Hostname: page-component-7dd5485656-g8tfn Total loading time: 0 Render date: 2025-10-29T22:12:38.083Z Has data issue: false hasContentIssue false
  • English
  • Français

Determination of zeolite-group mineral compositions by electron probe microanalysis

Published online by Cambridge University Press:  02 January 2018

L. S. Campbell ,
J. Charnock ,
A. Dyer ,
S. Hillier ,
S. Chenery ,
F. Stoppa ,
C. M. B. Henderson ,
R. Walcott  and
M. Rumsey
L. S. Campbell*
Affiliation:
School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Williamson Building, Oxford Road, Manchester M13 9PL, UK
J. Charnock
Affiliation:
School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Williamson Building, Oxford Road, Manchester M13 9PL, UK
A. Dyer
Affiliation:
Materials and Physics Research Centre, University of Salford M5 4WT, UK
S. Hillier
Affiliation:
James Hutton Institute, Craigiebuckler, Aberdeen AB15 8QH, UK Swedish University of Agricultural Sciences, SLU, Department of Soil & Environment, SE-75007 Uppsala, Sweden
S. Chenery
Affiliation:
British Geological Survey, Keyworth, Nottingham NG12 5GG, UK
F. Stoppa
Affiliation:
Department of Psychological, Humanistic and Territory Sciences of G.d’Annunzio University Chieti-Pescara, 66100 Chieti, Italy
C. M. B. Henderson
Affiliation:
School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Williamson Building, Oxford Road, Manchester M13 9PL, UK
R. Walcott
Affiliation:
Department of Natural Sciences, National Museums Scotland, Chambers Street, Edinburgh EH1 1JF, UK
M. Rumsey
Affiliation:
Department of Mineralogy, The Natural History Museum, Cromwell Road, London SW7 5BD, UK
*
E-mail: Linda.Campbell@manchester.ac.uk
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

A new protocol for the quantitative determination of zeolite-group mineral compositions by electron probe microanalysis (wavelength-dispersive spectrometry) under ambient conditions, is presented. The method overcomes the most serious challenges for this mineral group, including new confidence in the fundamentally important Si-Al ratio. Development tests were undertaken on a set of natural zeolite candidate reference samples, representing the compositional extremes of Na, K, Cs, Mg, Ca, Sr and Ba zeolites, to demonstrate and assess the extent of beam interaction effects on each oxide component for each mineral. These tests highlight the variability and impact of component mobility due to beam interaction, and show that it can be minimized with recommended operating conditions of 15 kV, 2 nA, a defocused, 20 μm spot size, and element prioritizing with the spectrometer configuration. The protocol represents a pragmatic solution that works, but provides scope for additional optimization where required. Vital to the determination of high-quality results is the attention to careful preparations and the employment of strict criteria for data reduction and quality control, including the monitoring and removal of non-zeolitic contaminants from the data (mainly Fe and clay phases). Essential quality criteria include the zeolite-specific parameters of R value (Si/(Si + Al + Fe3+), the 'E%' charge-balance calculation, and the weight percent of non-hydrous total oxides. When these criteria are applied in conjunction with the recommended analytical operating conditions, excellent inter-batch reproducibility is demonstrated. Application of the method to zeolites with complex solid-solution compositions is effective, enabling more precise geochemical discrimination for occurrence-composition studies. Phase validation for the reference set was conducted satisfactorily with the use of X-ray diffraction and laser-ablation inductively-coupled plasma mass spectroscopy.

Keywords

natural zeoliteelectron microprobeanalytical protocolmineral compositionssolid solution

Information

Type
Research Article
Information
Mineralogical Magazine , Volume 80 , Issue 5 , August 2016 , pp. 781 - 807
Creative Commons
Creative Common License - CCCreative Common License - BY
Copyright © The Mineralogical Society of Great Britain and Ireland 2016 This is an Open Access article, distributed under the terms of the Creative Commons Attribution license. (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted re-use, distribution, and reproduction in any medium, provided the original work is properly cited.
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2016

