Review of the principel and method for EPMA in-situ analysis of Fe oxidation state

ZHANG Chao; LI Xiaoyan

doi:10.16152/j.cnki.xdxbzr.2025-03-008

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Review of the principel and method for EPMA in-situ analysis of Fe oxidation state

更新时间：2025-06-26

- Review of the principel and method for EPMA in-situ analysis of Fe oxidation state
- Journal of Northwest University (Natural Science Edition) Vol. 55, Issue 3, Pages: 585-600(2025)
- 作者机构：
  
  西北大学　地质学系/大陆演化与早期生命全国重点实验室，陕西　西安　 710069
- 作者简介：
- 基金信息：
- DOI：10.16152/j.cnki.xdxbzr.2025-03-008
  CLC： P575;P595
- Received：15 March 2025，
  
  Published：25 June 2025
- 稿件说明：
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ZHANG Chao, LI Xiaoyan. Review of the principel and method for EPMA in-situ analysis of Fe oxidation state[J]. Journal of northwest university (natural science edition), 2025, 55(3): 585-600.
DOI：

ZHANG Chao, LI Xiaoyan. Review of the principel and method for EPMA in-situ analysis of Fe oxidation state[J]. Journal of northwest university (natural science edition), 2025, 55(3): 585-600. DOI： 10.16152/j.cnki.xdxbzr.2025-03-008.

摘要

氧化还原状态不仅是评估星球宜居性的关键因素，也是地球内部圈层和表层环境之间物质循环和耦合演化的重要驱动力。铁（Fe）是类地行星中含量最高的变价元素，因此Fe价态（通常用Fe

/ΣFe或Fe

/Fe

表示）是反映体系氧逸度的关键参数。该文详细探讨了电子探针在测定地质样品Fe价态的理论基础及其应用方法，分析了与之相关的X射线的激发与吸收原理、自吸收效应以及配位场理论，阐释了Fe价态测定依赖的

线系谱线特征。在此基础上，对比了峰肩法与峰位漂移法的优缺点，展示了不同样品在电子轰击下的损伤情况。研究表明，电子探针直接测定Fe价态方法具有广泛的应用前景和明显的技术优势，但仍需根据不同样品的特点优化测试条件和流程，以提高测试的准确性和可靠性。该研究为进一步开发和推广Fe价态测定方法提供了理论支持和实践指导，具有重要的地球科学研究意义。

Abstract

The redox state is not only a key factor in assessing planetary habitability

but also a crucial variable connecting Earth's interior spheres and surface environment via mass recycling and co-variation. Iron (Fe)

as the most abundant multivalent element in terrestrial planets

its oxidation state (expressed as Fe

/ΣFe or Fe

/Fe

) being the most important parameter reflecting the oxygen fugacity of the system. This study thoroughly investigates the application and theoretical foundation of electron probe microanalysis (EPMA) in the determination of Fe oxidation states in geological samples. We comprehensively analyzed the principles of X-ray emission and absorption

self-absorption effect

and crystal field theory

providing a detailed elucidation of the spectral characteristics of Fe's

-series lines. Accordingly

we compared the advantages and disadvantages of the peak shift method and the flank method

and examined the damage inflicted on samples under electron bombardment. The results demonstrate that EPMA holds extensive application potential and overwhelming advantages in the determination of Fe oxidation state

but the analytical protocol and condition must be optimized to enhance test accuracy and reliability according to the characteristics of different samples. This research offers theoretical support and practical guidance for further development and promotion of Fe valence determination methods

holding significant

implications for earth science research.

关键词

Keywords

references

BÉZOS A , HUMLER E . The Fe 3+ /ΣFe ratios of MORB glasses and their implications for mantle melting [J ] . Geochimica et Cosmochimica Acta , 2005 , 69 ( 3 ): 711 - 725 .

