, Volume 25, Issue 4, pp 2531–2545 | Cite as

Removal of heavy metal and sulfate ions by cellulose derivative-based biosorbents

  • Xin Gao
  • Heng Zhang
  • Keli Chen
  • Jiali Zhou
  • Qixing Liu
Original Paper


A series of environmentally-friendly bagasse pith cellulose-based adsorbents were prepared in an attempt to retain Cu2+ and SO42− from aqueous solutions. The proof of ion adsorption on the biosorbents was identified from Fourier transform infrared spectroscopy and energy-dispersive X-ray spectroscopy-scanning electron microscope. The adsorption capacities were highly dependent on pH and the maximum uptakes of both ions were obtained at pH 5. An increase of solution temperature resulted in decreasing Cu2+ removal but enhancing SO42− adsorption. The kinetic studies showed that the adsorptions of copper and sulfate ions followed the pseudo-second-order kinetics. The analysis of isotherm data indicated that the Langmuir and Freundlich models were in good agreement with the sorptions of Cu2+ and SO42−, respectively. The proportion of carboxylate cellulose and quaternary ammonium-functionalized cellulose in biosorbents influenced on adsorption capacity of the above ions. The adsorption mechanism was mainly governed by ion exchange, complexation and electrostatic association.


Cellulose biosorbents Carboxylate cellulose Quaternary ammonium functionalization Bagasse pith Heavy metal and sulfate ions Adsorption mechanism 



The work was financially supported by National Natural Science Foundations of China (51363013), Science Research Foundation Project of Yunnan Municipal Education Commission (2016zzx045) and KMUST Scientific Research Foundation for the Introduction of Talent (KKSY201605058).

Supplementary material

10570_2018_1690_MOESM1_ESM.docx (980 kb)
Supplementary material 1 (DOCX 980 kb)


