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A XANES and EPMA study of Fe3+ in chlorite: Importance of oxychlorite and implications for cation site distribution and thermobarometry

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Published/Copyright: February 26, 2019
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American Mineralogist
From the journal American Mineralogist Volume 104 Issue 3

Abstract

Chlorite is a ubiquitous product of metamorphism, alteration of magmatic rocks and hydrothermal processes owing to its large stability field and wide compositional range. Its composition is governed by several substitutions and has been used as a geothermometer, on the basis of empirical, semi-empirical, and thermodynamic models. As in some other phyllosilicates of petrological interest, the oxidation state of iron in chlorite may differ from the usually assumed divalent state. However, the crystal chemistry of trivalent iron in chlorite remains poorly known, and the thermodynamic properties of ferric chlorite are missing from databases used for petrological modeling. As part of an attempt to fill this gap, we present results from in situ, micrometer-scale measurements of the oxidation state of iron in various chlorite-bearing samples. X-ray absorption near-edge spectroscopy (XANES) was combined with electron probe microanalysis (EPMA) on the same crystals. Results show iron oxidation states varying from ferrous to ferric; iron is in octahedral coordination in all ferromagnesian chlorites but to ~25% tetrahedral in the lithian chlorite cookeite (1.0 wt% Fe2O3(total)). Absolute amounts of ferric iron cover an unprecedented range (0 to ~30 wt% Fe2O3). For highly magnesian, ferric chlorite, Fe concentrations are low and can be accounted for by Al = Fe3+ substitution. In Fe-rich samples, Fe3+ may exceed 2 atoms per formula unit (pfu, 18 oxygen basis). When structural formulas are normalized to 28 charges corresponding to the standard O10(OH)8 anionic basis, these measurements define the exchange vector of a di-trioctahedral-type substitution: 3 VI(Mg, Fe2+) = VI□ + 2 VIFe3+, as described in earlier studies. However, structural formulas calculated on the basis of the oxygen contents actually measured by EPMA show that this trend is an artifact, due to the neglect of variations in the number of protons in the structure. Our measurements indicate increasing hydrogen deficiency with increasing Fe3+ content, up to ~ 2 H+ pfu in the Fe3+-rich chlorite samples, corresponding to a net exchange vector of the type R2+ + H+ = Fe3+. These results do not support substitutions toward di-trioctahedral ferric end-members, and highlight the need for considering substitution toward an “oxychlorite” (i.e., H-deficient) ferric component, close to tri-trioctahedral, with an O12(OH)6 anionic basis, even in green, pristine-looking chlorite. The effects of iron oxidation and H deficiency on chlorite geothermometers were explored. They are deterring if H deficiency is ignored but, given the sensitivity of most thermometers to octahedral vacancy, the assumption Fetotal = Fe2+ is still safer than using high measured Fe3+ contents and the standard 28 charge basis, which artificially increases vacancies. In such ferric chlorites, EPMA measurement of oxygen allows a fair estimate of H content if Fe3+/Fe2+ is known; it should be more systematically implemented. For the same reasons, literature data reporting Fe3+-rich chlorite with vacancy content along the possibly artificial di-trioctahedral-type substitution should be verified. With the help of constraints from thermodynamic models, charge balance, crystal symmetry, and proton loss, a new cation site distribution is proposed for di-tri- to tri-trioctahedral chlorites in the Fe2+-Fe3+-Mg-Al-Si-O-H system, allowing a more realistic thermodynamic handling of their solid solutions.

Keywords: Chlorite; oxychlorite; hydrogen deficiency; XANES; EPMA; ferric iron incorporation; geothermometry; solid solution; cation site distribution

  1. Funding This work was financially supported by the CNRS INSU programs and by French state funds managed by the ANR within the Investissements d’Avenir program under reference ANR-11-IDEX-0004-02, and more specifically within the framework of the Cluster of Excellence MATISSE led by Sorbonne Université, This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

Acknowledgments

We are grateful to Franck Bourdelle, Loïc Labrousse, Bruno Reynard, and Olivier Vidal for constructive discussion and to Michel Fialin, Nicolas Rividi, Sakura Pascarelli, Olivier Mathon, Antonio Lanzirotti, and Matt Newville for technical advice and support. Thanks are also extended to Rainer Altherr, Guillaume Bonnet, Colette Derré, Anne-Céline Ganzhorn, Michael Jentzer, Loïc Labrousse, Benjamin Lefeuvre, Alexis Plunder, Julien Reynes, Mathieu Soret, and Alberto Vitale-Brovarone for providing some of the chlorite-bearing samples. Constructive reviews by Darby Dyar and Atsuyuki Inoue led to substantial improvements of the manuscript and are gratefully acknowledged.

