In this paper, possibilities and limits of the application of REE3+ luminescence (especially the Nd3+4F3/2 → 4I9/2 emission) as structural probe are evaluated. Important factors controlling the Nd3+ luminescence signal are discussed, including effects of the crystal-field, crystal orientation, structural state, and temperature. Particular attention was paid to the study of the accessory minerals zircon (ZrSiO4), xenotime–(Y) (YPO4), monazite–(Ce) (CePO4) and their synthetic analogues. Based on these examples we review in short that (1) REE3+ luminescence can be used as non-destructive phase identification method, (2) the intensities of certain luminescence bands are strongly influenced by crystal orientation effects, and (3) increased widths of REE3+-related emission bands are a strong indicator for structural disorder. We discuss the potential of luminescence spectroscopy, complementary to Raman spectroscopy, for the quantitative estimation of chemical (and potentially also radiation-induced) disorder. For the latter, emissions of Nd3+-related centres are found to be promising candidates.
In this study, we present a new concept based on the steady-state, laser-induced photoluminescence of Nd3+, which aims at a direct determination of the amorphous fraction fa in monazite- and xenotime-type orthophosphates on a micrometer scale. Polycrystalline, cold-pressed, sintered LaPO4, and YPO4 ceramics were exposed to quadruple Au-ion irradiation with ion energies 35 MeV (50% of the respective total fluence), 22 MeV (21%), 14 MeV (16%), and 7 MeV (13%). Total irradiation fluences were varied in the range 1.6 × 1013–6.5 × 1013 ions/cm2. Ion-irradiation resulted in amorphization and damage accumulation unto a depth of ~5 μm below the irradiated surfaces. The amorphous fraction created was quantified by means of surface-sensitive grazing-incidence X-ray diffraction and photoluminescence spectroscopy using state-of-the-art confocal spectrometers with spatial resolution in the μm range. Monazite-type LaPO4 was found to be more susceptible to ion-irradiation induced damage accumulation than xenotime-type YPO4. Transmission electron microscopy of lamella cut from irradiated surfaces with the focused-ion beam technique confirmed damage depth-profiles with those obtained from PL hyperspectral mapping. Potential analytical advantages that arise from an improved characterization and quantification of radiation damage (i.e., fa) on the μm-scale are discussed.
Gem-quality zircon megacrysts occur in placer deposits in the Central Highlands, Vietnam, and have euhedral to anhedral crystal shapes with dimensions of ~3 cm in length. These zircons have primary inclusions of calcite, olivine, and corundum. Secondary quartz, baddeleyite, hematite, and CO2 fluid inclusions were found in close proximity to cracks and tubular channels. LA-ICP-MS U-Pb ages of analyzed zircon samples yielded two age populations of ca. 1.0 Ma and ca. 6.5 Ma, that were consistent with the ages of alkali basalt eruptions in the Central Highlands at Buon Ma Thuot (5.80–1.67 Ma), Pleiku (4.30–0.80 Ma), and Xuan Loc (0.83–0.44 Ma). The zircon geochemical signatures and primary inclusions suggested a genesis from carbonatite-dominant melts as a result of partial melting of a metasomatized lithospheric mantle source, but not from the host alkali basalt. Chondrite-normalized rare earth element patterns showed a pronounced positive Ce, but negligible Eu anomalies. Detailed hyperspectral Dy3+ photoluminescence images of zircon megacrysts revealed resorption and re-growth processes.
We present a new methodology for laser-induced steady-state photoluminescence (PL) spectroscopy of Dy3+ that aims at a direct quantification of the amorphous fraction fa present in zircon (ZrSiO4), which undergoes a transition from a crystalline to a metamict state due to cumulative self-irradiation damage caused by the radioactive decay of substituted U and Th. Using state-of-the-art confocal spectrometers attached to optical microscopes, measurements may be performed non-destructively on the micrometre length-scale with the option to visualize radiation-damage patterns as revealed by hyperspectral PL maps. Zircon from the Ratnapura district (Sri Lanka, ~520 Ma), was used as reference material to substantiate the applicability of the proposed method. The accumulation of radiation damage in this material was investigated in detail and obtained fa values correlate with calculated α-doses in accordance to the direct impact model reported variously in the literature. The impact of chemically-induced, heterogeneous broadening of Raman and Dy3+ emission spectral bands is discussed on two examples from Mt. Malosa district, Malawi. A mean weighted U-Pb isotope age of 111 ± 1 Ma (pegmatitic-type) and a discordia age of 112 ± 1.6 Ma (hydrothermal-type) as obtained by LA-ICP-MS confirm their close genetic and temporal relationship. Studied zircon examples demonstrate that the amount of radiation damage present may have a substantial effect on the precision of LA-ICP-MS ages, but cannot be considered an exclusive cause for bias of obtained isotope ages.