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Contributions to Mineralogy and Petrology

, Volume 166, Issue 2, pp 423–434 | Cite as

Quantification of the ferric/ferrous iron ratio in silicates by scanning transmission X-ray microscopy at the Fe L2,3 edges

  • Franck BourdelleEmail author
  • Karim Benzerara
  • Olivier Beyssac
  • Julie Cosmidis
  • Daniel R. Neuville
  • Gordon E. BrownJr.
  • Erwan Paineau
Original Paper

Abstract

Estimation of Fe3+/ΣFe ratios in materials at the submicrometre scale has been a long-standing challenge in the Earth and environmental sciences because of the usefulness of this ratio in estimating redox conditions as well as for geothermometry. To date, few quantitative methods with submicrometric resolution have been developed for this purpose, and most of them have used electron energy-loss spectroscopy carried out in the ultra-high vacuum environment of a transmission electron microscope (TEM). Scanning transmission X-ray microscopy (STXM) is a relatively new technique complementary to TEM and is increasingly being used in the Earth sciences. Here, we detail an analytical procedure to quantify the Fe3+/ΣFe ratio in silicates using Fe L2,3-edge X-ray absorption near edge structure (XANES) spectra obtained by STXM, and we discuss its advantages and limitations. Two different methods for retrieving Fe3+/ΣFe ratios from XANES spectra are calibrated using reference samples with known Fe3+ content by independent approaches. The first method uses the intensity ratio of the two major peaks at the L3-edge. This method allows mapping of Fe3+/ΣFe ratios at a spatial scale better than 50 nm by the acquisition of 5 images only. The second method employs a 2-eV-wide integration window centred on the L2 maximum for Fe3+, which is compared to the total integral intensity of the Fe L2-edge. These two approaches are applied to metapelites from the Glarus massif (Switzerland), containing micrometre-sized chlorite and illite grains and prepared as ultrathin foils by focused ion beam milling. Nanometre-scale mapping of iron redox in these samples is presented and shows evidence of compositional zonation. The existence of such zonation has crucial implications for geothermometry and illustrates the importance of being able to measure Fe3+/ΣFe ratios at the submicrometre scale in geological samples.

Keywords

Ferric/ferrous iron STXM XANES spectroscopy L2,3-edge Redox mapping Silicate 

Notes

Acknowledgments

We are most grateful to the Lawrence Berkeley National Lab and especially to Tolek Tyliszczak for his scientific support, and the Paul Scherrer Institute, Swiss Light Source. We would like to thank the materials characterisation department of IFP Energies nouvelles-Lyon and the laboratory of CP2M-Université Aix-Marseille, for technical advice. Thanks are also extended to Nicolas Menguy for his scientific help and to Christian Chopin (ENS, Paris), Daniel Beaufort (IC2MP, Poitiers), Patricia Patrier (IC2MP, Poitiers) and the Muséum National d’Histoire Naturelle. This study was supported by a grant from the Simone and Cino del Duca Foundation.

