Utilization of agro-waste for removal of toxic hexavalent chromium: surface interaction and mass transfer studies

  • R. P. Mokkapati
  • V. N. Ratnakaram
  • J. S. Mokkapati
Original Paper


Abundantly available agricultural waste materials (banana bunch, sorghum stem and casuarinas fruit) are processed with negligible cost and are found to be highly suitable as biosorbents for chromium(VI) removal from aqueous environment due to high surface area and functional groups of adsorbents. The equilibrium data have been analyzed for the adsorbate–adsorbate/adsorbent interactions and found to be fitted to the data in the order, Hill–de Boer ≥ Fowler–Guggenheim ≅ Frumkin > Kiselev. To determine the characteristic parameters for process design, mass transfer studies have been carried out using two-parameter isotherm models (Harkins–Jura, Halsey, Smith, El-Awady and Flory–Huggins) and three-parameter isotherm models (Redlich–Peterson and Sips) which are applied to the experimental data. The fitness of the isotherms describes that both mono- and multilayer adsorptions occur in the present studied three biosorbents in preference to the latter. The mechanism of adsorption has been studied using diffusion kinetic models (viz. liquid film diffusion, Dunwald–Wagner intra-particle diffusion model and moving boundary model) and described the possibility of diffusion in the order of banana bunch–stem powder > sorghum stem powder > casuarinas fruit powder in terms of diffusion coefficients. In essence of all the results, the selected adsorbents can be used as a potential adsorbent for the removal of Cr(VI) from aqueous solutions.


Agricultural waste Biosorption Chromium(VI) removal Diffusion Mass transfer Surface interaction 



The authors are highly thankful to Acharya Nagarjuna University, SAIF (IIT-Madras), and Bangalore Institute of Technology for providing the support for conducting the research work and analysis of samples.

Supplementary material

13762_2017_1443_MOESM1_ESM.docx (1.1 mb)
Supplementary material 1 (DOCX 1167 kb)


