Abstract
Core-level and valence-band X-ray photoelectron spectroscopy was employed to study the dose-dependent radiation effects in the short-range order and the electronic structure of natural U, Th-bearing zircon near-surface layers. Single crystals from different localities (Ratanakiri, Cambodia; Mud Tank, Australia; Highlands, Sri Lanka) exhibiting wide variations in the accumulated radiation dose D≈(0 ÷ 9.2)·1018 α-decays/g was investigated. The dose values obtained by electron probe microanalysis and Raman micro-spectroscopy were used to correlate the samples with the two percolation transitions (p1, p2) in the amorphous-crystalline structure of damaged zircon. The dose-dependent variations in Eb (530.9–531.3, 101.7–102.4, 182.8- 183.3 eV) and FWHM (1.32–2.57, 1.47–1.77, 1.16 -1.55 eV) of the O1s, Si2p, and Zr3d5/2 core levels, respectively, were attributed to changes in the ensemble of non-equivalent short-range order structures. An increase in the dose resulted in the complication of the oxygen sublattice, with the following nearest environments of O atoms: (1) O (Si, [8]Zr, [8]Zr), Eb = 530.8–531.2 eV, the amount of > ~3.5 apfu (at D < p1); (2) O (Si, Si) and/or O (Si, Si, [8]Zr), Eb = 532.6 eV, the amount of ~ 0.5 ÷ 0.8 apfu (at p1 < D < p2); (3) O (Si, [7]Zr, [7]Zr), Eb = 531.6 eV, determined when the O (Si, [8]Zr, [8]Zr) amount is of ~ 1.7 apfu (at D > p2). For the first time, under an increase in the radiation dose, the oppositely directed changes in the effective charges of Si and Zr cations were detected in damaged zircon. This phenomenon was assigned to an increase in the content of the short-range order fragments characteristic of pure oxides SiO2 (namely, Si-O-Si) and ZrO2 (namely, [7]Zr) as well as to the influence of the anions O (Si, Si, [8]Zr), and the assignment was independently confirmed by the valence band analysis. The sequence of transformations in the Si-O and Zr-O sublattices was shown to be not concurrent: a partial polymerization of SiO4 tetrahedra occurs mainly at low and medium doses (D < p2) both in the crystalline and amorphous fractions, while the 7-coordinated atoms [7]Zr are mainly observed at higher doses (D > p2) in the amorphous fraction.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data availability
Experimental data are available from the authors in the form of numerical and graphic files; it can be provided upon request.
References
Balan E, Neuville DR, Trocellier P, Fritsch E, Muller J-P, Calas G (2001) Metamictization and chemical durability of detrital zircon. Am Mineral 86:1025–1033. https://doi.org/10.2138/am-2001-8-909
Balan E, Trocellier P, Jupille J, Fritsch E, Muller J-P, Calas G (2001) Surface chemistry of weathered zircons. Chem Geol 18:13–22. https://doi.org/10.1016/S0009-2541(01)00271-6
Bancroft GM, Nesbitt HW, Ho R, Shaw DM, Tse JS, Biesinger MC (2009) Toward a comprehensive understanding of solid-state core-level XPS linewidths: experimental and theoretical studies on the Si 2p and O 1s linewidths in silicates. Phys Rev B 80:075405. https://doi.org/10.1103/PhysRevB.80.075405
Barinsky RL, Kulikova IM (1977) Metamict transformation in some niobates and zircons according to X-ray absorption spectra. Phys Chem Miner 1:325–333. https://doi.org/10.1007/BF00308843
Barr TL (1991) Recent advances in X-ray photoelectron spectroscopy studies of oxides. J Vac Sci Technol A 9:1793–1805. https://doi.org/10.1116/1.577464
Batsanov SS (2000) Structural chemistry (facts and dependencies). Moscow Dialogue-MSU 2000: 291 P. ISBN 5-89209-597-5 (in Russian)
Batsanov SS (2001) Development of pauling’s concepts of geometric characteristics of atoms. Crystallogr Rep 46(6):891–897. https://doi.org/10.1134/1.1420814