References

  1. Bajt S, Sutton SR, Delaney JS (1994) X-ray microprobe analysis of iron oxidation-states in silicates and oxides using X-ray-absorption near-edge structure (XANES). Geochim Cosmochim Ac 58(23):5209–5214CrossRefGoogle Scholar
  2. Beaufort D, Patrier P, Meunier A, Ottaviani MM (1992) Chemical variations in assemblages including epidote and/or chlorite in the fossil hydrothermal system of Saint Martin (Lesser Antilles). J Volcanol Geoth Res 51:95–114CrossRefGoogle Scholar
  3. Benzerara K, Miot J, Morin G, Ona-Nguema G, Skouri-Panet F, Ferard C (2011a) Significance, mechanisms and environmental implications of microbial biomineralization. C R Geosci 343(2–3):160–167CrossRefGoogle Scholar
  4. Benzerara K, Menguy N, Obst M, Stolarski J, Mazur M, Tylisczak T, Brown GE Jr, Meibom A (2011b) Study of the crystallographic architecture of corals at the nanoscale by scanning transmission X-ray microscopy and transmission electron microscopy. Ultramicroscopy 111(8):1268–1275CrossRefGoogle Scholar
  5. Bernard S, Benzerara K, Beyssac O, Brown GE Jr (2010) Multiscale characterization of pyritized plant tissues in blueschist facies metamorphic rocks. Geochim Cosmochim Ac 74(17):5054–5068CrossRefGoogle Scholar
  6. Berry AJ, O’Neill HS, Jayasuriya KD, Campbell SJ, Foran GJ (2003) XANES calibrations for the oxidation state of iron in a silicate glass 88(7):967–977Google Scholar
  7. Berry AJ, Yaxley GM, Woodland AB, Foran GJ (2010) A XANES calibration for determining the oxidation state of iron in mantle garnet. Chem Geol 278(1–2):31–37CrossRefGoogle Scholar
  8. Bluhm H, Andersson K, Araki T, Benzerara K, Brown JGE, Dynes JJ, Ghosal S, Gilles MK, Hansen HC, Hemminger JC, Hitchcock AP, Ketteler G, Kilcoyne ALD, Kneedler E, Lawrence JR, Leppard GG, Majzlam J, Mun BS, Myneni SCB, Nilsson A, Ogasawara H, Ogletree DF, Pecher K, Salmeron M, Shuh DK, Tonner B, Tyliszczak T, Warwick T, Yoon TH (2006) Soft Xray microscopy and spectroscopy at the molecular environmental science beamline at the advanced light source. J Electron Spectrosc 150:86–104CrossRefGoogle Scholar
  9. Bolfan-Casanova N, Munoz M, McCammon C, Deloule E, Ferot A, Demouchy S, France L, Andrault D, Pascarelli S (2012) Ferric iron and water incorporation in wadsleyite under hydrous and oxidizing conditions: a XANES, Mossbauer, and SIMS study. Am Mineral 97(8–9):1483–1493CrossRefGoogle Scholar
  10. Boulard E, Menguy N, Auzende AL, Benzerara K, Bureau H, Antonangeli D, Corgne A, Morard G, Siebert J, Perrillat JP, Guyot F, Fiquet G (2012) Experimental investigation of the stability of Fe-rich carbonates in the lower mantle. J Geophys Res-Solid Earth 117(B2)Google Scholar
  11. Bourdelle F, Parra T, Beyssac O, Chopin C, Moreau F (2012) Ultrathin section preparation of phyllosilicates by focused ion beam milling for quantitative analysis by TEM-EDX. Appl Clay Sci 59–60:121–130CrossRefGoogle Scholar
  12. Bourdelle F, Parra T, Beyssac O, Chopin C, Vidal O (2013a) Clay minerals as geo-thermometer: a comparative study based on high spatial resolution analyses of illite and chlorite in Gulf Coast sandstones (Texas, USA). Am Mineral 98(5–6):914–926CrossRefGoogle Scholar
  13. Bourdelle F, Parra T, Chopin C, Beyssac O (2013b) A new chlorite geothermometer for diagenetic to low-grade metamorphic conditions. Contrib Mineral Petr 165:723–735CrossRefGoogle Scholar
  14. Brotton SJ, Shapiro R, van der Laan G, Guo J, Glans PA, Ajello JM (2007) Valence state fossils in Proterozoic stromatolites by L-edge X-ray absorption spectroscopy. J Geophys Res-Biogeosci 112:G3CrossRefGoogle Scholar
  15. Carlut J, Benzerara K, Horen H, Menguy N, Janots D, Findling N, Addad A, Machouk I (2010) Microscopy study of biologically mediated alteration of natural mid-oceanic ridge basalts and magnetic implications. J Geophys Res-Biogeosci 115(G4)Google Scholar
  16. Chen CT, Idzerda YU, Lin HJ, Smith NV, Meigs G, Chaban E, Ho GH, Pellegrin E, Sette F (1995) Experimental confirmation of the X-ray magnetic circular-dichroism sum-rules for iron and cobalt. Phys Rev Lett 75(1):152–155CrossRefGoogle Scholar
  17. Cressey G, Henderson CMB, Vanderlaan G (1993) Use of L-edge X-Ray-absorption spectroscopy to characterize multiple valence states of 3d transition-metals: a new probe for mineralogical and geochemical research. Phys Chem Miner 20(2):111–119CrossRefGoogle Scholar
