Topics in Catalysis

, Volume 61, Issue 15–17, pp 1653–1664 | Cite as

Decontamination of 1,2-Dichloroethane DNAPL in Contaminated Groundwater by Polymer-Modified Zero-Valent Iron Nanoparticles

  • Ndumiso Vukile Mdlovu
  • Kuen-Song LinEmail author
  • Sat Septian Dwitya
  • Chung-Yu Chen
  • Chao-Lung Chiang
Original Paper


Remediation of dense non-aqueous phase liquids (DNAPLs) contaminants in groundwater has received considerable attention in the environmental field. Generally, DNAPLs can flow with groundwater and further infiltrate down to deeper aquitard zone that is difficult to be removed by pumping. The DNAPLs may also contaminate the soil and groundwater concurrently in the duration of flowing with groundwater slowly. In this study, remediation of 1,2-dichloroethane (1,2-DCE) in DNAPL contaminated groundwater was studied by a reductive reaction with polyethylenimine (PEI) surface-modified zero-valent iron nanoparticles (PEI-nZVI). The prepared PEI-nZVI was injected into upstream wells and reach the plume of DNAPLs down with the flowing groundwater. Moreover, nZVI was further characterized after field injection and 1-day reaction with the contaminants to assess its effectiveness for the on-site reduction of 1,2-DCE. After direct injection of PEI-nZVI into the contaminated plume, the concentrations of 1,2-DCE was significantly reduced. Moreover, the plume was decontaminated to nontoxic species onto the highly active nZVI. By using resistivity image profiling (RIP), the conductivity data of modified nZVI solution and sampled groundwater were similar. In addition, RIP can reveal complex subsurface DNAPLs structures by dense sampling of resistivity variation at shallow depth. Additionally, X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy studies indicated that after the reductive reaction, nZVI and PEI-nZVI were oxidized to Fe3O4. The interatomic distances for the reacted samples were 1.95 Å and 1.93 Å, respectively. The combined technique of floating surface-modified nZVI and RIP method would be economically and environmentally attractive.

Graphical Abstract


Zero-valent iron nanoparticles Polyethylenimine DNAPLs Chemical reduction Injection method Decontamination Groundwater remediation 



The financial support of Ministry of Science and Technology (MOST), Taiwan (MOST 103-2621-M-155-001) is gratefully acknowledged. We also thank Prof. Y. W. Yang, Dr. J. F. Lee, and Dr. Jeng-Lung Chen from Taiwan National Synchrotron Radiation Research Center (NSRRC) for their help in the XANES/EXAFS experiments or data analyses. We finally thank Prof C.H. Yang from National Central University (NCU) who helped us with the Resistivity Image Profiling (RIP) experiments.


