Zero-Valent Iron: Impact of Anions Present during Synthesis on Subsequent Nanoparticle Reactivity
Publication: Journal of Environmental Engineering
Volume 137, Issue 10
Abstract
Zero-valent iron particles are an effective remediation technology for ground water contaminated with halogenated organic compounds. In particular, nanoscale zero-valent iron is a promising material for remediation because of its high specific surface area, which results in faster rate constants and more effective use of the iron. An aspect of iron nanoparticle reactivity that has not been explored is the impact of anions present during iron metal nanoparticle synthesis. Solutions containing chloride, phosphate, sulfate, and nitrate anions and ferric ions were used to generate iron oxide nanoparticles. The resulting materials were dialyzed to remove dissolved by-products and then dried and reduced by hydrogen gas at high temperature. The reactivity of the resulting zero-valent iron nanoparticles was quantified by monitoring the kinetics as well as products of carbon tetrachloride reduction, and significant differences in reactivity and chloroform yield were observed. The reactivity of nanoparticles prepared in the presence of sulfate and phosphate demonstrated the highest reactivity and chloroform yield. Furthermore, substantial variations in the solid-state products of oxidation (magnetite, iron sulfide, goethite, etc.) were also observed.
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Acknowledgments
The authors thank the University of Minnesota and the DOE Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences (CSGB) Division for funding this work. Ancillary support was provided by the Minnesota Water Resources Center. Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from the NSF through the MRSEC program.
References
Baer, D. R. Jr., Windisch, C. F., and Jones, R. H. (1992a). “Application of combined surface analysis/corrosion cell experiments to stress corrosion cracking research.” Proc., Parkins Symp. on Fundamental Aspects of Stress Corrosion Cracking, S. Bruemmer, ed., Tms, Warrendale, PA, 511–528.
Baer, D. R. Jr., Windisch, C. F., Soran, T. F., Jones, R. H., and Engelhard, M. H. (1992b). “Influence of adsorbed and implanted sulfur on the corrosion of iron in calcium nitrate at 60°C.” J. Vac. Sci. Technol. A, 10(5), 3007–3111.
Bennett, P., He, F., Zhao, D., Aiken, B., and Feldman, L. (2010). “In situ testing of metallic iron nanoparticle mobility and reactivity in a shallow granular aquifer.” J. Contam. Hydrol., 116(1–4), 35–46.
Bransfield, S. J., Cwiertny, D. M., Roberts, A. L., and Fairbrother, D. H. (2006). “Influence of copper loading and surface coverage on the reactivity of granular iron toward 1,1,1-trichloroethane.” Environ. Sci. Technol., 40(5), 1485–1490.
Chun, C. L., Baer, D. R., Matson, D. W., Amonette, J. E., and Penn, R. L. (2010). “Characterization and reactivity of iron nanoparticles prepared with added Cu, Pd, and Ni.” Environ. Sci. Technol., 44(13), 5079–5085.
Cwiertny, D. M., Bransfield, S. J., Livi, K. J. T., Fairbrother, D. H., and Roberts, A. L. (2006). “Exploring the influence of granular iron additives on 1,1,1-trichloroethane reduction.” Environ. Sci. Technol., 40(21), 6837–6843.
Cwiertny, D. M., Bransfield, S. J., and Roberts, A. L. (2007). “Influence of the oxidizing species on the reactivity of iron-based bimetallic reductants.” Environ. Sci. Technol., 41(10), 3734–3740.
Devlin, J. F., and Allin, K. O. (2005). “Major anion effects on the kinetics and reactivity of granular iron in glass-encased magnet batch reactor experiments.” Environ. Sci. Technol., 39(6), 1868–1874.
Elliot, D. W., and Zhang, W.-X. (2001). “Field assessment of nanoscale bimetallic particles for groundwater treatment.” Environ. Sci. Technol., 35(24), 4922–4926.
Elsner, M., Lacrampe-Couloume, G., Mancini, S., Burns, L., and Sherwood-Lollar, B. (2010). “Carbon isotope analysis to evaluate nanoscale Fe(O) treatment at a chlorohydrocarbon contaminated site.” Ground Water Monit. Rem., 30(3), 79–95.
Elsner, M., Schwarzenbach, R. P., and Haderlein, S. B. (2004). “Reactivity of Fe(II)-bearing minerals toward reductive transformation of organic contaminants.” Environ. Sci. Technol., 38(3), 799–807.
Erbs, J. (2008). “Insight on the reactivity of environmental iron containing nanoparticles.” Ph.D. thesis, Univ. of Minnesota, Minneapolis.
Forsyth, J. B., Johnson, C. E., and Wilkinsons, C. (1970). “The magnetic structure of vivianite, .” J. Phys. C, 3(5), 1127–1139.
Gillham, R. W., and O’Hannesin, S. (1994). “Enhanced degradation of halogenated aliphatics by zero-valent iron.” Ground Water, 32(6), 958–967.
Hassan, S. M. (2000). “Reduction of halogenated hydrocarbons in aqueous media: I. Involvement of sulfur in iron catalysis.” Chemosphere, 40(12), 1357–1363.
Johnson, T. L., Scherer, M. M., and Tratnyek, P. G. (1996). “Kinetics of halogenated organic compound degradation by iron metal.” Environ. Sci. Technol., 30(8), 2634–2640.
