Keywords:Zircon Xenotime Monazite Titanite Laser-induced REE photoluminescence Raman artefact Laser-induced photoluminescence of trivalent rare-earth elements (REEs), which is obtained as analytical artefacts in Raman spectra of selected accessory minerals, was studied. Spectra of natural titanite, monazite-(Ce), xenotime-(Y), and zircon samples from various geological environments were compared with emission spectra of synthetic, flux-grown analogues doped with REEs. The latter is of great importance to identify potentially mistakable bands as either Raman or PL signal, and to assign them to certain REE centres. In the samples investigated, various REE centres are excited selectively using 473, 514, 532, 633, and 785 nm laser excitation. Their assignment was verified by photoluminescence-excitation experiments. Luminescence spectral patterns of zircon and titanite vary in dependence of trace-REE concentrations, hence reflecting geochemical growth conditions. "REE artefacts" in Raman spectra of accessory minerals may be used as fingerprint tool for mineral phaseidentification. The distribution of REE emission-intensities, revealed by hyperspectral mapping, opens up the opportunity to visualise mineral textures, complementary to cathodoluminescence imaging-techniques.

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.

A series of natural zircon samples (with U concentrations of 140-2600 ppm and ranging from well crystalline to severely radiation damaged) were investigated by means of REE 3+ photoluminescence spectroscopy. We found systematic changes in REE 3+ emissions depending on the accumulated radiation damage expressed by the effective time-integrated a-dose of zircon samples. Structural reconstitution as caused by dry annealing resulted in intensity gains and decreases of half-widths of REE 3+ emissions. The band half-widths of distinct luminescence Stark's levels of the 4 F 9/2 → 6 H 13/2 transition of Dy 3+ (~17 250 cm-1 ; ~580 nm wavelength) and the 4 F 3/2 → 4 I 9/2 transition of Nd 3+ (~11 300 cm-1 ; ~885 nm wavelength) were found to correlate sensitively with the degree of radiation damage accumulated. These REE 3+ emissions are proposed as potential measure of the irradiation-induced structural disorder of zircon. The two emissions are considered particularly suitable because (1) they are commonly detected in PL spectra of natural zircon, and (2) they are hardly biased by other emissions or Stark's levels. Preliminary calibration curves that relate band-width increases to the a dose were established using a suite of well-characterized Sri Lankan zircon. Band broadening upon increasing corpuscular self-irradiation is assigned to increasing structural destruction, i.e., the increasing perturbation of REE 3+ cationic lattice sites. Possible advantages of REE 3+ luminescence spectroscopy, complementary to Raman spectroscopy, as method to quantify structural radiation damage are discussed.

Abstract. The intertidal bivalve Katelysia rhytiphora, endemic to south Australia and Tasmania, is used here for pulsed Sr-labelling experiments in aquaculture experiments to visualize shell growth at the micro- to nanoscale. The ventral margin area of the outer shell layer composed of (i) an outermost outer shell layer (oOSL) with compound composite prismatic architecture with three hierarchical orders of prisms and (ii) an innermost outer shell layer (iOSL) with crossed-acicular architecture consisting of intersecting lamellae bundles. All structural orders in both layers are enveloped by an organic sheath and the smallest mineralized units are nano-granules. Electron backscatter diffraction reveals a strong preferred orientation of the aragonite c axes perpendicular to the growth layers, while the a and b axes are scattered within a plane normal to the local growth direction and >46 % twin grain boundaries are detected. The Young's modulus shows a girdle-like maximum of elastically stiffer orientations for the shell following the inner shell surface. For 6 d, the bivalves were subjected twice to seawater with an increased Sr concentration of 18× mean ocean water by dissolving 144 µg g−1 Sr (159.88 Sr∕Ca mmol ∕ mol) in seawater. The pulse labelling intervals in the shell are 17× (oOSL) and 12× (iOSL) enriched in Sr relative to the Sr-spiked seawater. All architectural units in the shell are transected by the Sr label, demonstrating shell growth to progress homogeneously instead of forming one individual architectural unit after the other. Distribution coefficients, DSr ∕ Ca, for labelled and unlabelled shells are similar to shell proportions formed in the wild (0.12 to 0.15). All DSr ∕ Ca values are lower than values for equilibrium partitioning of Sr in synthetic aragonite.

Lamellae of 1.5 µm thickness, prepared from well-crystallised monazite–(Ce) and zircon samples using the focused-ion-beam technique, were subjected to triple irradiation with 1 MeV Au+ ions (15.6% of the respective total fluence), 4 MeV Au2+ ions (21.9%) and 10 MeV Au3+ ions (62.5%). Total irradiation fluences were varied in the range 4.5 × 1012 – 1.2 × 1014 ions/cm2. The highest fluence resulted in amorphisation of both minerals; all other irradiations (i.e. up to 4.5 × 1013 ions/cm2) resulted in moderate to severe damage. Lamellae were subjected to Raman and laser-induced photoluminescence analysis, in order to provide a means of quantifying irradiation effects using these two micro-spectroscopy techniques. Based on extensive Monte Carlo calculations and subsequent defect-density estimates, irradiation-induced spectroscopic changes are compared with those of naturally self-irradiated samples. The finding that ion irradiation of monazite–(Ce) may cause severe damage or even amorphisation, is in apparent contrast to the general observation that naturally self-irradiated monazite–(Ce) does not become metamict (i.e. irradiation-amorphised), in spite of high self-irradiation doses. This is predominantly assigned to the continuous low-temperature damage annealing undergone by this mineral; other possible causes are discussed. According to cautious estimates, monazite–(Ce) samples of Mesoproterozoic to Cretaceous ages have stored only about 1% of the total damage experienced. In contrast, damage in ion-irradiated and naturally self-irradiated zircon is on the same order; reasons for the observed slight differences are discussed. We may assess that in zircon, alpha decays create significantly less than 103 Frenkel-type defect pairs per event, which is much lower than previous estimates. Amorphisation occurs at defect densities of about 0.10 dpa (displacements per lattice atom).Electronic supplementary materialThe online version of this article (10.1007/s00269-018-0975-9) contains supplementary material, which is available to authorized users.

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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 f a 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., f a) on the μm-scale are discussed.

high-pressure cell for systematic in situ investigations of micro-scale processes in gas hydrates using confocal micro-Raman spectroscopy. -