Comparative study of yttrium and rare-earth element behaviours in fluorine-rich hydrothermal fluids

The mineral fluorite is utilized as a probe to investigate the behaviour of the pseudolanthanide yttrium with respect to the lanthanides (rare-earth elements, REE) in fluorine-rich hydrothermal solutions. Hydrothermal vein fluorites are characterized by the close association of Y and REE, but in contrast to igneous and clastic rocks they show variable and nonchondritic Y/Ho ratios of up to 200. This suggests that Y and Ho, although similar in charge and size, may be fractionated in fluorine-rich medium-temperature aqueous fluids. In such solutions Y acts as a pseudolanthanide heavier than Lu. Y/Ho ratios of hydrothermal siderites are slightly below those of chondrites, suggesting that in (bi)carbonate-rich siderite-precipitating solutions Y may act as a Sm-like light pseudolanthanide. This indicates that Y-Ho fractionation is not a sourcerelated phenomenon but depends on fluid composition. Based on these results it is strongly recommended that discussions of normalized REE patterns in general should be extended to normalized Rare-Earth-and-Yttrium (REY) patterns (Y inserted between Dy and Ho), because the slightly variable behaviour of the pseudolanthanide yttrium with respect to the REE may provide additional geochemical information. Available thermodynamic data suggest a negative correlation between Y/Ho and La/Ho during migration of a fluoriteprecipitating hydrothermal solution. Cogenetic fluorites, therefore, should display either similar Y/Ho and similar La/Ho ratios, or a negative correlation between these ratios. This criterion may help to choose samples suitable for Sm-Nd isotopic studies prior to isotope analysis. However, in cogenetic hydrothermal vein fluorites the range of Y/Ho ratios is often almost negligible compared to the range of La/Ho ratios. This may be explained by modification of REE distributions by post-precipitation processes involving (partial) loss of a separate LREE-enriched phase. The presence of variable amounts of such an accessory phase in most fluorite samples is revealed by experiments employing stepwise incomplete fluorite decomposition. Fluorites derived from and deposited near to igneous rocks apparently display chondritic Y/Ho ratios close to those of their igneous source-rocks. However, a positive Y_SN anomaly is likely to develop as the distance between sites of REY mobilization and deposition increases.