Journal of Soils and Sediments

, Volume 15, Issue 5, pp 1130–1138 | Cite as

Competitive adsorption of cadmium and aluminum onto fresh and oxidized biochars during aging processes

Soils, Sec 3 • Remediation and Management of Contaminated or Degraded Lands • Research Article



Fresh biochar was shown to effectively reduce concentrations of heavy metal in soil, but the influences of the aging processes of biochar and competitions from other elements are warranted to precisely evaluate the long-term effect of biochar. This work investigated the effects of water washing, oxidation, and coexistence of aluminum (Al) on cadmium (Cd) adsorption by biochars and oxidized biochars.

Materials and methods

The Cd adsorption and the competitive adsorption of Cd and Al to rice straw-derived biochars, before and after oxidation by HNO3/H2SO4, were investigated. Meanwhile, the structural characteristics and surface charges of primary and oxidized biochars, with and without Cd loading, were analyzed by scanning electron microscopy, fourier-transform infrared spectroscopy, and zeta potential.

Results and discussion

The adsorption of Cd onto fresh biochars was dominated by surface complexation of oxygen-containing functional groups via esterification reactions, which was regulated by solution pH. Oxidization (aging) introduced carboxylic functional groups to biochar surfaces, which served as additional binding sites for Cd. The Cd binding to biochars was significantly affected by the coexistence of Al via acidification and competition for adsorption sites.


The biochars exhibited high sorption capacities of Cd in soil, but soil acidification led to a counteractive of biochar’s liming effect and a reduction of Cd-binding sites; thus, the long-term effect of biochar for heavy metal immobilization should be paid more attention in acidic soil.


