Environmental Science and Pollution Research

, Volume 26, Issue 5, pp 5176–5188 | Cite as

Magnetic Fe3O4 assembled on nZVI supported on activated carbon fiber for Cr(VI) and Cu(II) removal from aqueous solution through a permeable reactive column

  • Guangzhou QuEmail author
  • Danyang Zeng
  • Rongjie Chu
  • Tiecheng Wang
  • Dongli Liang
  • Hong Qiang
Research Article


Magnetic Fe3O4 assembled on nanoscale zero-valent iron (nZVI) supported on an activated carbon fiber (ACF) to form nanoscale magnetic composites (nZVI-Fe3O4/ACF) for removing Cr(VI) and Cu(II) from aqueous solution through a permeable reactive column was synthesized via an in situ reduction method. The nZVI-Fe3O4/ACF composites and the interaction between nZVI-Fe3O4/ACF and both Cr and Cu ions were characterized by field emission scanning electron microscopy (FESEM) with EDX, TEM, XRD, and XPS. Batch experiments were used to analyze the effects of main factors on Cr(VI) removal and investigate the simultaneous removal of Cr(VI) and Cu(II) through a permeable reactive column. The results indicated that the ACF and Fe3O4 can inhibit the agglomeration and enhance the dispersibility of nZVI, and Fe3O4 and nZVI displayed good synergetic effects. The removal efficiency of Cr(VI) improved with the increase amount of Fe3O4 in the nZVI-Fe3O4/ACF composites. With low initial concentration of Cr(VI) and acidic conditions, ~ 90% of 20.0 mg·L−1 Cr(VI) in the solution was removed after 60 min. The removal of Cr(VI) was also affected by coexisting ions. The removal efficiency of 10.0 mg·L−1 Cu(II) was ~ 100% after 45 min of reaction, and the presence of Cu(II) can accelerate the reduction of Cr(VI). The simultaneous removal mechanisms of Cr(VI) and Cu(II) by the nZVI-Fe3O4/ACF composites also were proposed.


Activated carbon fiber Heavy metal Magnetic Fe3O4 Nanoscale zero-valent iron Removal mechanisms 



The authors would also like to thank Prof. Dionysios D. Dionysiou from University of Cincinnati for the valuable suggestions to this paper.

Funding information

The authors gratefully acknowledge the financial support provided by the Overseas Student’s Science and Technology Activities Project Merit Funding of Shanxi Province (grant No. A279021705), the Key Laboratory of Jiangxi Province for Persistent Control and Resources Recycle (Nanchang Hangkong University, grant No. ES201780295), and the Fundamental Research Funds for the Central Universities (grant No. 2452017106).