References cited

Aja, S.U., and Dyar, M.D. (2002) The stability of Fe–Mg chlorites in hydrothermal solutions—I. Results of experimental investigations. Applied Geochemistry, 17, 1219–1239.10.1016/S0883-2927(01)00131-7Search in Google Scholar

Aja, S., Omotoso, O., Bertoldi, C., Dachs, E., and Benisek, A. (2015) The structure and thermochemistry of three Fe-Mg chlorites. Clays and Clay Minerals, 63, 351–367.10.1346/CCMN.2015.0630502Search in Google Scholar

Altherr, R., Soder, C., Meyer, H.-P., Ludwig, T., and Böhm, M. (2017) Ardennite in a high-P/T meta-conglomerate near Vitolište in the westernmost Vardar zone, Republic of Macedonia. European Journal of Mineralogy, 29, 473–489.10.1127/ejm/2017/0029-2610Search in Google Scholar

Bajt, S., Sutton, S., and Delaney, J. (1994) X-ray microprobe analysis of iron oxidation states in silicates and oxides using X-ray absorption near edge structure (XANES). Geochimica et Cosmochimica Acta, 58, 5209–5214.10.1016/0016-7037(94)90305-0Search in Google Scholar

Bastin, G.F., and Heijligers, H.J.M. (1989) Quantitative electron probe microanalysis of oxygen, 168 p. Eindhoven University of Technology.Search in Google Scholar

Beaufort, D., Rigault, C., Billon, S., Billault, V., Inoue, A., Inoue, S., and Patrier, P. (2015) Chlorite and chloritization processes through mixed-layer mineral series in low-temperature geological systems—a review. Clay Minerals, 50, 497–523.10.1180/claymin.2015.050.4.06Search in Google Scholar

Billault, V., Beaufort, D., Patrier, P., and Petit, S. (2002) Crystal chemistry of Fe-sudoites from uranium deposits of the Athabasca Basin (Saskatchewan, Canada). Clays and Clay Minerals, 50, 70–81.10.1346/000986002761002847Search in Google Scholar

Bourdelle, F., and Cathelineau, M. (2015) Low-temperature chlorite geothermometry: a graphical representation based on a T-R2+-Si diagram. European Journal of Mineralogy, 27, 617–626.10.1127/ejm/2015/0027-2467Search in Google Scholar

Bourdelle, F., Parra, T., Chopin, C., and Beyssac, O. (2013a) A new chlorite geothermometer for diagenetic to low-grade metamorphic conditions. Contributions to Mineralogy and Petrology, 165, 723–735.10.1007/s00410-012-0832-7Search in Google Scholar

Bourdelle, F., Benzerara, K., Beyssac, O., Cosmidis, J., Neuville, D.R., Brown, G.E., and Paineau, E. (2013b) Quantification of the ferric/ferrous iron ratio in silicates by scanning transmission X-ray microscopy at the Fe L2,3 edges. Contributions to Mineralogy and Petrology, 166, 423–434.10.1007/s00410-013-0883-4Search in Google Scholar

Cathelineau, M. (1988) Cation site occupancy in chlorites and illites as a function of temperature. Clay Minerals, 23, 471–485.10.1180/claymin.1988.023.4.13Search in Google Scholar

Chatterjee, N.D. (1966) On the widespread occurrence of oxidized chlorites in the Pennine zone of the western Italian Alps. Contributions to Mineralogy and Petrology, 12, 325–339.10.1007/BF00616818Search in Google Scholar

Chermak, J.A., and Rimstidt, J.D. (1989) Estimating the thermodynamic properties (ΔGf0 and ΔHf0) of silicate minerals at 298 K from the sum of polyhedral contributions. American Mineralogist, 74, 1023–1031.Search in Google Scholar

De Andrade, V., Susini, J., Salomé, M., Beraldin, O., Rigault, C., Heymes, T., Lewin, E., and Vidal, O. (2011) Submicrometer hyperspectral X-ray imaging of heterogeneous rocks and geomaterials: Applications at the Fe K-edge. Analytical Chemistry, 83, 4220–4227.10.1021/ac200559rSearch in Google Scholar

