Journal of Nanoparticle Research

, Volume 11, Issue 4, pp 807–819 | Cite as

Rapid and controlled transformation of nitrate in water and brine by stabilized iron nanoparticles

Research Paper


Highly reactive zero-valent iron (ZVI) nanoparticles stabilized with carboxymethyl cellulose (CMC) were tested for reduction of nitrate in fresh water and brine. Batch kinetic tests showed that the pseudo first-order rate constant (kobs) with the stabilized nanoparticles was five times greater than that for non-stabilized counterparts. The stabilizer not only increased the specific surface area of the nanoparticles, but also increased the reactive particle surface. The allocation between the two reduction products, NH4+ and N2, can be manipulated by varying the ZVI-to-nitrate molar ratio and/or applying a Cu–Pd bimetallic catalyst. Greater CMC-to-ZVI ratios lead to faster nitrate reduction. Application of a 0.05 M HEPES buffer increased the kobs value by 15 times compared to that without pH control. Although the presence of 6% NaCl decreased kobs by 30%, 100% nitrate was transformed within 2 h in the saline water. The technology provides a powerful alternative for treating water with concentrated nitrate such as ion exchange brine.


Denitrification Ion exchange brine Nanoparticles Nitrate Reduction Sodium carboxymethyl cellulose Zero-valent iron (ZVI) Water treatment 