COTTRELL E , LANZIROTTI A , MYSEN B , et al . A Mössbauer-based XANES calibration for hydrous basalt glasses reveals radiation-induced oxidation of Fe [J ] . American Mineralogist , 2018 , 103 ( 4 ): 489 - 501 .

LI X Y , ZHANG C , ALMEEV R R , et al . Electron probe microanalysis of Fe 2+ /ΣFe ratios in calcic and sodic-calcic amphibole and biotite using the flank method [J ] . Chemical Geology , 2019 , 509 : 152 - 162 .

ZHANG C , ALMEEV R R , HUGHES E C , et al . Electron microprobe technique for the determination of iron oxidation state in silicate glasses [J ] . American Mineralogist , 2018 , 103 ( 9 ): 1445 - 1454 .

LAMB W M , GUILLEMETTE R , POPP R K , et al . Determination of Fe 3+ /Fe using the electron microprobe: A calibration for amphiboles [J ] . American Mineralogist , 2012 , 97 ( 5/6 ): 951 - 961 .

WILKE M , BEHRENS H , BURKHARD D J M , et al . The oxidation state of iron in silicic melt at 500 MPa water pressure [J ] . Chemical Geology , 2002 , 189 ( 1/2 ): 55 - 67 .

ZHANG H L , COTTRELL E , SOLHEID P A , et al . Determination of Fe 3+ /ΣFe of XANES basaltic glass standards by Mössbauer spectroscopy and its application to the oxidation state of iron in MORB [J ] . Chemical Geology , 2018 , 479 : 166 - 175 .

COTTRELL E , KELLEY K A , LANZIROTTI A , et al . High-precision determination of iron oxidation state in silicate glasses using XANES [J ] . Chemical Geology , 2009 , 268 ( 3/4 ): 167 - 179 .

GROSVENOR A P , KOBE B A , BIESINGER M C , et al . Investigation of multiplet splitting of Fe 2p XPS spectra and bonding in iron compounds [J ] . Surface and Interface Analysis , 2004 , 36 ( 12 ): 1564 - 1574 .

SCHINGARO E , LACALAMITA M , SCORDARI F , et al . 3T-phlogopite from Kasenyi kamafugite (SW Uganda): EPMA, XPS, FTIR, and SCXRD study [J ] . American Mineralogist , 2013 , 98 ( 4 ): 709 - 717 .

ARONNIEMI M , SAINIO J , LAHTINEN J . Chemical state quantification of iron and chromium oxides using XPS: The effect of the background subtraction method [J ] . Surface Science , 2005 , 578 ( 1/2/3 ): 108 - 123 .

GARVIE L A J , BUSECK P R . Ratios of ferrous to ferric iron from nanometre-sized areas in minerals [J ] . Nature , 1998 , 396 : 667 - 670 .

MIEDEMA P S , DE GROOT F M F . The iron L edges: Fe 2p X-ray absorption and electron energy loss spectroscopy [J ] . Journal of Electron Spectroscopy and Related Phenomena , 2013 , 187 : 32 - 48 .

VAN AKEN P A , LIEBSCHER B . Quantification of ferrous/ferric ratios in minerals: New evaluation schemes of Fe L 23 electron energy-loss near-edge spectra [J ] . Physics and Chemistry of Minerals , 2002 , 29 ( 3 ): 188 - 200 .

MCCAMMON C A . A Mössbauer milliprobe: Practical considerations [J ] . Hyperfine Interactions , 1994 , 92 ( 1 ): 1235 - 1239 .

MCCAMMON C A , GRIFFIN W L , SHEE S R , et al . Oxidation during metasomatism in ultramafic xenoliths from the Wesselton kimberlite, South Africa: Implications for the survival of diamond [J ] . Contributions to Mineralogy and Petrology , 2001 , 141 ( 3 ): 287 - 296 .

SOBOLEV V N , MCCAMMON C A , TAYLOR L A , et al . Precise Mössbauer milliprobe determination of ferric iron in rock-forming minerals and limitations of electron microprobe analysis [J ] . American Mineralogist , 1999 , 84 ( 1/2 ): 78 - 85 .

