Skip to main content Accessibility help

We use cookies to distinguish you from other users and to provide you with a better experience on our websites. Close this message to accept cookies or find out how to manage your cookie settings.

Close cookie message
×
Hostname: page-component-669899f699-ggqkh Total loading time: 0 Render date: 2025-05-03T23:02:58.673Z Has data issue: false hasContentIssue false

13 - Mössbauer Spectroscopy

from Part IV - Spectroscopy

Published online by Cambridge University Press:  06 July 2019

By
James M. Byrne  and
Andreas Kappler
Edited by
Janice P. L. Kenney ,
Harish Veeramani  and
Daniel S. Alessi
Janice P. L. Kenney
Affiliation:
MacEwan University, Edmonton
Harish Veeramani
Affiliation:
Carleton University, Ottawa
Daniel S. Alessi
Affiliation:
University of Alberta
Get access

Summary

Following the discovery almost half a century ago of the resonant emission and absorption of gamma rays in 191Ir by Rudolf Mössbauer (Mossbauer, ), the effect that takes his name has been utilized by many studies to explore a wide range of elements and minerals. Recently, a renewed interest in the application of Mössbauer spectroscopy in geosciences, particularly with regard to nanomaterials and Mars (Klingelhöfer et al., ), has led to the technique becoming an increasingly important tool. This is especially true for 57Fe mineralogy, where the technique is capable of selectively determining the oxidation state and mineralogy of Fe in samples of environmental soils and sediments, which might be dominated by a wide range of mineral phases that might not ordinarily be measurable with conventional techniques.

The purpose of this chapter is to give a general overview of Mössbauer spectroscopy to the non-specialist. While there are many elements that are able to undergo the Mössbauer effect, we focus on 57Fe in particular in order to help encourage its use in the field of geomicrobiology. As such, many important factors will not be covered here, and the reader is encouraged to look at additional material to obtain a more comprehensive understanding of the theory of Mössbauer spectroscopy. Some example reviews include references (Dyar et al., ; Greenwood and Gibb, ; Gütlich et al., , ; Murad and Cashion, ). Furthermore, when considering whether the technique is potentially useful in a study, it is always advisable to combine the results and observations obtained through Mössbauer spectroscopy with information obtained through diffraction, imaging, or synchrotron-based techniques to obtain a complete story of the nature of a sample. This chapter has been broken up into separate sections, including a brief introduction to the theory behind Mössbauer spectroscopy; the parameters that are obtained from each spectrum and provide the necessary information required for fitting; some experimental details about how measurements are carried out and should be prepared; and finally, the applications of the technique and how it can be used to determine the oxidation states and mineral identities of samples.

Type
Chapter
Information
Analytical Geomicrobiology
A Handbook of Instrumental Techniques
 , pp. 314 - 338
Publisher: Cambridge University Press
Print publication year: 2019

