Rare Earth Element Behavior During Incongruent Weathering and Varying Discharge Conditions in Silicate Dominated River Systems: The Australian Victorian Alps

The distribution of rare earth elements (REE) and trace elements was measured by ICP-MS on fresh, slightly weathered and weathered granite and surface water samples from a network of 11 pristine rivers draining the Australian Victorian Alps during (i) high and (ii) low discharge conditions. River water REE concentrations are largely derived from atmospheric precipitation (rain, snow), as indicated by similar Chondrite normalized REE patterns (higher LREE over HREE; negative Ce anomalies, positive Eu anomalies) and similar total REE concentrations during both dry and wet seasons. Calculations based on the covariance between REE and Cl concentrations and oxygen and hydrogen isotopes indicate precipitation input coupled with subsequent evaporation may account for 30% o 100% of dissolved REE in stream waters. The dissolved contribution to the granitic substratum to stream water comes mainly from the transformation of plagioclase to smectite, kaolinite and gibbsite and minor apatite dissolution. However, since most REE of the regional granite are present in accessory minerals (titanite, zircon, etc.) they do not significantly contribute to the river REE pool. REE concentrations drop sharply downstream as a result of dilution and chemical attenuation. A trend of downstream enrichment of the heavier REE is due to selective partitioning of the lighter REE (as both free REE or REECO3 complexes) to hydrous oxides of suspended Al which, in turn, is controlled by a downstream increase of pH to values > 6.1 (for free REE) and > 7.3 (for REECO3 complexes). Although most circumneutral waters were supersaturated with REE phosphate compounds, precipitation of LnPO4 is not believed to have been a dominant process because the predicted phosphate fractionation pattern is inconsistent with the observed trends. Negative saturation indices of hydrous ferric oxides also militate against surface complexation onto goethite. Instead, REE attenuation most likely resulted from adsorption onto hydrous aluminium oxide. Seasonally, higher total REE concentrations during the dry season are due to longer residence time of water within rock fractures as well as high rainfall REE concentrations which, for the summer of 2007, might be related to organic carbon rich dust released after bushfires in the region. Lower pH values and low oxidation potentials at that time also contribute to raise REE concentrations through desorption.