  1. Abderrahim O, Ferrah N, Didi MA, Villemin D (2011) A new sorbent for europium nitrate extraction: phosphonic acid grafted on polystyrene resin. J Radioanal Nucl Chem 290(2):267–275CrossRefGoogle Scholar
  2. Arabloo M, Ghazanfari MH, Rashtchian D (2015) Spotlight on kinetic and equilibrium adsorption of a new surfactant onto sandstone minerals: a comparative study. J Taiwan Inst Chem E 50:12–23CrossRefGoogle Scholar
  3. ASTM (1972) Annual book of ASTM standards part-23. American society for testing and materials, PhiladelphiaGoogle Scholar
  4. Aytas S, Turkozu DA, Gok C (2011) Biosorption of uranium (VI) by bi-functionalized low cost biocomposite adsorbent. Desalination 280(1):354–362CrossRefGoogle Scholar
  5. Cattani E, Costa MJ, Torricella F, Levizzani V, Silva AM (2006) Influence of aerosol particles from biomass burning on cloud microphysical properties and radioactive forcing. Atmos Res 82(1):310–327CrossRefGoogle Scholar
  6. Cazalbou S, Bertrand G, Drouet C (2015) Tetracycline-loaded biomimetic apatite: an adsorption study. J Phys Chem B 119(7):3014–3024CrossRefGoogle Scholar
  7. Cieślak-Golonka M (1996) Toxic and mutagenic effects of chromium (VI) A review. Polyhedron 15(21):3667–3689CrossRefGoogle Scholar
  8. Davoudinejad M, Ghorbanian SA (2013) Modeling of adsorption isotherm of benzoic compounds onto GAC and introducing three new isotherm models using new concept of Adsorption Effective Surface (AES). Sci Res Essays 8(46):2263–2275Google Scholar
  9. De Boer JH (1953) The dynamical character of adsorption. Oxford University Press, OxfordGoogle Scholar
  10. Deans JR, Dixon BG (1992) Uptake of Pb2+ and Cu2+ by novel biopolymers. Water Res 26(4):469–472CrossRefGoogle Scholar
  11. Flory PJ (1942) Thermodynamics of high polymer solutions. J Chem Phys 10(1):51–61CrossRefGoogle Scholar
  12. Fourest E, Roux JC (1992) Heavy metal biosorption by fungal mycelial by-products: mechanisms and influence of pH. Appl Microbiol Biotechnol 37(3):399–403CrossRefGoogle Scholar
  13. Fowler RH, Guggenheim EA (1949) Statistical thermodynamics. Cambridge University Press, London, pp 431–450Google Scholar
  14. Gautam RK, Mudhoo A, Lofrano G et al (2014) Biomass-derived biosorbents for metal ions sequestration: adsorbent modification and activation methods and adsorbent regeneration. J Environ Chem Eng 2(1):239–259CrossRefGoogle Scholar
  15. Gobara M, Baraka A, Zaghloul B (2015) Green corrosion inhibitor for carbon steel in sulfuric acid medium from “Calotropis Gigantiea” latex. Res Chem Intermed 41(12):9885–9901CrossRefGoogle Scholar
  16. Gustafsson Ö, Kruså M, Zencak Z et al (2009) Brown clouds over South Asia: biomass or fossil fuel combustion? Science 323(5913):495–498CrossRefGoogle Scholar
  17. Guyon P, Frank GP, Welling M et al (2005) Airborne measurements of trace gas and aerosol particle emissions from biomass burning in Amazonia. Atmos Chem Phys 5(11):2989–3002CrossRefGoogle Scholar
  18. Halsey G (1948) Physical adsorption on non-uniform surfaces. J Chem Phys 16(10):931–937CrossRefGoogle Scholar
  19. Hamdaoui O, Naffrechoux E (2007) Modeling of adsorption isotherms of phenol and chlorophenols onto granular activated carbon: Part I. Two-parameter models and equations allowing determination of thermodynamic parameters. J Hazard Mater 147(1):381–394CrossRefGoogle Scholar
  20. Hill TL (1946) Statistical mechanics of multimolecular adsorption II. Localized and mobile adsorption and absorption. J Chem Phys 14(7):441–453CrossRefGoogle Scholar
  21. Huggins ML (1942) Some properties of solutions of long-chain compounds. J Phys Chem 46(1):151–158CrossRefGoogle Scholar
  22. IARI (2012) Crop residues management with conservation agriculture: potential, constraints and policy needs. Indian Agricultural Research Institute, New DelhiGoogle Scholar
  23. Igwe JC, Abia AA (2003) Maize cob and husk as adsorbents for removal of Cd, Pb and Zn ions from wastewater. Phys Sci 2(8):83–94Google Scholar