Aging processes Al Cd Competitive adsorption Oxidized biochar 


  1. Ahmad M, Rajapaksha AU, Lim JE, Zhang M, Bolan N, Mohan D, Vithanage M, Lee SS, Ok YS (2014) Biochar as a sorbent for contaminant management in soil and water: a review. Chemosphere 99:19–33CrossRefGoogle Scholar
  2. Angelo LC, Mangrich AS, Mantovani KM, dos Santos SS (2014) Loading of VO2+ and Cu2+ to partially oxidized charcoal fines rejected from brazilian metallurgical industry. J Soils Sediments 14:353–359CrossRefGoogle Scholar
  3. Cao XD, Ma L, Gao B, Harris W (2009a) Dairy-manure derived biochar effectively sorbs lead and atrazine. Environ Sci Technol 43:3285–3291CrossRefGoogle Scholar
  4. Cao YZ, Wang SY, Zhang G, Luo JY, Lu SY (2009b) Chemical characteristics of wet precipitation at an urban site of Guangzhou, South China. Atmos Res 94:462–469CrossRefGoogle Scholar
  5. Chappaz A, Curtis PJ (2013) Integrating empirically dissolved organic matter quality for wham vi using the dom optical properties: a case study of Cu-Al-DOM interactions. Environ Sci Technol 47:2001–2007CrossRefGoogle Scholar
  6. Chen BL, Yuan MX (2011) Enhanced sorption of polycyclic aromatic hydrocarbons by soil amended with biochar. J Soils Sediments 11:62–71CrossRefGoogle Scholar
  7. Chen BL, Zhou DD, Zhu LZ (2008) Transitional adsorption and partition of nonpolar and polar aromatic contaminants by biochars of pine needles with different pyrolytic temperatures. Environ Sci Technol 42:5137–5143CrossRefGoogle Scholar
  8. Chen BL, Yuan MX, Qian LB (2012) Enhanced bioremediation of PAH-contaminated soil by immobilized bacteria with plant residue and biochar as carriers. J Soils Sediments 12:1350–1359CrossRefGoogle Scholar
  9. Chen ZM, Xiao X, Chen BL, Zhu LL (2015) Quantification of chemical states, dissociation constants and contents of oxygen-containing groups on the surface of biochars produced at different temperatures. Environ Sci Technol 49:309–317CrossRefGoogle Scholar
  10. Cheng CH, Lehmann J (2009) Ageing of black carbon along a temperature gradient. Chemosphere 75:1021–1027CrossRefGoogle Scholar
  11. Chingombe P, Saha B, Wakeman RJ (2005) Surface modification and characterisation of a coal-based activated carbon. Carbon 43:3132–3143CrossRefGoogle Scholar
  12. Cho HH, Wepasnick K, Smith BA, Bangash FK, Fairbrother DH, Ball WP (2010) Sorption of aqueous Zn ii and Cd ii by multiwall carbon nanotubes: the relative roles of oxygen-containing functional groups and graphenic carbon. Langmuir 26:967–981CrossRefGoogle Scholar
  13. Cronan CS, Schofield CL (1979) Aluminum leaching response to acid precipitation—effects on high-elevation watersheds in the northeast. Science 204:304–306CrossRefGoogle Scholar
  14. Dong H, Du H, Wickramasinghe SR, Qian X (2009) The effects of chemical substitution and polymerization on the pK(a) values of sulfonic acids. J Phys Chem B 113:14094–14101CrossRefGoogle Scholar
  15. Downie A, Munroe P, Cowie A, Van Zwieten L, Lau DMS (2012) Biochar as a geoengineering climate solution: hazard identification and risk management. Crit Rev Environ Sci Technol 42:225–250CrossRefGoogle Scholar
  16. Ehrlich H, Demadis KD, Pokrovsky OS, Koutsoukos PG (2010) Modern views on desilicification: biosilica and abiotic silica dissolution in natural and artificial environments. Chem Rev 110:4656–4689CrossRefGoogle Scholar
  17. El-Hendawy A-NA (2003) Influence of HNO3 oxidation on the structure and adsorptive properties of corncob-based activated carbon. Carbon 41:713–722CrossRefGoogle Scholar
  18. Evanko CR, Dzombak DA (1998) Influence of structural features on sorption of NOM-analogue organic acids to goethite. Environ Sci Technol 32:2846–2855CrossRefGoogle Scholar
  19. Fang GD, Gao J, Liu C, Dionysiou DD, Wang Y, Zhou DM (2014) Key role of persistent free radicals in hydrogen peroxide activation by biochar: implications to organic contaminant degradation. Environ Sci Technol 48:1902–1910CrossRefGoogle Scholar
  20. Foy CD, Chaney RL, White MC (1978) Physiology of metal toxicity in plants. Annu Rev Plant Physiol 29:511–566CrossRefGoogle Scholar
  21. Guo JH, Liu XJ, Zhang Y, Shen JL, Han WX, Zhang WF, Christie P, Goulding KWT, Vitousek PM, Zhang FS (2010) Significant acidification in major chinese croplands. Science 327:1008–1010CrossRefGoogle Scholar
  22. Hale SE, Hanley K, Lehmann J, Zimmerman AR, Cornelissen G (2011) Effects of chemical, biological, and physical aging as well as soil addition on the sorption of pyrene to activated carbon and biochar. Environ Sci Technol 45:10445–10453CrossRefGoogle Scholar
  23. Houben D, Evrard L, Sonnet P (2013) Mobility, bioavailability and pH-dependent leaching of cadmium, zinc and lead in a contaminated soil amended with biochar. Chemosphere 92:1450–1457CrossRefGoogle Scholar
  24. Jiang J, Xu RK, Jiang TY, Li Z (2012) Immobilization of Cu(ii), Pb(ii) and Cd(ii) by the addition of rice straw derived biochar to a simulated polluted ultisol. J Hazard Mater 229:145–150CrossRefGoogle Scholar
  25. Lehmann J (2007) A handful of carbon. Nature 447:143–144CrossRefGoogle Scholar
  26. Lin Y, Munroe P, Joseph S, Kimber S, Van Zwieten L (2012) Nanoscale organo-mineral reactions of biochars in ferrosol: an investigation using microscopy. Plant Soil 357:369–380CrossRefGoogle Scholar
  27. Lou G, Huang PM (1988) Hydroxy-aluminosilicate interlayers in montmorillonite—implications for acidic environments. Nature 335:625–627CrossRefGoogle Scholar
