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Synthesis of nontronite and other Fe-rich smectites: a critical review

  • S. Petit (a1), F. Baron (a2) and A. Decarreau (a1)


The synthesis of clay minerals has been studied for decades in an attempt to better understand their formation in natural environments and more recently to obtain clay minerals with controlled compositions and properties. Even though nontronite has been synthesized successfully since 1935, the process is not a straightforward and has been poorly documented. In the present review concerning the synthesis of nontronite and other Fe-rich smectites, the experiments attempted in the past are discussed critically in light of the most recent data. Most notably, the application of relationships established recently, thanks to synthetic smectitic series, have allowed us to refine the chemical compositions of some nontronites synthesized previously.


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Andrieux, P. & Petit, S. (2010) Hydrothermal synthesis of dioctahedral smectites: The Al-Fe chemical series. Part I: Influence of experimental conditions. Applied Clay Science, 48, 517.
Baldermann, A., Dohrmann, R., Kaufhold, S., Nickel, C., Leetofsky-Papst, I. & Dietzel, M. (2014) The Fe-Mg-saponite solid solution series: a hydrothermal synthesis study. Clay Minerals, 49, 391415.
Baron, F. (2016) Lefer dans les smectites: une approche par synthese minerale. PhD thesis, Poitiers University, France.
Baron, F., Petit, S., Tertre, E. & Decarreau, A. (2016a) Influence of aqueous Si and Fe speciation on tetrahedral Fe(III) substitutions in nontronites: A clay synthesis approach. Clays and Clay Minerals, 64, 189203.
Baron, F., Pushparaj, S.S.C., Fontaine, C., Sivaiah, M.V., Decarreau, A. & Petit, S. (2016b) Microwave-assisted hydrothermal synthesis of Ni-Mg layered silicate clays. Current Microwave Chemistry, 3, 8589.
Baron, F., Petit, S., Pentrák, M., Decarreau, A. & Stucki, J. (2017) Revisiting the nontronite Mössbauer spectra. American Mineralogist, 102, 15011515.
Berger, G., Meunier, A. & Beaufort, D. (2014) Clay mineral formation on Mars: Chemical constraints and possible contribution of basalt out-gassing. Planetary and Space Science, 95, 25–32.
Bonnin, D., Calas, G., Suquet, H., & Pezerat, H. (1985) Sites occupancy of Fe + in Garfield nontronite: A spectroscopic study. Physics and Chemistry of Minerals, 12, 5564.
Brigatti, M.F., Galán, E. & Theng, B.K.G. (2013) Structure and mineralogy of clay minerals. Smectites. Pp. 42-45 in: Handbook of Clay Sciences, 2nd edition (F. Bergaya & G. Lagaly, editors). Elsevier, Amsterdam.
Caillèlre, S., Hénin, S. & Esquevin, J. (1953) Syntheses ä basse température de phyllites ferriferes. Comptes Rendus Académie Sciences (Paris), 237, 1724–1726.
Caillèlre, S., Hénin, S. & Esquevin, J. (1955) Syntheses ä basse température de quelques minéraux ferriferes (silicates, oxydes). Bulletin Société Française Minéralogie Cristallographie, 78, 227241.
Cardile, C.M. & Johnston, J.H. (1985) Structural studies of nontronites with different iron contents by 57Fe Mössbauer spectroscopy. Clays and Clay Minerals, 33, 295300.
Carter, J., Poulet, F., Bibring I-R, Mangold, N. & Murchie, S. (2013) Hydrous minerals on Mars as seen by the CRISM and OMEGA imaging spectrometers: Updated global view. Journal of Geophysical Research: Planets, 118, 831858.
Carter, J., Loizeau, D., Mangold, N., Poulet, F. & Bibring, J.-P. (2015) Widespread surface weathering on early Mars: A case for a warmer and wetter climate. Icarus, 248, 373382.
Cashion, J.D., Gates, W.P. & Thomson, A. (2008) Mössbauer and IR analysis of iron sites in four ferruginous smectites. Clay Minerals, 43, 8393.
Decarreau, A & Bonnin, D. (1986) Synthesis and crystal-logenesis at low temperature of Fe (III)-smectites by evolution of coprecipitated gels: Experiments in partially reducing conditions. Clay Minerals, 21, 861–877.
Decarreau, A. & Petit, S. (2014) Fe3+/Al3+ partitioning between tetrahedral and octahedral sites in dioctahedral smectites. Clay Minerals, 49, 657665.
Decarreau, A., Bonnin, D., Badaut-Trauth, D., Couty, R. & Kaiser, P. (1987) Synthesis and crystallogenesis of ferric smectite by evolution of Si-Fe coprecipitates in oxidizing conditions. Clay Minerals, 22, 207223.
