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The Effect of Smectite on the Corrosion of Iron Metal

Published online by Cambridge University Press:  01 January 2024

Barbara A. Balko ,
Stephanie A. Bossé ,
Anne E. Cade ,
Elise F. Jones-Landry ,
James E. Amonette  and
John L. Daschbach
Barbara A. Balko*
Affiliation:
Chemistry Department, Lewis & Clark College, Portland, OR 97219 USA
Stephanie A. Bossé
Affiliation:
Chemistry Department, Lewis & Clark College, Portland, OR 97219 USA
Anne E. Cade
Affiliation:
Chemistry Department, Lewis & Clark College, Portland, OR 97219 USA
Elise F. Jones-Landry
Affiliation:
Chemistry Department, Lewis & Clark College, Portland, OR 97219 USA
James E. Amonette
Affiliation:
Fundamental and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA 99352 USA
John L. Daschbach
Affiliation:
Fundamental and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA 99352 USA Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA 99352 USA
*
*E-mail address of corresponding author: [email protected]
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Abstract

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The combination of zero-valent iron (ZVI) and a clay-type amendment is often observed to have a synergistic effect on the rate of reduction reactions. In the present study, electrochemical techniques were used to determine the mechanism of interaction between the iron (Fe) and smectite clay minerals. Iron electrodes coated with an evaporated smectite suspension (clay-modified iron electrodes, CMIEs) were prepared using five different smectites: SAz-1, SWa-1, STx-1, SWy-1, and SHCa-1. All the smectites were exchanged with Na+ and one sample of SWy-1 was also exchanged with Mg2+. Potentiodynamic polarization scans and cyclic voltammograms were taken using the CMIEs and uncoated but passivated Fe electrodes. These electrochemical experiments, along with measurements of the amount of Fe2+ and Fe3+ sorbed in the smectite coating, suggested that the smectite removed the passive layer of the underlying Fe electrode during the evaporation process. Cyclic voltammograms taken after the CMIEs were biased at the active-passive transition potential for varying amounts of time suggested that the smectite limited growth of a passive layer, preventing passivation. These results are attributed to the Brønsted acidity of the smectite as well as to its ability to sorb Fe cations. Oxides that did form on the surface of the Fe in the presence of the smectite when it was biased anodically were reduced at a different electrochemical potential from those that form on the surface of an uncoated Fe electrode under otherwise similar conditions; this difference suggested that the smectite reacted with the Fe2+ formed from the oxidation of the underlying Fe. No significant correlation could be found between the ability of the smectite to remove the Fe passive film and the smectite type. The results have implications for the mixing of sediments and Fe particles in permeable reactive barriers, underground storage of radioactive waste in steel canisters, and the use of smectite supports in preventing aggregation of nano-sized zero-valent iron.

Keywords

Clay BarrierFe-Clay InteractionsFe CorrosionMontmorillonitePermeable Reactive BarrierSmectiteZero-Valent Iron
Type
Article
Information
Clays and Clay Minerals , Volume 60 , Issue 2 , April 2012 , pp. 136 - 152
Copyright
Copyright © Clay Minerals Society 2012

References