  1. Alowitz MJ, Scherer MM (2002) Kinetics of nitrate, nitrite, and Cr(VI) reduction by iron metal. Environ Sci Technol 36:299–306PubMedCrossRefGoogle Scholar
  2. Chen XY, Zhang Y, Chen GH (2003) Appropriate conditions or maximizing catalytic reduction efficiency of nitrate into nitrogen gas in groundwater. Water Res 37:2489–2495PubMedCrossRefGoogle Scholar
  3. Chen S-S, Hsu H-D, Li C-W (2004) A new method to produce nanoscale iron for nitrate removal. J Nanopart Res 6:639–647CrossRefGoogle Scholar
  4. Cheng IF, Muftikian R, Fernando Q, Korte N (1997) Reduction of nitrate to ammonia by zero-valent iron. Chemosphere 35:2689–2695CrossRefGoogle Scholar
  5. Choe S, Chang Y-Y, Hwang K-Y, Khim J (2000) Kinetics of reductive denitrification by nanoscale zero-valent iron. Chemosphere 41:1307–1311PubMedCrossRefGoogle Scholar
  6. Clesceri LS, Greenberg AE, Eaton AD (1998) Standard methods for the examination of water and wastewater, 20th edn. American Public Health Association, Washington, DCGoogle Scholar
  7. Clifford DA (1999) Ion exchange and inorganic adsorption. In: Lettermam RD (ed) Water quality and treatment, 5th edn. McGraw Hill, New York, pp 9.1–9.91Google Scholar
  8. Clifford DA, Liu X (1993a) Ion exchange for nitrate removal. J Am Water Works Assoc 85:135–143Google Scholar
  9. Clifford DA, Liu X (1993b) Biological denitrification of spent regenerant brine using a sequencing batch reactor. Water Res 27:1477–1484CrossRefGoogle Scholar
  10. Cox JL, Hallen RT, Lllga MA (1994) Thermochemical nitrate destruction. Environ Sci Technol 28:423–428CrossRefGoogle Scholar
  11. Fan AM, Steinberg VE (1996) Health implications of nitrate and nitrite in drinking water: an update on methemoglobinemia occurrence and reproductive and developmental toxicity. Regul Toxicol Pharmacol 23:35–43PubMedCrossRefGoogle Scholar
  12. Glass C, Silverstein J (1999) Denitrification of high-nitrate, high-salinity wastewater. Water Res 33:223–229CrossRefGoogle Scholar
  13. Glavee GN, Klabunde KJ, Sorensen CM, Hadjipanayis GC (1995) Chemistry of borohydride reduction of iron(II) and iron(III) ions in aqueous and nonaqueous media. Formation of nanoscale Fe, FeB, and Fe2B powders. Inorg Chem 34:28–35CrossRefGoogle Scholar
  14. Grittini G, Malcomson M, Fernando Q, Korte N (1995) Rapid dechlorination of polychlorinated biphenyls on the surface of a Pd/Fe bimetallic system. Environ Sci Technol 29:2898–2900CrossRefGoogle Scholar
  15. He F, Zhao D (2005) Preparation and characterization of a new class of starch-stabilized bimetallic nanoparticles for degradation of chlorinated hydrocarbons in water. Environ Sci Technol 39:3314–3320PubMedCrossRefGoogle Scholar
  16. He F, Zhao D (2007a) Manipulating the size and dispersibility of zero-valent iron nanoparticles by use of carboxymethyl cellulose stabilizers. Environ Sci Technol 41:6216–6221PubMedCrossRefGoogle Scholar
  17. He F, Zhao D (2007b) Hydrodechlorination of trichloroethene using stabilized Fe/Pd nanoparticles: reaction mechanism and effects of stabilizer and reaction conditions. Appl Catal B—Environ (in press)Google Scholar
  18. He F, Zhao D, Liu J, Roberts CB (2007) Stabilization of Fe–Pd nanoparticles with sodium carboxymethyl cellulose for enhanced transport and dechlorination of trichloroethylene in soil and groundwater. Ind Eng Chem Res 46:29–34CrossRefGoogle Scholar
  19. Horold S, Vorlop K-D, Tacke T, Sell M (1993) Development of catalysts for a selective nitrate and nitrite removal from drinking water. Catal Today 17:21–30CrossRefGoogle Scholar
  20. Huang YH, Zhang TC (2004) Effects of low pH on nitrate reduction by iron powder. Water Res 38:2631–2642PubMedCrossRefGoogle Scholar
  21. Huang YH, Zhang TC (2005) Enhancement of nitrate reduction in Fe0-packed columns by selected cations. J Environ Eng 131:603–611CrossRefGoogle Scholar
  22. Huang C-P, Wang H-W, Chiu P-C (1998) Nitrate reduction by metallic iron. Water Res 32:2257–2264CrossRefGoogle Scholar
  23. Johnson TL, Scherer MM, Tratnyek PG (1996) Kinetics of halogenated organic compound degradation by iron metal. Environ Sci Technol 30:2634–2640CrossRefGoogle Scholar
  24. Kielemoes J, De Boever P, Verstraete W (2000) Influence of denitrification on the corrosion of iron and stainless steel powder. Environ Sci Technol 34:663–671CrossRefGoogle Scholar
  25. Kim J, Benjamin MM (2004) Modeling a novel ion exchange process for arsenic and nitrate removal. Water Res 38:2053–2062PubMedCrossRefGoogle Scholar
  26. Labelle MA, Juteau P, Jolicoeur M, Villemur R, Parent S, Comeau Y (2005) Seawater denitrification in a closed mesocosm by a submerged moving bed biofilm reactor. Water Res 39:3409–3417PubMedCrossRefGoogle Scholar
  27. Lemaignen L, Tong C, Begon V, Burch R, Chadwick D (2002) Catalytic denitrification of water with palladium-based catalysts supported on activated carbons. Catal Today 75:43–48CrossRefGoogle Scholar
  28. Liou YH, Lo SL, Lin CJ, Hu CY, Kuan WH, Weng SC (2005a) Methods for accelerating nitrate reduction using zerovalent iron at near-neutral pH: effects of H2-reducing pretreatment and copper deposition. Environ Sci Technol 39:9643–9648PubMedCrossRefGoogle Scholar