Begg BD, Hess NJ, Weber WJ, Conradson SD, Scheiger MJ, Ewing RC (2000) XAS and XRD study of annealed 238Pu- and 239Pu-substituted zircons (Zr0.92Pu0.08SiO4). J Nucl Mater 278:121–224. https://doi.org/10.1016/S0022-3115(99)00256-1
Black LP, Gulson BL (1978) The age of the mud tank carbonatite, strangways range, northern territory. BMR J Aust Geol Geophys 3:227–232
Chakoumakos BC, Murakami T, Lumpkin GR, Ewing RC (1987) Alpha-decay-induced fracturing in zircon: the transition from the crystalline to the metamict state. Science 236:1556–1559. https://doi.org/10.1126/science.236.4808.1556
Chambers SA, Ohsawa T, Wang CM, Lyubinetsky I, Jaffe JE (2009) Band offsets at the epitaxial anatase TiO2/n-SrTiO3(001) interface. Surf Sci 603:771–780. https://doi.org/10.1063/1.1625113
Chanturia VA, Bunin IZ, Ryazantseva MV, Chanturia EL, Khabarova IA, Koporulina EV, Anashkina NE (2017) Modification of structural, chemical and process properties of rare metal minerals under treatment by high-voltage nanosecond pulses. J Min Sci 53:718–733. https://doi.org/10.1134/S1062739117042704
Du J, Davanathan R, René CL, Weber WJ (2012) First-principles calculations of the electronic structure, phase transition and properties of ZrSiO4 polymorphs. Comput Theor Chem 987:62–70. https://doi.org/10.1016/j.comptc.2011.03.033
Duval Y, Mielczarski JA, Pokrovsky OS, Mielczarski E, Ehrhardt JJ (2002) Evidence of the existence of three types of species at the quartz-aqueous solution interface at pH 0–10: surface group quantification and surface complexation modeling. J Phys Chem B 202:2937–2945. https://doi.org/10.1021/jp012818s
Ewing RC (2007) Displaced by radiation. Nature 445:161–162. https://doi.org/10.1038/445161a
Ewing RC, Lutze W, Weber WJ (1995) Zircon: a host-phase for the disposal of weapons plutonium. J Mater Res 10:243–246. https://doi.org/10.1557/JMR.1995.0243
Ewing RC, Meldrum A, Wang L, Weber WJ, Corrales LR (2003) Radiation effects in zircon. In: Hanchar JM, Hoskin PWO (eds) Zircon, reviews in mineralogy and geochemistry, V53. Mineralogical society of America, Washington, pp 387–425
Fadley CS (2010) X-ray photoelectron spectroscopy: Progress and perspectives. J Electron Spectros Relat Phenomena 178–179:2–32. https://doi.org/10.1016/j.elspec.2010.01.006
Farges F (1994) The structure of metamict zircon: a temperature-dependent EXAFS study. Phys Chem Miner 20:504–514. https://doi.org/10.1007/BF00203221
Farges F, Calas G (1991) Structural analysis of radiation damage in zircon and thorite: an X-ray absorption spectroscopic study. Am Mineral 76:60–73
Farnan I (1999) 29Si NMR characterization of the crystalline-amorphous transition in ZrSiO4. Phase Transit 69:47–60. https://doi.org/10.1080/01411599908208007
Farnan I, Salje EKH (2001) The degree and nature of radiation damage in zircon observed by 29Si nuclear magnetic resonance. J Appl Phys 89:2084–2090. https://doi.org/10.1063/1.1343523
Farnan I, Cho H, Weber WJ (2007) Quantification of actinide α-radiation damage in minerals and ceramics. Nature 445:190–193. https://doi.org/10.1038/nature05425
Finch RJ, Hanchar JM (2003) Structure and chemistry of zircon and zircon-group minerals. In: Hanchar JM, Hoskin PWO (eds) Zircon, reviews in mineralogy and geochemistry, V53. Mineralogical society of America, Washington, pp 1–25
Geisler T, Pidgeon RT, von Bronswijk W, Pleysier R (2001) Kinetics of thermal recovery and recrystallization of partially metamict zircon: a Raman spectroscopic study. Eur J Mineral 13:1163–1176. https://doi.org/10.1127/0935-1221/2001/0013-1163
Geisler T, Trachenko K, Rios S, Dove MT, Salje EKH (2003) Impact of self-irradiation damage on the aqueous durability of zircon (ZrSiO4): implications for its suitability as a nuclear waste form. J Phys Condens Matter 15:L597–L605. https://doi.org/10.1088/0953-8984/15/37/L07