Adams, J.M. Clapp, T.V. and Clement, D.E., 1983 Catalysis by montmorillonites Clay Minerals 18 411–421.CrossRefGoogle Scholar
Agrawal, A. and Tratnyek, P.G., 1996 Reduction of nitro aromatic compounds by zero-valent iron metal Environmental Science & Technology 30 153–160.CrossRefGoogle Scholar
Amonette, J.E., Fitch, A., 2002 Iron redox chemistry of clays and oxides: environmental applications Electrochemical Properties of Clays Aurora, Colorado, USA Workshop Lecture Series 10, The Clay Minerals Society 89–147.Google Scholar
Amonette, J.E. Camacho, E.A. and Divanfard, H.A., 1996 Reduction of chlorinated hydrocarbons by Fe(II)-bearing smectite 33rd Annual Meeting Gatlinburg, Tennessee, USA The Clay Minerals Society.Google Scholar
Babić, R. Metikoš-Huković, M. and Pilić, Z., 2003 Passivity of mild steel in borate buffer solution containing tannin Corrosion 59 890–896.CrossRefGoogle Scholar
Bard, A.J. Mallouk, T., Murray, R.W., 1992 Electrodes modified with clays, zeolites, and related microporous solids Molecular Design of Electrode Surfaces 427.Google Scholar
Bardwell, J.A. MacDougall, B. and Graham, M.J., 1988 Use of 18O/SIMS and electrochemical techniques to study the reduction and breakdown of passive oxide films on iron Journal of the Electrochemical Society 135 413–418.CrossRefGoogle Scholar
Büchler, M. Schmuki, P. and Böhni, H., 1998 Iron passivity in borate buffer: formation of a deposit layer and its influence on the semiconducting properties Journal of the Electrochemical Society 145 609–614.CrossRefGoogle Scholar
Carlson, L. Karnland, O. Oversby, V.M. Rance, A.P. Smart, N.R. Snellman, M. Vähänen, M. and Werme, L.O., 2007 Experimental studies of the interactions between anaerobically corroding iron and bentonite Physics and Chemistry of the Earth 32 334–345.CrossRefGoogle Scholar
Cervini-Silva, J. Wu, J. Larson, R.A. and Stucki, J.W., 2000 Transformation of chloropicrin in the presence of ironbearing clay minerals Environmental Science & Technology 34 915–917.CrossRefGoogle Scholar
Cervini-Silva, J. Larson, R.A. Wu, J. and Stucki, J.W., 2001 Transformation of chlorinated aliphatic compounds by ferruginous smectite Environmental Science & Technology 35 805–809.CrossRefGoogle ScholarPubMed
Cervini-Silva, J. Larson, R.A. Wu, J. and Stucki, J.W., 2002 Dechlorination of pentachloroethane by commercial Fe and ferruginous smectite Chemosphere 47 971–976.10.1016/S0045-6535(02)00056-5CrossRefGoogle ScholarPubMed
Cervini-Silva, J. Kostka, J.E. Larson, R.A. Stucki, J.W. and Wu, J., 2003 Dehydrochlorination of 1,1,1-trichloroethane and pentachloroethane by microbially reduced ferruginous smectite Environmental Toxicology and Chemistry 22 1046–1050.Google ScholarPubMed
Deng, H. Ishikawa, I. Yoneya, M. and Nanjo, H., 2004 Reconstruction in air of an iron passive film formed at–0.4 V in a borate buffer solution Journal of Physical Chemistry B 108 9139–9146.CrossRefGoogle Scholar
Deng, H. Nanjo, H. Qian, P. Xia, Z. and Ishikawa, I., 2006 Evolution of passivity in air exposure of an iron passive film Electrochimica Acta 52 187–193.CrossRefGoogle Scholar
Diez-Perez, I. Gorostiza, P. Sanz, F. and Muller, C., 2001 First stages of electrochemical growth of the passive film on iron Journal of the Electrochemical Society 148 B307–B313.CrossRefGoogle Scholar
Féron, D. Crusset, D. and Gras, J.M., 2008 Corrosion issues in nuclear waste disposal Journal of Nuclear Materials 379 16–23.CrossRefGoogle Scholar
Fitch, A., 1990 Clay-modified electrodes: A review Clays and Clay Minerals 38 391–400.CrossRefGoogle Scholar
