Hostname: page-component-76fb5796d-22dnz Total loading time: 0 Render date: 2024-04-25T12:13:06.625Z Has data issue: false hasContentIssue false
  • English
  • Français

Crystallographic Site Distribution and Redox Activity of Fe in Nontronites Determined by Optical Spectroscopy

Published online by Cambridge University Press:  01 January 2024

Rose B. Merola  and
Molly M. McGuire
Rose B. Merola
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
Get access Rights & Permissions [Opens in a new window]

Abstract

Optical absorption spectroscopy has the potential to uncover many characteristics of Fe-bearing, redox-active smectites that have heretofore been hidden. The purpose of this study was to exploit this technique to reveal the temperature dependence of the spectra and to characterize the behavior of octahedral and tetrahedral Fe(III) under various stages of reduction. The Uley nontronites, NAu-1 and NAu-2, were compared using optical spectroscopy, which probed the crystallographic-site distribution of Fe in the clay structures as well as the resulting differences in the reduction process in the two minerals. All of the major differences in the spectra of the two minerals in the wavelength range 450–950 nm are due to the presence of a significant amount of tetrahedral Fe(III) in NAu-2. In situ observation of the optical spectra of NAu-1 suspensions as a function of the degree of reduction reveals a steady increase in the dominant intervalence charge transfer (IVCT) band and the resulting blue-green color as the Fe(II) content of the octahedral sheet increases. Although the spectrum of NAu-2 at ∼50% reduction looks nearly identical to the spectrum of NAu-1 at a similar state of reduction, the spectra corresponding to the initial stages of reduction are quite different. Stepwise reduction of NAu-2 causes a rapid decrease in the absorbance features due to crystal-field transitions of tetrahedral Fe(III) before the IVCT band appears, suggesting that tetrahedral Fe(III) is preferentially reduced before the octahedral Fe(III). The intensity of the absorbance features due to tetrahedral Fe(III) also exhibit an inverse temperature dependence, suggesting that they are enhanced due to exchange-coupling with Fe(III) ions in neighboring sites. Spectra of NAu-1 at liquid nitrogen temperature, therefore, allowed the identification of a small amount of tetrahedral Fe(III) in NAu-1 that had not been noted previously.

Keywords

NAu-1NAu-2NontronitesOptical SpectraReductionTetrahedral Fe(III)
Type
Research Article
Information
Clays and Clay Minerals , Volume 57 , Issue 6 , December 2009 , pp. 771 - 778
Copyright
Copyright © The Clay Minerals Society 2009