De Grave, E., Vandenbruwaene, J., and Van Bockstael, M. (1987) 57Fe Mössbauer Spectroscopic Analysis of Chlorite. Physics and Chemistry of Minerals, 15, 173–180.10.1007/BF00308781Search in Google Scholar

Droop, G.T.R. (1987) A general equation for estimating Fe3+ concentrations in ferromagnesian silicates and oxides from microprobe analyses, using stoichiometric criteria. Mineralogical Magazine, 51, 431–435.10.1180/minmag.1987.051.361.10Search in Google Scholar

Dubacq, B., and Plunder, A. (2018) Controls on trace element distribution in oxides and silicates. Journal of Petrology, 59, 2, 233–256.10.1093/petrology/egy027Search in Google Scholar

Dyar, M.D., Perry, C.L., Rebbert, C.R., Dutrow, B.L., Holdaway, M.J., and Lang, H.M. (1991a) Mössbauer spectroscopy of synthetic and naturally occurring staurolite. American Mineralogist, 76, 27–41.Search in Google Scholar

Dyar, M.D., Colucci, M.T., and Guidotti, C.V. (1991b) Forgotten major elements: Hydrogen and oxygen variation in biotite from metapelites. Geology, 19, 1029–1032.10.1130/0091-7613(1991)019<1029:FMEHAO>2.3.CO;2Search in Google Scholar

Dyar, M.D., Guidotti, C.V., Holdaway, M.J., and Colucci, M. (1993) Nonstoichiometric hydrogen contents in common rock-forming hydroxyl silicates. Geochimica et Cosmochimica Acta, 57, 2913–2918.10.1016/0016-7037(93)90399-HSearch in Google Scholar

Dyar, M.D., Delaney, J.S., and Sutton, S.R. (2001) Fe XANES spectra of iron-rich micas. European Journal of Mineralogy, 13, 1079–1098.10.1127/0935-1221/2001/0013-1079Search in Google Scholar

Emmons, W.H., and Larsen, E.S. (1923) Geology and ore deposits of the Creede district, Colorado. USGS Bulletin, 718, 198 p.Search in Google Scholar

Evans, K.A., Dyar, M.D., Reddy, S.M., Lanzirotti, A., Adams, D.T., and Tailby, N. (2014) Variation in XANES in biotite as a function of orientation, crystal composition, and metamorphic history. American Mineralogist, 99, 443–457.10.2138/am.2014.4222Search in Google Scholar

Farges, F., Lefrère, Y., Rossano, S., Berthereau, A., Calas, G., and Brown, G.E. (2004) The effect of redox state on the local structural environment of iron in silicate glasses: A combined XAFS spectroscopy, molecular dynamics, and bond valence study. Journal of Non-Crystalline Solids, 344, 176–188.10.1016/j.jnoncrysol.2004.07.050Search in Google Scholar

Fialin, M., Wagner, C., Métrich, N., Humler, E., Galoisy, L., and Bézos, A. (2001) Fe3+/Σ Fe vs. Fe Lα peak energy for minerals and glasses: Recent advances with the electron microprobe. American Mineralogist, 86, 456–465.10.2138/am-2001-0409Search in Google Scholar

Fiege, A., Ruprecht, P., Simon, A.C., Bell, A.C., Göttlicher, J., Newville, M., Lanzirotti, T., and Moore, G. (2017) Calibration of Fe XANES for high-precision determination of Fe oxidation state in glasses: Comparison of new and existing results obtained at different synchrotron radiation sources. American Mineralogist, 102, 369–380.10.2138/am-2017-5822Search in Google Scholar

Foster, M. D. (1962) Interpretation of the composition and a classification of the chlorites. U.S. Geological Survey Professional Paper 414-A, p. A1–A33.10.3133/pp414ASearch in Google Scholar

Galoisy, L., Calas, G., and Arrio, M.A. (2001) High-resolution XANES spectra of iron in minerals and glasses: structural information from the pre-edge region. Chemical Geology, 174, 307–319.10.1016/S0009-2541(00)00322-3Search in Google Scholar

Garvie, L.A., and Craven, A.J. (1994) Electron-beam-induced reduction of Mn4+ in manganese oxides as revealed by parallel EELS. Ultramicroscopy, 54, 83–92.10.1016/0304-3991(94)90094-9Search in Google Scholar