Decarreau, A., Petit, S., Vieillard Ph. & Dabert, N. (2004) Hydrothermal synthesis of aegirine at 200°C. European Journal of Mineralogy, 16, 85–90.
Decarreau, A., Petit, S., Martin, F., Farges, F., Vieillard, P. & Joussein, E. (2008) Hydrothermal synthesis, between 75 and 150°C, ofhigh charge ferric nontronites. Clays and Clay Minerals, 56, 322337.
Ehlmann, B.L., Berger, G., Mangold, N., Michalski, J.R., Catling, D.C., Ruff, S.W., Chassefiere, E., Niles, P.B., Chevrier V & Poulet, F. (2013) Geochemical con-sequences of widespread clay mineral formation in Mars’ ancient crust. Space Science Reviews, 174, 329364.
Ewell, R.H. & Insley, H. (1935) Hydrothermal synthesis of kaolinite, dickite, beidellite and nontronite. Journal of the National Bureau of Standards, 15, 173186.
Farmer, V.C. (1997) Conversion of ferruginous allophones to ferruginous beidellites at 95°C under alkaline conditions with alternating oxidation and reduction. Clay and Clay Minerals, 45, 591597.
Farmer, Y.C., Krishnamurti, G.S.R. & Huang, P.M. (1991) Synthetic allophone and layer-silicates formation in SiO2-Al2O3-FeO-Fe2O3-MgO-H2O systems at 23 °C and 89°C in a calcareous environment. Clays and Clay Minerals, 39, 561570.
Farmer, Y.C., McHardy, W.J., Elsass, F. & Robert, M. (1994) hk-ordering in aluminous nontronite and saponite synthesized near 90°C: effects of synthesis conditions on nontronite composition and ordering. Clays and Clay Minerals, 42, 180186.
Gates, W.P. (2005) Infrared spectroscopy and the chemistry of dioctahedral smectites. Pp. 125-168 in: The Application of Vibrational Spectroscopy to Clay Minerals and Layered Double Hydroxides (J.T. Kloprogge, editor). CMS Workshop Lectures, 13, The Clay Minerals Society, Aurora, Colorado, USA.
Gaudin, A., Grauby, O., Noack, Y., Decarreau, A. & Petit, S. (2004a) The actual crystal chemistry of ferric smectites from the lateritic nickel ore of Murin Murin (Western Australia). I. XRD and multi-scale chemical approaches. Clay Minerals, 39, 301–315.
Gaudin, A., Petit, S., Rose, J., Martin, F., Decarreau, A., Noack Y & Borscheneck, D. (2004b) The accurate crystal chemistry of ferric smectites from the lateritic nickel ore of Murrin Murrin (Western Australia). II. Spectroscopic (IR and EXAFS) approaches. Clay Minerals, 39, 453467.
Goodman, B.A., Russell, J.D., Fraser, A.D. & Woodhams, F.W.D (1976) A Mössbauer and IR spectroscopic study of the structure of nontronite. Clays Clay Minerals, 24, 5359.
Grauby, O. (1993) Nature et étendue des solutions solides octaedriques argileuses. Approche par Synthese minérale. PhD thesis, Poitiers University, France
Grauby, O., Petit, S., Decarreau, A. & Baronnet, A. (1994) The nontronite-saponite series: an experimental approach. European Journal of Mineralogy, 6, 99112.
Gupta, V.K., Mohan, D. & Saini, V.K. (2006) Studies on the interaction of some azo dyes (naphthol red-J and direct orange) with nontronite mineral. Journal of Colloid and Interface Science, 298, 7986.
Güven, N. (1988) Smectites. Pp. 497-559 in: Hydrous Phyllosilicates (Exclusive of Micas). (S.W. Bailey, editor). Reviews in Mineralogy, 19. Mineralogical Society of America, Washington, D.C.
Hamilton, G. & Furtwängler, W (1951) Synthese von Nontronit. Tschermaks Mineralogishe und Petrographische Mitteilungen, 2, 397—406.
Harder, H. (1976) Nontronite synthesis at low temperature. Chemical Geology, 18, 169180.
Harder, H. (1978) Synthesis of iron layer silicate minerals undernatural conditions. Clays and Clay Minerals, 26, 6572.
Hofstetter, T.B., Neumann, A. & Schwarzenbach, R.P. (2006) Reduction of nitroaromatic compounds by Fe (II) species associated with iron-rich smectites. Environmental Science & Technology, 40, 235–242.