  1. Aguayo-Villarreal IA, Bonilla-Petriciolet A, Muñiz-Valencia R (2017) Preparation of activated carbons from pecan nutshell and their application in the antagonistic adsorption of heavy metal ions. J Mol Liq 230:686–695CrossRefGoogle Scholar
  2. Anirudhan TS, Nima J, Divya PL (2013) Adsorption of chromium(VI) from aqueous solutions by glycidylmethacrylate-grafted-densified cellulose with quaternary ammonium groups. Appl Surf Sci 279:441–449CrossRefGoogle Scholar
  3. Bediako JK, Wei W, Kim S et al (2015) Removal of heavy metals from aqueous phases using chemically modified waste Lyocell fiber. J Hazard Mater 299:550–561CrossRefGoogle Scholar
  4. Bozbas S, Boz Y (2016) Low-cost biosorbent: Anadara inaequivalvis shells for removal of Pb(II) and Cu(II) from aqueous solution. Process Saf Environ Prot 103:144–152CrossRefGoogle Scholar
  5. Cai J, Zhang L (2005) Rapid dissolution of cellulose in LiOH/urea and NaOH/urea aqueous solutions. Macromol Biosci 5:539–548CrossRefGoogle Scholar
  6. Chang JJ, Lu YF, Chen JQ et al (2016) Simultaneous removals of nitrate and sulfate and the adverse effects of gravel-based biofilters with flower straws added as exogenous carbon source. Ecol Eng 95:189–197CrossRefGoogle Scholar
  7. Dong CH, Zhang FL, Pang ZQ et al (2016) Efficient and selective adsorption of multi-metal ions using sulfonated cellulose as adsorbent. Carbohydr Polym 151:230–236CrossRefGoogle Scholar
  8. Dou WX, Zhou Z, Jiang LM et al (2017) Sulfate removal from wastewater using ettringite precipitation: magnesium ion inhibition and process optimization. J Environ Manag 196:518–526CrossRefGoogle Scholar
  9. Duodu GO, Goonetilleke A, Ayoko G (2016) Comparison of pollution indices for the assessment of heavy metal in Brisbane River sediment. Environ Pollut 219:1077–1091CrossRefGoogle Scholar
  10. Fawzy M, Nasr M, Adel S et al (2016) Environmental approach and artificial intelligence for Ni(II) and Cd(II) biosorption from aqueous solution using Typha domingensis biomass. Ecol Eng 95:743–752CrossRefGoogle Scholar
  11. Freundlich HMF (1906) Uber die adsorption in losungen. Z Phys Chem Leipz 57:385–470Google Scholar
  12. Gao X, Chen KL, Zhang H et al (2014) Isolation and characterization of cellulose obtained from bagasse pith by oxygen-containing agents. BioResources 9:4094–4107Google Scholar
  13. Gao X, Chen KL, Zhang H et al (2015) Characterization of cationic parenchyma cellulose derivative by rapid preparation of low microwave power. Iran Polym J 24:747–758CrossRefGoogle Scholar
  14. He X, Chen L, Wang YR et al (2014) Aerogels from quaternary ammonium-functionalized cellulose nanofibers for rapid removal of Cr(VI) from water. Carbohydr Polym 111:683–687CrossRefGoogle Scholar
  15. Ho YS, Mckay G (1998) Sorption of dye from aqueous solution by peat. Chem Eng J 70:115–124CrossRefGoogle Scholar
  16. Ho YS, Mckay G (1999) Pseudo-second order model for sorption processes. Process Biochem 34:451–464CrossRefGoogle Scholar
  17. Hokkanen S, Repo E, Westholm LJ et al (2014) Adsorption of Ni2+, Cd2+, PO4 3−, and NO3 from aqueous solutions by nanostructured microfibrillated cellulose modified with carbonated hydroxyapatite. Chem Eng J 252:64–74CrossRefGoogle Scholar
  18. Hokkanen S, Bhatnagar A, Sillanpää M (2016) A review on modification methods to cellulose-based adsorbents to improve adsorption capacity. Water Res 91:156–173CrossRefGoogle Scholar
  19. Hong TT, Okabe H, Hidaka Y et al (2017a) Removal of metal ions from aqueous solutions using carboxymethyl cellulose/sodium styrene sulfonate gels prepared by radiation grafting. Carbohydr Polym 157:335–343CrossRefGoogle Scholar
  20. Hong S, Cannon FS, Hou P et al (2017b) Adsorptive removal of sulfate from acid mine drainage by polypyrrole modified activated carbons: effects of polypyrrole deposition protocols and activated carbon source. Chemosphere 184:429–437CrossRefGoogle Scholar