Garvie, L.A., Zega, T.J., Rez, P., and Buseck, P.R. (2004) Nanometer-scale measurements of Fe3+/ΣFe by electron energy-loss spectroscopy: A cautionary note. American Mineralogist, 89, 1610–1616.10.2138/am-2004-11-1204Search in Google Scholar

Giles, C., Malgrange, C., Goulon, J., de Bergevin, F., Vettier, C., Fontaine, A., Dartyge, E., and Pizzini, S. (1994) Energy and polarization-tunable X-ray quarter-wave plates for energy dispersive absorption spectrometer. Nuclear Institute and Methods in Physics Research, 349, 622–625.10.1016/0168-9002(94)91235-1Search in Google Scholar

Hawthorne, F.C., Ungaretti, L., Oberti, R., Caucia, F., and Callegari, A. (1993) The crystal chemistry of staurolite; I, Crystal structure and site populations. The Canadian Mineralogist, 31, 551–582.Search in Google Scholar

Hawthorne, F.C., Oberta, R., Harlow, G.E., Maresch, W.V., Martin, R.F., Schumacher, J.C., and Welch, M.D. (2012) Nomenclature of the amphibole super-group. American Mineralogist, 97, 2031–2048.10.2138/am.2012.4276Search in Google Scholar

Henry, D.J., Novák, M., Hawthorne, F.C., Ertl, A., Dutrow, B., Uher, P., and Pezzotta, F. (2011) Nomenclature of the tourmaline supergroup minerals. American Mineralogist, 96, 895–913.10.2138/am.2011.3636Search in Google Scholar

Hillier, S., and Velde, B. (1991) Octahedral occupancy and the chemical composition of diagenetic (low-temperature) chlorites. Clay Minerals, 26, 149–168.10.1180/claymin.1991.026.2.01Search in Google Scholar

Höfer, H.E., Brey, G.P., Schulz-Dobrick, B., and Oberhänsli, R. (1994) The determination of the oxidation state of iron by the electron microprobe. European Journal of Mineralogy, 6, 407–418.10.1127/ejm/6/3/0407Search in Google Scholar

Holland, T.J.B., and Powell, R. (1998) An internally consistent thermodynamic data set for phases of petrological interest. Journal of Metamorphic Geology, 16, 309–343.10.1111/j.1525-1314.1998.00140.xSearch in Google Scholar

Holland, T., Baker, J., and Powell, R. (1998) Mixing properties and activity–composition relationships of chlorites in the system MgO-FeO-Al2O3-SiO2-H2O. European Journal of Mineralogy, 10, 395–406.10.1127/ejm/10/3/0395Search in Google Scholar

Inoue, S., and Kogure, T. (2016) High-angle annular dark field scanning transmission electron microscopic (HAADF-STEM) study of Fe-rich 7-Å-14-Å interstratified minerals from a hydrothermal deposit. Clay Minerals, 51, 603–613.10.1180/claymin.2016.051.4.05Search in Google Scholar

Inoue, A., Meunier, A., Patrier-Mas, P., Rigault, C., Beaufort, D., and Vieillard, P. (2009) Application of chemical geothermometry to low-temperature trioctahedral chlorites. Clays and Clay Minerals, 57, 371–382.10.1346/CCMN.2009.0570309Search in Google Scholar

Inoue, A., Inoué, S., and Utada, M. (2018) Application of chlorite thermometry to estimation of formation temperature and redox conditions. Clay Minerals, 53, 143–158.10.1180/clm.2018.10Search in Google Scholar

Lanari, P., Wagner, T., and Vidal, O. (2014) A thermodynamic model for ditrioctahedral chlorite from experimental and natural data in the system MgO-FeO-Al2O3-SiO2-H2O: Applications to P-T sections and geothermometry. Contributions to Mineralogy and Petrology, 167, 1–19.10.1007/s00410-014-0968-8Search in Google Scholar

Lanson, B., Lantenois, S., van Aken, P.A., Bauer, A., and Plançon, A. (2012) Experimental investigation of smectite interaction with metal iron at 80 °C: Structural characterization of newly formed Fe-rich phyllosilicates. American Mineralogist, 97, 864–871.10.2138/am.2012.4062Search in Google Scholar

