Hostname: page-component-cd9895bd7-mkpzs Total loading time: 0 Render date: 2024-12-26T03:28:09.513Z Has data issue: false hasContentIssue false
  • English
  • Français

Comparisons of Structural Fe Reduction in Smectites by Bacteria and Dithionite: An Infrared Spectroscopic Study

Published online by Cambridge University Press:  01 January 2024

Kangwon Lee ,
Joel E. Kostka  and
Joseph W. Stucki
Kangwon Lee
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois at Urbana-Champaign, Urbana, Illinois, USA
Joel E. Kostka
Affiliation:
Department of Oceanography, Florida State University, Talahassee, Florida, USA
Joseph W. Stucki*
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois at Urbana-Champaign, Urbana, Illinois, USA
*
*E-mail address of corresponding author: [email protected]
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

The reduction of structural Fe in smectite is mediated either abiotically, by reaction with dithionite, or biotically, by Fe-reducing bacteria. The effects of abiotic reduction on clay-surface chemistry are much better known than the effects of biotic reduction. Since bacteria are probably the principal agent for mediating redox processes in natural soils and sediments, further study is needed to ascertain the differences between biotic and abiotic reduction processes. The purpose of the present study was to compare the effects of dithionite (abiotic) and bacteria (biotic) reduction of structural Fe in smectites on the clay structure as observed by infrared spectroscopy. Three reference smectites, namely, Garfield nontronite, ferruginous smectite (SWa-1), and Upton, Wyoming, montmorillonite, were reduced to similar levels by either Shewanella oneidensis or by pH-buffered sodium dithionite. Each sample was then analyzed by Fourier transform infrared spectroscopy (FTIR). Parallel samples were reoxidized by bubbling O2 gas through the reduced suspension at room temperature prior to FTIR analysis. Redox states were quantified by chemical analysis, using 1, 10-phenanthroline. The reduction level achieved by dithionite was controlled to approximate that of the bacterial reduction treatment so that valid comparisons could be made between the two treatments. Bacterial reduction was achieved by incubating the Na-saturated smectites with S. oneidensis strain MR-1 in a minimal medium including 20 mM lactate. After redox treatment, the clay was washed four times with deoxygenated 5 mM NaCl. The sample was then prepared either as a self-supporting film for OH-stretching and deformation bands or as a deposit on ZnSe windows for Si-O stretching bands and placed inside a controlled atmosphere cell also fitted with ZnSe windows. The spectra from bacteria-treated samples were compared with dithionite-treated samples having a similar Fe(II) content. The changes observed in all three spectral regions (OH stretching, M2-O-H deformation, and Si-O stretching) for bacteria-reduced smectite were similar to results obtained at a comparable level of reduction by dithionite. In general, the shift of the structural OH vibration and the Si-O vibration, and the loss of intensity of OH groups, indicate that the bonding and/or symmetry properties in the octahedral and tetrahedral sheets changes as Fe(III) reduces to Fe(II). Upon reoxidation, peak positions and intensities of the reduced smectites were largely restored to the unaltered condition with some minor exceptions. These observations are interpreted to mean that bacterial reduction of Fe modifies the crystal structures of Fe-bearing smectites, but the overall effects are modest and of about the same extent as dithionite at similar levels of reduction. No extensive changes in clay structure were observed under conditions present in our model system.

Keywords

CyclesFerruginous SmectiteGarfieldMontmorilloniteNontroniteOxidationRedoxReductionShewanellaUpton
Type
Research Article
Information
Clays and Clay Minerals , Volume 54 , Issue 2 , April 2006 , pp. 195 - 208
Copyright
Copyright © 2006, The Clay Minerals Society

