Issue
Korean Journal of Chemical Engineering,
Vol.21, No.3, 621-628, 2004
Design Considerations for Groundwater Remediation using Reduced Metals
Use of reduced metals has attracted much attention since it possesses a great potential for eliminating reducible contaminants in groundwater such as heavy metals and chlorinated compounds. However, products of metalmediated reactions for many chlorinated hydrocarbons have not clearly been identified. In addition, consumption of the metals, generation and release of metal ions, formation of insoluble metal oxides and hydroxides on the clean metal surface, and rise of pH inevitably accompany the reactions. Due to these properties of metal-mediated reactions, the reaction rate could decrease as the reaction proceeds, and effluent quality could decay. It was shown in this study using chlorine mass balance and GC analysis that chloroform is formed from carbon tetrachloride by reduced iron. It is also well-known that nitrate is reduced mostly to ammonia by metals, which indicates that the metal process is inappropriate for denitrification of nitrate-contaminated aquifers. These results indicate that groundwater remediation using metal process requires careful consideration for the safety of reaction products. It was also shown that mixing rate strongly affects reaction rate since metal-mediated reaction occurs on the surface of metals. In addition, reaction rate was decreased due to metal hydroxide deposition on the surface of metal granules that was seen by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis. Generation of iron ions (consumption of reduced iron) released from reduction of zero-valent iron was also shown by using an ion chromatograph (IC). In this study, some methods were suggested to solve the above-mentioned problems. Acid washing appeared effective for removing corrosion products on the surface of metal granules, by which a reduction rate could be maintained high for an extended time of reaction. Use of iron sulfide decreased an extent of pH rise during metal-mediated reaction; thereby precipitation of insoluble metal (hydr)oxides is expectedly decreased. It was also shown that inexpensive iron scrap instead of fine metal powders can be used for metal processes.
[References]
  1. Agrawal A, Tratnyek PG, Environ. Sci. Technol., 30, 153, 1996
  2. Benner SG, Blowes DW, Gould WD, Herbert RB, Ptacek CJ, Environ. Sci. Technol., 33, 2783, 1999
  3. Blowes DW, Ptacek CJ, Jambor JL, Environ. Sci. Technol., 31, 3348, 1997
  4. Blowes DW, Ptacek CJ, Benner SG, McRae CT, Bennett TA, Puls RW, J. Contaminant Hydrol., 45, 123, 2000
  5. Burris DR, Campbell TI, Manoranjan VS, Environ. Sci. Technol., 29, 2850, 1995
  6. Butler EC, Hayes KF, Environ. Sci. Technol., 32, 1276, 1998
  7. Chang WD, Karra SB, Senkan SM, Environ. Sci. Technol., 20, 1243, 1986
  8. Chen JL, Al-Abed SR, Ryan JA, Li Z, J. Hazard. Mater., B83, 243, 2001
  9. Choe S, Chang YY, Hwang KY, Khim J, Chemosphere, 41, 1307, 2000
  10. Deng B, Burris DR, Campbell TJ, Environ. Sci. Technol., 33, 2651, 1999
  11. Dolan ME, McCarty PL, Environ. Sci. Technol., 29, 1892, 1995
  12. Fogler S, "Element of Chemical Reaction Engineering," 2nd ed., Prentice Hall, Englewood Cliffs, 1992
