Natural zircon crystals often show complex secondary textures that cut across primary growth zones. In zircon showing structural damage caused by self-irradiation, such textures are the result of a diffusion- reaction process in which a hydrous species diffuses inwards and “catalyzes” structural recovery. Nanoscale pores develop, solvent elements such as Ca, Al and Fe are gained, and radiogenic Pb is lost. In both aqueous fluids and melts, replacement of zircon with undamaged structure by a coupled dissolution- reprecipitation process can produce similar textures. The reacted domains usually have lower trace element contents and may contain micrometer-sized pores and inclusions of uranium, thorium and/or yttrium phases, originally in solid solution. Both processes have considerable implications for zircon geochronology

Nations using borosilicate glass as an immobilization material for radioactive waste have reinforced the importance of scientific collaboration to obtain a consensus on the mechanisms controlling the long-term dissolution rate of glass. This goal is deemed to be crucial for the development of reliable performance assessment models for geological disposal. The collaborating laboratories all conduct fundamental and/or applied research using modern materials science techniques. This paper briefly reviews the radioactive waste vitrification programs of the six participant nations and summarizes the current state of glass corrosion science, emphasizing the common scientific needs and justifications for on-going initiatives

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We present the results of a series of hydrothermal experiments on grains from two partially metamict zircon samples from Sri Lanka in the temperature range 350 to 650 ∞C and with different solutions (2 M AlCl 3 , 2 M CaCl 2 , pure H 2 O, and a multi-cation solution). Under these conditions, sharply bounded reaction fronts penetrated into the zircon grains and developed complex lobate and rim structures that resemble structures found in natural zircon systems. The reaction zones are characterized by a marked increase in the cathodoluminescence intensity, a decrease of the back-scattered electron emission, and an increased degree of structural order, as revealed by micro-Raman and infrared spectroscopy. Sensitive high-resolution ion microprobe and electron microprobe measurements revealed that the altered areas gained solvent cations (e.g., Ca 2+ , Ba 2+ , Mg 2+ , Al 3+ ) from the solution and lost variable amounts of Zr, Si, Hf, the REE, U, Th as well as radiogenic Pb. A comparison between "dry" and "hydrothermal" annealing trends shows that the kinetics of structural recovery, including recrystallization of the amorphous phase in metamict zircon, is strongly enhanced under hydrothermal conditions. This finding suggests that water "catalyzes" structural recovery processes in metamict zircon. We found that the structure of the reacted areas does not resemble that of crystalline zircon, i.e., is still characterized by a temperature-dependent degree of disorder, which would not be expected if the reaction is controlled by a coupled dissolution and re-precipitation process. Instead, the alteration process can be described best by a diffusion-reaction-recrystallization model. In this model, it is postulated that the diffusion of water into the metamict structure is the driving force for moving recrystallization fronts. We found that the rate and the extent of solid-state recrystallization of the amorphous phase is an important factor in determining the mobility of trace elements. This interpretation is indicated by the observation that trace elements, including U and Th, were preferentially lost during the reaction with a fluid at low temperatures, where recrystallization of the amorphous material was slow or not activated at all. The observed chemical alteration patterns are believed to reflect a competition between the kinetics of long-range diffusion and ion exchange and the kinetics of the short-range diffusion necessary for the recrystallization process.

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The chemical and structural alteration of metamict zircon crystals from a 619 ±17 (2σ) Ma old, posttectonic granite in the southern part of the Eastern Desert, Egypt was studied. The crystals show simple oscillatory growth zones with metamictization–induced fractures, which provided pathways for fluid infiltration. Electron and ion microprobe analyses reveal that metamict, i.e. U and Th–rich, areas are heavily enriched in Ca, Al, Fe, Mn, LREE, and a water species, and have lost Zr and Si as well as radiogenic Pb. These chemical changes are the result of an intensive reaction with a low–temperature (120—200°C) aqueous solution. The chemical reactions probably occurred within the amorphous regions of the metamict network. During the zircon–fluid interactions the metamict structure was partially recovered, as demonstrated by micro-Raman and -infrared measurements. A threshold degree of metamictization, as defined empirically by an α–decay dose, Dc, was necessary for zircons to undergo hydrothermal alteration. It is proposed that Dc marks the first percolation point, where the amorphous domains start to form percolating clusters in the metamict network and where bulk chemical diffusion is believed to increase dramatically. The time of the hydrothermal alteration is determined by a lower intercept age of a U-Pb SHRIMP discordia of 17.9 (2σ) Ma, which is in good agreement with an apatite fission track age of 22.2 (2σ) Ma. The hydrothermal alteration event occurred contemporaneously with the main rifting phase of the Red Sea and widespread low- temperature mineralizations along the Red Sea coast.

Sponges are probably the earliest branching animals, and their fossil record dates back to the Precambrian. Identifying their skeletal structure and composition is thus a crucial step in improving our understanding of the early evolution of metazoans. Here, we present the discovery of 505–million-year-old chitin, found in exceptionally well preserved Vauxia gracilenta sponges from the Middle Cambrian Burgess Shale. Our new findings indicate that, given the right fossilization conditions, chitin is stable for much longer than previously suspected. The preservation of chitin in these fossils opens new avenues for research into other ancient fossil groups.