Skip to main content
SpringerLink
Log in

Evaluation of scanning transmission X-ray microscopy at the Mn L2,3-edges as a potential probe for manganese redox state in natural silicates

  • Original Paper
  • Published:
Physics and Chemistry of Minerals Aims and scope Submit manuscript

Abstract

Determining the Mn valence variation at the nanometer scale will be an important advance in the study of heterogeneous natural silicates. Here, the potential of the scanning transmission X-ray microscopy at the Mn L2,3-edges (640–655 eV) as a probe for manganese redox state is evaluated. For this purpose, several natural Mn-silicates (rhodonite, ardennite, piemontite, Mn4+-silicate, jacobsite) were analysed to identify the spectral parameters most sensitive to the Mn valence, regardless of the coordination environment, the crystal field strength, the nature and the length of the metal–ligand bonds, and the intra-atomic Coulomb and spin–orbit interactions. Two suitable spectral empirical calibrations are thus proposed, linking the Mn valence to two peak intensity ratios: one ratio of intensities from two energy points of the L2 peak (at 651.7 and 655.2 eV), and one ratio of intensities from one energy point of the L2 peak (at 655.2 eV) and one of the L3 peak (at 641.6 eV). Thank to them, the first quantitative Mn valence maps are constructed, with a high spatial resolution (<40 nm pixel size), opening the way to exhaustive crystallochemical studies of silicates containing Mn with different valences.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

Availability of data and material

XANES spectra are available on request from franck.bourdelle@univ-lille.fr.

Code availability

Not applicable.

References

  • Albee AL, Chodos AA (1970) Semiquantitaive electron microscope determination of Fe2+/Fe3+ and Mn2+/Mn3+ in oxides and silicates and its application to petrologic problems. Am Mineral 55:491–501

    Google Scholar 

  • Benzerara K, Menguy N, Obst M, Stolarski J, Mazur M, Tylisczak T, Brown GE Jr, Meibom A (2011) Study of the crystallographic architecture of corals at the nanoscale by scanning transmission X-ray microscopy and transmission electron microscopy. Ultramicroscopy 111:1268–1275

    Article  Google Scholar 

  • Bobos I, Noronha F, Mateus A (2018) Fe-, Fe, Mn- and Fe, Mg-chlorite: a genetic linkage to W, (Cu, Mo) mineralization in the magmatic-hydrothermal system at Borralha, northern Portugal. Mineral Mag 82:S259–S279

    Article  Google Scholar 

  • Bosi F, Biagioni C, Pasero M (2019) Nomenclature and classification of the spinel supergroup. Eur J Mineral 31:183–192

    Article  Google Scholar 

  • Bourdelle F, Benzerara K, Beyssac O, Cosmidis J, Neuville DR, Brown GE, Paineau E (2013) Quantification of the ferric/ferrous iron ratio in silicates by scanning transmission X-ray microscopy at the Fe L2,3 edges. Contrib Mineral Petrol 166:423–434

    Article  Google Scholar 

  • Bourdelle F, Beyssac O, Parra T, Chopin C (2018) Nanoscale chemical zoning of chlorite and implications for low-temperature thermometry: application to the Glarus Alps (Switzerland). Lithos 314:551–561

    Article  Google Scholar 

  • 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:G3

    Article  Google Scholar 

  • Burns R (1993) Mineralogical applications of crystal field theory (Cambridge Topics in Mineral Physics and Chemistry). Cambridge University Press, Cambridge. https://doi.org/10.1017/CBO9780511524899

    Book  Google Scholar 

  • 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 75:152–155

    Article  Google Scholar 

  • Cuartero V, Lafuerza S, Rovezzi M, Garcia J, Blasco J, Subias G, Jiménez E (2016) X-ray absorption and emission spectroscopy study of Mn and Co valence and spin states in TbMn1−xCoxO3. Phys rev B 94:155117

    Article  Google Scholar 

  • de Groot FMF (1994) X-ray absorption and dichroism of transition metals and their compounds. J Electron Spectros Relat Phenomena 67:529–622

    Article  Google Scholar 

  • 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. Chem Phys Chem 11:951–962

