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Polarized ATR-FTIR investigation of Fe reduction in the Uley nontronites

Published online by Cambridge University Press:  01 January 2024

Bryan R. Bzdek  and
Molly M. McGuire
Bryan R. Bzdek
Affiliation:
Department of Chemistry, Bucknell University, Lewisburg, PA 17837, USA
Molly M. McGuire*
Affiliation:
Department of Chemistry, Bucknell University, Lewisburg, PA 17837, USA
*
* E-mail address of corresponding author: mmcguire@bucknell.edu
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Abstract

Reduction of structural Fe in smectites affects the surface chemical behavior of the clay, but the underlying mechanism and changes in clay structure are still in need of investigation, particularly with respect to changes in the tetrahedral sheet. The purpose of this study was to probe changes in the tetrahedral sheet that occur when structural Fe is reduced in the Uley nontronites, NAu-1 and NAu-2, using polarized attenuated total internal reflection Fourier-transform infrared spectroscopy. Despite the differences in their structures — NAu-2 has tetrahedral Fe3+ while NAu-1 does not — the changes observed in the Si-O stretching region were quite similar. Reduction results in a shift of the in-plane Si-O stretching modes to lower frequencies, while the out-of-plane Si-O stretch shifts to higher frequencies. The magnitude of these shifts is greater in NAu-2 than in NAu-1, but the crystallinity of the tetrahedral silicate sheet of NAu-2 is preserved upon reduction. In both nontronites, the orientation of the out-of-plane Si-O bond changes and becomes completely perpendicular to the basal (001) surface of the clay, indicating the formation of trioctahedral domains wherein the individual tetrahedra reorient relative to the plane of the clay layer.

Keywords

ATR-FTIRInfrared SpectroscopyNAu-1NAu-2NontroniteReduction
Type
Article
Information
Clays and Clay Minerals , Volume 57 , Issue 2 , April 2009 , pp. 227 - 233
Copyright
Copyright © The Clay Minerals Society 2009