Ilgen, A.G., Foster, A.L. & Trainor, T.P. (2012) Role of structural Fe in nontronite NAu-1 and dissolved Fe(II) in redox transformations of arsenic and antimony. Geochimica et Cosmochimica Acta, 94, 128145.
Jaisi, D.P., Dong, H., Plymale, A.E., Fredrickson, J.K., Zachara, J.M., Heald, S. & Liu, C.(2009) Reduction and long-term immobilization of technetium by Fe(II) associated with clay mineral nontronite. Chemical Geology, 264, 127138.
Kaufhold, S., Stucki, J.W., Finck, N., Steininger, R., Zimina, A., Dohrmann, R., Ufer, K., Pentrák, M. & Pentráková L. (2017) Tetrahedral charge and Fe content in dioctahedral smectites. Clay Minerals, 52, 5165.
Kloprogge, J.T., Komarneni, S. & Amonette, E. (1999) Synthesis of smectite clay minerals: a critical review. Clays and Clay Minerals, 47, 529554.
Kopp, O.C. (1967) Synthesis of grunerite and other phases in the system SiO2-NaOH-Fe-H2O. American Mineralogist, 52, 16811688.
Lajarige, C., Petit, S., Augas, C. & Decarreau, A. (1998) Stabilisation of Fe + ions in synthetic ferroan smectites. Comptes Rendus Académie Sciences Paris, 327, 789794.
Lantenois, S., Beny, J.M., Muller, F. & Champellier, R. (2007) Integration of Fe in natural and synthetic Al-pyrophyllites: an infrared spectroscopic study. Clays and Clay Minerals, 42, 129141.
Li, H., Li, Y., Xiang, L., Huang, Q., QiuJ., Zhang, H., Sivaiah, M.V., Baron, F., Barrault, J., Petit, S. & Valange, S. (2015) Heterogeneous photo-Fenton decolorization of Orange II over Al-pillared Fe-smectite: Response surface approach, degradation pathway, and toxicity evaluation. Journal of Hazardous Materials, 287, 3241.
Liu, R., Xiao, D., Guo, Y., Wang, Z. & Liu, I (2014) A novel photosensitized Fenton reaction catalyzed by sand-wiched iron in synthetic nontronite. RSC Advances, 4, 1295812963.
MacGregor-Ramiasa, M., Abrahamsson, C., Röding, M. & Nydén, M. (2015) Magnetic alignment of nontronite dispersions. Applied Clay Science, 116, 167–174.
Madejova, I, Komadel, P. & Čičel, B. (1994) Infrared study of octahedral site populations in smectites. Clay Minerals, 29, 319326.
Mangold, N., Baratoux, D., Witasse, O., Encrenaz, T. & Sotin, C. (2016) Mars: a small terrestrial planet. The Astronomy and Astrophysics Review, 24, 15.
Meunier, A., Mas, A., Beaufort, D., Patrier, P. & Dudoignon, P. (2008) Clay minerals in basalt-hawaiite rocks from Mururoa atoll, French Polynesia. II. Petrography and geochemistry. Clays and Clay Minerals, 56, 730–750.
Meunier, A., Petit, S., Ehlmann, B.L., Dudoignon, P., Westall, F., Mas, A., El Albani, A. & Ferrage, E. (2012) Magmatic precipitation as a possible origin of Noachian clays on Mars. Nature Geoscience, 5, 739743.
Michot, L.J., Bihannic, I., Maddi, S., Baravian, C., Levitz, P. & Davidson, P. (2008) Sol-gel and isotropic/nematic transitions in aqueous suspensions of natural nontronite clay. Influence of particle anisotropy. 1. features of the I.N transition. Langmuir, 24, 3127–3139.
Michot, L.J., Baravian, C., Bihannic, I., Maddi, S., Moyne, C., Duval, J.F.L., Levitz, P. & Davidson, P. (2009) Solgel and isotropic/nematic transitions in aqueous suspensions of natural nontronite clay. Influence of particle anisotropy. 2. Gel structure and mechanical properties. Langmuir, 25, 3127–3139.
Michot, L.J., Paineau, E., Bihannic, I., Maddi, S., Duval, J.F.L., Baravian, C., Davidson P & Levitz, P. (2013) Isotropic/nematic and sol/gel transitions in aqueous suspensions of size selected nontronite NAu-1. Clay Minerals, 48, 663685.
Milliken, R.E., & Bish, D.L. (2010) Sources and sinks of clay minerals on Mars. Philosophical Magazine, 90, 22932308.
Mizutani, T., Fukushima, Y., Okada, A., Kamigaito, O. & Kobayashi T (1991) Synthesis of 1:1 and 2:1 iron phyllosilicates and characterization of their iron state by Mössbauer spectroscopy. Clay and Clay Minerals, 39, 381386.