  29. Liou YH, Lo SL, Lin CJ, Kuan WH, Weng SC (2005b) Chemical reduction of an unbuffered nitrate solution using catalyzed and uncatalyzed nanoscale iron particles. J Hazard Mater 127:102–110PubMedCrossRefGoogle Scholar
  30. Liu Y, Majetich SA, Tilton RD, Sholl DS, Lowry GV (2005) TCE dechlorination rates, pathways, and efficiency of nanoscale iron particles with different properties. Environ Sci Technol 39:1338–1345PubMedCrossRefGoogle Scholar
  31. Mikami I, Sakamoto Y, Yoshinaga Y, Okuhara T (2003) Kinetic and adsorption studies on the hydrogenation of nitrate and nitrite in water using Pd–Cu on active carbon support. Appl Catal 44:79–86CrossRefGoogle Scholar
  32. Mishra D, Farrell J (2005) Understanding nitrate reactions with zerovalent iron using Tafel analysis and electrochemical impedance spectroscopy. Environ Sci Technol 39:645–650PubMedCrossRefGoogle Scholar
  33. Mueller DK, Helsel DR (1996) Nutrients in the nation’s waters-too much of a good thing? US Geological Survey, Reston, VA, USGoogle Scholar
  34. Nolan BT, Ruddy BC, Hitt KJ, Helsel DR (1997) Risk of nitrate in groundwaters of the United States—a national perspective. Environ Sci Technol 31:2229–2236CrossRefGoogle Scholar
  35. Nuhogl A, Pekdemir T, Yildiz E, Keskinler B, Akay G (2002) Drinking water denitrification by a membrane bio-reactor. Water Res 36:1155–1166PubMedCrossRefGoogle Scholar
  36. Okeke BC, Giblin T, Frankenberger WT (2002) Reduction of perchlorate and nitrate by salt tolerant bacteria. Environ Pollut 118:357–363PubMedCrossRefGoogle Scholar
  37. Peel JW, Reddy KJ, Sullivan BP, Bowen JM (2003) Electrocatalytic reduction of nitrate in water. Water Res 37:2512–2519PubMedCrossRefGoogle Scholar
  38. Peyton BM, Mormile MR, Petersen JN (2001) Nitrate reduction with halomonas Campisalis: kinetics of denitrification at pH 9 and 12.5% NaCl. Water Res 35:4237–4242PubMedCrossRefGoogle Scholar
  39. Rautenbach R, Kopp W, Hellekes R, Teter R, Van Opbergen G (1986) Separation of nitrate from well water by membrane processes (reverse osmosis/elecrodialysis reversal). Aqua 5:279–282Google Scholar
  40. Schreier CG, Reinhard M (1995) Catalytic hydrodehalogenation of chlorinated ethylenes using palladium and hydrogen for the treatment of contaminated water. Chemosphere 31:3475–3487CrossRefGoogle Scholar
  41. Siantar DP, Schreier CG, Chou C-S, Reinhard M (1996) Treatment of 1,2-dibromo-3-chloropropane and nitrate-contaminated water with zero-valent iron or hydrogen/palladium catalysts. Water Res 30:2315–2322CrossRefGoogle Scholar
  42. Smith RL, Buckwalter SP, Repert DA, Miller DN (2005) Small-scale, hydrogen-oxidizing-denitrifying bioreactor for treatment of nitrate-contaminated drinking water. Water Res 39:2014–2023PubMedCrossRefGoogle Scholar
  43. Sohn K, Kang SW, Ahn S, Woo M, Yang S-K (2006) Fe(0) nanoparticles for nitrate reduction: stability, reactivity, and transformation. Environ Sci Technol 40:5514–5519PubMedCrossRefGoogle Scholar
  44. Sorenson J, Thorling L (1991) Stimulation by lepidocrocite (γ-FeOOH) of Fe(II)-dependent nitrite reduction. Geochim Cosmochim Acta 55:1289–1294CrossRefADSGoogle Scholar
  45. Su C, Puls RW (2004) Nitrate reduction by zerovalent iron: effects of formate, oxalate, citrate, chloride, sulfate, borate, and phosphate. Environ Sci Technol 38:2715–2720PubMedCrossRefGoogle Scholar
  46. U.S. Environmental Protection Agency (1995) Drinking water regulations and health advisories. Washington, DC, USAGoogle Scholar
  47. Van der Hoek JP, Latour PJM, Klapwijk A (1987) Denitrification with methanol in the presence of high salt concentrations and at high pH levels. Appl Microbiol Biotechnol 27:199–205CrossRefGoogle Scholar
  48. Van der Hoek JP, Van der Hoek WF, Klapwijk A (1988) Nitrate removal from ground water: use of a nitrate selective resin and a low concentrated regenerant. Water Air Soil Pollut 37:41–53CrossRefGoogle Scholar
  49. Wang CB, Zhang WX (1997) Synthesizing nanoscale iron particles for rapid and complete dechlorination of TCE and PCBs. Environ Sci Technol 31:2154–2156CrossRefGoogle Scholar
  50. Xiong Z, Zhao D, Pan G (2007) Rapid and complete destruction of perchlorate in water and ion-exchange brine using stabilized zero-valent iron nanoparticles. Water Res 41:3497–3505PubMedCrossRefGoogle Scholar
  51. Yang GC, Lee HL (2005) Chemical reduction of nitrate by nanosized iron: kinetics and pathways. Water Res 39:884–894PubMedCrossRefGoogle Scholar
  52. Zhang TC, Huang YH (2005) Effects of selected Good’s pH buffers on nitrate reduction by iron powder. J Environ Eng 131:461–470CrossRefGoogle Scholar
  53. Zhang WX, Wang CB, Lien HL (1998) Treatment of chlorinated organic contaminants with nanoscale bimetallic particles. Catal Today 40:387–395CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2008

Authors and Affiliations

  1. 1.Environmental Engineering Program, Department of Civil Engineering, 238 Harbert Engineering CenterAuburn UniversityAuburnUSA
  2. 2.Research Center for Eco-Environmental SciencesChinese Academy of SciencesBeijingChina

Personalised recommendations