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Book purchase

Temporarily unavailable

References

13.6 References

Bernal, J. D., Dasgupta, D. R. and Mackay, A. L. 1959. The oxides and hydroxides of iron and their structural inter-relationships. Clay Minerals Bulletin, 4, 15.Google Scholar
Brown, A. R., Wincott, P. L., Laverne, J. A., et al. 2014. The impact of γ radiation on the bioavailability of Fe(III) minerals for microbial respiration. Environmental Science & Technology, 48, 10672–10680.Google Scholar
Byrne, J. M., Coker, V. S., Cespedes, E., et al. 2014. Biosynthesis of zinc substituted magnetite nanoparticles with enhanced magnetic properties. Advanced Functional Materials, 24, 2518–2529.Google Scholar
Byrne, J. M., Coker, V. S., Moise, S., et al. 2013. Controlled cobalt doping in biogenic magnetite nanoparticles. Journal of the Royal Society Interface, 10, 20130134.CrossRefGoogle ScholarPubMed
Byrne, J. M., Klueglein, N., Pearce, C., et al. 2015. Redox cycling of Fe(II) and Fe(III) in magnetite by Fe-metabolizing bacteria. Science, 347, 1473–1476.Google Scholar
Byrne, J. M., Telling, N. D., Coker, V. S., et al. 2011. Control of nanoparticle size, reactivity and magnetic properties during the bioproduction of magnetite by Geobacter sulfurreducens. Nanotechnology, 22, 455709.Google Scholar
Chadwick, J., Jones, D. H., Thomas, M. F., Tatlock, G. J. and Devenish, R. W. 1986. A Mössbauer study of ferrihydrite and aluminium substituted ferrihydrites. Journal of Magnetism and Magnetic Materials, 61, 88–100.Google Scholar
Chaudhuri, S. K., Lack, J. G. and Coates, J. D. 2001. Biogenic magnetite formation through anaerobic biooxidation of Fe(II). Applied and Environmental Microbiology, 67, 2844–2848.Google Scholar
Chen, C., Kukkadapu, R. and Sparks, D. L. 2015. Influence of coprecipitated organic matter on Fe2+(aq)-catalyzed transformation of ferrihydrite: Implications for carbon dynamics. Environmental Science & Technology, 49, 10927–10936.Google Scholar
Cornell, R. M. and Schwertmann, U. 2003. The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses, Weinheim, Germany, Wiley-VCH.Google Scholar
Cutting, R. S., Coker, V. S., Fellowes, J. W., Lloyd, J. R. and Vaughan, D. J. 2009. Mineralogical and morphological constraints on the reduction of Fe(III) minerals by Geobacter sulfurreducens. Geochimica et Cosmochimica Acta, 73, 4004–4022.Google Scholar
Cuttler, A., Man, V., Cranshaw, T. and Longworth, G. 1990. A Mössbauer study of green rust precipitates: I. Preparations from sulphate solutions. Clay Minerals, 25, 289–301.Google Scholar
De Grave, E. and Van Alboom, A. 1991. Evaluation of ferrous and ferric Mössbauer fractions. Physics and Chemistry of Minerals, 18, 337–342.Google Scholar
Dippon, U., Pantke, C., Porsch, K., Larese-Casanova, P. and Kappler, A. 2012. Potential function of added minerals as nucleation sites and effect of humic substances on mineral formation by the nitrate-reducing Fe(II)-oxidizing strain Acidovorax sp. BoFeN1. Environmental Science & Technology, 46, 6556–6565.Google Scholar
Dippon, U., Schmidt, C., Behrens, S. and Kappler, A. 2015. Secondary mineral formation during ferrihydrite reduction by Shewanella oneidensis MR-1 depends on incubation vessel orientation and resulting gradients of cells, Fe2+ and Fe3+ minerals. Geomicrobiology Journal, 32, 868–877.Google Scholar
Dong, H., Fredrickson, J. K., Kennedy, D. W., et al. 2000. Mineral transformations associated with the microbial reduction of magnetite. Chemical Geology, 169, 299–318.Google Scholar
Drits, V., Sakharov, B., Salyn, A. and Manceau, A. 1993. Structural model for ferrihydrite. Clay Minerals, 28, 185–207.Google Scholar
Dyar, M. D., Agresti, D. G., Schaefer, M. W., Grant, C. A. and Sklute, E. C. 2006. Mössbauer spectroscopy of earth and planetary materials. Annual Review of Earth and Planetary Sciences, 34, 83–125.Google Scholar
Eickhoff, M., Obst, M., Schröder, C., et al. 2014. Nickel partitioning in biogenic and abiogenic ferrihydrite: The influence of silica and implications for ancient environments. Geochimica et Cosmochimica Acta, 140, 65–79.Google Scholar
Ericsson, T., Krishnamurthy, A. and Srivastava, B. K. 1986. Morin-transition in Ti-substituted hematite: A Mössbauer study. Physica Scripta, 33, 88.Google Scholar
