Binding and transport of rare earth elements by organic and iron-rich nanocolloids in Alaskan rivers, as revealed by field-flow fractionation and ICP-MS

Water samples were collected from six small rivers in the Yukon River basin in central Alaska to examine the role of nanocolloids (0.5-40 nm) in the dynamics and transport of rare earth elements (REEs) in northern high latitude watersheds influenced by permafrost. Total dissolved (<0.45 mu m) concentrations and the 'nanocolloidal size distributions' (0.5-40 nm) of UV-absorbing dissolved organic matter, Fe, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu were determined by on-line coupling of flow field-flow fractionation (FFF) with a UV-absorbance detector and ICP-MS. Total dissolved and nanocolloidal concentrations of the REEs co-varied with dissolved organic carbon (DOC) in all rivers and between spring flood and late summer baseflow. The nanocolloidal size distributions indicated the presence of three major components of nanocolloids: the 0.5-3 nm 'fulvic-rich nanocolloids' occurring throughout the sampling season, the 'organic/iron-rich nanocolloids' residing in the <8 nm size range during the spring flood, and the 4-40 nm iron-rich nanocolloids occurring during summer baseflow. REEs associated with all the three components of nanocolloids, but the proportions associated with the fulvic-rich nanocolloids during summer baseflow increased with increasing REE molar mass, which is consistent with the increase in stability of organic REE-complexes with increasing REE molar mass. Normalization of the measured REE-concentrations with the average REE-concentrations of the upper continental crust revealed a dynamic change in the physicochemical fractionation of REEs. During the spring flood, REE-binding in all the rivers was dominated by the <8 nm organic/iron-rich nanocolloids, likely being eroded from the upper organic-rich soil horizon by the strong surface runoff of snowmelt water. During the summer, the REE-binding in rivers with large groundwater input was dominated by small (<0.5 nm) organic and/or inorganic complexes, while lower proportions of the REEs were associated with both the 0.5-3 nm fulvic rich and 4-40 nm iron rich nanocolloids and with larger >40 nm colloids. In a river sampled at higher altitude, the <8 nm organic/iron-rich and 440 nm iron-rich nanocolloids dominated the REE-binding also during the summer, which could be a result of persistent permafrost confining water flows to the upper organic-rich soil horizons. (C) 2012 Elsevier Ltd. All rights reserved.