MCCAMMON C . Mössbauer spectroscopy with high spatial resolution: Spotlight on geoscience [M ] // YOSHIDA Y , LANGOUCHE G . Modern Mössbauer spectroscopy: New challenges based on cutting-edge techniques . Singapore : Springer Singapore , 2021 : 221 - 266 .

GABORIEAU M , LAUBIER M , BOLFAN-CASANOVA N , et al . Determination of Fe 3+ /ΣFe of olivine-hosted melt inclusions using Mössbauer and XANES spectroscopy [J ] . Chemical Geology , 2020 , 547 : 119646 .

LE LOSQ C , BERRY A J , KENDRICK M A , et al . Determination of the oxidation state of iron in Mid-Ocean Ridge basalt glasses by Raman spectroscopy [J ] . American Mineralogist , 2019 , 104 ( 7 ): 1032 - 1042 .

WELSCH A M , KNIPPING J L , BEHRENS H . Fe-oxidation state in alkali-trisilicate glasses: A Raman spectroscopic study [J ] . Journal of Non-Crystalline Solids , 2017 , 471 : 28 - 38 .

DI MURO A , MÉTRICH N , MERCIER M , et al . Micro-Raman determination of iron redox state in dry natural glasses: Application to peralkaline rhyolites and basalts [J ] . Chemical Geology , 2009 , 259 ( 1/2 ): 78 - 88 .

DYAR M D , BREVES E A , GUNTER M E , et al . Use of multivariate analysis for synchrotron micro-XANES analysis of iron valence state in amphiboles [J ] . American Mineralogist , 2016 , 101 ( 5 ): 1171 - 1189 .

DYAR M D , BREVES E A , EMERSON E , et al . Accurate determination of ferric iron in garnets by bulk Mössbauer spectroscopy and synchrotron micro-XANES [J ] . American Mineralogist , 2012 , 97 ( 10 ): 1726 - 1740 .

CALVIN S . XAFS for everyone [M ] . Oxfordshire, UK : Taylor & Francis , 2013 .

GOLDSTEIN J , NEWBURY D E , ECHLIN P , et al . Scanning electron microscopy and X-ray microanalysis [M ] . 3rd ed . New York : Springer US , 2012 .

RÉMOND G , MYKLEBUST R , FIALIN M , et al . Decomposition of wavelength dispersive X-ray spectra [J ] . Journal of Research of the National Institute of Standards and Technology , 2002 , 107 ( 6 ): 509 - 529 .

FM D G , FUGGLE J C , THOLE B T , et al . 2p X-ray absorption of 3d transition-metal compounds: An atomic multiplet description including the crystal field [J ] . Physical Review B , 1990 , 42 ( 9 ): 5459 - 5468 .

FM D G , FUGGLE J C , THOLE B T , et al . L 2, 3 x-ray-absorption edges of d 0 compounds: K + , Ca 2+ , Sc 3+ , and Ti 4+ in O h (octahedral) symmetry [J ] . Physical Review B , 1990 , 41 ( 2 ): 928 - 937 .

HÖFER H E , BREY G P , SCHULZ-DOBRICK B , et al . The determination of the oxidation state of iron by the electron microprobe [J ] . European Journal of Mineralogy , 1994 , 6 ( 3 ): 407 - 418 .

FUGGLE J C , MÅRTENSSON N . Core-level binding energies in metals [J ] . Journal of Electron Spectroscopy and Related Phenomena , 1980 , 21 ( 3 ): 275 - 281 .

DE GROOT F . High-resolution X-ray emission and X-ray absorption spectroscopy [J ] . Chemical Reviews , 2001 , 101 ( 6 ): 1779 - 1808 .