Ginster U, Reiners PW, Nasdala L, Chutimun Chanmuang N (2019) Annealing kinetics of radiation damage in zircon. Geochim Cosmochim Acta 249:225–246. https://doi.org/10.1016/j.gca.2019.01.033
Greczynski G, Hultman L (2018) Reliable determination of chemical state in x-ray photoelectron spectroscopy based on sample-work-function referencing to adventitious carbon: resolving the myth of apparent constant binding energy of the C 1s peak. Appl Surf Sci 451:99–103. https://doi.org/10.1016/j.apsusc.2018.04.226
Guittet MJ, Crocombette JP, Gautier-Soyer M (2001) Bonding and XPS chemical shifts in ZrSiO4 versus SiO2 and ZrO2: charge transfer and electrostatic effects. Phys Rev B 63:125117. https://doi.org/10.1103/PhysRevB.63.125117
Haensel T, Reinmöller M, Lorenz P, Beenken WJD, Krischok S, Ahmed SI-U (2012) Valence band structure of cellulose and lignin studied by XPS and DFT. Cellulose 19(3):1005–1011. https://doi.org/10.1007/s10570-012-9681-9
Hochella MF (1988) Auger electron and X-ray photolectron spectroscopies. In: Calas G, Hawthorne FC (eds) Reviews in mineralogy and geochemistry, V18. Mineralogical society of America, Washington, pp 573–637
Hoskin PWO, Schaltegger U (2003) The composition of zircon and igneous and metemorphic petrogenesis. In: Hanchar JM, Hoskin PWO (eds) Zircon, reviews in mineralogy and geochemistry, V53. Mineralogical society of America, Washington, pp 27–62
Iacona F, Kelly R, Marletta G (1999) X-ray photoelectron spectroscopy study of bombardment-induced compositional changes in ZrO2, SiO2, and ZrSiO4. J Vac Sci Technol A 17:2771–2778. https://doi.org/10.1116/1.581943
Kempe U, Thomas SM, Geipel G, Thomas R, Plötze M, Böttcher R, Grambole G, Hoentsch J, Trinkler M (2010) Optical absorption, luminescence, and electron paramagnetic resonance (EPR) spectroscopy of crystalline to metamict zircon: evidence for formation of uranyl, manganese, and other optically active centers. Am Mineral 95:335–347. https://doi.org/10.2138/am.2010.3248
Kempe U, Trinkler M, Pöppl A, Himcinschi C (2016) Coloration of natural zircon. Can Mineral 54:635–660. https://doi.org/10.3749/canmin.1500093
Krasnobayev AA, Votyakov SL, Krokhalev VYa (1988) Spectroscopy of zircons. Nauka, Moscow ((in Russian))
Lucovsky G (2006) Electronic structure and chemical bonding in high-K transition metal and lanthanide series rare earth alternative gate dielectrics: applications to direct tunneling and defects at dielectric interfaces. In: Demkov AA, Navrotsky A (eds) Materials fundamentals of gate dielectrics. Springer Science and Business Media 109–178
Moulder JF, Stickle WF, Sobol PE, Bomben KD (1992) Handbook of X-ray photoelectron spectroscopy. Perkin-Elmer Corp, Eden, Prairie, MN, US
Murakami T, Chakoumakos BC, Ewing RC, Lumpkin GR, Weber WJ (1991) Alpha-decay event damage in zircon. Am Mineral 76:1510–1532
Nasdala L, Wolf D, Irmer G (1995) The degree of metamictization in zircon: a Raman spectroscopic study. Eur J Mineral 7:471–478. https://doi.org/10.1127/ejm/7/3/0471
Nasdala L, Pidgeon RT, Wolf D (1996) Heterogeneous metamictization of zircon on a microscale. Geochim Cosmochim Acta 60:1091–1097. https://doi.org/10.1016/0016-7037(95)00454-8
Nasdala L, Wenzel M, Vavra G, Irmer G, Wenzel T, Kober B (2001) Metamictization of natural zircon accumulation versus thermal annealing of radioactivity-induced damage. Contrib to Mineral Petrol 141:125–144. https://doi.org/10.1007/s004100000235
Nasdala L, Zhang M, Kempe U, Panczer G, Gaft M, Andrut M, Plotze M (2003) Spectroscopic methods applied to zircon. In: Hanchar JM, Hoskin PWO (eds) Zircon, reviews in mineralogy and geochemistry, V53. Mineralogical society of America, Washington, pp 427–467