References

Bear, A.N., Giordano, G., Giampaolo, C. and Cas, R.A.F.. (2009) Volcanological constraints on the post-emplacement zeolitisation of ignimbrites and geoarchaeological implications for Etruscan tomb construction (6th-3rd century B.C) in the Tufo Rosso a Scorie Nere, Vico Caldera, central Italy. Journal of Volcanology and Geothermal Research, 183, 183–200.CrossRefGoogle Scholar
Bish, D.L. and Carey, J.W. (2001) Thermal properties of natural zeolites. Pp. 403—452.in: Natural Zeolites: Occurrence, Properties, Applications (D. Bish and D. Ming, editors) Reviews in Mineralogy and Geochemistry, 45. Mineralogical Society of America and Geochemical Society, Washington DC.CrossRefGoogle Scholar
Bish, D.L. and Ming, D.W. (Editors) (2001) Natural Zeolites: Occurrence, Properties, Applications. Reviews in Mineralogy and Geochemistry, 45.Mineralogical Society of America and Geochemical Society, Washington DC, 654pp.CrossRefGoogle Scholar
Campbell, L.S., Dyer, A., Williams, C. and Lythgoe, P.R. (2012) The masquerade of alkaline-carbonatitic tuffs by zeolites: A new global pathfinder hypothesis. Mineralium Deposita, 47, 371–382.CrossRefGoogle Scholar
Campbell, L.S., Dyer, A., Williams, C. and Lythgoe, P.R. (2013) Exploring the preservation of alkaline-carbonatitic extrusive rocks in relation to continent formation. Mineralogical Magazine, 77, Abstract p. 814.Google Scholar
Campbell, L.S., Charnock, J. and Dyer, A. (2014) Regional prospecting: Can we couple large-scale exploration data with novel geochemical discrimin-ation? [Abstracts of the 38th Annual Meeting of the Mineral Deposits Studies Group, Southampton, UK]. Applied Earth Science: Transactions of the Institutions of Mining and Metallurgy: Section B, 124, 25–26.Google Scholar
Campbell, L.S., Charnock, J., Pearce, N.J.G.. and Dyer, A. (2015) Partial proxies for geochemical discrimination in Italian altered tuffs. Abstracts of the 51st Annual Meeting of the Volcanic and Magmatic Studies Group, Norwich, UK, p. 53.Google Scholar
Cappelletti, P., Petrosino, P., de Gennaro, M., Colella, A., Graziano, S.F., D'Amore, M., Mercurio, M., Cerri, G., de Gennaro, R., Rapisardo, G. and Langella, A. (2015) The “Tufo Giallo Della Via Tiberina” (Sabatini Volcanic District, central Italy): A complex system of lithification in a pyroclastic current deposit. Mineralogy and Petrology, 109, 85–101.CrossRefGoogle Scholar
Cazaux, J. (2004) About the mechanisms of charging in EPMA, SEM, and ESEM with their time evolution. Microscopy and Microanalysis, 10, 670—684.CrossRefGoogle ScholarPubMed
Čejka, J., Corma, A. and Zones, S. (2010) Zeolites and Catalysis: Synthesis, Reactions and Applications Wiley-VCH, Germany.CrossRefGoogle Scholar
Chipera, S.J. and Apps, J.A. (2001) Geochemical stability of natural zeolites. Pp. 117—161.in: Natural Zeolites: Occurrence, Properties, Applications (D. Bish and D. Ming, editors) Reviews in Mineralogy and Geochemistry, 45. Mineralogical Society of America and Geochemical Society, , Washington DC.Google Scholar
Colella, C. (1996) Ion exchange equilibria in zeolite minerals. Mineralium Deposita, 31, 554—562.CrossRefGoogle Scholar
Dakovič, A., Trgo, M. and Langella, A. (editors) (2014) Book of Extended Abstracts. Zeolite 2014: The 9th International Conference on the Occurrence, Properties and Utilization of Natural Zeolites. Belgrade, Serbia, 258pp.Google Scholar
Danisi, R.M., Armbruster, T and Nagashima, M. (2015) Structural intergrowth of merlinoite/phillipsite and its temperature-dependent dehydration behaviour: a single-crystal X-ray study. Mineralogical Magazine, 79, 191–203.CrossRefGoogle Scholar
Deer, R.A., Howie, W.A., Wise, W.S. and Zussman, J. (2004) Rock Forming Minerals, Volume 4B. Framework silicates: Silica Minerals, Feldspathoids and the Zeolites. 2nd edition. The Geological Society, London, 982pp.Google Scholar
Dyer, A. (1988) An Introduction to Zeolite Molecular Sieves. John Wiley and Sons, 149 pp.Google Scholar