  1. Calderon B, Fullana A (2015) Heavy metal release due to aging effect during zero valent iron nanoparticles remediation. Water Res 83:1–9CrossRefGoogle Scholar
  2. Carroll DO, Sleep B, Krol M, Boparai H, Kocur C (2013) Nanoscale zero valent iron and bimetallic particles for contaminated site remediation. Adv Water Resour 51:104–122CrossRefGoogle Scholar
  3. Coelho FS, Ardisson JD, Moura FCC, Lago RM, Murad E, Fabris JD (2008) Potential application of highly reactive Fe(0)/Fe3O4 composites for the reduction of Cr(VI) environmental contaminants. Chemosphere 71:90–96CrossRefGoogle Scholar
  4. Crane RA, Scott TB (2012) Nanoscale zero-valent iron: future prospects for an emerging water treatment technology. J Hazard Mater 211:112–125CrossRefGoogle Scholar
  5. Diao ZH, Xu XR, Jiang D, Kong LJ, Sun YX, Hu YX, Hao QW, Chen H (2016) Bentonite-supported nanoscale zero-valent iron/persulfate system for the simultaneous removal of Cr(VI) and phenol from aqueous solutions. Chem Eng J 302:213–222CrossRefGoogle Scholar
  6. Dong HR, Deng JM, Xie YK, Zhang C, Jiang Z, Cheng YJ, Hou KJ, Zeng GM (2017) Stabilization of nanoscale zero-valent iron (nZVI) with modified biochar for Cr(VI) removal from aqueous solution. J Hazard Mater 332:79–86CrossRefGoogle Scholar
  7. Dries J, Bastiaens L, Springael D, Agathos SN, Diels L (2004) Competition for sorption and degradation of chlorinated ethenes in batch zero-valent iron systems. Environ Sci Technol 38:2879–2884CrossRefGoogle Scholar
  8. Ezzatahmadi N, Ayoko GA, Millar GJ, Speight R, Yan C, Li JH, Li SZ, Zhu JX, Xi YF (2017) Clay-supported nanoscale zero-valent iron composite materials for the remediation of contaminated aqueous solutions: a review. Chem Eng J 312:336–350CrossRefGoogle Scholar
  9. Fu FL, Dionysiou DD, Liu H (2014) The use of zero-valent iron for groundwater remediation and wastewater treatment: a review. J Hazard Mater 267:194–205CrossRefGoogle Scholar
  10. Fu RB, Yang YP, Xu Z, Zhang X, Guo XP, Bi DS (2015) The removal of chromium(VI) and lead(II) from groundwater using sepiolite-supported nanoscale zero-valent iron (S-NZVI). Chemosphere 138:726–734CrossRefGoogle Scholar
  11. Gillham RW, O’Hannesin SF (1994) Enhanced degradation of halogenated aliphatics by zero-valent iron. Ground Water 32:958–967CrossRefGoogle Scholar
  12. Hu CY, Lo SL, Liou YH, Hsu YW, Shih K, Lin CJ (2010) Hexavalent chromium removal from near natural water by copper-iron bimetallic particles. Water Res 44:3101–3108CrossRefGoogle Scholar
  13. Hu XB, Liu BZ, Deng YH, Chen HZ, Luo S, Sun C, Yang P, Yang SG (2011) Adsorption and heterogeneous Fenton degradation of 17α-methyltestosterone on nano Fe3O4/MWCNTs in aqueous solution. Appl Catal B Environ 107:274–283CrossRefGoogle Scholar
  14. Huang CP, Wang HW, Chiu PC (1998) Nitrate reduction by metallic iron. Water Res 32:2257–2264CrossRefGoogle Scholar
  15. Huang PP, Ye ZF, Xie WM, Chen Q, Li J, Xu ZC, Yao MS (2013) Rapid magnetic removal of aqueous heavy metals and their relevant mechanisms using nanoscale zero valent iron (nZVI) particles. Water Res 47:4050–4058CrossRefGoogle Scholar
  16. Johnson TL, Scherer MM, Tratnyek PG (1996) Kinetics of halogenated organic compound degradation by iron metal. Environ Sci Technol 30:2634–2640CrossRefGoogle Scholar
  17. Kang YS, Risbud S, Rabolt JF, Pieter S (1996) Synthesis and characterization of nanometer-size Fe3O4 and γ-Fe2O3 particles. Chem Mater 8:2209–2211CrossRefGoogle Scholar
  18. Kochany EL, Harms S, Milburn R, Sprah G, Nadarajah N (1994) Degradation of carbon tetrachloride in the presence of iron and sulphur containing compounds. Chemosphere 29:1477–1489CrossRefGoogle Scholar
  19. Kong XK, Han ZT, Zhang W, Song L, Li H (2016) Synthesis of zeolite-supported microscale zero-valent iron for the removal of Cr6+ and Cd2+ from aqueous solution. J Environ Manag 169:84–90CrossRefGoogle Scholar
  20. Legrand L, Figuigui AE, Mercier F, Chausse A (2004) Reduction of aqueous chromate by Fe(II)/Fe(III) carbonate green rust: kinetic and mechanistic studies. Environ Sci Technol 38:4587–4595CrossRefGoogle Scholar
  21. Li SL, Wang W, Liang FP, Zhang WX (2017) Heavy metal removal using nanoscale zero-valent iron (nZVI): theory and application. J Hazard Mater 322:163–171CrossRefGoogle Scholar
  22. Ling L, Pan BC, Zhang WX (2015) Removal of selenium from water with nanoscale zero-valent iron: mechanisms of intraparticle reduction of Se(IV). Water Res 71:274–281CrossRefGoogle Scholar
  23. Liu TZ, Rao P, Mak MS, Wang P, Lo IM (2009) Removal of co-present chromate and arsenate by zero-valent iron in groundwater with humic acid and bicarbonate. Water Res 43:2540–2548CrossRefGoogle Scholar
  24. Liu TY, Yang X, Wang ZL, Yan XX (2013) Enhanced chitosan beads-supported Fe(0)-nanoparticles for removal of heavy metals from electroplating wastewater in permeable reactive barriers. Water Res 47:6691–6700CrossRefGoogle Scholar
  25. Liu Q, Xu MJ, Li F, Wu T, Li YJ (2016) Rapid and effective removal of Cr(VI) from aqueous solutions using the FeCl3/NaBH4 system. Chem Eng J 296:340–348CrossRefGoogle Scholar