POUCHOU J L , PICHOIR F . Quantitative analysis of homogeneous or stratified microvolumes applying the model "PAP" [M ] // HEINRICH K F J , NEWBURY D E . Electron Probe Quantitation . Boston, MA : Springer US , 1991 : 31 - 75 .

LLOVET X , MOY A , FOURNELLE J H . Electron probe microanalysis of transition metals using L lines: The effect of self-absorption [J ] . Microscopy and Microanalysis , 2022 , 28 ( 1 ): 123 - 137 .

TERAUCHI M , SATO Y K , YOKOYAMA T D , et al . Simple derivation of L-absorption spectra of 3d transition metal elements by the self-absorption effect observed in soft X-ray emission spectra [J ] . Microscopy , 2024 , 73 ( 5 ): 451 - 455 .

LIEFELD R J . Soft X-ray emission spectra at threshold excitation [M ] // FABIAN D J . Soft X-ray band spectra the electronic structure of metals materialsls . London and New York : Academic Press . 1968 : 133 .

FISCHER D W . Molecular-orbital Interpretation of the soft X-ray L II, III emission and absorption spectra from some titanium and vanadium compounds [J ] . Journal of Applied Physics , 1970 , 41 ( 9 ): 3561 - 3569 .

FISCHER D W , BAUN W L . Band structure and the titanium L II, III X-ray emission and absorption spectra from pure metal, oxides, nitride, carbide, and boride [J ] . Journal of Applied Physics , 1968 , 39 ( 10 ): 4757 - 4776 .

EL-KHOLY S , ULMER K . Absolute determination of L III -binding energy in nickel from self-absorption measurements [J ] . Zeitschrift für Physik B Condensed Matter , 1980 , 38 ( 1 ): 1 - 9 .

BURGÄZY F , JAEGER H , SCHULZE K , et al . X-ray emission and X-ray self-absorption in the high- T c superconductor YBa 2 Cu 3 O 6.9 and other copper oxides [J ] . Zeitschrift für Naturforschung A , 1989 , 44 ( 3 ): 180 - 188 .

YOKOYAMA T D , TAKAHASHI H , KOSHIYA S , et al . Analytical technique for self-absorption structure of iron L-emission spectra obtained by soft X-ray emission spectrometer [J ] . Microscopy , 2022 , 71 ( 3 ): 169 - 174 .

BURNS R G . Mineralogical applications of crystal field theory [M ] . 2nd ed . Cambridge, UK : Cambridge University Press , 1993 .

LEVER A B P . Inorganic electronic spectroscopy [M ] . 2nd ed . Amsterdam : Elsevier , 1984 .

DROUBAY T , CHAMBERS S A . Surface-sensitive Fe 2 p photoemission spectra for α-Fe 2 O 3 (0001): The influence of symmetry and crystal-field strength [J ] . Physical Review B , 2001 , 64 ( 20 ): 205414 .

LIN J F , SPEZIALE S , MAO Z , et al . Effects of the electronic spin transitions of iron in lower mantle minerals: Implications for deep mantle geophysics and geochemistry [J ] . Reviews of Geophysics , 2013 , 51 ( 2 ): 244 - 275 .

HSU H , UMEMOTO K . Structural transition and re-emergence of iron's total electron spin in (Mg, Fe)O at ultrahigh pressure [J ] . Nature Communications , 2022 , 13 ( 1 ): 2780 .

NOMURA R , OZAWA H , TATENO S , et al . Spin crossover and iron-rich silicate melt in the Earth's deep mantle [J ] . Nature , 2011 , 473 : 199 - 202 .

VAN DER LAAN G , KIRKMAN I W . The 2p absorption spectra of 3d transition metal compounds in tetrahedral and octahedral symmetry [J ] . Journal of Physics: Condensed Matter , 1992 , 4 ( 16 ): 4189 - 4204 .