Dyer, A. (2000) Applications of natural zeolites in the treatment of nuclear wastes and fall-out. Pp. 319–368.in: Environmental Mineralogy: Microbial Interactions, Anthropogenic Influences, Contaminated Land and Waste Management (J.D. Cotter-Howells, L.S. Campbell, E. Valsami-Jones and M. Batchelder (editors). Mineralogical Society Special Publication, 9. Mineralogical Society of Great Britain and Ireland, London.Google Scholar
Dyer, A. (2007) Ion-exchange properties of zeolites and related materials. Pp. 525—553.in: Introduction to Zeolite Science and Practice, 3rd Revised Edition (J. Čejka, H. VanBekkum, A. Corma and F. Schüth, editors). Studies in Surface Science and Catalysis, 168. Elsevier Science Bv, Amsterdam.Google Scholar
Dyer, A., Newton, J. and Pillinger, M. (2010) Synthesis and characterisation of mesoporous silica phases containing heteroatoms, and their cation exchange properties. Part 3. Measurement of distribution coefficients for uptake of 137-Cs, 89-Sr and 57-Co radioisotopes. Microporous and Mesoporous Materials, 130, 56–62.CrossRefGoogle Scholar
Eisenman, G. (1962) Cation selective glass electrodes and their mode of operation. Biophysical Journal, 2, 259–323.CrossRefGoogle ScholarPubMed
Fakhfakh, S., Jbara, O., Rondot, S., Hadjadj, A., Patat, J.M. and Fakhfakh, Z. (2010) Analysis of electrical charging and discharging kinetics of different glasses under electron irradiation in a scanning electron microscope. Journal of Applied Physics, 108, 093705.CrossRefGoogle Scholar
Fischer, R.X. (2014) Natural zeolites - a treasure in zeolite science. (Invited contribution). Zeolite 2014. The 9th International Conference on the Occurrence, Properties, and Utilization of Natural Zeolites, Belgrade, Serbia. Book of Abstracts, 11.Google Scholar
Gatta, G.D., Rotiroti, N., Bellatreccia, F. and Della Ventura, G. (2007) Crystal chemistry of leucite from the Roman Comagmatic Province (central Italy): A multi-methodological study. Mineralogical Magazine, 71, 671–682.CrossRefGoogle Scholar
Gatta, G.D., Cappelletti, P., Rotiroti, N., Slebodnick, C. and Rinaldi, R. (2009) New insights into the crystal structure and crystal chemistry of the zeolite phillip-site. American Mineralogist, 94, 190–199.CrossRefGoogle Scholar
Giampaolo, C. and Lombardi, G. (1994) Thermal-behavior of analcimes from 2 different genetic environments. European Journal of Mineralogy, 6, 285–289.CrossRefGoogle Scholar
Giampaolo, C., Godano, R.F., DiSabatino, B. andBarrese, E. (1997) The alteration of leucite-bearing rocks: A possible mechanism. European Journal of Mineralogy, 9, 1277–1291.CrossRefGoogle Scholar
Giampaolo, C., Lo Mastro, S., De Rita D., Giordano, G. (2008) Lateral and vertical zeolite grade variations in the Tufo Lionato ignimbrite unit (Colli Albani, Roma, Central Italy). Zeolite ‘06: The 7th International Conference of the Occurrence, Properties and Utilization of Natural Zeolites, Socorro, New Mexico, USA. Book of Abstracts, 119–120.Google Scholar
Harjula, R., Lehto, J., Pothuis, J.H., Dyer, A. and Townsend, R.P. (1993) Ion-exchange in zeolites. 2. Hydrolysis and dissolution of zeolites NaX and NaY. Journal of the Chemical Society -Faraday Transactions, 89, 971–976.CrossRefGoogle Scholar
Hay, R.L. and Sheppard, R.A. (2001) Occurrence of zeolites in sedimentary rocks: An overview. Pp. 217—234.in: Natural Zeolites: Occurrence, Properties, Applications (D. Bish and D. Ming, editors) Reviews in Mineralogy and Geochemistry, 45. Mineralogical Society of America and Geochemical Society, Washington DC.Google Scholar
Heister, L.E., O'Day, P.A., Brooks, C.K., Neuhoff, P.S. and Bird, D.K. (2001) Pyroclastic deposits within the East Greenland Tertiary flood basalts. Journal of the Geological Society, 158, 269–284.CrossRefGoogle Scholar
Henderson, C.M.B.., Bell, A.M.T.., Kohn, S.C. and Page, C.S. (1998) Leucite-pollucite structure-type variability and the structure of a synthetic end-member calcium wairakite (CaA12Si4O12.2H2O). Mineralogical Magazine, 62, 165–178.CrossRefGoogle Scholar
