Skip to main content

Biochar Modified by Nano-manganese Dioxide as Adsorbent and Oxidant for Oxytetracycline


Biochar has limited capacity to adsorb oxytetracycline (OTC). Here we have used bamboo willow biochar (BC) as a carrier to produce nMnO2-loaded biochars (MBC) by a co-precipitation method. Their chemical compositions, morphological features, specific surface area, and surface functional groups were observed or determined. Batch experiments were conducted to assess the effects of reaction time, initial OTC concentrations, pH, salt concentrations, and natural organic matter (NOM) on OTC removal. Kinetics and isotherms indicated that OTC was mainly adsorbed via chemical interactions, and mono- and multi-layer adsorption occurred on the surface. MBC removed 19–25 times more OTC than BC, and the removal was highest at near-neutral pH, not influenced by NaCl (2, 10 mM), slighted reduced by NOM (0–20 mg L−1), and enhanced by NaHCO3 (2, 10 mM). Besides being an adsorbent, MBC acted as an oxidant and degraded 58.5% of OTC at 24 h.

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4


  1. Aghababaei A, Ncibi MC, Sillanpää M (2017) Optimized removal of oxytetracycline and cadmium from contaminated waters using chemically-activated and pyrolyzed biochars from forest and wood-processing residues. Bioresour Technol 239:28–36

    CAS  Article  Google Scholar 

  2. Chen WR, Huang CH (2011) Transformation kinetics and pathways of tetracycline antibiotics with manganese oxide. Environ Pollut 159(5):1092–1100

    CAS  Article  Google Scholar 

  3. Gao J, Hedman C, Liu C et al (2012) Transformation of sulfamethazine by manganese oxide in aqueous solution. Environ Sci Technol 46:2642–2651

    CAS  Article  Google Scholar 

  4. Gao ML, Zhang Y, Gong XL et al (2018) Removal mechanism of di-n-butyl phthalate and oxytetracycline from aqueous solutions by nano-manganese dioxide modified biochar. Environ Sci Pollut Res 25:7796–7907

    CAS  Article  Google Scholar 

  5. Jang HM, Yoo S, Choi YK et al (2018) Adsorption isotherm, kinetic modeling and mechanism of tetracycline on Pinus taeda-derived activated biochar. Bioresour Technol 259:24–31

    CAS  Article  Google Scholar 

  6. Jeong J, Song WH, Cooper WJ et al (2010) Degradation of tetracycline antibiotics: mechanisms and kinetic studies for advanced oxidation/reduction processes. Chemosphere 78(5):533–540

    CAS  Article  Google Scholar 

  7. Jia MY, Wang F, Jin X et al (2016) Metal ion-oxytetracycline interactions on maize straw biochar pyrolyzed at different temperatures. Chem Eng J 304:934–940

    CAS  Article  Google Scholar 

  8. Jung KW, Lee SY, Lee YJ et al (2019) Ultrasound-assisted heterogeneous Fenton-like process for bisphenol a removal at neutral pH using hierarchically structured manganese dioxide/biochar nanocomposites as catalysts. Ultrason Sonochem 57:22–28

    CAS  Article  Google Scholar 

  9. Liang J, Li XM, Yu ZG et al (2017) Amorphous MnO2 modified biochar derived from aerobically composted swine manure for adsorption of Pb(II) and Cd(II). ACS Sustain Chem Eng 5:5049–5058

    CAS  Article  Google Scholar 

  10. Mahamallik P, Saha S, Pal A (2015) Tetracycline degradation in aquatic environment by highly porous MnO2 nanosheet assembly. Chem Eng J 276:155–165

    CAS  Article  Google Scholar 

  11. Narvaez OMR, Hernandez JMP, Goonetilleke A et al (2019) Biochar-supported nanomaterials for environmental applications. J Ind Eng Chem 78:21–33

    Article  Google Scholar 

  12. Peiris C, Gunatilake SR, Mlsna TE et al (2017) Biochar based removal of antibiotic sulfonamides and tetracyclines in aquatic environments: a critical review. Bioresour Technol 246:150–159

    CAS  Article  Google Scholar 

  13. Rubert KF, Pedersen JA (2006) Kinetics of oxytetracycline reaction with a hydrous manganese oxide. Environ Sci Technol 40:7216–7221

    CAS  Article  Google Scholar 

  14. Song Z, Ma YL, Li CE (2019) The residual tetracycline in pharmaceutical wastewater was effectively removed by using MnO2/graphene nanocomposite. Sci Total Environ 651:580–590

    CAS  Article  Google Scholar 

  15. Wei J, Tu C, Yuan GD et al (2019) Assessing the effect of pyrolysis temperature on the molecular properties and copper sorption capacity of a halophyte biochar. Environ Pollut 251:56–65

    CAS  Article  Google Scholar 

  16. Wu J, Lu J, Zhang C, Zhang ZH et al (2019) Adsorptive removal of tetracyclines and fluoroquinolones using Yak dung biochar. B Environ Contam Tox 102:407–412

    CAS  Article  Google Scholar 

  17. Xiao L, Feng LR, Yuan GD et al (2019) Low-cost field production of biochars and their properties. Environ Geochem Health.

    Article  Google Scholar 

  18. Xie MX, Chen W, Xu ZY et al (2014) Adsorption of sulfonamides to demineralized pine wood biochars prepared under different thermochemical conditions. Environ Pollut 186:187–194

    CAS  Article  Google Scholar 

  19. Yuan L, Yan M, Huang ZZ et al (2019) Influences of pH and metal ions on the interactions of oxytetracycline onto nano-hydroxyapatite and their co-adsorption behavior in aqueous solution. J Colloid Interface Sci 541:101–131

    CAS  Article  Google Scholar 

  20. Zhao YP, Gu XY, Gao SX et al (2012) Adsorption of tetracycline (TC) onto montmorillonite: cations and humic acid effects. Geoderma 183–184:12–18

    Article  Google Scholar 

  21. Zhou YY, Liu XC, Xiang YJ et al (2017) Modification of biochar derived from sawdust and its application in removal of tetracycline and copper from aqueous solution: adsorption mechanism and modelling. Bioresour Technol 245:266–273

    CAS  Article  Google Scholar 

Download references


This research was supported by Chinese National Key Research and Development Program (2016YFD0200303) and National Natural Science Foundation of China (41977139).

Author information



Corresponding author

Correspondence to Guodong Yuan.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher's Note

Publisher's Note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Feng, L., Yuan, G., Xiao, L. et al. Biochar Modified by Nano-manganese Dioxide as Adsorbent and Oxidant for Oxytetracycline. Bull Environ Contam Toxicol 107, 269–275 (2021).

Download citation


  • Biochar
  • Oxytetracycline
  • Nano-manganese dioxide
  • Adsorption
  • Degradation