Frenkel, M., 1974 Surface acidity of montmorillonites Clays and Clay Minerals 22 435–441.CrossRefGoogle Scholar
Frost, R.L. Xi, Y. and He, H., 2009 Synthesis, characterization of palygorskite supported zero-valent iron and its application for methylene blue adsorption Journal of Colloid and Interface Science 341 153–161.CrossRefGoogle ScholarPubMed
Gibbs, M.M., 1979 A simple method for the rapid determination of iron in natural waters Water Research 13 295–297.CrossRefGoogle Scholar
Gillham, R.W. and O’Hannesin, S.F., 1994 Enhanced degradation of halogenated aliphatics by zero-valent iron Ground Water 32 958–967.CrossRefGoogle Scholar
Gu, B. Liang, L. Dickey, M.J. Yin, X. and Dai, S., 1998 Reductive precipitation of uranium(VI) by zero-valent iron Environmental Science & Technology 32 3366–3373.CrossRefGoogle Scholar
Gu, C. Jia, H. Li, H. Teppen, B.J. and Boyd, S.A., 2010 Synthesis of highly reactive subnano-sized zero-valent iron using smectite clay templates Environmental Science & Technology 44 4258–4263.CrossRefGoogle ScholarPubMed
Hofstetter, T.B. Schwarzenbach, R.P. and Haderlein, S.B., 2003 Reactivity of Fe(II) species associated with clay minerals Environmental Science & Technology 37 519–528.CrossRefGoogle ScholarPubMed
Hofstetter, T.B. Neumann, A. and Schwarzenbach, R., 2006 Reduction of nitroaromatic compounds by Fe(II) species associated with iron-rich smectites Environmental Science & Technology 40 235–242.CrossRefGoogle ScholarPubMed
Ilton, E.S. Heald, S.M. Smith, S.C. Elbert, D. and Liu, C., 2006 Reduction of uranyl in the interlayer region of low iron micas under anoxic and aerobic conditions Environmental Science & Technology 40 5003–5009.CrossRefGoogle ScholarPubMed
Jackson, M.L., 1979.Soil Chemistry Analysis–Advanced CourseGoogle Scholar
Jackson, M.L. Whittig, L.D. and Pennington, R.P., 1950 Segregation procedure for the mineralogical analysis of soils Soil Science Society of America Proceedings 14 77–81.CrossRefGoogle Scholar
Jaisi, D.P. Dong, H. Plymale, A.E. Fredrickson, J.K. Zachara, J.M. Heald, S. and Liu, C., 2009 Reduction and long-term immobilization of technetium by Fe(II) associated with clay mineral nontronite Chemical Geology 264 127–138.CrossRefGoogle Scholar
Jensen, W.B., 2008 The origin of the rubber policeman Journal of Chemical Education 85 776.CrossRefGoogle Scholar
Jia, H. Gu, C. Boyd, S.A. Teppen, B.J. Johnston, C.T. Song, C. and Li, H., 2011 Comparison of reactivity of nanoscaled zero-valent iron formed on clay surfaces Soil Science Society of America Journal 75 357–364.CrossRefGoogle Scholar
Johnson, T.L. Scherer, M.M. and Tratnyek, P.G., 1996 Kinetics of halogenated organic compound degradation by iron metal Environmental Science & Technology 30 2634–2640.CrossRefGoogle Scholar
Joo, P. and Fitch, A., 1996 Ionic and molecular transport in hydrophobized montmorilllonite films: An electrochemical survey Environmental Science & Technology 30 2681–2686.10.1021/es950728tCrossRefGoogle Scholar
Jovancicevic, V. Kainthla, R.C. Tang, Z. Yang, B. and Bockris, J.O.M., 1987 The passive film on iron: an ellipsometric-spectroscopic study Langmuir 3 388–395.CrossRefGoogle Scholar
Katsenovich, Y. and Miralles-Wilhelm, F.R., 2009 Evaluation of nanoscale zerovalent iron particles for trichloroethene degradation in clayey soils Science of the Total Environment 407 4986–4993.CrossRefGoogle ScholarPubMed