    Article  Google Scholar 

  • Donnay G, Allmann R (1968) Si3O10 groups in the crystal structure of ardennite. Acta Cryst B 24:845

    Article  Google Scholar 

  • Garvie LAJ, Craven AJ (1994) High-resolution parallel electron energy-loss spectroscopy of Mn L2,3-edges in inorganic manganese compounds. Phys Chem Miner 21:191–206

    Article  Google Scholar 

  • Garvie LAJ, Craven AJ, Brydson R (1994) Use of electron-energy loss near-edge fine structure in the study of minerals. Am Mineral 79:411–425

    Google Scholar 

  • Hanhan S, Smith AM, Obst M, Hitchcock AP (2009) Optimization of analysis of soft X-ray spectromicroscopy at the Ca 2p edge. J Electron Spectros 173:44–49

    Article  Google Scholar 

  • Hitchcock AP (2012) aXis 2000 analysis of X-ray images and spectra. McMaster University, Hamilton

    Google Scholar 

  • Ilton ES, Post JE, Heaney PJ, Ling FT, Kerisit SN (2016) XPS determination of Mn oxidation states in Mn (hydr)oxides. Appl Surf Sci 366:475–485

    Article  Google Scholar 

  • Inoue A, Inoue S, Utada M (2018) Application of chlorite thermometry to estimation of formation temperature and redox conditions. Clay Miner 53:143–158

    Article  Google Scholar 

  • Kubin M, Guo M, Kroll T, Löchel H, Källman E, Baker ML, Mitzner R, Gul S, Kern J, Föhlisch A, Erko A, Bergmann U, Yachandra V, Yano J, Lundberg M, Wernet P (2018) Probing the oxidation state of transition metal complexes: a case study on how charge and spin densities determine Mn L-edge X-ray absorption energies. Chem Sci 9:6813

    Article  Google Scholar 

  • 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 Petrol 138:17–26

    Article  Google Scholar 

  • Livi KJT, Lafferty B, Zhu M, Zhang S, Gaillot A-C, Sparks DL (2012) Electron energy-loss safe-dose limits for manganese valence measurements in environmentally relevant manganese oxides. Environ Sci Technol 46:970–976

    Article  Google Scholar 

  • Loomer D, Al T, Weaver L, Cogswell S (2007) Manganese valence imaging in Mn minerals at the nanoscale using STEM-EELS. Am Mineral 92:72–79

    Article  Google Scholar 

  • Manceau A, Gallup DL (2005) Nanometer-sized divalent manganese-hydrous silicate domains in geothermal brine precipitates. Am Mineral 90:371–381

    Article  Google Scholar 

  • Manceau A, Marcus MA, Grangeon S (2012) Determination of Mn valence states in mixed-valent manganates by XANES spectroscopy. Am Mineral 97:816–827

    Article  Google Scholar 

  • Morales F, de Groot FMF, Glatzel P, Kleimenov E, Bluhm H, Hävecker M, Knop-Gericke A, Weckhuysen BM (2004) In Situ X-ray Absorption of Co/Mn/TiO2 catalysts for Fischer-Tropsch synthesis. J Phys Chem B 108:16201–16207

    Article  Google Scholar 

  • Nagashima M, Armbruster T (2010) Ardennite, tiragalloite and medaite: structural control of (As5+, V5+, Si4+)O4 tetrahedra in silicates. Mineral Mag 74:55–71

    Article  Google Scholar 

  • Nelson WR, Griffen DT (2005) Crystal chemistry of Zn-rich rhodonite (“fowlerite”). Am Mineral 90:969–983

    Article  Google Scholar 

  • Nishida S, Kobayashi S, Kumamoto A, Ikeno H, Mizoguchi T, Tanaka I, Ikuhara Y, Yamamoto T (2013) Effect of local coordination of Mn on Mn-L2,3 edge electron energy loss spectrum. J Appl Phys 114:054906

    Article  Google Scholar 

  • Pecher K, McCubbery D, Kneedler E, Rothe J, Bargar J, Meigs G, Cox L, Nealson K, Tonner B (2003) Quantitative charge state analysis of manganese biominerals in aqueous suspension using Scanning Transmission X-ray Microscopy (STXM). Geochim Cosmochim Acta 67:1089–1098