CRESSEY G , HENDERSON M B , VAN DER LAAN G . Use of L -edge X-ray absorption spectroscopy to characterize multiple valence states of 3 d transition metals; a new probe for mineralogical and geochemical research [J ] . Physics and Chemistry of Minerals , 1993 , 20 ( 2 ): 111 - 119 .

DE GROOT F M F . Differences between L 3 and L 2 X-ray absorption spectra [J ] . Physica B: Condensed Matter , 1995 , 208 : 15 - 18 .

GARVIE L A J , CRAVEN A J , BRYDSON R . Use of electron-energy loss near-edge fine structure in the study of minerals [J ] . American Mineralogist , 1994 , 79 : 411 - 425 .

WHITE W B , MOORE R K . Interpretation of the spin-allowed bands of Fe 2+ in silicate garnets [J ] . American Mineralogist , 1972 , 57 ( 11/12 ): 1692 - 1710 .

ATKINS P , OVERTON T , ROURKE J , et al . Shriver and Atkins' inorganic chemistry [M ] . 5th ed . Oxford : Oxford University Press , 2010 .

WILKE M , PARTZSCH G M , BERNHARDT R , et al . Determination of the iron oxidation state in basaltic glasses using XANES at the K-edge [J ] . Chemical Geology , 2004 , 213 ( 1/2/3 ): 71 - 87 .

BOTCHARNIKOV R E , KOEPKE J , HOLTZ F , et al . The effect of water activity on the oxidation and structural state of Fe in a ferro-basaltic melt [J ] . Geochimica et Cosmochimica Acta , 2005 , 69 ( 21 ): 5071 - 5085 .

HOǍFER H E . Quantification of Fe 2+ /Fe 3+ by electron microprobe analysis: New developments [M ] . Berlin : Springer . 2002 : 239 - 248 .

WOODLAND A B , ROSS C R . A crystallographic and mössbauer spectroscopy study of https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=83754963&type= https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=83754939&type= https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=83754956&type= , (almandine-"skiagite") and https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=83754940&type= https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=83754973&type= https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=83754964&type= (andradite-"skiagite") garnet solid solutions [J ] . Physics and Chemistry of Minerals , 1994 , 21 ( 3 ): 117 - 132 .

BRIGATTI M F , GUGGENHEIM S . Mica crystal chemistry and the influence of pressure, temperature, and solid solution on atomistic models [J ] . Reviews in Mineralogy and Geochemistry , 2002 , 46 ( 1 ): 1 - 97 .

DYAR M . A review of Mössbaue data on trioctahedral micas: Evidence for tetrahedral Fe 3+ and cation ordering [J ] . American Mineralogist , 1987 , 72 : 102 - 112 .

DYAR M D . Mössbauer spectra of biotite from metapelites [J ] . American Mineralogist , 1990 , 75 ( 5/6 ): 656 - 666 .

HAWTHORNE F C , OBERTI R . Amphiboles: Crystal chemistry [J ] . Reviews in Mineralogy and Geochemistry , 2007 , 67 ( 1 ): 1 - 54 .

LI X Y , ZHANG C , BEHRENS H , et al . Calculating biotite formula from electron microprobe analysis data using a machine learning method based on principal components regression [J ] . Lithos , 2020 , 356 : 105371 .

LI X Y , ZHANG C , BEHRENS H , et al . Calculating amphibole formula from electron microprobe analysis data using a machine learning method based on principal components regression [J ] . Lithos , 2020 , 362 : 105469 .

FIALIN M , BÉZOS A , WAGNER C , et al . Quantitative electron microprobe analysis of Fe 3+ /ΣFe: Basic concepts and experimental protocol for glasses [J ] . American Mineralogist , 2004 , 89 ( 4 ): 654 - 662 .

HÖFER H E , BREY G P . The iron oxidation state of garnet by electron microprobe: Its determination with the flank method combined with major-element analysis [J ] . American Mineralogist , 2007 , 92 ( 5/6 ): 873 - 885 .