References

Angell, C.L. and Schaffer, P.C., (1965) Infrared spectroscopic investigations of zeolites and adsorbed molecules. I. Structural OH groups Journal of Physical Chemistry 69 3463–3470 10.1021/j100894a037.CrossRefGoogle Scholar
Benning, L.G. Phoenix, V.R. Yee, N. and Tobin, M.J., (2004) Molecular characterization of cyanobacterial silicification using synchrotron infrared micro-spectroscopy Geochimica et Cosmochimica Acta 68 729–741 10.1016/S0016-7037(03)00489-7.CrossRefGoogle Scholar
Boivin, P. Favre, F. Hammecker, C. Maeght, J.L. Delariviere, J. Poussin, J.C. and Wopereis, M.C.S., (2002) Processes driving soil solution chemistry in a flooded rice-cropped vertisol: analysis of long-time monitoring data Geoderma 110 87–107 10.1016/S0016-7061(02)00226-4.CrossRefGoogle Scholar
Choo-Smith, L.-P. Maquelin, K. Van Vreeswijk, T. Brunning, H.A. Puppeis, G.J. Ngo Thi, N.A. Kirschner, C. Naumann, D. Ami, D. Villa, A.M. Orsini, F. Doglia, S.M. Lamfarraj, H. and Sockalingum, G.D., (2001) Investigating microbial (mciro)colony heterogeneity by vibrational spectroscopy Applied and Environmental Microbiology 67 1461–1469 10.1128/AEM.67.4.1461-1469.2001.CrossRefGoogle Scholar
Dong, H. Kostka, J.E. and Kim, J., (2003) Microscopic evidence for microbial dissolution of smectite Clays and Clay Minerals 51 502–512 10.1346/CCMN.2003.0510504.CrossRefGoogle Scholar
Farmer, V.C., (1974) Infrared Spectra of Minerals London The Mineralogical Society 10.1180/mono-4 524 pp.CrossRefGoogle Scholar
Farmer, V.C. and Russell, J.D., (1964) The infra-red spectra of layer silicates Spectrochimica Acta 20 1149–1173 10.1016/0371-1951(64)80165-X.CrossRefGoogle Scholar
Favre, F. Tessier, D. Abdelmoula, M. Genin, J.M. Gates, W.P. and Boivin, P., (2002) Iron reduction and changes in cation exchange capacity in intermittently waterlogged soil European Journal of Soil Science 53 175–183 10.1046/j.1365-2389.2002.00423.x.CrossRefGoogle Scholar
Favre, F. Jaunet, A.M. Pernes, M. Badraoui, M. Boivin, P. and Tessier, D., (2004) Changes in clay organization due to structural iron reduction in a flooded vertisol Clay Minerals 39 123–134 10.1180/0009855043920125.CrossRefGoogle Scholar
Fialips, C.-I. Huo, D. Yan, L. Wu, J. and Stucki, J.W., (2002) Infared study of reduced and reduced-reoxidized ferruginous smectite Clays and Clay Minerals 50 455–469 10.1346/000986002320514181.CrossRefGoogle Scholar
Fialips, C.-I. Huo, D. Yan, L. Wu, J. and Stucki, J.W., (2002) Effect of iron oxidation state on the IR spectra of Garfield nontronite American Mineralogist 87 630–641 10.2138/am-2002-5-605.CrossRefGoogle Scholar
Gates, W.P. and Kloprogge, J.T., (2005) Infrared spectroscopy and the chemistry of dioctahedral smectites The Application of Vibrational Spectroscopy to Clay Minerals and Layered Double Hydroxides Aurora, CO The Clay Minerals Society 125–168.Google Scholar
Gates, W.P. Stucki, J.W. and Kirkpatrick, R.J., (1996) Structural properties of reduced Upton montmorillonite Physics and Chemistry of Minerals 23 535–541 10.1007/BF00242003.CrossRefGoogle Scholar
Goodman, B.A. Russell, J.D. Fraser, A.R. and Woodhams, F.D., (1976) A Mössbauer and I.R. spectroscopic study of the structure of nontronite Clays and Clay Minerals 24 53–59 10.1346/CCMN.1976.0240201.CrossRefGoogle Scholar
Huo, D., (1997) Infrared study of oxidized and reduced nontronite and Ca-K competition in the interlayer Urbana University of Illinois PhD Dissertation.Google Scholar
Huo, D. Fialips, C.-I. and Stucki, J.W., (2004) Effects of structural Fe oxidation state on physical-chemical properties of smectites: evidence from infrared spectroscopy Japanese Society of Soil Physics 96 3–10.Google Scholar
Kim, J. Furukawa, Y. Daulton, T.E. Lavoie, D. and Newell, S.W., (2003) Characterization of microbially Fe(III) reduced nontronite: environmental cell-transmission electron microscopy study Clays and Clay Minerals 51 382–389 10.1346/CCMN.2003.0510403.CrossRefGoogle Scholar