  18. Crocombette JP, Pollak M, Jollet F, Thromat N, Gautiersoyer M (1995) X-Ray-absorption spectroscopy at the Fe L(2,3) threshold in iron-oxides. Phys Rev B 52(5):3143–3150CrossRefGoogle Scholar
  19. de Andrade V, Vidal O, Lewin E, O’Brien P, Agard P (2006) Quantification of electron microprobe compositional maps of rock thin sections: an optimized method and examples. J Metamorph Geol 24(7):655–668CrossRefGoogle Scholar
  20. de Groot FMF, de Smit E, van Schooneveld MM, Aramburo LR, Weckhuysen BM (2010) In-situ scanning transmission X-ray microscopy of catalytic solids and related nanomaterials. ChemPhysChem 11(5):951–962CrossRefGoogle Scholar
  21. de Smit E, Swart I, Creemer JF, Hoveling GH, Gilles MK, Tyliszczak T, Kooyman PJ, Zandbergen HW, Morin C, Weckhuysen BM, de Groot FMF (2008) Nanoscale chemical imaging of a working catalyst by scanning transmission X-ray microscopy. Nature 456(7219):U222–U239CrossRefGoogle Scholar
  22. Fialin M, Bézos A, Wagner C, Magnien V, Humler E (2004) Quantitative electron microprobe analysis of Fe3+/ΣFe: basic concepts and experimental protocol for glasses. Am Mineral 89(4):654–662Google Scholar
  23. Garvie LA, Zega TJ, Rez P, Buseck PR (2004) Nanometer-scale measurements of Fe3+/ΣFe by electron energy-loss spectroscopy: a cautionary note. Am Mineral 89(11–12):1610–1616Google Scholar
  24. Hanhan S, Smith AM, Obst M, Hitchcock AP (2009) Optimization of analysis of soft X-ray spectromicroscopy at the Ca 2p edge. J Electron Spectrosc 173(1):44–49CrossRefGoogle Scholar
  25. Heaney PJ, Vicenzi EP, Giannuzzi LA, Livi KJT (2001) Focused ion beam milling: a method of site-specific sample extraction for microanalysis of Earth and planetary materials. Am Mineral 86(9):1094–1099Google Scholar
  26. Heijboer WM, Battiston AA, Knop-Gericke A, Havecker M, Mayer R, Bluhm H, Schlogl R, Weckhuysen BM, Koningsberger DC, de Groot FMF (2003) In-situ soft X-ray absorption of over-exchanged Fe/ZSM5. J Phys Chem B 107(47):13069–13075CrossRefGoogle Scholar
  27. Hitchcock AP (2012) aXis 2000 analysis of X-ray images and spectra. McMaster University, HamiltonGoogle Scholar
  28. Inoue A, Meunier A, Patrier-Mas P, Rigault C, Beaufort D, Vieillard P (2009) Application of chemical geothermometry to low temperature trioctahedral chlorites. Clay Clay Miner 57(3):371–382CrossRefGoogle Scholar
  29. Joswig W, Amthauer G, Takeuchi Y (1986) Neutron-diffraction and Mössbauer spectroscopic study of clintonite (xanthophyllite). Am Mineral 71:1194–1197Google Scholar
  30. Keeling JL, Raven MD, Gates WP (2000) Geology and characterization of two hydrothermal nontronites from weathered metamorphic rocks at the Uley graphite mine South Australia. Clay Clay Miner 48(5):537–548CrossRefGoogle Scholar
  31. Lahfid A, Beyssac O, Deville E, Negro F, Chopin C, Goffe B (2010) Evolution of the Raman spectrum of carbonaceous material in low-grade metasediments of the Glarus Alps (Switzerland). Terra Nova 22(5):354–360CrossRefGoogle Scholar
  32. Lam KP, Hitchcock AP, Obst M, Lawrence JR, Swerhone GDW, Leppard GG, Tyliszczak T, Karunakaran C, Wang J, Kaznatcheev K, Bazylinski DA, Lins U (2010) Characterizing magnetism of individual magnetosomes by X-ray magnetic circular dichroism in a scanning transmission X-ray microscope. Chem Geol 270(1–4):110–116CrossRefGoogle Scholar
  33. Lauterbach S, McCammon CA, van Aken P, Langenhorst F, Seifert F (2000) Mossbauer and ELNES spectroscopy of (Mg, Fe)(Si, Al)O3 perovskite: a highly oxidised component of the lower mantle. Contrib Mineral Petr 138(1):17–26CrossRefGoogle Scholar
  34. Magnien V, Neuville DR, Cormier L, Mysen BO, Briois V, Belin S, Pinet O, Richet P (2004) Kinetics of iron oxidation in silicate melts: a preliminary XANES study. Chem Geol 213(1–3):253–263CrossRefGoogle Scholar
  35. Miot J, Benzerara K, Morin G, Kappler A, Bernard S, Obst M, Ferard C, Skouri-Panet F, Guigner JM, Posth N, Galvez M, Brown GE Jr, Guyot F (2009) Iron biomineralization by anaerobic neutrophilic iron-oxidizing bacteria. Geochim Cosmochim Ac 73(3):696–711CrossRefGoogle Scholar
  36. Miot J, Maclellan K, Benzerara K, Boisset N (2011) Preservation of protein globules and peptidoglycan in the mineralized cell wall of nitrate-reducing, iron (II)-oxidizing bacteria: a cryo-electron microscopy study. Geobiology 9(6):459–470CrossRefGoogle Scholar