Henderson, C.M.B.., Hamilton, D.L. and Waters, J.P. (2014) Phase equilibria in NaAlSiO4-KAlSiO4-SiO2-H2O at 100 MPa pressure: Equilibrium leucite composition and the enigma of primary analcime in blairmorites revisited. Mineralogical Magazine, 78, 171—202.CrossRefGoogle Scholar
Kearns, S. and Buse, B. (2012) X-ray microanalysis of volcanic ash. IOP Conference Series: Materials Science and Engineering, 32, Abstract 012013.CrossRefGoogle Scholar
Kim, E., Lee, T., Kim, H., Jung, W.-J., Han, D.-Y., Baik, H., Choi, N. and Choi, J. (2014) Chemical vapor deposition on chabazite (CHA) zeolite membranes for effective post-combustion CO2 capture. Environmental Science & Technology, 48, 14828–14836.CrossRefGoogle ScholarPubMed
Langella, A., Cappelletti, P. and de' Gennaro, R. (2001) Zeolites in closed hydrologic systems. Pp. 235—260. in: Natural Zeolites: Occurrence, Properties, Applications (D. Bish and D. Ming, editors) Reviews in Mineralogy and Geochemistry, 45. Mineralogical Society of America and Geochemical Society, Washington DC.Google Scholar
Langella, A., Bish, D.L., Cappelletti, P., Cerri, G., Colella, A., de Gennaro, R., Graziano, S.F., Perrotta, A., Scarpati, C. and de Gennaro, M. (2013) New insights into the mineralogical facies distribution of Campanian Ignimbrite, a relevant Italian industrial material. Applied Clay Science, 72, 55—73.CrossRefGoogle Scholar
Line, C.M.B.., Putnis, A., Putnis, C. and Giampaolo, C. (1995) The dehydration kinetics and microtexture of analcime from 2 parageneses. American Mineralogist, 80, 268–279.CrossRefGoogle Scholar
Merlet, C. and Llovet, X. (2012) Uncertainty and capability of quantitative EPMA at low voltage — A review. Materials Science and Engineering, 32, Abstract 012016.Google Scholar
Morgan, G. and London, D. (1996) Optimizing the electron microprobe analysis of hydrous alkali alumino silicate glasses. American Mineralogist, 81, 1176—1185.CrossRefGoogle Scholar
Morgan, G.B. and London, D. (2005) Effect of current density on the electron microprobe analysis of alkali alumino silicate glasses. American Mineralogist, 90, 1131–1138.CrossRefGoogle Scholar
Neuhoff, P.S. and Ruhl, L.S. (2006) Mechanisms and geochemical significance of Si-Al substitution in zeolite solid solutions. Chemical Geology, 225, 373—387.CrossRefGoogle Scholar
Neuhoff, P.S., Fridriksson, Th. and Bird, D.K. (2000) Zeolite parageneses in the North Atlantic Igneous Province: Implications for geotectonics and groundwater quality of basaltic crust. International Geology Review, 42, 15-44. Reprinted in: Frontiers in Geochemistry: Global Inorganic Geochemistry (Konrad Krauskopf Volume 1) (W.G. Ernst, editor). Geological Society of America, International Book Series, 5, 271–300.Google Scholar
Passaglia, E. (1970) Crystal chemistry of chabazites. American Mineralogist, 55, 1278–1301.Google Scholar
Passaglia, E. and Sheppard, R.A. (2001) The crystal chemistry of zeolites. Pp. 69—116.in: Natural Zeolites: Occurrence, Properties, Applications (D. Bish and D. Ming, editors) Reviews in Mineralogy and Geochemistry, 45. Mineralogical Society of America and Geochemical Society, Washington DC.Google Scholar
Passaglia, E., Vezzalini, G. and Carnevali, R. (1990) Diagenetic chabazites and phillipsites in Italy — crystal-chemistry and genesis. European Journal of Mineralogy, 2, 827–839.CrossRefGoogle Scholar
Pearce, N.J.G.., Abbott, P.M. and Martin-Jones, C. (2014) Microbeam methods for the analysis of glass in finegrained tephra deposits: A smart perspective on current and future trends. Marine Tephrochronology, 398, 29–6.Google Scholar
Pekov, I.V., Turchkova, A.G., Chukanov, N.V., Zadov, A.E. and Grishin, B.G. (2000) Chabazite-Sr (SrCa) [Al2Si4012]-6H20 - A new zeolite from the Lovozero Massif, Kola peninsula. Zapiski Vserossiyskogo Mineralogicheskogo Obshchestva, 129, 52—58.Google Scholar