Klausen, J. Vikesland, P.J. Kohn, T. Burris, D.R. Ball, W.P. and Roberts, A.L., 2003 Longevity of granular iron in groundwater treatment processes: Solution composition effects on reduction of organohalides and nitroaromatic compounds Environmental Science & Technology 37 1208–1218.CrossRefGoogle ScholarPubMed
Kohn, T. Kane, S.R. Fairbrother, D.H. and Roberts, A.L., 2003 Investigation of the inhibitory effect of silica on the degradation of 1,1,1-trichloroethane by granular iron Environmental Science & Technology 37 5806–5812.CrossRefGoogle ScholarPubMed
Kohn, T. Livi, J.T. Roberts, A.L. and Vikesland, P.J., 2005 Longevity of granular iron in groundwater treatment processes: Corrosion product development Environmental Science & Technology 39 2867–2879.CrossRefGoogle ScholarPubMed
Krishnamurti, G.S.R. Violante, A. and Huang, P.M., 1998 Influence of montmorillonite on Fe(II) oxidation products Clay Minerals 33 205–212.CrossRefGoogle Scholar
Lear, P.R. and Stucki, J.W., 1989 Effects of iron oxidation state on the specific surface area of nontronite Clays and Clay Minerals 37 547–552.CrossRefGoogle Scholar
Lee, H.-J. Chun, B.-S. Kim, W.-C. Chung, M. and Park, J.-W., 2006 Zero valent iron and clay mixtures for removal of trichloroethylene, chromium(VI), and nitrate Environmental Technology 27 299–306.CrossRefGoogle ScholarPubMed
Li, S. Wu, P. Li, H. Zhu, N. Li, P. Wu, J. Wang, X. and Dang, Z., 2010 Synthesis and chararacterization of organomontmorillonite supported iron nanoparticles Applied Clay Science 50 330–336.CrossRefGoogle Scholar
Liu, J. and Macdonald, D.D., 2001 The passivity of iron in the presence of ethylenediaminetetraacetic acid: II The defect and electronic structures of the barrier layer. Journal of the Electrochemical Society 148 B425–B430.Google Scholar
Madsen, F.T., 1998 Clay mineralogical investigations related to nuclear waste disposal Clay Minerals 33 109–129.CrossRefGoogle Scholar
Matheson, L.J. and Tratnyek, P.G., 1994 Reductive dehalogenation of chlorinated methanes by iron metal Environmental Science & Technology 28 2045–2053.CrossRefGoogle ScholarPubMed
Merola, R.B. Fournier, E.D. and McGuire, M.M., 2007 Spectroscopic investigations of Fe2+ complexation on nontronite clay Langmuir 23 1223–1226.CrossRefGoogle ScholarPubMed
Modiano, S. Fugivara, C.S. and Benedetti, A.V., 2004 Effect of citrate ions on the electrochemical behavior of lowcarbon steel in borate buffer solutions Corrosion Science 46 529–545.CrossRefGoogle Scholar
Mortland, M.M. and Raman, K.V., 1968 Surface acidity of smectites in relation to hydration, exchangeable cation, and structure Clays and Clay Minerals 16 393–398.CrossRefGoogle Scholar
Neumann, A. Hofstetter, T.B. Lüssi, M. Cirpka, O.A. Petit, S. and Schwarzenbach, R., 2008 Assessing the redox reactivity of structural iron in smectites using nitroaromatic compounds as kinetic probes Environmental Science & Technology 42 8381–8387.CrossRefGoogle ScholarPubMed
Neumann, A. Hofstetter, T.B. Lüssi, M. Cirpka, O.A. Petit, S. and Schwarzenbach, R.P., 2008 Assessing the redox reactivity of structural iron in smectities using nitroaromatic compounds as kinetic probes Environmental Science & Technology 42 8381–8387.CrossRefGoogle ScholarPubMed
Neumann, A. Hofstetter, T.B. Skarpeli-Liati, M. and Schwarzenbach, R.P., 2009 Reduction of polychlorinated ethanes and carbon tetrachloride by structural Fe(II) in smectites Environmental Science & Technology 43 4082–4089.CrossRefGoogle ScholarPubMed