  24. Imaga C, Abia AA (2015) Kinetics and mechanisms of chromium (VI) ion sorption using carbonized and modified sorghum (Sorghum bicolor) hull of two pore sizes (CMSH 150 µm and 250µm. Int J Chem Process Eng Res 2(4):44–58CrossRefGoogle Scholar
  25. Irwin A (2014) Black carbon: tackling crop-residue burning in South Asia. Glob Change 83:8–11Google Scholar
  26. Ismail Z, Bedderi AM (2009) Potential of water hyacinth as a removal agent for heavy metals from petroleum refinery effluents. Water Air Soil Pollut 199(1–4):57–65CrossRefGoogle Scholar
  27. Ismail Z, Salim K, Othman SZ et al (2013a) Determining and comparing the levels of heavy metal concentrations in two selected urban river water. Measurement 46(10):4135–4144CrossRefGoogle Scholar
  28. Ismail Z, Tai JC, Kong KK et al (2013b) Using data envelopment analysis in comparing the environmental performance and technical efficiency of selected companies in their global petroleum operations. Measurement 46(9):3401–3413CrossRefGoogle Scholar
  29. Jovanović DS (1969) Physical adsorption of gases. I: isotherms for monolayer and multilayer adsorption. Colloid Polym Sci 235:1203–1214Google Scholar
  30. Jura G, Harkins WD (1946) Surfaces of solids. XIV. A unitary thermodynamic theory of the adsorption of vapors on solids and of insoluble films on liquid subphases. J Am Chem Soc 68(10):1941–1952CrossRefGoogle Scholar
  31. Karaca S, Gürses A, Ejder M, Açıkyıldız M (2006) Adsorptive removal of phosphate from aqueous solutions using raw and calcinated dolomite. J Hazard Mater 128(2):273–279CrossRefGoogle Scholar
  32. Karthikaiselvi R, Subhashini S (2014) Study of adsorption properties and inhibition of mild steel corrosion in hydrochloric acid media by water soluble composite poly (vinyl alcohol-o-methoxy aniline). J Assoc Arab Univ Basic Appl Sci 16:74–82Google Scholar
  33. Kiselev AV (1958) Vapor adsorption in the formation of adsorbate molecule complexes on the surface. Kolloid Zhur 20:338–348Google Scholar
  34. Koubaissy B, Toufaily J, El-Murr M et al (2012) Adsorption kinetics and equilibrium of phenol drifts on three zeolites. Cent Eur J Eng 2(3):435–444Google Scholar
  35. Kumar PA, Ray M, Chakraborty S (2007) Hexavalent chromium removal from wastewater using aniline formaldehyde condensate coated silica gel. J Hazard Mater 143(1):24–32CrossRefGoogle Scholar
  36. Kumar KY, Muralidhara HB, Arthoba NY, Balasubramanyam J et al (2013) Low-cost synthesis of metal oxide nanoparticles and their application in adsorption of commercial dye and heavy metal ion in aqueous solution. Powder Technol 246:125–136CrossRefGoogle Scholar
  37. Kumara NT, Hamdan N, Petra MI, Tennakoon KU, Ekanayake P (2014) Equilibrium isotherm studies of adsorption of pigments extracted from kuduk-kuduk (Melastoma Malabathricum L.) pulp onto TIO2 nanoparticles. J Chem. doi: 10.1155/2014/468975 Google Scholar
  38. Lata S, Singh PK, Samadder SR (2015) Regeneration of adsorbents and recovery of heavy metals: a review. Int J Environ Sci Technol 12(4):1461–1478CrossRefGoogle Scholar
  39. Li X, Li A, Long M, Tian X (2015) Equilibrium and kinetic studies of copper biosorption by dead Ceriporia lacerata biomass isolated from the litter of an invasive plant in China. J Environ Health Sci Eng 13(1):13–21CrossRefGoogle Scholar
  40. Mishra SP (2014) Adsorption–desorption of heavy metal ions. Curr Sci 107(4):601–612Google Scholar
  41. Nwabanne JT, Okafor VN (2012) Adsorption and thermodynamics study of the inhibition of corrosion of mild steel in H2SO4 medium using Vernonia amygdalina. JMMCE 11(9):885CrossRefGoogle Scholar
  42. Obot IB, Obi-Egbedi N, Umoren SA (2009) Adsorption characteristics and corrosion inhibitive properties of clotrimazole for aluminium corrosion in hydrochloric acid. Int J Electrochem Sci 4(6):863–877Google Scholar