  1. 1.
    Mo L, Ye LS, Wu J, Stahl RG, Grosso NR, Wang JC (2017) Field application at a DNAPL-contaminated site in Nanjing and discussion of a source search algorithm based on stochastic modeling and Kalman filter. Environ Earth Sci 76:92CrossRefGoogle Scholar
  2. 2.
    Hara SO, Krug T, Quinn J, Clausen C, Geiger C (2006) Field and laboratory evaluation of the treatment of DNAPL source zones using emulsified zero-valent iron. Remed J 16:35–56CrossRefGoogle Scholar
  3. 3.
    Fu F, Dionysios 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
  4. 4.
    Lin KS, Mdlovu NV, Chen CY, Chiang CL (2018) Degradation of TCE, PCE, and 1, 2-DCE DNAPLs in contaminated groundwater using polyethylenimine-modified zero-valent iron nanoparticles. J Clean Prod 175:456–466CrossRefGoogle Scholar
  5. 5.
    Lee CC, Doong RA (2014) Enhanced dechlorination of tetrachloroethylene by polyethylene glycol-coated zerovalent silicon in the presence of nickel ions. Appl Catal B 144:182–188CrossRefGoogle Scholar
  6. 6.
    Sheu YT, Lien PJ, Chen KF, Ou JH, Kao CM (2016) Application of NZVI-contained emulsified substrate to bioremediate PCE-contaminated groundwater–a pilot-scale study. Chem Eng J 304:714–727CrossRefGoogle Scholar
  7. 7.
    Olson MR, Sale TC, Shackelford CD, Bozzini C, Skeean J (2012) Chlorinated solvent source-zone remediation via ZVI-clay soil mixing: 1-year results. Ground Water Monit Remediat 32:63–74CrossRefGoogle Scholar
  8. 8.
    Wu M, Cheng Z, Qin G, Lei M, Wu J, Wu J, Hu BX, Lin J (2018) The change of representative elementary volume of DNAPL influenced by surface active agents during long-term remediation period in heterogeneous porous media. Sci Total Environ 625:1175–1190CrossRefGoogle Scholar
  9. 9.
    Ojala S, Pitkäaho S, Laitinen T, Koivikko NN, Brahmi R, Gaálová J, Matejova L, Kucherov A, Päivärinta S, Hirschmann C, Nevanperä TI (2011) Catalysis in VOC abatement. Top Catal 54:1224–1256CrossRefGoogle Scholar
  10. 10.
    Heron G, Bierschenk J, Swift R, Watson R, Kominek M (2016) Thermal DNAPL source zone treatment impact on a CVOC plume. Ground Water Monit Remediat 36:26–37CrossRefGoogle Scholar
  11. 11.
    Anderson MR, Johnson RL, Pankow JF (1992) Dissolution of dense chlorinated solvents into ground water: 1. Dissolution from a well-defined residual source. Groundwater 30:250–256CrossRefGoogle Scholar
  12. 12.
    EPA J (1996) Pump-and-treat ground-water remediation: a guide for decision makers and practitioners. EPA/625/R-95/005. Office of Research and Development, Washington DCGoogle Scholar
  13. 13.
    Baker RS, Nielsen SG, Heron G, Ploug N (2016) How effective is thermal remediation of DNAPL source zones in reducing groundwater concentrations? Ground Water Monit Remediat 36:38–53CrossRefGoogle Scholar
  14. 14.
    Kaifas D, Malleret L, Kumar N, Fétimi W, Bruno MC, Sergent M, Doumenq P (2014) Assessment of potential positive effects of nZVI surface modification and concentration levels on TCE dechlorination in the presence of competing strong oxidants, using an experimental design. Sci Total Environ 481:335–342CrossRefGoogle Scholar
  15. 15.
    Lin CC, Chen SC (2016) Enhanced reactivity of nanoscale zero-valent iron prepared by a rotating packed bed with blade packings. Adv Powder Technol 27(2):(2016) 323–329CrossRefGoogle Scholar
  16. 16.
    Mu Y, Jia F, Ai Z, Zhang L (2017) Iron oxide shell mediated environmental remediation properties of nano zero-valent iron. Environ Sci Nano 1:27–45CrossRefGoogle Scholar
  17. 17.
    Tratnyek PG, Johnson RL (2006) Nanotechnologies for environmental cleanup. Nano Today 1:44–48CrossRefGoogle Scholar
  18. 18.
    Taghavy A, Costanza J, Pennell KD, Abriola LM (2010) Effectiveness of nanoscale zero-valent iron for treatment of a PCE-DNAPL source zone. J Contam Hydrol 118:128–142CrossRefPubMedPubMedCentralGoogle Scholar
  19. 19.
    Zhang WX (2003) Nanoscale iron particles for environmental remediation: an overview. J Nanopart Res 5:323–332CrossRefGoogle Scholar
  20. 20.
    Phenrat T, Saleh N, Sirk K, Kim HJ, Tilton RD, Lowry GV (2008) Stabilization of aqueous nanoscale zerovalent iron dispersions by anionic polyelectrolytes: adsorbed anionic polyelectrolyte layer properties and their effect on aggregation and sedimentation. J Nanopart Res 10:795–814CrossRefGoogle Scholar
  21. 21.
    Goswami L, Kim KH, Deep A, Das P, Bhattacharya SS, Kumar S, Adelodun AA (2017) Engineered nano particles: nature, behavior, and effect on the environment. J Environ Manage 196:297–315CrossRefGoogle Scholar
  22. 22.