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References

Cardile, C.M., 1989 Tetrahedral iron in smectite: A critical comment Clays and Clay Minerals 37 185–188 10.1346/CCMN.1989.0370211.CrossRefGoogle Scholar
Cervini-Silva, J. Wu, J. Larson, R.A. and Stucki, J.W., 2000 Transformation of chloropicrin in the presence of iron-bearing clay minerals Environmental Science and Technology 34 915–917 10.1021/es990900j.CrossRefGoogle Scholar
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 10.1002/etc.5620220511.Google ScholarPubMed
Drits, V.A. and Manceau, A., 2000 A model for the mechanism of Fe3+ to Fe2+ reduction in dioctahedral smectites Clays Clay Minerals 48 185–195 10.1346/CCMN.2000.0480204.CrossRefGoogle Scholar
Eisner, M. Schwarzenbach, R.P. and Haderlein, S.B., 2004 Reactivity of Fe(II)-bearing minerals toward reductive transformation of organic contaminants Environmental Science and Technology 38 799–807 10.1021/es0345569.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
Fialips, C.-I. Huo, D. Yan, L. Wu, J. and Stucki, J.W., 2002 Infrared 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 Fe oxidation state on the IR spectra of Garfield nontronite American Mineralogist 87 630–641 10.2138/am-2002-5-605.CrossRefGoogle Scholar
Frost, R.L. Kloprogge, J.T. and Ding, Z., 2002 The Garfield and Uley nontronites — an infrared spectroscopic comparison Spectrochimica Acta Part A 58 1881–1894 10.1016/S1386-1425(01)00638-2.CrossRefGoogle ScholarPubMed
Gates, W.P. Slade, P.G. Manceau, A. and Lanson, B., 2002 Site occupancies by iron in nontronites Clays and Clay Minerals 50 223–239 10.1346/000986002760832829.CrossRefGoogle Scholar
Hofstetter, T.B. Neumann, A. and Schwarzenbach, R.P., 2006 Reduction of nitroaromoatic compounds by Fe(II) species associated with iron-rich smectites Environmental Science and Technology 40 235–242 10.1021/es0515147.CrossRefGoogle ScholarPubMed
Jaisi, D.P. Kukkadapu, R.K. Eberl, D.D. and Dong, H., 2005 Control of Fe(III) site occupancy on the rate and extent of microbial reduction of Fe(III) in nontronite Geochimica et Cosmochimica Acta 69 5429–5440 10.1016/j.gca.2005.07.008.CrossRefGoogle Scholar
Johnston, C.T. and Premachandra, G.S., 2001 Polarized ATR-FTIR study of smectite in aqueous suspension Langmuir 17 3712–3718 10.1021/la010184a.CrossRefGoogle Scholar
Keeling, J.L. Raven, M.D. and Gates, W.P., 2000 Geology and characterization of two hydrothermal nontronites from weathered metamorphic rocks at the Uley Graphite Mine, South Australia Clays and Clay Minerals 48 537–548 10.1346/CCMN.2000.0480506.CrossRefGoogle Scholar
Kloprogge, J.T. Frost, R.L. and Kloprogge, J.T., 2005 Infrared emission spectroscopy of clay minerals Application of Vibrational Spectroscopy to Clay Minerals and Layered Double Hydroxides Boulder, Colorado, USA The Clay Minerals Society 99–124.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
Komadel, P. Madejová, J. and Stucki, J.W., 1995 Reduction and reoxidation of nontronite: Questions of reversability Clays and Clay Minerals 43 105–110 10.1346/CCMN.1995.0430112.CrossRefGoogle Scholar
Lee, J.H. and Guggenheim, S., 1981 Single crystal X-ray refinement of pyrophyllite-1Tc American Mineralogist 66 350–357.Google Scholar
Lee, K. Kostka, J.E. and Stucki, J.W., 2006 Comparisons of structural Fe reduction in smectites by bacteria and dithionite: An infrared spectroscopic study Clays and Clay Minerals 54 195–208 10.1346/CCMN.2006.0540205.CrossRefGoogle Scholar
Madejová, J., 2003 FTIR techniques in clay mineral studies Vibrational Spectroscopy 31 1–10 10.1016/S0924-2031(02)00065-6.CrossRefGoogle Scholar
Manceau, A. Drits, V.A. Lanson, B. Chateigner, J. Wu, J. Huo, D. Gates, W.P. and Stucki, J.W., 2000 Oxidation-reduction mechanism of iron in dioctahedral smectites: II. Crystal chemistry of reduced Garfield nontronite American Mineralogist 85 153–172 10.2138/am-2000-0115.CrossRefGoogle Scholar
Merola, R.B. Fournier, E.D. and McGuire, M.M., 2007 Spectroscopic investigations of Fe2+ complexation on nontronite clay Langmuir 23 1223–1226 10.1021/la062467e.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 and Technology 35 2244–2251 10.1021/es001578b.CrossRefGoogle ScholarPubMed
Ribeiro, F.R. Lee, K. Stucki, J.W. Fabris, J.D. and Pecchio, M., 2004 Effects of redox reactions on the structure of Garfield nontronite: A Mössbauer spectroscopic study Applied Mineralogy, Developments in Science and Technology Sao Paulo, Brazil ICAM 467–470.Google Scholar
Ribeiro, F.R. Stucki, J.W. Larson, R.A. Marley, K.A. Komadel, P. Fabris, J.D., Pecchio, M. Andrade, F.R.D. D’Agostino, L.Z. Kahn, H. Sant’Agostino, L.M. and Tassinari, M.M.M.L., 2004 Degradation of oxamyl by redox-modified smectites: Effects of pH, layer charge, and extent of Fe reduction Applied Mineralogy, Developments in Science and Technology Sao Paulo, Brazil ICAM 471–474.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
Vaniman, D. (2001) Standard operating procedure for clay mineral and zeolite separation. Los Alamos National Laboratory, SOP-09.05.Google Scholar
Xu, J.C. Stucki, J.W. Wu, J. Kostka, J.E. and Sims, G.K., 2001 Fate of atrazine and alachlor in redox-treated ferruginous smectite Environmental Toxicology and Chemistry 20 2717–2724 10.1002/etc.5620201210.Google ScholarPubMed
Yan, L.B. and Bailey, G.W., 2001 Sorption and abiotic redox transformation of nitrobenzene at the smectite-water interface Journal of Colloid and Interface Science 241 142–153 10.1006/jcis.2001.7735.CrossRefGoogle ScholarPubMed
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