  43. Orr PT, Jones GJ, Hamilton GR (2004) Removal of saxitoxins from drinking water by granular activated carbon, ozone and hydrogen peroxide: implications for compliance with the Australian drinking water guidelines. Water Res 38(20):4455–4461CrossRefGoogle Scholar
  44. Prapagdee S, Piyatiratitivorakul S, Petsom A (2014) Activation of cassava stem biochar by physico-chemical method for stimulating chromium removal efficiency from aqueous solution. Environ Asia 7(2):60–69Google Scholar
  45. Prasad RK, Srivastava SN (2009) Sorption of distillery spent wash onto fly ash: kinetics and mass transfer studies. Chem Eng J 146(1):90–97CrossRefGoogle Scholar
  46. Raji F, Pakizeh M (2014) Kinetic and thermodynamic studies of Hg(VI) adsorption onto MCM-41 modified by ZnCl2. Appl Surf Sci 301:568–575CrossRefGoogle Scholar
  47. Ramya PM, Jayasravanthi M, Venkata NR, Dulla BJ (2015a) Chemical oxygen demand reduction from coffee processing waste water: a comparative study on usage of biosorbents prepared from agricultural wastes. GNEST J 17(172):291–300Google Scholar
  48. Ramya PM, Jayasravanthi M, Venkata NR (2015b) Kinetic, thermodynamic and equilibrium studies on removal of hexavalent chromium from aqueous solutions using agro-waste biomaterials, Casuarina equisetifolia L. and Sorghum bicolor. Korean J Chem Eng 33(8):2374–2383. doi: 10.1007/s11814-016-0078-6 Google Scholar
  49. Ramya PM, Jayasravanthi M, Venkata NR (2016) Kinetic, isotherm and thermodynamics investigation on adsorption of divalent copper using agro-waste biomaterials, Musa acuminata, Casuarina equisetifolia L. and Sorghum bicolor. Pol J Chem Technol 18(2):1–10. doi: 10.1515/pjct-2016-0031 CrossRefGoogle Scholar
  50. Rana P, Mohan N, Rajagopal C (2004) Electrochemical removal of chromium from wastewater by using carbon aerogel electrodes. Water Res 38(12):2811–2820CrossRefGoogle Scholar
  51. Rathnakumar S, Sheeja RY, Murugesan T (2009) Removal of copper (VI) from aqueous solutions using teak (Tectona grandis Lf) leaves. Int J Chem Mol Nucl Mater Metall Eng 3(8):433–437Google Scholar
  52. Sabirneeza AA, Subhashini S (2014) Poly (vinyl alcohol–proline) as corrosion inhibitor for mild steel in 1 M hydrochloric acid. Int J Ind Chem 5(3–4):111–120CrossRefGoogle Scholar
  53. Sharma AR, Kharol SK, Badarinath KV, Singh D (2010) Impact of agriculture crop residue burning on atmospheric aerosol loading: a study over Punjab State, India. Ann Geophys Atmos Hydrosp 28(2):367–379CrossRefGoogle Scholar
  54. Sips R (1948) On the structure of a catalyst surface. J Chem Phys 16(5):490–495CrossRefGoogle Scholar
  55. USDHHS, US Department of Health and Human Services (1991) Toxicological Profile for Chromium. Public Health Service Agency for Toxic substances and Diseases Registry, Washington, DCGoogle Scholar
  56. van der Werf GR, Randerson JT, Giglio L, Collatz GJ, Kasibhatla PS, Arellano AF Jr (2006) Inter-annual variability in global biomass burning emissions from 1997 to 2004. Atmos Chem Phys 6(11):3423–3441CrossRefGoogle Scholar
  57. Vasudevan S, Lakshmi J, Sozhan G (2010) Studies relating to removal of arsenate by electrochemical coagulation: optimization, kinetics, coagulant characterization. Sep Sci Technol 45(9):1313–1325CrossRefGoogle Scholar
  58. WHO, World Health Organization (2004) Guidelines for drinking-water quality, 3rd edn. Recommendations, GenevaGoogle Scholar
  59. Yonli AH, Khalid M, Batonneau-Gener I et al (2011) Removal of phenolic pollutants from water over BEA and HY zeolites in batch conditions. J Chem Chem Eng 5(5):429–434Google Scholar

Copyright information

© Islamic Azad University (IAU) 2017

Authors and Affiliations

  • R. P. Mokkapati
    • 1
  • V. N. Ratnakaram
    • 2
  • J. S. Mokkapati
    • 3
  1. 1.Department of ChemistryANUCET, Acharya Nagarjuna UniversityGunturIndia
  2. 2.GITAM UniversityBengaluruIndia
  3. 3.Institute of Environmental SciencesJagiellonian UniversityKrakówPoland

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