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 μm) 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 4–40 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.