Nasdala L, Reiners PW, Garver JI, Kennedy AK, Stern RA, Balan E, Wirth R (2004) Incomplete retention of radiation damage in zircon from Sri Lanka. Am Mineral 89:219–231. https://doi.org/10.2138/am-2004-0126
Nefedov VI, Vovna VI (1987) Electronic structure of chemical compounds. Nauka, Moscow ((in Russian))
Nesbitt HW, Bancroft GM (2014) High resolution core- and valence-level XPS studies of the properties (structural, chemical and bonding) of silicate minerals and glasses. In: Henderson GS, Neuville DR, Downs RT (eds) Spectroscopic methods in mineralogy and materals sciences, reviews in mineralogy and geochemistry, vol 78. Mineralogical society of America, Washington, pp 271–329
Palenik CS, Nasdala L, Ewing RC (2003) Radiation damage in zircon. Am Mineral 88:770–781. https://doi.org/10.2138/am-2003-5-606
Pidgeon RT, Nasdala L, Todt W (1998) Determination of radiation damage ages on parts of zircon grains by Raman microprobe: implications for annealing history and U-Pb stability. Mineral Mag 62A:1174–1175. https://doi.org/10.1180/minmag.1998.62A.2.280
Rignanese G-M, Gonze X, Pasquarello A (2001) First-principles study of structural, electronic, dynamical, and dielectric properties of zircon. Phys Rev B 63:104305. https://doi.org/10.1103/PhysRevB.63.104305
Rios S, Salje EKH, Zhang M, Ewing RC (2000) Amorphization in zircon: evidence for direct impact damage. J Phys Condens Matter 12:2401–2412. https://doi.org/10.1088/0953-8984/12/11/306
Salje EKH, Chrosch J, Ewing RC (1999) Is «metamictization» of zircon a phase transition? Amer Mineral 84:1107–1116. https://doi.org/10.2138/am-1999-7-813
Shchapova YuV, Votyakov SL, Kuznetsov MV, Ivanovsky AL (2010) Influence of radiation defects on electronic structure of zircon from X-ray photoelectronic spectroscopy data. J Struct Chem 4:687–692. https://doi.org/10.1007/s10947-010-0096-x
Shchapova YuV, Zamyatin DA, Votyakov SL, Zhidkov IS, Kukharenko AI, Cholakh SO (2020) Atomic and electronic structure of zircon according to high-resolution X-ray photoelectron spectroscopy: methodological aspects. In: Votyakov SL, Kiseleva DV, Grokhovskii VI, Shchapova YuV (eds) minerals: structure, properties, methods of investigation. Proceedings of the 10th all-Russian youth scientific conference. Springer Nature Switzerland AG https://doi.org/10.1007/978-3-030-49468-1_29
Siegbahn K (1974) Electron spectroscopy: an outlook. J Electron Spectros Relat Phenomena 5:3–97. https://doi.org/10.1016/0368-2048(74)85005-X
Trachenko KO, Dove MT, Salje EKH (2001) Atomistic modelling of radiation damage in zircon. J Phys Condens Matter 13:1947–1959. https://doi.org/10.1088/0953-8984/13/9/317
Trachenko K, Dove MT, Salje EKH (2003) Large swelling and percolation in irradiated zircon. J Phys Condens Matter 15:L1–L7. https://doi.org/10.1088/0953-8984/15/2/101
Trachenko K, Dove MT, Geisler T, Todorov I, Smith B (2004) Radiation damage effects and percolation theory. J Phys Condens Matter 16:S2623–S2627. https://doi.org/10.1088/0953-8984/16/27/002
Trachenko K, Pruneda JM, Artacho E, Dove MT (2005) How the nature of the chemical bond governs resistance to amorphization by radiation damage. Phys Rev B 71:184104. https://doi.org/10.1103/PhysRevB.71.184104
Urusov VS (1987) Theoritical crystal chemistry. MSU, Moscow ((in Russian))
Váczi T, Nasdala L (2017) Electron-beam-induced annealing of natural zircon: a Raman spectroscopic study. Phys Chem Miner 44:389–401. https://doi.org/10.1007/s00269-016-0866-x
Votyakov SL, Shchapova YuV, Khiller VV (2011) Crystal chemistry and physics of radiation and thermal effects in some U-Th-bearing minerals as the basis for the chemical microprobe age dating. Yekanerinburg, Publishing house of Ural Branch of RAS 330 ISBN 978-594332-091-0 (in Russian)