Neumann, A. Sander, M. Hofstetter, T.B., Tratnyek, P.G. Grundl, T.J. and Haderlein, S.B., 2012 Redox properties of structural Fe in clay minerals Aquatic Redox Chemistry Washington, D.C. ACS Symposium Series, 1071, The American Chemical Society 361–379.Google Scholar
Nurmi, J.T. Bandstra, J.Z. and Tratnyek, P.G., 2004 Packed powder electrodes for characterizing the reactivity of granular iron in borate solutions Journal of the Electrochemical Society 151 B347–B353.CrossRefGoogle Scholar
Nurmi, J.T. Tratnyek, P.G. Sarathy, V. Baer, D.R. Amonette, J.E. Pecher, K. Wang, C. Linehan, J.C. Matson, D.W. Penn, R.L. and Driessen, M.D., 2005 Characterization and properties of metallic iron nanoparticles: Spectroscopy, electrochemistry, and kinetics Environmental Science & Technology 39 1221–1230.CrossRefGoogle ScholarPubMed
Nzengung, V.A. Castillo, R.M. Gates, W.P. and Mills, G.L., 2001 Abiotic transformation of perchloroethylene in homogeneous dithionite solution and in suspensions of dithionite-treated clay minerals Environmental Science & Technology 35 2244–2251.CrossRefGoogle ScholarPubMed
Oblonsky, L.J. and Devine, T.M., 1995 A surface enhanced Raman spectroscopic study of the passive films formed in borate buffer on iron, nickel, chromium and stainless steel Corrosion Science 37 17–41.CrossRefGoogle Scholar
Oh, Y.J. Song, H. Shin, S.S. Choi, S.J. and Kim, Y.-H., 2007 Effect of amorphous silica and silica sand on removal of chromium(VI) by zero-valent iron Chemosphere 66 858–865.CrossRefGoogle ScholarPubMed
Olphen, H.V. and Fripiat, J.J., 1979 Data Handbook for Clay Materials and Other Non-Metallic Minerals New York Pergamon Press.Google Scholar
Peretyazhko, T. Zachara, J.M. Heald, S.M. Jeon, B.-H. Kukkadapu, R.K. Liu, C. Moore, D. and Resch, C.T., 2009 Heterogeneous reduction of Tc(VII) by Fe(II) at the solid-water interface Geochimica et Cosmochimica Acta 72 1521–1539.CrossRefGoogle Scholar
Powell, R.M. and Puls, R.W., 1997 Proton generation by dissolution of intrinsic or augmented aluminosilicate minerals for in situ contaminant remediation by zero-valence-state iron Environmental Science & Technology 31 2244–2251.CrossRefGoogle Scholar
Powell, R.M. Puls, R.W. Hightower, S.K. and Sabatini, D.A., 1995 Coupled iron corrosion and chromate reduction: Mechanisms for subsurface remediation Environmental Science & Technology 29 1913–1922.CrossRefGoogle ScholarPubMed
Rabideau, A.J. Shen, P. and Khandelwal, A., 1999 Feasibility of amending slurry walls with zero-valent iron Journal of Geotechnical and Geoenvironmental Engineering April 330–333.CrossRefGoogle Scholar
Research, EGPA, 1987 Electrochemistry and Corrosion: Overview and Techniques Application Note Corr-4 1–16.Google Scholar
Reynolds, G.W. Hoff, J.T. and Gillham, R.W., 1990 Sampling bias caused by materials used to monitor halocarbons in groundwater Environmental Science & Technology 24 135–142.CrossRefGoogle Scholar
Roberts, A.L. Totten, L.A. Arnold, W.A. Burris, D.R. and Campbell, T.J., 1996 Reductive elimination of chlorinated ethylenes by zero-valent metals Environmental Science & Technology 30 2654–2659.CrossRefGoogle Scholar
Rodriguez, E.A. Amonette, J.E. Divanfard, H.R. and Marquez, J.F., 1999 Use of Fe(II) associated with layer silicates for remediation of groundwater contaminated by CCl4, TCE and TNT Environmental Molecular Sciences Symposia and First User’s Meeting Washington, USA Abstracts with Program, Pacific Northwest National Laboratory 41–42.Google Scholar