Lougear, A., Grodzicki, M., Bertoldi, C., Trautwein, A.X., Steiner, K., and Amthauer, G. (2000) Mössbauer and molecular orbital study of chlorites. Physics and Chemistry of Minerals, 27, 258–269.10.1007/s002690050255Search in Google Scholar

Muñoz, M., Vidal, O., Marcaillou, C., Pascarelli, S., Mathon, O., and Farges, F. (2013) Iron oxidation state in phyllosilicate single crystals using Fe-K pre-edge and XANES spectroscopy: Effects of the linear polarization of the synchrotron X-ray beam. American Mineralogist, 98, 1187–1197.10.2138/am.2013.4289Search in Google Scholar

Namur, O., Hatert, F., Grandjean, F., Long, G.J., Krins, N., Fransolet, A.-M., Vander Auwera, J., and Charlier, B. (2009) Ti substitution mechanisms in phlogopites from the Suwalki massif-type anorthosite, NE Poland. European Journal of Mineralogy, 21, 397–406.10.1127/0935-1221/2009/0021-1894Search in Google Scholar

Nelson, D.O., and Guggenheim, S. (1993) Inferred limitations to the oxidation of Fe in chlorite: A high-temperature single-crystal X-ray study. American Mineralogist, 78, 1197–1207.Search in Google Scholar

Newville, M. (2014) Fundamentals of XAFS. Reviews in Mineralogy and Geochemistry, 78, 33–74.10.2138/rmg.2014.78.2Search in Google Scholar

Peacor, D.R., Rouse, R.C., and Bailey, S.W. (1988) Crystal structure of franklin-furnaceite; a tri-dioctahedral zincosilicate intermediate between chlorite and mica. American Mineralogist, 73, 876–887.Search in Google Scholar

Pfalzer, P., Urbach, J.-P., Klemm, M., Horn, S., DenBoer, M.L., Frenkel, A.I., and Kirkland, J.P. (1999) Elimination of self-absorption in fluorescence hard-X-ray absorption spectra. Physical Review B, 60, 9335–9339.10.1103/PhysRevB.60.9335Search in Google Scholar

Plunder, A., Agard, P., Chopin, C., Pourteau, A., and Okay, A.I. (2015) Accretion, underplating and exhumation along a subduction interface: From subduction initiation to continental subduction (Tavçanli zone, W. Turkey). Lithos, 226, 233–254.10.1016/j.lithos.2015.01.007Search in Google Scholar

Raeburn, S.P., Ilton, E.S., and Veblen, D.R. (1997) Quantitative determination of the oxidation state of iron in biotite using X-ray photoelectron spectroscopy: II. In situ analyses. Geochimica et Cosmochimica Acta, 61, 4519–4530.10.1016/S0016-7037(97)00264-0Search in Google Scholar

Rona, P.A. (1984) Hydrothermal mineralization at seafloor spreading centers. Earth-Science Reviews, 20, 1–104.10.1016/0012-8252(84)90080-1Search in Google Scholar

Rule, A.C., and Bailey, S.W. (1987) Refinement of the crystal structure of a monoclinic ferroan clinochlore. Clays and Clay Minerals, 35, 129–138.10.1346/CCMN.1987.0350205Search in Google Scholar

Sainz-Diaz, I.C., Hernández-Laguna, A., and Dove, T.M. (2001) Theoretical modelling of cis-vacant and trans-vacant configurations in the octahedral sheet of illites and smectites. Physics and Chemistry of Minerals, 28, 322–331.10.1007/s002690100156Search in Google Scholar

Shannon, R.D. (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica, 32, 751–767.10.1107/S0567739476001551Search in Google Scholar

Smith, J.V. (1968) The crystal structure of staurolite. American Mineralogist, 53, 1139–1155.Search in Google Scholar

Smyth, J.R., Dyar, M.D., May, H.M., Bricker, O.P., and Acker, J.G. (1997) Crystal structure refinement and Mössbauer spectroscopy of an ordered, triclinic clinochlore. Clays and Clay Minerals, 45, 544–550.10.1346/CCMN.1997.0450406Search in Google Scholar

Trincal, V., and Lanari, P. (2016) Al-free di-trioctahedral substitution in chlorite and a ferri-sudoite end-member. Clay Minerals, 51, 675–689.10.1180/claymin.2016.051.4.09Search in Google Scholar

