Measuring the distribution of trace elements amongst dissolved colloidal species as a fingerprint for the contribution of tributaries to large boreal rivers

Organic and inorganic colloids play important roles governing the speciation, transport, and bioaccessibility of trace elements in aquatic systems. These carriers are especially important in the boreal zone, where rivers that contain high concentrations of iron and organic matter are prevalent. The distribution of trace elements amongst different colloidal species (or "speciation profile") can therefore be useful as a fingerprint to detect different trace element sources and for tracking colloid transformations, with implications for bioaccessibility. Asymmetrical flow field-flow fractionation coupled to an inductively coupled plasma mass spectrometer was applied to detect the source of trace elements based on their speciation profile along a 125-km stretch of a large river in the Canadian boreal forest. Both the concentration and proportion of bound trace elements were increased by tributary inputs: bound As, Co, Fe, Mn, Pb, U, and Zn increased monotonically from upstream to downstream, increasingly resembling the speciation profile of tributaries. Principal component (PC) analysis also revealed tributary contributions of bound Cu, Ni, Th, V, and Y reflecting their higher concentrations in tributaries, and PC scores also increased monotonically from upstream-downstream. Monotonically decreasing concentrations of mainly ionic and small (i.e.ca. 300 Da) As, Ba, Mo, and U species were also observed from upstream-downstream.