Rubim, J.C., 1993 In situ raman and reflectance spectra of iron electrodes in borate buffer solution containing 2,2’- bipyridine Journal of the Electrochemical Society 140 1601–1606.CrossRefGoogle Scholar
Sawyer, D.T. Sobkowiak, A. and Roberts, J.L., 1995 Electrochemistry for Chemists Inc., New York John Wiley & Sons.Google Scholar
Schaefer, M.V. Gorski, C.A. and Scherer, M.M., 2011 Spectroscopic evidence for interfacial Fe(II)–Fe(III) electron transfer in a clay mineral Environmental Science & Technology 45 540–545.CrossRefGoogle Scholar
Scherer, M.M. Westall, J.C. Ziomek-Moroz, M. and Tratnyek, P.G., 1997 Kinetics of carbon tetrachloride reduction at an oxide-free iron electrode Environmental Science & Technology 31 2385–2391.CrossRefGoogle Scholar
Schultz, C.A. and Grundl, T.J., 2000 pH dependence on reduction rate of 4-Cl-nitrobenzene by Fe(II)/montmorillonite systems Environmental Science & Technology 34 3641–3648.CrossRefGoogle Scholar
Schultz, C. and Grundl, T., 2004 pH dependence of ferrous sorption onto two smectite clays Chemosphere 57 1301–1306.CrossRefGoogle ScholarPubMed
Sikora, E. and Macdonald, D.D., 2000 The passivity of iron in the presence of ethylenediaminetetraacetic acid: I General electrochemical behavior. Journal of the Electrochemical Society 147 4087–4092.CrossRefGoogle Scholar
Smart, N.R. Rance, A.P. and Werme, L.O., 2004 Anaerobic corrosion of steel in bentonite Materials Research Society Symposium Proceedings 807 441–446.CrossRefGoogle Scholar
Soma, Y. and Soma, M., 1989 Chemical reactions of organic compounds on clay surfaces Environmental Health Perspectives 83 205–214.CrossRefGoogle ScholarPubMed
Source Clay Physical/Chemical Data (February 21, 2012).Google Scholar
Stookey, L.L., 1970 Ferrozine–a new spectrophotometric reagent for iron Analytical Chemistry 42 779–781.CrossRefGoogle Scholar
Subramanian, P. and Fitch, A., 1992 Diffusional transport of solutes through clay: use of clay-modified electrodes Environmental Science & Technology 26 1775–1779.CrossRefGoogle Scholar
Tanner, C.B. and Jackson, M.L., 1948 Nomographs of sedimentation times for soil particles under gravity or centrifugal acceleration Soil Science Society of America Proceedings 12 60–65.CrossRefGoogle Scholar
Thompson, D.W. and Mitchell, C.J., 1993 The hydrolytic precipitation of iron in aqueous dispersions of mineral particles Colloids and Surfaces A: Physicochemical and Engineering Aspects 73 103–115.CrossRefGoogle Scholar
Tratnyek, P.G., 1996 Putting corrosion to use: Remediation of contaminated groundwater with zero-valent metals Chemical Industry (London) 499–503.Google Scholar
Vela, M.W. Vilche, J.R. and Arvia, A.J., 1986 The dissolution and passivation of polycrystalline iron electrodes in boric acid-borate buffer solutions in the 7.5–9.2 pH range Journal of Applied Electrochemistry 16 490–504.CrossRefGoogle Scholar
Virtanen, S. Schmuki, P. Davenport, A.J. and Vitus, C. M., 1997 Dissolution of thin iron oxide films used as models for iron passive films studied by in situ X-ray absorption near-edge spectroscopy Journal of the Electrochemical Society 144 198–204.CrossRefGoogle Scholar
Wei, J. Furrer, G. Kaufmann, S. and Schulin, R., 2001 Influence of clay minerals on the hydrolysis of carbamate pesticides Environmental Science & Technology 35 2226–2232.CrossRefGoogle ScholarPubMed
Zen, J.-M. Jeng, S.-H. and Chen, H.-J., 1996 Catalysis of the electroreduction of hydrogen peroxide by nontronite clay coatings on glassy carbon electrodes Journal of Electroanalytical Chemistry 408 157–163.CrossRefGoogle Scholar