Tröger, L., Arvanitis, D., Baberschke, K., Michaelis, H., Grimm, U., and Zschech, E. (1992) Full correction of the self-absorption in soft-fluorescence extended X-ray-absorption fine-structure. Physical Review B, 46, 3283–3289.10.1103/PhysRevB.46.3283Search in Google Scholar PubMed

van Aken, P. A., and Liebscher, B. (2002) Quantification of ferrous/ferric ratios in minerals: New evaluation schemes of Fe L2,3 electron energy-loss near-edge spectra. Physics and Chemistry of Minerals, 29, 188–200.10.1007/s00269-001-0222-6Search in Google Scholar

van Hinsberg, V.J., Vriend, S.P., and Schumacher, J.C. (2005) A new method to calculate end-member thermodynamic properties of minerals from their constituent polyhedra I: Enthalpy, entropy and molar volume. Journal of metamorphic Geology, 23, 165–180.10.1111/j.1525-1314.2005.00569.xSearch in Google Scholar

Vidal, O., Parra, T., and Trotet, F. (2001) A thermodynamic model for Fe-Mg aluminous chlorite using data from phase equilibrium experiments and natural pelitic assemblages in the 100°C to 600°C, 1 to 25kb range. American Journal of Science, 301, 557–592.10.2475/ajs.301.6.557Search in Google Scholar

Vidal, O., Parra, T., and Vieillard, P. (2005) Thermodynamic properties of the Tschermak solid solution in Fe-chlorite: Application to natural examples and possible role of oxidation. American Mineralogist, 90, 347–358.10.2138/am.2005.1554Search in Google Scholar

Vidal, O., De Andrade, V., Lewin, E., Muñoz, M., Parra, T., and Pascarelli, S. (2006) P-T-deformation-Fe3+/Fe2+ mapping at the thin section scale and comparison with XANES mapping: Application to a garnet-bearing metapelite from the Sambagawa metamorphic belt (Japan). Journal of Metamorphic Geology, 24, 669–683.10.1111/j.1525-1314.2006.00661.xSearch in Google Scholar

Vidal, O., Lanari, P., Muñoz, M., Bourdelle, F., and De Andrade, V. (2016) Deciphering temperature, pressure, and oxygen activity conditions of chlorite formation. Clay Minerals, 51, 615–633.10.1180/claymin.2016.051.4.06Search in Google Scholar

Virgo, D., and Popp, R.K. (2000) Hydrogen deficiency in mantle-derived phlogopites. American Mineralogist, 85, 753–759.10.2138/am-2000-5-614Search in Google Scholar

Walker, J.R., and Bish, D.L. (1992) Application of Rietveld refinement techniques to a disordered IIb Mg-chamosite. Clays and Clay Minerals, 40, 319–322.10.1346/CCMN.1992.0400311Search in Google Scholar

Walshe, J.L. (1986) A six-component chlorite solid solution model and the conditions of chlorite formation in hydrothermal and geothermal systems. Economic Geology, 81, 681–703.10.2113/gsecongeo.81.3.681Search in Google Scholar

Walshe, J.L., and Solomon, M. (1981) An investigation into the environment of formation of the volcanic-hosted Mt. Lyell copper deposits using geology, mineralogy, stable isotopes, and a six-component chlorite solid solution model. Economic Geology, 76, 246–284.10.2113/gsecongeo.76.2.246Search in Google Scholar

Welch, M.D., and Marshall, W.G. (2001) High-pressure behavior of clinochlore. American Mineralogist, 86, 1380–1386.10.2138/am-2001-11-1206Search in Google Scholar

White, E.W., and McKinstry, H.A. (1966) Chemical effect on X-ray absorption-edge fine structure. Advances in X-ray Analysis, 9, 376–392.10.1007/978-1-4684-7633-0_34Search in Google Scholar

Wilke, M., Farges, F., Petit, P.E., Brown, J.G., and Martin, F. (2001) Oxidation state and coordination of Fe in minerals: An Fe K-XANES spectroscopic study. American Mineralogist, 86, 714–730.10.2138/am-2001-5-612Search in Google Scholar

Wilke, M., Partzsch, G.M., Bernhardt, R., and Lattard, D. (2005) Determination of the iron oxidation state in basaltic glasses using XANES at the K-edge. Chemical Geology, 220, 143–161.10.1016/j.chemgeo.2005.03.004Search in Google Scholar

