The parisite-(Ce) enigma: challenges in the identification of fluorcarbonate minerals.

A multi-methodological study was conducted in order to provide further insight into the structural and compositional complexity of rare earth element (REE) fluorcarbonates, with particular attention to their correct assignment to a mineral species. Polycrystals from La Pita Mine, Municipality de Maripí, Boyacá Department, Colombia, show syntaxic intergrowth of parisite-(Ce) with röntgenite-(Ce) and a phase which is assigned to B 3 S 4 (i.e., bastnäsite-3-synchisite-4; still unnamed) fluorcarbonate. Transmission electron microscope (TEM) images reveal well-ordered stacking patterns of two monoclinic polytypes of parisite-(Ce) as well as heavily disordered layer sequences with varying lattice fringe spacings. The crystal structure refinement from single crystal X-ray diffraction data - impeded by twinning, complex stacking patterns, sequential and compositional faults - indicates that the dominant parisite-(Ce) polytype M 1 has space group Cc. Parisite-(Ce), the B 3 S 4 phase and röntgenite-(Ce) show different BSE intensities from high to low. Raman spectroscopic analyses of parisite-(Ce), the B 3 S 4 phase and röntgenite-(Ce) reveal different intensity ratios of the three symmetric CO3 stretching bands at around 1100 cm-1. We propose to non-destructively differentiate parisite-(Ce) and röntgenite-(Ce) by their 1092 cm-1 / 1081 cm-1 ν1(CO3) band height ratio.

The absence of metamictisation in natural monazite.

The actinide-containing mineral monazite-(Ce) is a common accessory rock component that bears petrogenetic information, is widely used in geochronology and thermochronology, and is considered as potential host material for immobilisation of radioactive waste. Natural samples of this mineral show merely moderate degrees of radiation damage, despite having sustained high self-irradiation induced by the decay of Th and U (for the sample studied herein 8.9 ± 0.3 × 1019 α/g). This is assigned to low damage-annealing temperature of monazite-(Ce) and "alpha-particle-assisted reconstitution". Here we show that the response of monazite-(Ce) to alpha radiation changes dramatically, depending on the damage state. Only in radiation-damaged monazite-(Ce), 4He ions cause gradual structural restoration. In contrast, its high-temperature annealed (i.e. well crystalline) analogue and synthetic CePO4 experience He-irradiation damage. Alpha-assisted annealing contributes to preventing irradiation-induced amorphisation ("metamictisation") of monazite-(Ce); however, this process is only significant above a certain damage level.

Irradiation effects in monazite-(Ce) and zircon: Raman and photoluminescence study of Au-irradiated FIB foils.

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).

GZ7 and GZ8 - Two Zircon Reference Materials for SIMS U-Pb Geochronology.

Here, we document a detailed characterisation of two zircon gemstones, GZ7 and GZ8. Both stones had the same mass at 19.2 carats (3.84 g) each; both came from placer deposits in the Ratnapura district, Sri Lanka. The U-Pb data are in both cases concordant within the uncertainties of decay constants and yield weighted mean 206Pb/238U ages (95% confidence uncertainty) of 530.26 Ma ± 0.05 Ma (GZ7) and 543.92 Ma ± 0.06 Ma (GZ8). Neither GZ7 nor GZ8 have been subjected to any gem enhancement by heating. Structure-related parameters correspond well with the calculated alpha doses of 1.48 × 1018 g-1 (GZ7) and 2.53 × 1018 g-1 (GZ8), respectively, and the (U-Th)/He ages of 438 Ma ± 3 Ma (2s) for GZ7 and 426 Ma ± 9 Ma (2s) for GZ8 are typical of unheated zircon from Sri Lanka. The mean U mass fractions are 680 µg g-1 (GZ7) and 1305 µg g-1 (GZ8). The two zircon samples are proposed as reference materials for SIMS (secondary ion mass spectrometry) U-Pb geochronology. In addition, GZ7 (Ti mass fractions 25.08 µg g-1 ± 0.18 µg g-1; 95% confidence uncertainty) may prove useful as reference material for Ti-in-zircon temperature estimates.

Factors affecting the Nd3+ (REE3+) luminescence of minerals.

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.

Phase decomposition upon alteration of radiation-damaged monazite-(ce) from moss, Østfold, norway.

The internal textures of crystals of moderately radiation-damaged monazite-(Ce) from Moss, Norway, indicate heavy, secondary chemical alteration. In fact, the cm-sized specimens are no longer mono-mineral monazite but rather a composite consisting of monazite-(Ce) and apatite pervaded by several generations of fractures filled with sulphides and a phase rich in Th, Y, and Si. This composite is virtually a 'pseudomorph' after primary euhedral monazite crystals whose faces are still well preserved. The chemical alteration has resulted in major reworking and decomposition of the primary crystals, with potentially uncontrolled elemental changes, including extensive release of Th from the primary monazite and local redeposition of radionuclides in fracture fillings. This seems to question the general alteration-resistance of orthophosphate phases in a low-temperature, 'wet' environment, and hence their suitability as potential host ceramics for the long-term immobilisation of radioactive waste.

Probing cooperative interactions of tailor-made nucleation surfaces and macromolecules: a bioinspired route to hollow micrometer-sized calcium carbonate particles.

It is well known that the formation of biominerals by living organisms is governed by the cooperation of soluble and insoluble macromolecules with peculiar interfacial properties. To date, most of the studies on mineralization processes involve model systems that account only for the existence of one organic matrix and thus disregard the interaction between the soluble and insoluble organic components that is crucial for a better understanding of the processes taking place at the inorganic-organic interface. We have set up a model system composed of a matrix surface, which is composed of a self-assembled monolayer (SAM) and a soluble component, poly(aspartic acid). It could be demonstrated that the phase selection of calcium carbonate and the morphology of the resulting particles are determined by the stabilization of amorphous precursor particles by the polymer and the interaction between polymer and SAM. The morphology of the hollow vaterite microspheres are reminiscent to a 3D analogue of the so-called "coffee-stain effect", where the transformation from a voluminous hydrated, amorphous material to a more dense crystalline material leads to the formation of hollow spheres from massive spherical microparticles.

Morphosynthesis of strontianite nanowires using polyacrylate templates tethered onto self-assembled monolayers.

Strontianite nanowires have been synthesized on self-assembled monolayers (SAM) in the presence of polyacrylate templates. The morphology of this product exhibits characteristic differences from that of products obtained in the absence of polyacrylate. It is demonstrated that the template-induced crystallization process involves the interaction between the SAM surface, polyacrylate (a dissolved polyelectrolyte), and the cations/anions in solution. By the combination of these components, hierarchically ordered mineral hybrid structures are formed.