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Anderson, W.L. Stucki, J.W., Mortland, M.M. Farmer, V.C., 1979 Effect of structural Fe2+ on visible absorption spectra of nontronite suspensions Proceedings of the VI International Clay Conference Amsterdam Elsevier 75–83.Google Scholar
Boparai, H.K. Shea, P.J. Comfort, S.D. and Snow, D.D., 2006 Dechlorinating chloroacetanilide herbicides by dithionite-treated aquifer sediment and surface soil Environmental Science & Technology 40 3043–3049 10.1021/es051915m.CrossRefGoogle ScholarPubMed
Burns, R.G., 1981 Intervalence transitions in mixed-valence minerals of iron and titanium Annual Reviews in Earth and Planetary Science 9 345–383 10.1146/annurev.ea.09.050181.002021.CrossRefGoogle Scholar
Burns, R.G., 1993 Mineralogical Applications of Crystal Field Theory Cambridge, UK Cambridge University Press 10.1017/CBO9780511524899.CrossRefGoogle Scholar
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 & Technology 34 915–917 10.1021/es990900j.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 10.1021/es0015592.CrossRefGoogle 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 10.1002/etc.5620220511.Google ScholarPubMed
Eisner, M. Schwarzenbach, R.P. and Haderlein, S.B., 2004 Reactivity of Fe(II)-bearing minerals toward reductive transformation of organic contaminants Environmental Science & Technology 38 799–807 10.1021/es0345569.CrossRefGoogle Scholar
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. Schwarzenbach, R.P. and Haderlein, S.B., 2003 Reactivity of Fe(II) species associated with clay minerals Environmental Science & Technology 37 519–528 10.1021/es025955r.CrossRefGoogle ScholarPubMed
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 & 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
Jaisi, D.P. Dong, H. and Liu, C., 2007 Kinetic analysis of microbial reduction of Fe(III) in nontronite Environmental Science & Technology 41 2437–2444 10.1021/es0619399.CrossRefGoogle ScholarPubMed
Jung, B. and Batchelor, B., 2007 Influence of iron-bearing phyllosilicates on the dechlorination kinetics of 1,1,1-trichloroethane in Fe(II)/cement slurries Chemosphere 68 1254–1261 10.1016/j.chemosphere.2007.01.057.CrossRefGoogle Scholar
Karickhoff, S.W. and Bailey, G.W., 1973 Optical absorption spectra of clay minerals Clays and Clay Minerals 21 59–70 10.1346/CCMN.1973.0210109.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
Kim, J. Furukawa, Y. Dong, H. and Newell, S.W., 2005 The effect of microbial Fe(III) reduction on smectite flocculation Clays and Clay Minerals 53 572–579 10.1346/CCMN.2005.0530603.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. Wu, J. Nealson, K.H. and Stucki, J.W., 1999 The impact of structural Fe(III) reduction by bacteria on the surface chemistry of smectite clay minerals Geochimica et Cosmochimica Acta 63 3705–3713 10.1016/S0016-7037(99)00199-4.CrossRefGoogle Scholar
Kriegman-King, M.R. and Reinhard, M., 1992 Transformation of carbon tetrachloride in the presence of sulfide, biotite and vermiculite Environmental Science & Technology 26 2198–2206 10.1021/es00035a019.CrossRefGoogle Scholar
Kubelka, P. and Munk, F., 1931 Ein beitrig zur optik der Farbanstriche Zeitschrift fur technische Physik 12 593–620.Google Scholar
Lear, P.R. and Stucki, J.W., 1987 Intervalence electron transfer and magnetic exchange in reduced nontronite Clays and Clay Minerals 35 373–378 10.1346/CCMN.1987.0350507.CrossRefGoogle Scholar
Li, Y. Vali, H. Sears, S.K. Yang, J. Deng, B. and Zhang, C.L., 2004 Iron reduction and alteration of nontronite NAu-2 by a sulfate-reducing bacterium Geochimica et Cosmochimica Acta 68 3251–3260 10.1016/j.gca.2004.03.004.CrossRefGoogle Scholar
Luca, V. and Cardile, C.M., 1989 Improved detection of tetrahedral Fe3+ in nontronite SWa-1 by Mössbauer spectroscopy Clay Minerals 24 555–559 10.1180/claymin.1989.024.3.09.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
Neumann, A. Hofstetter, T.B. Luessi, M. Cirpka, O.A. Petit, S. and Schwarzenbach, R.P., 2008 Assessing the redox reactivity of structural iron in smectites using nitroaromatic compounds as kinetic probes Environmental Science & Technology 42 8381–8387 10.1021/es801840x.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 10.1021/es001578b.CrossRefGoogle ScholarPubMed
O’Reilly, S.E. Watkins, J. and Furukawa, Y., 2005 Secondary mineral formation associated with respiration of nontronite, NAu-1 by iron reducing bacteria Geochemical Transactions 6 67–76 10.1186/1467-4866-6-67.CrossRefGoogle ScholarPubMed
Ribeiro, F.R. Stucki, J.W. Larson, R.A. Marley, K.A. Komadel, P. Fabris, J.D. and Pecchio, M., 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
Rossman, G.R. and Hawthorne, F.C., 1988 Optical spectroscopy Spectroscopic Methods in Mineralogy and Geology Washington, D.C. Mineralogical Society of America 207–254 10.1515/9781501508974-009.CrossRefGoogle Scholar
Scheinost, A.C. Chavernas, A. Barrón, V. and Torrent, J., 1998 Use and limitations of second-derivative diffuse reflectance spectroscopy in the visible to near-infrared range to identify and quantify Fe oxide minerals in soils Clays and Clay Minerals 46 528–536 10.1346/CCMN.1998.0460506.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 10.1021/es990931e.CrossRefGoogle Scholar
Sherman, D.M., 1985 The electronic structures of Fe3+ coordination sites in iron oxides; applications to spectra, bonding, and magnetism Physics and Chemistry of Minerals 12 161–175 10.1007/BF00308210.CrossRefGoogle Scholar
Sherman, D.M. and Vergo, N., 1988 Optical (diffuse reflectance) and Mössbauer study of nontronite and related Fe-bearing smectites American Mineralogist 73 1346–1354.Google Scholar
Smith, G. Strens, R.G.J. and Strens, R.G.J., 1976 Intervalence-transfer absorption in some silicate, oxide and phosphate minerals The Physics of Minerals and Rocks New York Wiley 583–612.Google Scholar
Sorensen, K.C. Stucki, J.W. Warner, R.E. and Plewa, M.J., 2004 Alteration of mammalian-cell toxicity of pesticides by structural iron(II) in ferruginous smectite Environmental Science & Technology 38 4383–4389 10.1021/es035151r.CrossRefGoogle ScholarPubMed
Stucki, J.W. Lee, K. Zhang, L. and Larson, R.A., 2002 Effects of iron oxidation state on the surface and structural properties of smectites Pure and Applied Chemistry 74 2145–2158 10.1351/pac200274112145.CrossRefGoogle Scholar
Taran, M.N. Langer, K. and Platonov, A.N., 1996 Pressure- and temperature-effects on exchange-coupled-pair bands in electronic spectra of some oxygen-based iron-bearing minerals Physics and Chemistry of Minerals 23 230–236 10.1007/BF00207754.CrossRefGoogle Scholar
Tor, J.M. Xu, C.F. Stucki, J.W. Wander, M.M. and Sims, G.K., 2000 Trifluralin degradation under microbially induced nitrate and Fe(III) reducing conditions Environmental Science & Technology 34 3148–3152 10.1021/es9912473.CrossRefGoogle Scholar
Vaniman, D., 2001 Standard operating procedure for clay mineral and zeolite separation NM, USA Los Alamos National Laboratory SOP-09.05.Google Scholar
Wu, J., Xia, Y., and Stucki, J.W. (2004) Color temperature indicator. US Patent No. 6,712,996.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
Zhang, G. Dong, H. Kim, J. and Eberl, D.D., 2007 Microbial reduction of structural Fe3+ in nontronite by a thermophilic bacterium and its role in promoting the smectite to illite reaction American Mineralogist 92 1411–1419 10.2138/am.2007.2498.CrossRefGoogle Scholar