    Article  Google Scholar 

  • Pérez-Dieste V, Crain JN, Kirakosian A, McChesney JL, Arenholz E, Young AT, Denlinger JD, Ederer DL, Callcott TA, Lopez-Rivera SA, Himpsel FJ (2004) Unoccupied orbitals of 3d transition metals in ZnS. Phys Rev B 70:085205

    Article  Google Scholar 

  • 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

  • Risch M, Stoerzinger KA, Han B, Regier TZ, Peak D, Sayed SY, Wei C, Xu Z, Shao-Horn Y (2017) Redox processes of manganese oxide in catalyzing oxygen evolution and reduction: an in situ soft X-ray absorption spectroscopy study. J Phys Chem C 121:17682–17692

    Article  Google Scholar 

  • Smyth JR, Bish DL (1988) Crystal structures and cation sites of the rock-forming minerals London and Boston (Unwin-Hyman Ltd.). Mineral Mag 52:733–734

    Google Scholar 

  • Sussenberger A, Pospiech S, Schmidt ST (2018) [MnO vertical bar SiO2, Al2O3, FeO, MgO] balanced log-ratio in chlorites: a tool for chemo-stratigraphic mapping and proxy for the depositional environment. 16th International Clay Conference (ICC) Location: Granada. Clay miner 53:351–375

    Article  Google Scholar 

  • Tan H, Verbeeck J, Abakumov A, van Tendeloo G (2012) Oxidation state and chemical shift investigation in transition metal oxides by EELS. Ultramicroscopy 116:24–33

    Article  Google Scholar 

  • 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 29:188–200

    Article  Google Scholar 

  • Van der Laan G, Kirkman IW (1992) The 2p absorption spectra of 3d transition metal compounds in tetrahedral and octahedral symmetry. J Phys: Condens Matter 4:4189–4204

    Google Scholar 

  • Wang H, Friedrich S, Li L, Mao Z, Ge P, Balasubramanian M, Patil DS (2018) L-edge sum rule analysis on 3d transition metal sites: from d10 to d0 and towards application to extremely dilute metallo-enzymes. Phys Chem Chem Phys 20:8166–8176

    Article  Google Scholar 

  • Zhang S, Livi KJT, Gaillot A-C, Stone AT, Veblen DR (2010) Determination of manganese valence states in (Mn3+, Mn4+) minerals by electron energy-loss spectroscopy. Am Mineral 95:1741–1746

    Article  Google Scholar 

Download references

Acknowledgements

We are most grateful to the PSI SLS synchrotron, especially Benjamin Watts (PolLux beamline) for technical advice. Thanks are extended to Philippe Recourt (LOG, Univ. Lille) for sample preparation and to Francis Coune for providing ardennite sample. The authors wish also to thank the editor and the two anonymous reviewers for comments and suggestions that improved the paper. This study was financially supported by LGCgE.

Funding

This study was financially supported by LGCgE (laboratory funds).

Author information

Authors and Affiliations

  1. Univ. Lille, Institut Mines-Télécom, Univ. Artois, Junia, ULR 4515 - LGCgE, Laboratoire de Génie Civil et géo-Environnement, 59000, Lille, France

    Franck Bourdelle, Emily Lloret & Cyril Durand

  2. University of Orléans, CNRS, BRGM, ISTO, UMR 7327, 45071, Orleans, France

    Laura Airaghi

Authors
  1. Franck Bourdelle
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Emily Lloret
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Cyril Durand
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Laura Airaghi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Franck Bourdelle.

Ethics declarations

Conflicts of interest

Not applicable.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Bourdelle, F., Lloret, E., Durand, C. et al. Evaluation of scanning transmission X-ray microscopy at the Mn L2,3-edges as a potential probe for manganese redox state in natural silicates. Phys Chem Minerals 48, 18 (2021). https://doi.org/10.1007/s00269-021-01142-w

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00269-021-01142-w

Keywords

Search

Navigation