Weber WJ, Ewing RC, Wang LM (1994) The radiation-induced crystalline-to-amorphous transition in zircon. J Mater Research 9:688–698. https://doi.org/10.1557/JMR.1994.0688
Wopenka B, Jolliff BL, Zinner E, Kremser DT (1996) Trace element zoning and incipient metamictization in a lunar zircon: application of three microprobe techniques. Am Mineral 81:902–912. https://doi.org/10.1557/JMR.1994.0688
Zakaznova-Herzog VP, Nesbitt HW, Bancroft GM, Tse JS, Gao X, Skinner W (2005) High-resolution valence-band XPS spectra of the nonconductors quartz and olivine. Phys Rev B 72:205113. https://doi.org/10.1103/PhysRevB.72.205113
Zakaznova-Herzog VP, Nesbitt HW, Bancroft GM, Tse JS (2006) High resolution core and valence band XPS spectra of non-conductor pyroxenes. Surf Sci 600:3175–3186. https://doi.org/10.1016/j.susc.2006.06.012
Zakaznova-Herzog VP, Nesbitt HW, Bancroft GM, Tse JS (2008) Characterization of leached layers on olivine and pyroxenes using high-resolution XPS and density functional calculation. Geochim Cosmochim Acta 72:69–86. https://doi.org/10.1016/j.gca.2007.09.031
Zamyatin DA, Shchapova YuV, Votyakov SL, Nasdala L, Lenz C (2017) Alteration and chemical U-Th-total Pb dating of heterogeneous high-uranium zircon from a pegmatite from the Aduiskii massif, middle Urals, Russia. Mineral Petrol 111:1–23. https://doi.org/10.1007/s00710-017-0513-3
Zeug M, Nasdala L, Wanthanachaisaeng B, Balmer WA, Corfu F, Wildner M (2018) Blue Zircon from Ratanakiri, Cambodia. J Gemmol 36:112–132. https://doi.org/10.15506/JoG.2018.36.2.112
Zhang M, Salje EKH (2001) Infrared spectroscopic analysis of zircon: radiation damage and the metamict state. J Phys Condens Matter 13:3057–3071. https://doi.org/10.1088/0953-8984/13/13/317
Zhang M, Salje EKH, Ewing RC, Farnan I, Ríos S, Schlüter J, Leggo P (2000) α-decay damage and recrystallization in zircon: Evidence for an intermediate state from infrared spectroscopy. J Phys Condens Matter 12:5189–5199. https://doi.org/10.1088/0953-8984/12/24/310
Zhang M, Salje EKH, Farnan I, Graeme-Barber A, Daniel P, Ewing RC, Clark AM, Lennox H (2000) Metamictization of zircon: Raman spectroscopic study. J Phys Condens Matter 12:1915–1925. https://doi.org/10.1088/0953-8984/12/8/333
Acknowledgements
This work was supported by the Russian Foundation for Basic Research (RFBR), project 18-05-01153. Electron probe microanalysis was supported by the Russian Science Foundation (RSF), project 16-17-10283-P. The authors are grateful to Prof. L.Nasdala for providing the Ratanakiri zircon sample for research. We would like to thank Thomas A. Beavitt and Natalia G. Popova for their linguistic support.
Funding
The work was supported by the Russian Foundation for Basic Research, project 18-05-01153. Electron probe microanalysis was supported by the Russian Science Foundation, project 16-17-10283-P.
Author information
Authors and Affiliations
Contributions
Conceptualization: Yu.V.S; Methodology: D.A.Z, I.S.Z, A.I.K, S.O.C; Formal analysis and investigation: I.S.Z, A.I.K, D.A.Z, Yu.V.S; Writing—original draft preparation: Yu.V.S; Writing—review and editing: D.A.Z, S.L.V, Yu.V.S, I.S.Z, A.I.K; Funding acquisition: Yu.V.S, S.L.V; Resources: S.O.C.
Corresponding author
Ethics declarations
Conflicts of interest
The authors declare that they have no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Shchapova, Y.V., Zamyatin, D.A., Votyakov, S.L. et al. Short-range order and electronic structure of radiation-damaged zircon according to X-ray photoelectron spectroscopy. Phys Chem Minerals 47, 51 (2020). https://doi.org/10.1007/s00269-020-01120-8
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00269-020-01120-8