ALBEE A L , CHODOS A A . Semiquantitative electron microprobe determination of Fe 2+ /Fe 3+ and Mn 2+ /Mn 3+ in oxides and silicates and its application to petrologic problems [J ] . American Mineralogist , 1970 , 55 ( 3/4 ): 491 - 501 .

FIALIN M , WAGNER C , MÉTRICH N , et al . Fe 3+ /∑Fe vs. Fe L α peak energy for minerals and glasses: Recent advances with the electron microprobe [J ] . American Mineralogist , 2001 , 86 ( 4 ): 456 - 465 .

MALASPINA N , POLI S , FUMAGALLI P . The oxidation state of metasomatized mantle wedge: Insights from C-O-H-bearing garnet peridotite [J ] . Journal of Petrology , 2009 , 50 ( 8 ): 1533 - 1552 .

TAO R B , FEI Y W , BULLOCK E S , et al . Experimental investigation of Fe 3+ -rich majoritic garnet and its effect on majorite geobarometer [J ] . Geochimica et Cosmochimica Acta , 2018 , 225 : 1 - 16 .

LI X L , SONG S G , ZHANG L F , et al . Application of microprobe-based flank method analysis of Fe 3+ in garnet of North Qilian eclogite and its geological implication [J ] . Science Bulletin , 2018 , 63 ( 5 ): 300 - 305 .

SHAIKH A M , BUSSWEILER Y , VILJOEN F , et al . Redox state of the Dharwar craton root as inferred from eclogite and peridotite sourced mantle cargo, with implications for kimberlite and lamproite magma formation [J ] . Contributions to Mineralogy and Petrology , 2023 , 178 ( 12 ): 86 .

TANG M , LEE C T A , COSTIN G , et al . Recycling reduced iron at the base of magmatic orogens [J ] . Earth and Planetary Science Letters , 2019 , 528 : 115827 .

HÖFER H E , BREY G P , OBERHÄNSLI R . The determination of the oxidation state of iron in synthetic garnets by X-ray spectroscopy with the electron microprobe [J ] . Physics and Chemistry of Minerals , 1996 , 23 ( 4 ): 241 .

HUGHES E C , BEN B S , KEARNS S L , et al . High spatial resolution analysis of the iron oxidation state in silicate glasses using the electron probe [J ] . American Mineralogist , 2018 , 103 ( 9 ): 1473 - 1486 .

ENDERS M , SPEER D , MARESCH W V , et al . Ferric/ferrous iron ratios in sodic amphiboles: Mössbauer analysis, stoichiometry-based model calculations and the high-resolution microanalytical flank method [J ] . Contributions to Mineralogy and Petrology , 2000 , 140 ( 2 ): 135 - 147 .

HÖFER H E , WEINBRUCH S , MCCAMMON C A , et al . Comparison of two electron probe microanalysis techniques to determine ferric iron in synthetic wüstite samples [J ] . European Journal of Mineralogy , 2000 , 12 ( 1 ): 63 - 71 .

PARK R L , HOUSTON J E . L-shell soft-X-ray appearance-potential spectra of the 3d transition metals [J ] . Physical Review B , 1972 , 6 ( 4 ): 1073 .

MORGAN G B , LONDON D . Optimizing the electron microprobe analysis of hydrous alkali aluminosilicate glasses [J ] . American Mineralogist , 1996 , 81 ( 9/10 ): 1176 - 1185 .

FIALIN M , WAGNER C . Redox kinetics of iron in alkali silicate glasses exposed to ionizing beams: Examples with the electron microprobe [J ] . Journal of Non-Crystalline Solids , 2012 , 358 ( 12/13 ): 1617 - 1623 .

WAGNER C , DELOULE E , FIALIN M , et al . Dehydrogenation of kaersutitic amphibole under electron beam excitation recorded by changes in Fe 3+ /ΣFe: An EMP and SIMS study [J ] . American Mineralogist , 2008 , 93 ( 8/9 ): 1273 - 1281 .

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