Forester, D. W. and Koon, N. C. 1969. Mössbauer investigation of metamagnetic FeCO3. Journal of Applied Physics, 40, 1316–1317.Google Scholar
Forsyth, J. B., Johnson, C. E. and Wilkinson, C. 1970. The magnetic structure of vivianite, Fe3(PO4)2.8H2O. Journal of Physics C: Solid State Physics, 3, 1127.Google Scholar
Fortin, D., Leppard, G. G. and Tessier, A. 1993. Characteristics of lacustrine diagenetic iron oxyhydroxides. Geochimica et Cosmochimica Acta, 57, 4391–4404.Google Scholar
Frankel, R. B., Papaefthymiou, G. C., Blakemore, R. P. and O’Brien, W. 1983. Fe3O4 precipitation in magnetotactic bacteria. Biochimica et Biophysica Acta (BBA) – Molecular Cell Research, 763, 147–159.Google Scholar
Fysh, S. and Clark, P. 1982. Aluminous hematite: A Mössbauer study. Physics and Chemistry of Minerals, 8, 257–267.Google Scholar
Génin, J.-M. R., Bourrié, G., Trolard, F., et al. 1998. Thermodynamic equilibria in aqueous suspensions of synthetic and natural Fe(II)−Fe(III) green Rusts:  Occurrences of the mineral in hydromorphic soils. Environmental Science & Technology, 32, 1058–1068.Google Scholar
Gonser, U. and Grant, R. W. 1967. Determination of spin directions and electric field gradient axes in vivianite by polarized recoil-free γ-rays. Physica Status Solidi (B), 21, 331–342.Google Scholar
Gorski, C. A., Handler, R. M., Beard, B. L., et al. 2012. Fe atom exchange between aqueous Fe2+ and magnetite. Environmental Science & Technology, 46, 12399–12407.Google Scholar
Gorski, C. A. and Scherer, M. M. 2010. Determination of nanoparticulate magnetite stoichiometry by Mössbauer spectroscopy, acidic dissolution, and powder X-ray diffraction: A critical review. American Mineralogist, 95, 1017–1026.Google Scholar
Greenwood, N. N. and Gibb, T. C. 1971. Mössbauer Spectroscopy, London, Chapman and Hall Ltd.Google Scholar
Gütlich, P., Bill, E. and Trautwein, A. X. 2010. Mössbauer Spectroscopy and Transition Metal Chemistry: Fundamentals and Applications, Berlin Heidelberg, Springer Science & Business Media.Google Scholar
Gütlich, P., Schröder, C. and Schünemann, V. 2012. Mössbauer spectroscopy—an indispensable tool in solid state research. Spectroscopy Europe, 24, 21.Google Scholar
Handler, R. M., Beard, B. L., Johnson, C. M. and Scherer, M. M. 2009. Atom exchange between aqueous Fe(II) and goethite: An Fe isotope tracer study. Environmental Science & Technology, 43, 1102–1107.Google Scholar
Hirt, A. M., Lanci, L., Dobson, J., Weidler, P. and Gehring, A. U. 2002. Low-temperature magnetic properties of lepidocrocite. Journal of Geophysical Research: Solid Earth, 107, EPM 5–1-EPM 5–9.Google Scholar
Hohmann, C., Winkler, E., Morin, G. and Kappler, A. 2010. Anaerobic Fe(II)-oxidizing bacteria show As resistance and immobilize As during Fe(III) mineral precipitation. Environmental Science & Technology, 44, 94–101.Google Scholar
Housley, R. M., Gonser, U. and Grant, R. W. 1968. Mössbauer determination of the Debye-Waller factor in single-crystal absorbers. Physical Review Letters, 20, 1279–1282.Google Scholar
Klein, C. 2005. Some Precambrian banded iron-formations (BIFs) from around the world: Their age, geologic setting, mineralogy, metamorphism, geochemistry, and origins. American Mineralogist, 90, 1473–1499.Google Scholar
Klingelhöfer, G., Morris, R. V., Bernhardt, B., et al. 2003. Athena MIMOS II Mössbauer spectrometer investigation. Journal of Geophysical Research: Planets, 108, 8067.Google Scholar
Klingelhöfer, G., Morris, R. V., Bernhardt, B., et al. 2004. Jarosite and hematite at Meridiani Planum from Opportunity’s Mössbauer spectrometer. Science, 306, 1740–1745.Google Scholar
Klingelhöfer, G., Morris, R. V., De Souza, P. A., Jr., Rodionov, D. and Schröder, C. 2006. Two earth years of Mössbauer studies of the surface of Mars with MIMOS II. Hyperfine Interactions, 170, 169–177.Google Scholar
Klueglein, N. and Kappler, A. 2012. Abiotic oxidation of Fe(II) by reactive nitrogen species in cultures of the nitrate-reducing Fe(II) oxidizer Acidovorax sp. BoFeN1 – questioning the existence of enzymatic Fe(II) oxidation. Geobiology, 11, 396.Google Scholar
Kündig, W., Bömmel, H., Constabaris, G. and Lindquist, R. H. 1966. Some properties of supported small a-Fe2O3 particles determined with the Mössbauer effect. Physical Review, 142, 327–333.Google Scholar