Jones, R. H. Jr., Windisch, C. F., Arey, B. W., and Baer, D. R. (1990). “Grain boundary chemistry effects on the intergranular stress corrosion of iron alloys in sulfate and nitrate solutions.” Corrosion, 47, 542–544.
Kim, Y.-H., and Carraway, E. R. (2003). “Reductive dechlorination of TCE by zero valent bimetals.” Environ. Technol., 24(1), 69–75.
King, H. E., and Prewitt, C. T. (1982). “High-pressure and high-temperature polymorphism of iron sulfide.” Acta Crystallogr., B38, 1877–1887.
Lien, H.-L., and Zhang, W.-X. (1999). “Transformation of chlorinated methanes by nanoscale iron particles.” J. Environ. Eng., 125(11), 1042–1047.
Lien, H.-L., and Zhang, W.-X. (2005). “Hydrodechlorination of chlorinated ethanes by nanoscale Pd/Fe bimetallic particles.” J. Environ. Eng., 131(1), 4–10.
Lipczyska-Kochany, E., Harms, S., Milburn, R., Sprah, G., and Nadarajah, H. (1994). “Degradation of carbon tetrachloride in the presence of iron and sulfur containing compounds.” Chemosphere, 29(7), 1477–1489.
Liu, Y., Choi, H., Dionysiou, D., and Lowry, G. V. (2005). “Trichloroethene hydrodechlorination in water by highly disordered monometallic nanoiron.” Chem. Mater., 17(21), 5315–5322.
Liu, Y., and Lowry, G. V. (2006). “Effect of particle age ( content) and solution pH on NZVI reactivity: evolution and TCE dechlorination.” Environ. Sci. Technol., 40(19), 6085–6090.
Liu, Y., Phenrat, T., and Lowry, G. V. (2007). “Effect of TCE concentration and dissolved groundwater solutes on NZVI-promoted TCE dechlorination and evolution.” Environ. Sci. Technol., 41(22), 7881–7887.
Matheson, L., and Tratnyek, P. G. (1994). “Reductive dehalogenation of chlorinated methanes by iron metal.” Environ. Sci. Technol., 28(12), 2045–2053.
McCormick, M. L., and Adriaens, P. (2004). “Carbon tetrachloride transformation on the surface of nanoscale biogenic magnetite particles.” Environ. Sci. Technol., 38(4), 1045–1053.
Moore, P. B. (1970). “Crystal chemistry of the basic iron phosphates.” Am. Mineral., 55, 135–169.
Okudera, H., Kihara, K., and Matsumoto, T. (1996). “Temperature dependence of structure parameters in natural magnetite: Single crystal X-ray studies from 126 to 773 K.” Acta Crystallogr., B52, 450–457.
Rietveld, H. M. (1969). “A profile refinement method for nuclear and magnetic structures.” J. Appl. Crystallogr., 2(2), 65–71.
Schwertmann, U., and Cornell, R. M. (2000). Iron oxides in the laboratory, 2nd Ed., Wiley-VCH, Weinheim, Germany.
Song, H., and Carraway, E. R. (2005). “Reduction of chlorinated ethanes by nanosized zero-valent iron: Kinetics, pathways, and effects of reaction conditions.” Environ. Sci. Technol., 39(16), 6237–6245.
Song, H., and Carraway, E. R. (2006). “Reduction of chlorinated methanes by nano-sized zero-valent iron. Kinetics, pathways, and effect of reaction conditions.” Environ. Eng. Sci., 23(2), 272–284.
Song, H., and Carraway, E. R. (2008). “Catalytic hydrodechlorination of chlorinated ethenes by nanoscale zero-valent iron.” Appl. Catal. B, 78(1–2), 53–60.
Tamara, M. L., and Butler, E. C. (2004). “Effects of iron purity and groundwater characteristics on rates and products in the degradation of carbon tetrachloride by iron metal.” Environ. Sci. Technol., 38(6), 1866–1876.
Wang, C.-B., and Zhang, W.-X. (1997). “Synthesizing nanoscale iron particles for rapid and complete dechlorination of TCE and PCBs.” Environ. Sci. Technol., 31(7), 2154–2156.
Waychunas, G. A. (1991). “Crystal chemistry of oxides and hydroxides.” Rev. Mineral., 25(1), 11–68.
Windisch, C. F., Baer, D. R., Jones, R. H., and Engelhard, M. H. (1992). “The influence of phosphorus on the corrosion of iron in calcium nitrate.” J. Electrochem. Soc., 139(2), 390–398.
Wyckoff, R. W. G. (1963). Crystal structures 1, 2nd Ed., Interscience, New York.
Xu, Y., and Zhang, W.-X. (2000). “Subcollodial Fe/Ag particles for reduction of chlorinated benzenes.” Ind. Eng. Chem. Res., 39(7), 2238–2244.
Zhang, W.-X., Wang, C.-B., and Lien, H.-L. (1998). “Treatment of chlorinated organic contaminants with nanoscale bimetallic particles.” Catal. Today, 40(4), 387–395.
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Published In
Journal of Environmental Engineering
Volume 137 • Issue 10 • October 2011
Pages: 889 - 896
Copyright
© 2011 American Society of Civil Engineers.
History
Received: Oct 12, 2010
Accepted: Apr 11, 2011
Published online: Apr 13, 2011
Published in print: Oct 1, 2011
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