  21. Hubbe MA, Hasan SH, Ducoste JJ (2011) Cellulosic substrates for removal of pollutants from aqueous systems: a review. 1. Metals. Bioresources 6:2161–2287Google Scholar
  22. Isobe N, Chen XX, Kim UJ et al (2013) TEMPO-oxidized cellulose hydrogel as a high-capacity and reusable heavy metal ion adsorbent. J Hazard Mater 260:195–201CrossRefGoogle Scholar
  23. Jakóbik-Kolon A, Bok-Badura J, Karoń K et al (2017) Hybrid pectin-based biosorbents for zinc ions removal. Carbohydr Polym 169:213–219CrossRefGoogle Scholar
  24. Jin XC, Xiang ZY, Liu QG et al (2017) Polyethyleneimine-bacterial cellulose bioadsorbent for effective removal of copper and lead ions from aqueous solution. Biores Technol 224:844–849CrossRefGoogle Scholar
  25. Kang HL, Liu RG, Huang Y (2015) Graft modification of cellulose: methods, properties and applications. Polymer 70:A1–A16CrossRefGoogle Scholar
  26. Karavan MD, Smirnov IV, Kleshnina SR et al (2017) Micelle mediated extraction of americium and europium by calix[4]arene phosphine oxides from nitric acid media. J Radioanal Nucl Chem 311:599–609CrossRefGoogle Scholar
  27. Ko D, Lee JS, Patel HA et al (2017) Selective removal of heavy metal ions by disulfide linked polymer networks. J Hazard Mater 332:140–148CrossRefGoogle Scholar
  28. Kumar R, Sharma RK, Singh AP (2017) Cellulose based grafted biosorbents—journey from lignocellulose biomass to toxic metal ions sorption application—a review. J Mol Liq 232:62–93CrossRefGoogle Scholar
  29. Langmuir I (1916) The constitution and fundamental properties of solids and liquids. J Am Chem Soc 38:2221–2295CrossRefGoogle Scholar
  30. Liang JZ, Chen XP, Wang LL et al (2017) Subcritical carbon dioxide-water hydrolysis of sugarcane bagasse pith for reducing sugars production. Biores Technol 228:147–155CrossRefGoogle Scholar
  31. Lin S, Xu M, Zhang W et al (2017) Quantitiative effects of amination degree on the magnetic iron oxide nanoparticles (MIONPs) using as adsorbents to remove aqueous heavy metal ions. J Hazard Mater 335:47–55CrossRefGoogle Scholar
  32. Liu C, Jin RN, Ouyang XK et al (2017) Adsorption behavior of carboxylated cellulose nanocrystal-polyethyleneimine composite for removal of Cr(VI) ions. Appl Surf Sci 408:77–87CrossRefGoogle Scholar
  33. Maatar W, Boufi S (2015) Poly(methacrylic acid-co-maleic acid) grafted nanofibrillated cellulose as a reusable novel heavy metal ions adsorbent. Carbohydr Polym 126:199–207CrossRefGoogle Scholar
  34. Madala S, Nadavala SK, Vudagandla S et al (2017) Equilibrium, kinetics and thermodynamics of Cadmium (II) biosorption on to composite chitosan biosorbent. Arab J Chem 10:S1883–S1893CrossRefGoogle Scholar
  35. Madzokere TC, Karthigeyan A (2017) Heavy metal ion effluent discharge containment using magnesium oxide (MgO) Nanoparticles. Mater Today Proc 4:9–18CrossRefGoogle Scholar
  36. Qiu WY, Ren FY, Xu Y et al (2004) Stretched Gaussian asymptotic behavior for fractional Giona–Roman equation on biased heterogeneous fractal structure in external force fields. Nonlinear Dyn 38:285–294CrossRefGoogle Scholar
  37. Runtti H, Tynjälä P, Tuomikoski S et al (2017) Utilisation of barium-modified analcime in sulphate removal: isotherms, kinetics and thermodynamics studies. J Water Process Eng 16:319–328CrossRefGoogle Scholar
  38. Saito T, Isogai A (2004) TEMPO-mediated oxidation of native cellulose. The effect of oxidation conditions on chemical and crystal structures of the water-insoluble fractions. Biomacromolecules 5:1983–1989CrossRefGoogle Scholar
  39. Saravanan R, Ravikumar L (2015) The use of new chemically modified cellulose for heavy metal ion adsorption and antimicrobial activities. J Water Resour Prot 7:530–545CrossRefGoogle Scholar
  40. Tang WW, He D, Zhang CY et al (2017) Optimization of sulfate removal from brachish water by membrane capacitive deionization (MCDI). Water Res 121:302–310CrossRefGoogle Scholar