Kündig, W. and Steven Hargrove, R. 1969. Electron hopping in magnetite. Solid State Communications, 7, 223–227.Google Scholar
Lagarec, K. and Rancourt, D. G. 1997. Extended Voigt-based analytic lineshape method for determining N-dimensional correlated hyperfine parameter distributions in Mössbauer spectroscopy. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 129, 266–280.Google Scholar
Larese-Casanova, P., Haderlein, S. B. and Kappler, A. 2010. Biomineralization of lepidocrocite and goethite by nitrate-reducing Fe(II)-oxidizing bacteria: Effect of pH, bicarbonate, phosphate, and humic acids. Geochimica et Cosmochimica Acta, 74, 3721–3734.Google Scholar
Larese-Casanova, P. and Scherer, M. M. 2007. Fe(II) sorption on hematite:  New insights based on spectroscopic measurements. Environmental Science & Technology, 41, 471–477.Google Scholar
Latta, D. E., Boyanov, M. I., Kemner, K. M., et al. 2012. Abiotic reduction of uranium by Fe(II) in soil. Applied Geochemistry, 27, 1512–1524.Google Scholar
Markovski, C., Byrne, J. M., Lalla, E., et al. 2017. Abiotic versus biotic iron mineral transformation studied by a miniaturized backscattering Mössbauer spectrometer (MIMOS II), X-ray diffraction and Raman spectroscopy. Icarus, 296, 49–58.Google Scholar
Michel, F. M., Ehm, L., Antao, S. M., et al. 2007. The structure of ferrihydrite, a nanocrystalline material. Science, 316, 1726–1729.Google Scholar
Mikutta, C., Mikutta, R., Bonneville, S., et al. 2008. Synthetic coprecipitates of exopolysaccharides and ferrihydrite. Part I: Characterization. Geochimica et Cosmochimica Acta, 72, 1111–1127.Google Scholar
Miot, J. and Etique, M. 2016. Formation and Transformation of Iron-Bearing Minerals by Iron(II)-Oxidizing and Iron(III)-Reducing Bacteria. In Iron Oxides, ed. Faivre, D., Weinheim, Germany, Wiley-VCH Verlag GmbH & Co. KGaA.Google Scholar
Miot, J., Li, J., Benzerara, K., et al. 2014. Formation of single domain magnetite by green rust oxidation promoted by microbial anaerobic nitrate-dependent iron oxidation. Geochimica et Cosmochimica Acta, 139, 327–343.Google Scholar
Morice, J. A., Rees, L. V. C. and Rickard, D. T. 1969. Mössbauer studies of iron sulphides. Journal of Inorganic and Nuclear Chemistry, 31, 3797–3802.Google Scholar
Mossbauer, R. L. 1958. Kernresonanzfluoreszenz von gammastrahlung in Ir-191. Zeitschrift Fur Physik, 151, 124–143.Google Scholar
Murad, E. 1988. The Mössbauer spectrum of “well”-crystallized ferrihydrite. Journal of Magnetism and Magnetic Materials, 74, 153–157.Google Scholar
Murad, E. 2010. Mössbauer spectroscopy of clays, soils and their mineral constituents. Clay Minerals, 45, 413–430.Google Scholar
Murad, E. and Cashion, J. 2004. Mössbauer Spectroscopy of Environmental Materials and their Industrial Utilization, USA, Kluwer Academic Publishers.Google Scholar
Murad, E. and Schwertmann, U. 1986. Influence of Al substitution and crystal size on the room-temperature Mössbauer spectrum of hematite. Clays and Clay Minerals, 34, 1–6.Google Scholar
Nitzsche, K. S., Lan, V. M., Trang, P. T. K., et al. 2015. Arsenic removal from drinking water by a household sand filter in Vietnam – Effect of filter usage practices on arsenic removal efficiency and microbiological water quality. Science of the Total Environment, 502, 526–536.Google Scholar
O’Loughlin, E. J.,Larese-Casanova, P.,Scherer, M. and Cook, R. 2007. Green rust formation from the bioreduction of γ–FeOOH (lepidocrocite): Comparison of several Shewanella species. Geomicrobiology Journal, 24, 211–230.Google Scholar
Pankhurst, Q. and Pollard, R. 1992. Structural and magnetic properties of ferrihydrite. Clays and Clay Minerals, 40, 268–272.Google Scholar
Pantke, C., Obst, M., Benzerara, K., et al. 2012. Green rust formation during Fe(II) oxidation by the nitrate-reducing Acidovorax sp. strain BoFeN1. Environmental Science & Technology, 46, 1439–1446.Google Scholar
Prescher, C., McCammon, C. and Dubrovinsky, L. 2012. MossA: A program for analyzing energy-domain Mossbauer spectra from conventional and synchrotron sources. Journal of Applied Crystallography, 45, 329–331.Google Scholar
Rancourt, D., McDonald, A., Lalonde, A. and Ping, J. 1993. Mössbauer absorber thicknesses for accurate site populations in Fe-bearing minerals. American Mineralogist, 78, 1–7.Google Scholar
