Subarctic wintertime dissolved iron speciation driven by thermal constraints on Fe(II) oxidation, dissolved organic matter and stream reach

We studied the seasonal variations in Fe(II), Fe(III), humic-like dissolved organic matter (DOM), nitrate and nitrite (NO3 + NO2), and silicate (Si(OH)4) in river waters of three subarctic rivers flowing into Hakodate Bay in southwestern Hokkaido, Japan from May 2010 to February 2014. High Fe(II) concentrations were detected in winter at the sampling sites where the river bottom was comprised of sandy or silty sediment, primarily the lower and middle reaches of the rivers. Conversely, from early spring to late autumn Fe(II) levels were low or undetectable. We infer that soluble Fe(II) concentration in these subarctic river waters is driven by the balance between the influx of Fe(II) to the river and the Fe(II) oxidation rates that determines the dynamics in Fe(II) concentration in the river water. The Fe(II) may originate from reductive dissolution of Fe(III) in the river sediment or from Fe(II)-bearing groundwater. The latter seems to be the most likely source during winter time. The high Fe(II) concentrations during winter is predominantly attributed to the extremely slow oxidation rate of Fe(II) to Fe(III) at low water temperature rather than to an actual increase in the flux of reduced Fe(II). Nevertheless, we propose that the flux of reduced Fe(II) from river sediments and groundwater in lowland area of the catchment to overlying river waters might be the most important sources of iron in river waters. This provides an important insight into the role of river processes and the interaction between climate and river morphology in determining the inputs of iron to subarctic coastal marine waters.