  41. Taseidifar M, Makavipour F, Pashley RM et al (2017) Removal of heavy metal ions from water using ion flotation. Environ Technol Innov 8:182–190CrossRefGoogle Scholar
  42. Temkin MI, Pyzhev V (1940) Kinetics of ammonia synthesis on promoted iron catalyst. Acta Physochim URSS 12:327–356Google Scholar
  43. Tian Y, Wu M, Liu RG et al (2011) Electrospun membrane of cellulose acetate for heavy metal ion adsorption in water treatment. Carbohydr Polym 83:743–748CrossRefGoogle Scholar
  44. Venäläinen SH, Hartikainen H (2017) Retention of metal and sulphate ions from acidic mining water by anionic nanofibrillated cellulose. Sci Total Environ 599–600:1608–1613CrossRefGoogle Scholar
  45. Vijayalakshmi K, Devi BM, Latha S et al (2017) Batch adsorption and desorption studies on the removal of lead (II) from aqueous solution using nanochitosan/sodium alginate/microcrystalline cellulose beads. Int J Biol Macromol 104(Part B):1483–1494CrossRefGoogle Scholar
  46. Wang FT, Pan YF, Cai PX et al (2017a) Single and binary adsorption of heavy metal ions from aqueous solutions using sugarcane cellulose-based adsorbent. Bioresour Technol 241:482–490CrossRefGoogle Scholar
  47. Wang N, Jin RN, Omer AM et al (2017b) Adsorption of Pb(II) from fish sauce using carboxylated cellulose nanocrystal: isotherm, kinetics, and thermodynamic studies. Int J Biol Macromol 102:232–240CrossRefGoogle Scholar
  48. Wang W, Liang T, Bai H et al (2018) All cellulose composites based on cellulose diacetate and nanofibrillated cellulose prepared by alkali treatment. Carbohydr Polym 179:297–304CrossRefGoogle Scholar
  49. Weber TW, Chakkravorti RK (1974) Pore and solid diffusion models for fixed-bed adsorbers. AIChE J 20:228–238CrossRefGoogle Scholar
  50. Weber WJ, Morris JC (1963) Kinetics of adsorption on carbon from solution. J Sanit Eng Div 89:31–60Google Scholar
  51. Xu F, Zhu TT, Rao QQ et al (2017) Fabrication of mesoporous lignin-based biosorbent from rice straw and its application for heavy-metal-ion removal. J Environ Sci 53:132–140CrossRefGoogle Scholar
  52. Yakout AA, El-Sokkary RH, Shreadah MA et al (2017) Cross-linked graphene oxide sheets via modified extracted cellulose with high metal adsorption. Carbohydr Polym 172:20–27CrossRefGoogle Scholar
  53. Yu H, Liu RG, Shen DW et al (2008) Arrangement of cellulose microfibrils in the wheat straw cell wall. Carbohydr Polym 72:122–127CrossRefGoogle Scholar
  54. Zewail TM, Yousef NS (2015) Kinetic study of heavy metal ions removal by ion exchange in batch conical air spouted bed. Alex Eng J 54:83–90CrossRefGoogle Scholar
  55. Zhang H, Gao X, Chen KK et al (2016) Maximizing the yield of water-soluble cellouronic acid sodium salt with high carboxyl content by 4-acetamide-TEMPO mediated oxidation of parenchyma cellulose from bagasse pith. Iran Polym J 25:465–474CrossRefGoogle Scholar
  56. Zhang YN, Chu CL, Li T et al (2017) A water quality management strategy for regionally protected water through health risk assessment and spatial distribution of heavy metal pollution in 3 marine reserves. Sci Total Environ 599–600:721–731CrossRefGoogle Scholar
  57. Zhou YM, Jin Q, Zhu TW et al (2011) Adsorption of chromium (VI) from aqueous solutions by cellulose modified with β-CD and quaternary ammonium groups. J Hazard Mater 187:303–310CrossRefGoogle Scholar
  58. Zhu Q, Wang Y, Li MF et al (2017) Activable carboxylic acid functionalized crystalline nanocellulose/PVA-co-PE composite nanofibrous membrane with enhanced adsorption for heavy metal ions. Sep Purif Technol 186:70–77CrossRefGoogle Scholar

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© Springer Science+Business Media B.V., part of Springer Nature 2018

Authors and Affiliations

  1. 1.Faculty of Chemical EngineeringKunming University of Science and TechnologyKunmingChina

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