Rancourt, D. G. and Ping, J. Y. 1991. Voigt-based methods for arbitrary-shape static hyperfine parameter distributions in Mössbauer spectroscopy. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 58, 85–97.Google Scholar
Roden, E. E. and Zachara, J. M. 1996. Microbial reduction of crystalline iron(iii) oxides:  Influence of oxide surface area and potential for cell growth. Environmental Science & Technology, 30, 1618–1628.Google Scholar
Sawicki, J. and Brown, D. 1998. Investigation of microbial–mineral interactions by Mössbauer spectroscopy. Hyperfine Interactions, 117, 371–382.Google Scholar
Srivastava, C. M., Shringi, S. N. and Babu, M. V. 1981. Mössbauer study of the low-temperature phase of magnetite. Physica Status Solidi (A), 65, 731–735.Google Scholar
Stookey, L. L. 1970. Ferrozine – a new spectrophotometric reagent for iron. Analytical Chemistry, 42, 779–781.Google Scholar
Swanner, E. D., Wu, W., Schoenberg, R., et al. 2015. Fractionation of Fe isotopes during Fe (II) oxidation by a marine photoferrotroph is controlled by the formation of organic Fe-complexes and colloidal Fe fractions. Geochimica et Cosmochimica Acta, 165, 44–61.Google Scholar
ThomasArrigo, L. K., Mikutta, C., Byrne, J., et al. 2014. Iron and arsenic speciation and distribution in organic flocs from streambeds of an arsenic-enriched peatland. Environmental Science & Technology, 48, 13218–13228.Google Scholar
van der Zee, C., Roberts, D. R., Rancourt, D. G. and Slomp, C. P. 2003. Nanogoethite is the dominant reactive oxyhydroxide phase in lake and marine sediments. Geology, 31, 993–996.Google Scholar
Vandenberghe, R. E., De Grave, E., De Bakker, P. M. A., Krs, M. and Hus, J. J. 1992. Mössbauer effect study of natural greigite. Hyperfine Interactions, 68, 319–322.Google Scholar
Vollrath, S., Behrends, T., Koch, C. B. and Cappellen, P. V. 2013. Effects of temperature on rates and mineral products of microbial Fe(II) oxidation by Leptothrix cholodnii at microaerobic conditions. Geochimica et Cosmochimica Acta, 108, 107–124.Google Scholar
Wan, M., Schröder, C. and Peiffer, S. 2017. Fe(III):S(-II) concentration ratio controls the pathway and the kinetics of pyrite formation during sulfidation of ferric hydroxides. Geochimica et Cosmochimica Acta, 217, 334–348.Google Scholar
Williams, A. G. B. and Scherer, M. M. 2004. Spectroscopic evidence for Fe(II)−Fe(III) electron transfer at the iron oxide−water interface. Environmental Science & Technology, 38, 4782–4790.Google Scholar
Žák, T. and Jirásková, Y. 2006. CONFIT: Mössbauer spectra fitting program. Surface and Interface Analysis, 38, 710–714.Google Scholar
Zegeye, A., Abdelmoula, M., Usman, M., Hanna, K. and Ruby, C. 2011. In situ monitoring of lepidocrocite bioreduction and magnetite formation by reflection Mössbauer spectroscopy. American Mineralogist, 96, 1410–1413.Google Scholar
Ziganshin, A. M., Ziganshina, E. E., Byrne, J., et al. 2015. Fe(III) mineral reduction followed by partial dissolution and reactive oxygen species generation during 2,4,6-trinitrotoluene transformation by the aerobic yeast Yarrowia lipolytica. AMB Express, 5(8), 1–12.Google Scholar

Save book to Kindle

To save this book to your Kindle, first ensure [email protected] is added to your Approved Personal Document E-mail List under your Personal Document Settings on the Manage Your Content and Devices page of your Amazon account. Then enter the ‘name’ part of your Kindle email address below. Find out more about saving to your Kindle.

Note you can select to save to either the @free.kindle.com or @kindle.com variations. ‘@free.kindle.com’ emails are free but can only be saved to your device when it is connected to wi-fi. ‘@kindle.com’ emails can be delivered even when you are not connected to wi-fi, but note that service fees apply.

Find out more about the Kindle Personal Document Service.

Available formats
×

Save book to Dropbox

To save content items to your account, please confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your account. Find out more about saving content to Dropbox.

Available formats
×

Save book to Google Drive

To save content items to your account, please confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your account. Find out more about saving content to Google Drive.

Available formats
×