  26. Lv XS, Xu J, Jiang GM, Xu XH (2011) Removal of chromium(VI) from wastewater by nanoscale zero-valent iron particles supported on multiwalled carbon nanotubes. Chemosphere 85:1204–1209CrossRefGoogle Scholar
  27. Lv AH, Hu C, Nie YL, Qu JH (2012a) Catalytic ozonation of toxic pollutants over magnetic cobalt-doped Fe3O4 suspensions. Appl Catal B Environ 117:246–252CrossRefGoogle Scholar
  28. Lv XS, Xu J, Jiang GM, Tang J, Xu XH (2012b) Highly active nanoscale zero-valent iron (nZVI)-Fe3O4 nanocomposites for the removal of chromium(VI) from aqueous solutions. J Colloid Interface Sci 369:460–469CrossRefGoogle Scholar
  29. Lv XS, Hu YJ, Tang J, Sheng TT, Jiang GM, Xu XH (2013) Effects of co-existing ions and natural organic matter on removal of chromium(VI) from aqueous solution by nanoscale zero valent iron (nZVI)-Fe3O4 nanocomposites. Chem Eng J 218:55–64CrossRefGoogle Scholar
  30. Lv XS, Xue XQ, Jiang GM, Wu DL, Sheng TT, Zhou HY, Xu XH (2014) Nanoscale zero-valent iron (nZVI) assembled on magnetic Fe3O4/graphene for chromium(VI) removal from aqueous solution. J Colloid Interface Sci 417:51–59CrossRefGoogle Scholar
  31. Paparazzo E (1987) XPS and auger spectroscopy studies on mixtures of the oxides SiO2, Al2O3, Fe2O3, and Cr2O3. J Electron Spectrosc Relat Phenom 43:97–112CrossRefGoogle Scholar
  32. Parks JL, Novak J, Macphee M, Itle C, Edwards M (2003) Effect of Ca on As release from ferric and alum residuals. J Am Water Works Assoc 95:108–118CrossRefGoogle Scholar
  33. Petala E, Dimos K, Douvalis A, Bakas T, Tucek J, Zboril R, Karakassides MA (2013) Nanoscale zero-valent iron supported on mesoporous silica: characterization and reactivity for Cr(VI) removal from aqueous solution. J Hazard Mater 261:295–306CrossRefGoogle Scholar
  34. Pullin H, Crane RA, Morgan DJ, Scott TB (2017) The effect of common groundwater anions on the aqueous corrosion of zero-valent iron nanoparticles and associated removal of aqueous copper and zinc. J Environ Chem Eng 5:1166–1173CrossRefGoogle Scholar
  35. Qu GZ, Kou LQ, Wang TC, Liang DL, Hu SB (2017) Evaluation of activated carbon fiber supported nanoscale zero-valent iron for chromium(VI) removal from groundwater in a permeable reactive column. J Environ Manag 201:378–387CrossRefGoogle Scholar
  36. Shi LN, Lin YM, Zhang X, Chen ZL (2011) Synthesis, characterization and kinetics of bentonite supported nZVI for the removal of Cr(VI) from aqueous solution. Chem Eng J 171:612–617CrossRefGoogle Scholar
  37. Tan L, Lu SY, Fang ZQ, Cheng W, Tsang EP (2017) Enhanced reductive debromination and subsequent oxidative ring-opening of decabromodiphenyl ether by integrated catalyst of nZVI supported on magnetic Fe3O4 nanoparticles. Appl Catal B Environ 200:200–210CrossRefGoogle Scholar
  38. Tanboonchuy V, Grisdanurak N, Liao CH (2012) Background species effect on aqueous arsenic removal by nano zero-valent iron using fractional factorial design. J Hazard Mater 205:40–46CrossRefGoogle Scholar
  39. Toli A, Chalastara K, Mystrioti C, Xenidis A, Papassiopi N (2016) Incorporation of zero valent iron nanoparticles in the matrix of cationic resin beads for the remediation of Cr(VI) contaminated waters. Environ Pollut 214:419–429CrossRefGoogle Scholar
  40. Üzüm Ç, Shahwan T, Eroğlu AE, Hallam KR, Scott TB, Lieberwirth I (2009) Synthesis and characterization of kaolinite-supported zero-valent iron nanoparticles and their application for the removal of aqueous Cu2+ and Co2+ ions. Appl Clay Sci 43:172–181CrossRefGoogle Scholar
  41. Xing ST, Zhou ZC, Ma ZC, Wu YS (2011) Characterization and reactivity of Fe3O4/FeMnOx core/shell nanoparticles for methylene blue discoloration with H2O2. Appl Catal B Environ 107:386–392CrossRefGoogle Scholar
  42. Xu FY, Deng SB, Xu J, Zhang W, Wu M, Wang B, Huang J, Yu G (2012) Highly active and stable Ni-Fe bimetal prepared by ball milling for catalytic hydrodechlorination of 4-chlorophenol. Environ Sci Technol 46:4576–4582CrossRefGoogle Scholar
  43. Zhang X, Lin S, Chen ZL, Megharaj M, Naidu R (2011) Kaolinite-supported nanoscale zero-valent iron for removal of Pb2+ from aqueous solution: reactivity, characterization and mechanism. Water Res 45:3481–3488CrossRefGoogle Scholar
  44. Zhu HJ, Jia YF, Wu X, Wang H (2009) Removal of arsenic from water by supported nano zero-valent iron on activated carbon. J Hazard Mater 172:1591–1596CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Guangzhou Qu
    • 1
    • 2
    Email author
  • Danyang Zeng
    • 1
  • Rongjie Chu
    • 1
  • Tiecheng Wang
    • 1
    • 2
  • Dongli Liang
    • 1
    • 2
  • Hong Qiang
    • 1
    • 2
  1. 1.College of Natural Resources and EnvironmentNorthwest A&F UniversityYanglingPeople’s Republic of China
  2. 2.Key Laboratory of Plant Nutrition and the Agri-environment in Northwest ChinaMinistry of AgricultureYanglingPeople’s Republic of China

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