  13. Fox BG, Froland WA, Jollie DR, Lipscomb JD, Biochemistry, 29, 6419, 1990
  14. Gillham RW, O'Hannesin ST, Groundwater, 32, 958, 1994
  15. Gillham RW, O'Hannesin ST, "Field Applications of Metal Enhanced Dehalogenation of Chlorinated Organic Contaminants," Proceedings of WEFTEC 95, 68th Annual Conference and Exposition, 2, 507, 1995
  16. Glod G, Angst W, Holliger C, Schwarzenbach RP, Environ. Sci. Technol., 31, 253, 1997
  17. Gotpagar J, Lyuksyutov S, Cohn R, Grulke E, Bhattacharyya D, Langmuir, 15(24), 8412, 1999
  18. Gu B, Phelps TJ, Liang L, Dickey MJ, Yin X, Dai S, Environ. Sci. Technol., 32, 3366, 1998
  19. Gu B, Phelps TJ, Liang L, Dickey MJ, Roh Y, Kinsall B, Palumbo AV, Jacobs GK, Environ. Sci. Technol., 33, 2170, 1999
  20. Haarstrick A, Kut OM, Heinzle E, Environ. Sci. Technol., 30, 817, 1996
  21. Hua I, Hoffmann MR, Environ. Sci. Technol., 30, 864, 1996
  22. Hung HM, Hoffmann MR, Environ. Sci. Technol., 32, 3011, 1998
  23. Kielemoes J, Boever PD, Verstraete W, Environ. Sci. Technol., 34, 663, 2000
  24. Kong SH, Kwon CI, Kim MH, Korean J. Chem. Eng., 20(2), 293, 2003
  25. Mackay DM, Cherry JA, Environ. Sci. Technol., 23, 630, 1989
  26. Shiu WY, Mackay D, J. Chem. Eng. Data, 42(1), 27, 1997
  27. Matheson LJ, Tratnyek PG, "Reduction of Nitrate and Nitrite by Iron Metal: Implications for Groundwater Remediation," Extended Abstract, American Chemical Society, San Francisco, CA, 13-17, April, 1994
  28. Mok YS, Kang HC, Cho MH, Nam IS, Korean J. Chem. Eng., 20(2), 239, 2003
  29. MSE Technology Applications, "Subsurface Barriers Monitoring and Varification Technologies," REport for U.S. Department of Energy (TTP #PE1-5-10-06), 1995
  30. NAS, "Alternatives for Ground Water Cleanup. Report of the National Academy of Science Committee on Ground Water Cleanup Alternatives," National Academy Press, Washington, DC, 1994
  31. Palmer PL, "Reactive Wall," In Situ Treatment Technology, Nyer, E.K., Fam, S., Kidd, D.F., Johns, F.J., Palmer, P.L., Boettcher, G., Crossman, T.L. and Suthersan, S.S., Eds., Lewis Publishers, Boca Raton, 1996
  32. Powell RM, Puls RW, Hightower SK, Sabatini DA, Environ. Sci. Technol., 29, 1913, 1995
  33. Puls RW, Blowes DW, Gillham RW, J. Hazard. Mater., 68, 109, 1999
  34. Puls RW, Paul CJ, Powell RM, Appl. Giochem., 14, 989, 1999
  35. Scherer MM, Balko BA, Tratnyek PG, "The Role of Oxides in Reduction Reactions at the Metal-Water Interface. In Kinetics and Mechanism of Reactions at the Mineral/Water Interface," ACS Symposium Series, Washington DC, 1998
  36. Shrimali M, Singh KP, Environ. Pollution, 112, 351, 2001
  37. Siantar DP, Schreier CG, Chou CS, Reinhard M, Water Res., 30, 2315, 1996
  38. Singer PC, Stum W, Science, 167, 1121, 1970
  39. Su C, Puls RW, Environ. Sci. Technol., 33, 163, 1999
  40. U.S. EPA, "Metal-Enhanced Dechlorination of Volatile Organic Compounds Using an Above-Ground Reactor," EPA/540/R-96-503, 1997
  41. U.S. EPA, "Metal-Enhanced Dechlorination of Volatile Organic Compounds Using an In-Situ Reactive Iron Wall," EPA/540/R-98/501, 1998
  42. Vogan JL, Focht RM, Clark DK, Graham SL, J. Hazard. Mater., 68, 97, 1999
  43. Weber EJ, Environ. Sci. Technol., 30, 716, 1996
  44. Wilson EK, Chem. Eng. News, July(1), 19, 1995