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

Kempe, Ulf; Thomas, Steven; Geipel, Gerhard; Thomas, Rainer; Plötze, Michael; Böttcher, R.; Grambole, G.; Hoentsch, Joachim; Trinkler, M. F.

doi:10.2138/am.2010.3248

Cited by 16 publications

(14 citation statements)

References 51 publications

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“…The CL intensities of the broad bands in the yellow to red region and of the narrow bands are higher at the surface of (001) than at that of (100), but both spectral patterns are quite similar each other. This confirms the results of the polarization effect on zircon CL obtained by Cesbron et al (1995) and Kempe et al (2010). In this study hereafter, all SEM -CL measurements have been conducted on the surface of (001) due to the higher gain of the CL intensity.…”

Section: Resultssupporting

confidence: 89%

“…According to Cesbron et al (1995) and Kempe et al (2010), the CL intensity of zircon is significantly affected by the crystallographic orientation of the zircon on the sample surface irradiated by the incident electron beam. CL spectra of MZ samples with surfaces specifically orientated perpendicular to c -and a -axes were measured under the same analytical conditions (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…The most important aspects to be resolved are the deconvolution of the superimposed spectral peaks for precise assignment of luminescent center and quantitative estimation of luminescence efficiency, radiation -induced effects on the CL for chronological usages, polarization factors related to crystallographic orientation and types of luminescence center, and temperature effects on the emission mechanism with quenching (e.g., Marshall, 1988;Ikenaga et al, 2000;Stevens -Kalceff, 2009;Kempe et al, 2010).…”

Section: Introductionmentioning

confidence: 99%

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Electron irradiation effects on cathodoluminescence in zircon

Tsuchiya

Kayama

Nishido

et al. 2013

Journal of Mineralogical and Petrological Sciences

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Cathodoluminescence (CL) measurements of zircon sample with two different geological ages have been conducted to clarify the polarization effect of different types of luminescence centers and the effects of electron -irradiation on CL. Polarization of CL has been confirmed in the emissions related to both defect and impurity centers in zircon. Prolonged exposure of electron irradiation reduces the CL intensities of broad bands related to intrinsic defect centers in the blue region and those of narrow bands attributed to Dy 3+ activator, whereas CL intensity of the broad bands attributed to metamictization in the yellow region increases with prolonged irradiation. Therefore, electron irradiation has a different effect on the emission mechanisms of defect centers observed in the blue and yellow regions.

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Section: Resultssupporting

confidence: 89%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electron irradiation effects on cathodoluminescence in zircon

Tsuchiya

Kayama

Nishido

et al. 2013

Journal of Mineralogical and Petrological Sciences

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“…[2,12,[89][90][91] The green samples from the literature are not all metamict, especially the samples not from Sri Lanka. [4,11,89,92,93] With the data of the unit cell volume, the theoretical density of zircon is calculated as 4.61 to 4.76 g/cm 3 . Comparing the FWHM value and the measured density of samples (Table S1), the data demonstrate trends in different structural states (in Figure 4).…”

Section: Resultsmentioning

confidence: 99%

Influence of metamictization on the gemological properties of natural zircon: A Raman spectroscopic study of zircons in the gemological collection of Abraham Gottlob Werner

Gao

Heide

2020

J Raman Spectroscopy

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Raman spectroscopy is a convenient, efficient, and non‐destructive technique that could estimate the metamictization degree of zircon, particularly for gem‐class or historical samples. The full width at half maximum value of the ν3(SiO4) band around 1000 cm−1 can classify the structural state of zircon as crystallized (the full width at half maximum value is less than 5 cm−1), intermediate (the full width at half maximum value ranges from 5 to 15 cm−1), and metamict (the full width at half maximum value is more than 15 cm−1). This study focuses on the zircon samples from Sri Lanka in the gemological collection of Abraham Gottlob Werner. These samples show red to green, according to the Munsell color system and the CIEL*C*h* color system, and their density is from 4.07 to 4.87 g/cm3. Comparing the color and metamictization degree data of zircon samples, crystallized zircon displays a more red tone with yellow. The green tone in zircon occurs with metamictization. The density of zircon could be an indicator of the metamictization degree as crystallized zircon is 4.57 to 4.70 g/cm3 in a 95% confidence interval, which matches the theoretical density (4.61–4.76 g/cm3) better, whereas metamict zircons present a density of 4.37–4.59 g/cm3, and the density of zircon decreases with metamictization. The metamictization has a significant influence on the gemological properties of zircon, whereas the typical color tone and low density can be a sign of the metamictization.

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“…Microstructures and microtextures such as twins, domains and fractures in the MZ samples were examined under a polarizing microscope and by an electron microscope using secondary electron and backscattered electron imaging as a preliminary observation to the CL and Raman analyses. Kempe et al (2010) and Tsuchiya et al (2014) pointed out a polarization effect of the luminescence in zircon. In this study, square slices (~5.0 × 5.0 × 1.0 mm) with the surfaces having same orientation (001) were prepared for annealing experiments, where the slices were cut off from a same large single crystal of the MZ.…”

Section: Samples and Methodsmentioning

confidence: 99%

Annealing effects on cathodoluminescence of zircon

Tsuchiya

Kayama

Nishido

et al. 2015

Journal of Mineralogical and Petrological Sciences

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Color cathodoluminescence (CL) images of zircon from southern Malawi (MZ) show mottled yellow CL emissions on a dull luminescent background by the annealing below 600°C, and relatively homogeneous blue emissions above 800°C. CL spectroscopy of the samples reveals a change of the luminescent features with an annealing temperature, and explains a variation of their colors and luminance observed by a CL microscope. Emission bands at 310 and 380 nm in an ultraviolet (UV) to blue CL are assigned to intrinsic centers in host lattice, narrow peaks at 475 and 580 nm to Dy 3+ impurity centers, and broad bands at 500 to 650 nm to Frenkeltype defects and SiO m n− groups. The former two show increases in emission intensities against annealing temperature, but the latter exhibits an increase in intensity up to 300°C and a decrease above 300 to 700°C. An increase in an annealing temperature leads to a reproduction of the intrinsic centers, which is responsible for an increase in UV-blue emission, in host lattice accompanied with a recrystallization from metamict state. An increase in the intensities of narrow peaks activated by Dy 3+ impurities may result possibly from a recovery of ionization due to the self-radiation and an energy transfer of other REEs to Dy 3+ activator. A gradual increase in yellow emission bands up to 300°C might be caused by a migration of the hole around a thermally-instable lattice defect and/or activated impurities into a more stable site related to Frenkel-type defects and SiO m n− groups, whereas the yellow should be subsequently reduced due to an elimination of these defects.

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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

Cited by 16 publications

References 51 publications

Electron irradiation effects on cathodoluminescence in zircon

Electron irradiation effects on cathodoluminescence in zircon

Influence of metamictization on the gemological properties of natural zircon: A Raman spectroscopic study of zircons in the gemological collection of Abraham Gottlob Werner

Annealing effects on cathodoluminescence of zircon

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