ithaca College Office of the Provost and Center of Faculty Excellence for financial support. This work made use of the Cornell Center for Materials Research Facilities for SEM characterization, which is supported by the National Science Foundation under Award Number DMR-1719875.

Author information

Correspondence to Alexandre H. Pinto.

Ethics declarations

Conflict of interest

On behalf of all authors, the corresponding author states that there is no conflict of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 495 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Kellner-Rogers, J.S., Taylor, J.K., Masud, A.M. et al. Kinetic and thermodynamic study of methylene blue adsorption onto chitosan: insights about metachromasy occurrence on wastewater remediation. Energ. Ecol. Environ. 4, 85–102 (2019).

Download citation


  • Methylene blue
  • Chitosan
  • Metachromasy
  • Wastewater remediation
  • Adsorption