Kim, J. Dong, H. Seabaugh, J. Newell, S.W. and Eberl, D.D., (2004) Role of microbes in the smectite to illite reaction Science 303 830–832 10.1126/science.1093245.CrossRefGoogle ScholarPubMed
Kirschner, C. Maquelin, K. Pina, P. Ngo Thi, N.A. Choo-Smith, L.-P. Sockalingum, G.D. Sandt, C. Ami, D. Orsini, F. Doglia, S.M. Allouch, P. Mainfait, M. Puppels, G.J. and Naumann, D., (2001) Classification and identification of enterococci: a comparative phenotypic, genotypic and vibrational spectroscopic study Journal of Clinical Microbiology 39 1763–1770 10.1128/JCM.39.5.1763-1770.2001.CrossRefGoogle ScholarPubMed
Komadel, P. and Stucki, J.W., (1988) Quantitative assay of minerals for Fe2+ and Fe3+ using 1,10-phenanthroline: III. A rapid photochemical method Clays and Clay Minerals 36 379–381 10.1346/CCMN.1988.0360415.CrossRefGoogle Scholar
Komadel, P. Lear, P.R. and Stucki, J.W., (1990) Reduction and reoxidation of nontronite: Extent of reduction and reaction rates Clays and Clay Minerals 38 203–208 10.1346/CCMN.1990.0380212.CrossRefGoogle Scholar
Kostka, J.E., (2002) Growth of iron(III)-reducing bacteria on clay minerals as the sole electron acceptor and comparison of growth yields on a variety of oxidized iron forms Applied and Environmental Microbiology 68 6256–6262 10.1128/AEM.68.12.6256-6262.2002.CrossRefGoogle ScholarPubMed
Kostka, J. Nealson, K.H., Burlage, R.S. Atlas, R. Stahl, D. Geesey, G. and Sayler, G., (1998) Isolation, cultivation and characterizations of iron- and manganese-reducing bacteria Techniques in Microbial Ecology New York Oxford University Press 58–78.Google Scholar
Kostka, J.E. Stucki, J.W. Nealson, K.H. and Wu, J., (1996) Reduction of structural Fe(III) in smectite by a pure culture of the Fe-reducing bacterium Shewanella putrefaciens strain MR-1 Clays and Clay Minerals 44 522–529 10.1346/CCMN.1996.0440411.CrossRefGoogle Scholar
Kostka, J.E. Haefele, E. Viehweger, R. and Stucki, J.W., (1999) Respiration and dissolution of Fe(III)-containing clay minerals by bacteria Environmental Science and Technology 33 3127–3133 10.1021/es990021x.CrossRefGoogle Scholar
Madejová, J. Komadel, P. and Čičel, B., (1994) Infrared study of octahedral site populations in smectites Clay Minerals 29 319–326 10.1180/claymin.1994.029.3.03.CrossRefGoogle Scholar
Manceau, A. Lanson, B. Drits, V.A. Chateigner, D. Gates, W.P. Wu, J. Huo, D. and Stucki, J.W., (2000) Oxidation-reduction mechanism of iron in dioctahedral smectites. 1. Crystal chemistry of oxidized reference nontronites American Mineralogist 85 133–152 10.2138/am-2000-0114.CrossRefGoogle Scholar
Manceau, A. Lanson, B. Drits, V.A. Chateigner, D. Wu, J. Huo, D. Gates, W.P. and Stucki, J.W., (2000) Oxidation-reduction mechanism of iron in dioctahedral smectites. 2. Structural chemistry of reduced Garfield nontronite American Mineralogist 85 153–172 10.2138/am-2000-0115.CrossRefGoogle Scholar
Maquelin, L. Kirschner, C. Choo-Smith, L.-P. van den Braak, N. Endtz, H.P.h. Naumann, D. and Puppels, G.J., (2002) Identification of medically relevant microorganisms by vibrational spectroscopy Journal of Microbiological Methods 51 255–271 10.1016/S0167-7012(02)00127-6.CrossRefGoogle ScholarPubMed
Myers, C.R. and Nealson, K.H., (1988) Bacterial manganese reduction and growth with manganese oxide as the sole electron acceptor Science 240 1319–1321 10.1126/science.240.4857.1319.CrossRefGoogle ScholarPubMed
Nealson, K.H. and Saffarini, D., (1994) Iron and magnanese in anaerobic respiration: Environmental significance, physiology and regulation Annual Reviews in Microbiology 48 311–343 10.1146/annurev.mi.48.100194.001523.CrossRefGoogle Scholar