Pham, T.D., Hudson, M.R., Brown, C.M. and Lobo, R.F. (2014) Molecular basis for the high CO2 adsorption capacity of chabazite zeolites. Chemsuschem, 7, 3031–3038.CrossRefGoogle ScholarPubMed
Putnis, C.V., Geisler, T., Schmid-Beurmann, P., Stephan, T. and Giampaolo, C. (2007) An experimental study of the replacement of leucite by analcime. American Mineralogist, 92, 19–26.CrossRefGoogle Scholar
Rigby, M., Droop, G., Plant, D. and Graser, P. (2008) Electron probe micro-analysis of oxygen in cordierite: Potential implications for the analysis of volatiles in minerals. South African Journal of Geology, 111, 239–250.CrossRefGoogle Scholar
Rinaldi, R., Smith, IV and Jung, G. (1975) Chemistry and paragenesis of faujasite, phillipsite and offretite from Sasbach, Kaiserstuhl, Germany. Neues Jahrbuch für Mineralogie: Abhandlungen, 433–443.Google Scholar
Saunders, K., Buse, B., Kilburn, M.R., Kearns, S. and Blundy, J. (2014) Nanoscale characterisation of crystal zoning. Chemical Geology, 364, 20–32.CrossRefGoogle Scholar
Utada, M. (2001) Zeolites in hydrothermally altered rocks. Pp. 305–322.in: Natural Zeolites: Occurrence, Properties, Applications (D. Bish and D. Ming, editors) Reviews in Mineralogy and Geochemistry, 45. Mineralogical Society of America and Geochemical Society, Washington DC.CrossRefGoogle Scholar
Vaggelli, G., Olmi, F. and Conticelli, S. (1999) Quantitative electron microprobe analyses of reference silicate mineral and glass samples. Acta Vulcanologica, 11, 297—303.Google Scholar
Vignaroli, G., Aldega, L., Balsamo, F., Billi, A., De Benedetti, A., De Filippis, L., Giordano, G. and Rossetti, E (2014) Away to hydrothermal paroxysm, Colli Albani Volcano, Italy. Geological Society of America Bulletin, B31139.Google Scholar
Wallace, S.H., Shaw, S., Morris, K., Small, J.S. and Burke, I.T. (2013) Alteration of sediments by hyperalkaline K-rich cement leachate: Implications for strontium adsorption and incorporation.Environmental Science & Technology, 47, 3694–3700.CrossRefGoogle Scholar
Wang, H.W. and Bish, D.L. (2012) Infrared spectro-scopic characterization of dehydration and accompanying phase transition behaviors in NAT-topology zeolites. Physics and Chemistry of Minerals, 39, 277–293.CrossRefGoogle Scholar
Wang, H.W. and Bish, D.L. (2014) Host-guest interactions in zeolites: Insights from the NAT-topology system. Zeolite 2014. The 9th International Conference on the Occurrence, Properties, and Utilization of Natural Zeolites, Belgrade, Serbia. Book of Abstracts, 239–240.Google Scholar
Weisenberger, T. and Spürgin, S. (2009) Zeolites in alkaline rocks of the Kaiserstuhl Volcanic Complex, SW Germany — new microprobe investigation and the relationship of zeolite mineralogy to the host rock. Geologica Belgica, 12, 75—91.Google Scholar
Weisenberger, T.B., Rahn, M., van der Lelij, R., Spikings, R.A. and Bucher, K. (2012) Timing of low-temperature mineral formation during exhumation and cooling in the Central Alps, Switzerland. Earth and Planetary Science Letters, 327, 1–8.Google Scholar
Weisenberger, T.B., Spürgin, S. and Lahaye, Y (2014) Hydrothermal alteration and zeolitization of the Fohberg phonolite, Kaiserstuhl Volcanic Complex, Germany. International Journal of Earth Sciences, 103, 2273–2300.CrossRefGoogle Scholar
Supplementary material: PDF

Campbell et al. supplementary material

Supplementary file 1

Download Campbell et al. supplementary material(PDF)
PDF 587.8 KB
Supplementary material: PDF

Campbell et al. supplementary material

Supplementary file 2

Download Campbell et al. supplementary material(PDF)
PDF 305.2 KB
Supplementary material: PDF

Campbell et al. supplementary material

Supplementary file 3

Download Campbell et al. supplementary material(PDF)
PDF 2.3 MB
Supplementary material: File

Campbell et al. supplementary material

Supplementary file 4

Download Campbell et al. supplementary material(File)
File 251.4 KB