Mustard, J.F., Murchie, S.L., Pelkey, S.M., Ehlmann, B.L., Milliken, R.E., Grant, J.A., Bibring 1-P, Poulet, F., Bishop, J., Dobrea, E.N. et al. (2008) Hydrated silicate minerals on Mars observed by the Mars Reconnaissance Orbiter CRISM instrument. Nature, 454, 305309.
Nagase, T., Iwasaki, T., Ebina, T., Hayashi, H., Onodera Y & Chandra Dutta, N. (1999) Hydrothermal synthesis of Fe-montmorillonite in Si-Fe-Mg system. Chemistry Letters, 4, 303304.
Neumann, A., Hofstetter, T.B., Skarpeli-Liati, M. & Schwarzenbach, R.P. (2009) Reduction of polychlori-nated ethanes and carbon tetrachloride by structural Fe(II) in smectites. Environmental Science & Technology, 43, 40824089.
Oyawoye, M.O. & Hirst, D.M. (1964) Occurrence of a montmorillonite mineral in the Nigerian younger granites at Ropp, Plateau Province, northern Nigeria. Clay Minerals, 5, 427433.
Paineau, E., Philippe, A.M., Antonova, K., Bihannic, I., Davidson, P., Dozov, I., Gabriel, J.C.P., Impéror-Clerc, M., Levitz, P., Meneau, F. & Michot, L.J. (2013) Liquid-crystalline properties of aqueous suspensions of natural clay nanosheets. Liquid Crystals Reviews, 1, 110126.
Petit, S., Decarreau, A., Gates, W., Andrieux, P & Grauby, O. (2015) Hydrothermal synthesis of dioctahedral smectites: The Al—Fe3+ chemical series. Part II: Crystal chemistry. Applied Clay Science, 104, 96–105.
Petit, S., Baron, F., Grauby, O. & Decarreau, A. (2016) Revisiting the cation mass-valence sum approach to assigning infrared OH-bands in dioctahedral smectites in the light of new data from synthetic Ga-Fe3+ smectites. Vibrational Spectroscopy, 87, 137–142.
Poulet, F., Bibring, J.P., Mustard, J.F., Gendrin, A., Mangold, N., Langevin, Y., Arvidson, R.E., Gondet, B., Gomez, C. & the Omega team (2005) Phyllosilicates on Mars and implications for early Martian climate. Nature, 438, 623637.
Slonimskaya, M.V., Besson, G., Daynyak, L.G., Tchoubar, C. & Drits, V.A. (1986) Interpretation of the IR spectra of celadonites, glauconites in the region of OH-stretching frequencies. Clay Minerals, 21, 377388.
Strese, H. & Hofmann, U. (1941) Synthesis of magnesian silicate gels with two dimensional regular structure. Zeitschrift für Anorganishe und Allgemeine Chemie, 247, 6595.
Tomita, K., Yamane, H. & Kawano, M. (1993) Synthesis of smectite from volcanic glass at low temperature. Clays and Clay Minerals, 41, 655661.
Weaver, C.E. & Pollard, L.D. (1973) The Chemistry of Clay Minerals. Elsevier, London.
Wilson, M.J. (2013) Smectite clay minerals (beidellite, pp. 257-277; nontronite, pp. 278-299) in: Sheet Silicates, Rock-Forming Minerals, vol. 3C (W.A. Deer, R.A. Howie & 1 Zussman, editors). The Geological Society, London.
Wray, J.J., Murchie, S.L., Squyres, S.W., Seelos, F.P. & Tornabene, L.L. (2009) Diverse aqueous environments on ancient Mars revealed in the southern highlands. Geology, 37, 10431046.
Yang, J., Kukkadapu, R.K., Dong, H., Shelobolina, E.S., Zhang 1 & Kim 1 (2012) Effects of redox cycling of iron in nontronite on reduction of technetium. Chemical Geology, 291, 206216.
Zen, J.-M., Jeng, S.-H. & Chen, H.-J. (1996) Catalysis of the electroreduction of hydrogen peroxide by non-tronite clay coatings on glassy carbon electrodes. Journal of Electroanalytical Chemistry, 408, 157163.
Zhang, D., Zhou, C.-H., Lin, C.-X., Tong, D.-S. & Yu, W.-H. (2010) Synthesis of clay minerals. Applied Clay Science, 50, 111.
Zhou, C-H. (2010) Emerging trends and challenges in synthetic clay-based materials and layered double hydroxides. Applied Clay Science, 48, 1–4.


Synthesis of nontronite and other Fe-rich smectites: a critical review

  • S. Petit (a1), F. Baron (a2) and A. Decarreau (a1)


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