  37. Munoz M, De Andrade V, Vidal O, Lewin E, Pascarelli S, Susini J (2006) Redox and speciation micromapping using dispersive X-ray absorption spectroscopy: Application to iron chlorite mineral of a metamorphic rock thin section. Geochem Geophys Geosyst 7(11)Google Scholar
  38. Raabe, J, Tzvetkov, G, Flechsig, U, Böge, M, Jaggi, A, Sarafimov, B, Vernooij, MGC, Huthwelker, T, Ade, H, Kilcoyne, D, Tyliszczak, T, Fink, RH Quitmann, C (2008) PolLux: A new facility for soft X-ray spectromicroscopy at the Swiss Light Source. Rev Sci Instrum 79(11)Google Scholar
  39. Raeburn SP, Ilton ES, Veblen DR (1997a) Quantitative determination of the oxidation state of iron in biotite using X-ray photoelectron spectroscopy: I Calibration. Geochim Cosmochim Ac 61(21):4519–4530CrossRefGoogle Scholar
  40. Raeburn SP, Ilton ES, Veblen DR (1997b) Quantitative determination of the oxidation state of iron in biotite using X-ray photoelectron spectroscopy: II In situ analyses. Geochim Cosmochim Ac 61(21):4531–4537CrossRefGoogle Scholar
  41. Rigault C (2010) Cristallochimie de Fer dans les chlorites de basse température : implications pour la géothermométrie et la détermination des paléoconditions redox dans les gisements d’Uranium. University of Poitiers, PoitiersGoogle Scholar
  42. Schingaro E, Scordari F, Mesto E, Brigatti MF, Pedrazzi G (2005) Cation-site partitioning in Ti-rich micas from Black Hill (Australia): a multi-technical approach. Clay Clay Miner 53(2):179–189CrossRefGoogle Scholar
  43. Schmid R, Wilke M, Oberhänsli R, Janssens K, Falkenberg G, Franz L, Gaab A (2003) Micro-XANES determination of ferric iron and its application in thermobarometry. Lithos 70(3–4):381–392CrossRefGoogle Scholar
  44. Stagno V, Ojwang DO, McCammon CA, Frost DJ (2013) The oxidation state of the mantle and the extraction of carbon from Earth’s interior. Nature 493:84–88CrossRefGoogle Scholar
  45. van Aken PA, Liebscher B (2002) Quantification of ferrous/ferric ratios in minerals: new evaluation schemes of Fe L-23 electron energy-loss near-edge spectra. Phys Chem Miner 29(3):188–200CrossRefGoogle Scholar
  46. van der Laan G, Kirkman IW (1992) The 2p Absorption-Spectra of 3d transition-metal compounds in tetrahedral and octahedral symmetry. J Phys-Condes Matter 4(16):4189–4204CrossRefGoogle Scholar
  47. Wasinger EC, de Groot FMF, Hedman B, Hodgson KO, Solomon EI (2003) L-edge X-ray absorption spectroscopy of non-heme iron sites: experimental determination of differential orbital covalency. J Am Chem Soc 125(42):12894–12906CrossRefGoogle Scholar
  48. Waychunas GA, Apted MJ, Brown GE Jr (1983) X-ray K-edge absorption spectra of Fe minerals and model compounds: near-edge structure. Phy Chem Min 10(1):1–9CrossRefGoogle Scholar
  49. Wilke M, Farges F, Petit PE, Brown GE Jr, Martin F (2001) Oxidation state and coordination of Fe in minerals: an FeK-XANES spectroscopic study. Am Mineral 86(5–6):714–730Google Scholar
  50. Wilke M, Hahn O, Woodland AB, Rickers K (2009) The oxidation state of iron determined by Fe K-edge XANES-application to iron gall ink in historical manuscripts. J Anal Atom Spectrom 24(10):1364–1372CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Franck Bourdelle
    • 1
    • 2
    Email author
  • Karim Benzerara
    • 1
  • Olivier Beyssac
    • 1
  • Julie Cosmidis
    • 1
  • Daniel R. Neuville
    • 3
  • Gordon E. BrownJr.
    • 4
    • 5
  • Erwan Paineau
    • 6
    • 7
  1. 1.IMPMC, UPMC-CNRSParis cedex 05France
  2. 2.GeoRessources, Université de Lorraine, UMR 7359 CNRSVandœuvre-lés-NancyFrance
  3. 3.Géochimie et Cosmochimie, Institut de Physique du Globe de ParisUniversité Paris Diderot, Sorbonne Paris Cité, UMR 7154 CNRSParisFrance
  4. 4.Surface and Aqueous Geochemistry Group, Department of Geological and Environmental SciencesStanford UniversityStanfordUSA
  5. 5.SLAC Natl Accelerator LabStanford Synchrotron Radiation LightsourceMenlo PkUSA
  6. 6.Laboratoire de Physique des SolidesUniversité Paris-Sud, UMR 8502 CNRSOrsay cedexFrance
  7. 7.Laboratoire Interdisciplinaire sur l’Organisation Nanométrique et SupramoléculaireCEA Saclay, IRAMISGif-sur-Yvette cedexFrance

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