Robert, J.-J. and Kodama, H., (1988) Generalization of the correlations between hydroxyl-stretching wavenumbers and composition of micas in the system K2O-MgO-Al2O3-SiO2-H2O: a single model for trioctahedral and dioctahedral micas American Journal of Science 288A 196–212.Google Scholar
Russell, J.D. Farmer, V.C. and Velde, B., (1970) Replacement of OH by OD in layer silicates, and identification of the vibrations of these groups in infrared spectra Mineralogical Magazine 37 869–879 10.1180/minmag.1970.037.292.01.CrossRefGoogle Scholar
Russell, J.D. Goodman, B.A. and Fraser, A.R., (1979) Infrared and Mössbauer studies of reduced nontronites Clays and Clay Minerals 27 63–71 10.1346/CCMN.1979.0270108.CrossRefGoogle Scholar
Scott, J.H. and Nealson, K.H., (1994) A biochemical study of the intermediary carbon metabolism of Shewanella putrefaciens Journal of Bacteriology 176 3408–3411 10.1128/jb.176.11.3408-3411.1994.CrossRefGoogle ScholarPubMed
Serratosa, J.M., (1960) Dehydration studies by infrared spectrosopy American Mineralogist 45 1101–1104.Google Scholar
Stubican, V. and Roy, R., (1961) Isomorphous substitution and infrared spectra of the layer silicates American Mineralogist 46 32–51.Google Scholar
Stucki, J.W. and Getty, P.J., (1986) Microbial reduction of iron in nontronite Agronomy Abstracts 1986 279.Google Scholar
Stucki, J.W. and Roth, C.B., (1976) Interpretation of infrared spectra of oxidized and reduced nontronite Clays and Clay Minerals 24 293–296 10.1346/CCMN.1976.0240604.CrossRefGoogle Scholar
Stucki, J.W. and Roth, C.B., (1977) Oxidation-reduction mechanism for structural iron in nontronite Soil Science Society of America Journal 41 808–814 10.2136/sssaj1977.03615995004100040041x.CrossRefGoogle Scholar
Stucki, J.W. Komadel, P. and Wilkinson, H.T., (1987) Microbial reduction of structural iron(III) in smectites Soil Science Society of America Journal 51 1663–1665 10.2136/sssaj1987.03615995005100060047x.CrossRefGoogle Scholar
Vantelon, D. Pelletier, M. Michot, L.J. Barres, O. and Thomas, F., (2001) Fe, Mg, and Al distribution in the octahedral sheet of montmorillonites. An infared study in the OH-bending region Clay Minerals 36 369–379 10.1180/000985501750539463.CrossRefGoogle Scholar
Wu, J. Roth, C.B. and Low, P.F., (1988) Biological reduction of structural Fe in sodium-nontronite Soil Science Society of America Journal 52 295–296 10.2136/sssaj1988.03615995005200010054x.CrossRefGoogle Scholar
Yan, L. and Stucki, J.W., (1999) Effects of structural Fe oxidation state on the coupling of interlayer water and structural Si-O stretching vibrations in montmorillonite Langmuir 15 4648–4657 10.1021/la9809022.CrossRefGoogle Scholar
Yan, L. and Stucki, J.W., (2000) Structural perturbations in the solid-water interface of redox transformed nontronite Journal of Colloid and Interface Science 225 429–439 10.1006/jcis.2000.6794.CrossRefGoogle ScholarPubMed
Yan, L. Low, P.F. and Roth, C.B., (1996) Enthalpy changes accompanying the collapse of montmorillonite layers and the penetration of electrolyte into interlayer space Journal of Colloid and Interface Science 182 417–424 10.1006/jcis.1996.0482.CrossRefGoogle Scholar
Yan, L. Low, P.F. and Roth, C.B., (1996) Swelling pressure of montmorillonite layers versus H-O-H bending frequency of the interlayer water Clays and Clay Minerals 44 749–765 10.1346/CCMN.1996.0440605.CrossRefGoogle Scholar
Yan, L. Roth, C.B. and Low, P.F., (1996) Changes in the Si-O vibrations of smectite layers accompanying the sorption of interlayer water Langmuir 12 4421–4429 10.1021/la960119e.CrossRefGoogle Scholar
Yan, L. Roth, C.B. and Low, P.F., (1996) Effects of monovalent, exchangeable cations and electrolytes on the infrared vibrations of smectite layers and interlayer water Journal of Colloid and Interface Science 184 663–670 10.1006/jcis.1996.0664.CrossRefGoogle ScholarPubMed