Wones, D.R. (1963) Phase equilibria of “ferriannite,” KFe3+2Fe+3Si3O10(OH)2. American Journal of Science, 261, 581–596.10.2475/ajs.261.6.581Search in Google Scholar

Yamashita, T., and Hayes, P. (2008) Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials. Applied Surface Science, 254, 2441–2449.10.1016/j.apsusc.2007.09.063Search in Google Scholar

Zanazzi, P.F., Montagnoli, M., Nazzareni, S., and Comodi, P. (2006) Structural effects of pressure on triclinic chlorite: A single-crystal study. American Mineralogist, 91, 1871–1878.10.2138/am.2006.2191Search in Google Scholar

Zane, A., Sassi, R., and Guidotti, C.V. (1998) New data on metamorphic chlorite as a petrogenetic indicator mineral, with special regard to greenschist-facies rocks. Canadian Mineralogist, 36, 713–726.Search in Google Scholar

Zazzi, Å., Hirsch, T.K., Leonova, E., Kaikkonen, A., Grins, J., Annersten, H., and Edén, M. (2006) Structural investigations of natural and synthetic chlorite minerals by X-ray diffraction, Mössbauer spectroscopy and solid-state nuclear magnetic resonance. Clays and Clay Minerals, 54, 252–265.10.1346/CCMN.2006.0540210Search in Google Scholar

Zheng, H., and Bailey, S.W. (1989) Structures of intergrown triclinic and monoclinic IIb chlorites from Kenya. Clays and Clay Minerals, 37, 308–316.10.1346/CCMN.1989.0370403Search in Google Scholar

Received: 2018-07-25
Accepted: 2018-11-27
Published Online: 2019-02-26
Published in Print: 2019-03-26

© 2019 Walter de Gruyter GmbH, Berlin/Boston

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  17. Trace element distributions in (Cu)-Pb-Sb sulfosalts from the Gutaishan Au-Sb deposit, South China: Implications for formation of high fineness native gold
  18. A-type carbonate in strontium phosphate apatites
  19. Discovery of a zinc-rich mineral on the surface of lunar orange pyroclastic beads
  20. In-situ mapping of ferric iron variations in lunar glasses using X-ray absorption spectroscopy
  21. Book Review
  22. Book Review
https://doi.org/10.2138/am-2019-6766
Keywords for this article
Chlorite; oxychlorite; hydrogen deficiency; XANES; EPMA; ferric iron incorporation; geothermometry; solid solution; cation site distribution

Articles in the same Issue

  1. Letter
  2. Chessboard structures: Atom-scale imaging of homologs from the kobellite series
  3. Special collection: Microporous materials: Crystal-chemistry, properties, and utilizations
  4. Highlighting the capability of zeolites for agro-chemicals contaminants removal from aqueous matrix: Evidence of 2-ethyl-6-methylaniline adsorption on ZSM-12
  5. Special collection: Physics and chemistry of earth's deep mantle and core
  6. Origin and consequences of non-stoichiometry in iron carbide Fe7C3
  7. Special collection: Isotopes, minerals, and petrology: Honoring John Valley
  8. Application of mineral equilibria to estimate fugacities of H2O, H2, and O2 in mantle xenoliths from the southwestern U.S.A.
  9. Review
  10. Composition, paragenesis, and alteration of the chevkinite group of minerals
  11. Articles
  12. Spinel-anorthosites on the Moon: Impact melt origins suggested by enthalpy constraints
  13. Fast diffusion path for water in silica glass
  14. Micro- and nano-scale textural and compositional zonation in plagioclase at the Black Mountain porphyry Cu deposit: Implications for magmatic processes
  15. A XANES and EPMA study of Fe3+ in chlorite: Importance of oxychlorite and implications for cation site distribution and thermobarometry
  16. Sound velocities across calcite phase transitions by Brillouin scattering spectroscopy
  17. Trace element distributions in (Cu)-Pb-Sb sulfosalts from the Gutaishan Au-Sb deposit, South China: Implications for formation of high fineness native gold
  18. A-type carbonate in strontium phosphate apatites
  19. Discovery of a zinc-rich mineral on the surface of lunar orange pyroclastic beads
  20. In-situ mapping of ferric iron variations in lunar glasses using X-ray absorption spectroscopy
  21. Book Review
  22. Book Review
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