    Oprčkal P, Mladenovič A, Vidmar J, Pranjić AM, Milačič R, Ščančar J (2017) Critical evaluation of the use of different nanoscale zero-valent iron particles for the treatment of effluent water from a small biological wastewater treatment plant. Chem Eng J 321:20–30CrossRefGoogle Scholar
  23. 23.
    Jie G, Wang W, Rondinone AJ, He F, Liang L (2015) Critical evaluation of the use of different nanoscale zero-valent iron particles for the treatment of effluent water from a small biological wastewater treatment plant. J Hazard Mater 300:443–450CrossRefGoogle Scholar
  24. 24.
    Chen Y, Pan B, Li H, Zhang W, Lv L, Wu J (2010) Selective removal of Cu(II) ions by using cation-exchange resin-supported polyethyleneimine (PEI) nanoclusters. Environ Sci Technol 44:3508–3513CrossRefGoogle Scholar
  25. 25.
    Hethnawi A, Nassar NN, Gerardo V (2017) Preparation and characterization of polyethylenimine-functionalized pyroxene nanoparticles and its application in wastewater treatment. Colloids Surf A Physicochem Eng Asp 525:20–30CrossRefGoogle Scholar
  26. 26.
    Chowdhury AI, Krol MM, Kocur CM, Boparai HK, Weber KP, Sleep BE, O’Carroll DM (2015) nZVI injection into variably saturated soils: field and modeling study. J Contam Hydrol 183:16–28CrossRefGoogle Scholar
  27. 27.
    Yang CH, Tong LT, Yu CY (2006) Integrating GPR and RIP methods for water surface detection of geological structures. Terr Atmos Ocean Sci 17:391–404CrossRefGoogle Scholar
  28. 28.
    Yang CH, Cheng PH, You JI, Louis L, Tsai L (2002) Significant resistivity changes in the fault zone associated with the 1999 Chi-Chi earthquake, west-central Taiwan. Tectonophysics 350:299–313CrossRefGoogle Scholar
  29. 29.
    Griffiths DH, Barker RD (1993) Two-dimensional resistivity imaging and modelling in areas of complex geology. J Appl Geophy 29:211–226CrossRefGoogle Scholar
  30. 30.
    Chambers JE, Kuras O, Meldrum PI, Ogilvy RD, Hollands J (2006) Electrical resistivity tomography applied to geologic, hydrogeologic, and engineering investigations at a former waste-disposal site. Geophysics 71:B231–B239CrossRefGoogle Scholar
  31. 31.
    Liu HC, Lin CP, Yang CH, Wang TP (2016) Geoelectrical mapping of the soil and groundwater contaminated site: Case study from Taiwan. In: Proceedings of the 7th international conference on environment and engineering geophysics (ICEEG) & summit forum of Chinese academy of engineering on engineering science and technology vol 71, pp 408–411Google Scholar
  32. 32.
    Yang CH, You JI, Tao MC (2002) High resistivities associated with DNAPL plume images by RIP technique. In: 2002 SEG annual meeting. Society of Exploration Geophysicists ID SEG-2002-1587: p 4Google Scholar
  33. 33.
    Lytle FW (1999) The EXAFS family tree: a personal history of the development of extended X-ray absorption fine structure. J Synchrotron Rad 6:123–134CrossRefGoogle Scholar
  34. 34.
    Ravel B, Newville MATHENA (2005) ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J Synchrotron Radiat 12:537–541CrossRefGoogle Scholar
  35. 35.
    Everett DH (1972) Manual of symbols and terminology for physicochemical quantities and units, appendix II: definitions, terminology and symbols in colloid and surface chemistry. Pure Appl Chem 31:577–638CrossRefGoogle Scholar
  36. 36.
    Sun YP, Li XQ, Zhang WX, Wang HP (2007) A method for the preparation of stable dispersion of zero-valent iron nanoparticles. Colloids Surf A Physicochem Eng Asp 308:60–66CrossRefGoogle Scholar
  37. 37.
    Lin KS, Dehvari K, Hsien MJ, Hsu PJ, Kuo H (2013) Degradation of TNT, RDX, and HMX explosive wastewaters using zero-valent iron nanoparticles. Propell Explos Pyrot 38:786–790CrossRefGoogle Scholar
  38. 38.
    Liang Y, Min X, Chai L, Wang M, Liyang W, Pan Q, Okido M (2017) Stabilization of arsenic sludge with mechanochemically modified zero-valent iron. Chemosphere 168:1142–1151CrossRefGoogle Scholar
  39. 39.
    Adhikari AK, Lin KS (2016) Improving CO2 adsorption capacities and CO2/N2 separation efficiencies of MOF-74 (Ni, Co) by doping palladium-containing activated carbon. Chem Eng J 284:1348–1360CrossRefGoogle Scholar
  40. 40.
    Meng Y, Gu D, Zhang F, Shi Y, Cheng L, Feng D, Wu Z, Chen Z, Wan Y, Stein A, Zhao D (2006) A family of highly ordered mesoporous polymer resin and carbon structures from organic–organic self-assembly. Chem Mater 18:4447–4464CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • Ndumiso Vukile Mdlovu
    • 1
  • Kuen-Song Lin
    • 1
    Email author
  • Sat Septian Dwitya
    • 1
  • Chung-Yu Chen
    • 1
  • Chao-Lung Chiang
    • 1
  1. 1.Department of Chemical Engineering and Materials Science/Environmental Technology Research CenterYuan Ze UniversityTaoyuanTaiwan, ROC

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