  28. Lu XQ, Chen ZL, Yang XH (1999) Spectroscopic study of aluminium speciation in removing humic substances by Al coagulation. Water Res 33:3271–3280CrossRefGoogle Scholar
  29. Lu HL, Zhang WH, Yang YX, Huang XF, Wang SZ, Qiu RL (2012) Relative distribution of Pb2+ sorption mechanisms by sludge-derived biochar. Water Res 46:854–862CrossRefGoogle Scholar
  30. Luo F, Song J, Xia WX, Dong MG, Chen MF, Soudek P (2014) Characterization of contaminants and evaluation of the suitability for land application of maize and sludge biochars. Environ Sci Pollut Res 21:8707–8717CrossRefGoogle Scholar
  31. Mimmo T, Marzadori C, Montecchio D, Gessa C (2005) Characterisation of Ca and Al-pectate gels by thermal analysis and FTIR spectroscopy. Carbohydr Res 340:2510–2519CrossRefGoogle Scholar
  32. Mohan D, Pittman CU, Bricka M, Smith F, Yancey B, Mohammad J, Steele PH, Alexandre-Franco MF, Gomez-Serrano V, Gong H (2007) Sorption of arsenic, cadmium, and lead by chars produced from fast pyrolysis of wood and bark during bio-oil production. J Colloid Interface Sci 310:57–73CrossRefGoogle Scholar
  33. Nguyen BT, Lehmann J, Kinyangi J, Smernik R, Riha SJ, Engelhard MH (2008) Long-term black carbon dynamics in cultivated soil. Biogeochemistry 89:295–308CrossRefGoogle Scholar
  34. Pinheiro JP, Mota AM, Benedetti MF (2000) Effect of aluminum competition on lead and cadmium binding to humic acids at variable ionic strength. Environ Sci Technol 34:5137–5143CrossRefGoogle Scholar
  35. Qian LB, Chen BL (2013) Dual role of biochars as adsorbents for aluminum: the effects of oxygen-containing organic components and the scattering of silicate particles. Environ Sci Technol 47:8759–8768Google Scholar
  36. Qian LB, Chen BL (2014) Interactions of aluminum with biochars and oxidized biochars: implications for the biochar aging process. J Agric Food Chem 62:373–380CrossRefGoogle Scholar
  37. Qian LB, Chen BL, Hu D (2013) Effective alleviation of aluminum phytotoxicity by manure-derived biochar. Environ Sci Technol 47:2737–2745CrossRefGoogle Scholar
  38. Saha B, Tai MH, Streat M (2001) Study of activated carbon after oxidation and subsequent treatment characterization. Process Saf Environ 79:211–217CrossRefGoogle Scholar
  39. Seredych M, Hulicova-Jurcakova D, Lu GQ, Bandosz TJ (2008) Surface functional groups of carbons and the effects of their chemical character, density and accessibility to ions on electrochemical performance. Carbon 46:1475–1488CrossRefGoogle Scholar
  40. Sun K, Gao B, Zhang ZY, Zhang GX, Zhao Y, Xing BS (2010) Sorption of atrazine and phenanthrene by organic matter fractions in soil and sediment. Environ Pollut 158:3520–3526CrossRefGoogle Scholar
  41. Uchimiya M, Bannon DI (2013) Solubility of lead and copper in biochar-amended small arms range soils: influence of soil organic carbon and pH. J Agric Food Chem 61:7679–7688CrossRefGoogle Scholar
  42. Uchimiya M, Chang S, Klasson KT (2011) Screening biochars for heavy metal retention in soil: role of oxygen functional groups. J Hazard Mater 190:432–441CrossRefGoogle Scholar
  43. Uchimiya M, Bannon DI, Wartelle LH (2012a) Retention of heavy metals by carboxyl functional groups of biochars in small arms range soil. J Agric Food Chem 60:1798–1809CrossRefGoogle Scholar
  44. Uchimiya M, Bannon DI, Wartelle LH, Lima IM, Klasson KT (2012b) Lead retention by broiler litter biochars in small arms range soil: impact of pyrolysis temperature. J Agric Food Chem 60:5035–5044CrossRefGoogle Scholar
  45. Wehr JB, Blamey FP, Hanna JV, Kopittke PM, Kerven GL, Menzies NW (2010) Hydrolysis and speciation of al bound to pectin and plant cell wall material and its reaction with the dye chrome azurol s. J Agric Food Chem 58:5553–60CrossRefGoogle Scholar
  46. Woolf D, Amonette JE, Street-Perrott FA, Lehmann J, Joseph S (2010) Sustainable biochar to mitigate global climate change. Nat Commun 1:1–9CrossRefGoogle Scholar
  47. Xiao X, Chen BL, Zhu LZ (2014) Transformation, morphology and dissolution of silicon and carbon in rice straw derived biochars under different pyrolytic temperatures. Environ Sci Technol 48:3411–3419CrossRefGoogle Scholar
  48. Xu YL, Chen BL (2015) Organic carbon and inorganic silicon speciation in rice-bran-derived biochars affect its capacity to adsorb cadmium in solution. J Soils Sediments 15:60–70CrossRefGoogle Scholar
  49. Xu RK, Zhao AZ (2013) Effect of biochars on adsorption of Cu(ii), Pb(ii) and Cd(ii) by three variable charge soils from Southern China. Environ Sci Pollut Res 20:8491–8501CrossRefGoogle Scholar
  50. Yao FX, Arbestain MC, Virgel S, Blanco F, Arostegui J, Macia-Agullo JA, Macias F (2010) Simulated geochemical weathering of a mineral ash-rich biochar in a modified soxhlet reactor. Chemosphere 80:724–732CrossRefGoogle Scholar
  51. Zhang XK, Wang HL, He LZ, Lu KP, Sarmah A, Li JW, Bolan NS, Pei JC, Huang HG (2013a) Using biochar for remediation of soils contaminated with heavy metals and organic pollutants. Environ Sci Pollut Res 20:8472–8483CrossRefGoogle Scholar
  52. Zhang Z, Solaiman ZM, Meney K, Murphy DV, Rengel Z (2013b) Biochars immobilize soil cadmium, but do not improve growth of emergent wetland species juncus subsecundus in cadmium-contaminated soil. J Soils Sediments 13:140–151CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  1. 1.Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil ScienceChinese Academy of SciencesNanjingChina
  2. 2.Department of Environmental ScienceZhejiang UniversityHangzhouChina

Personalised recommendations