Coupling of reactive riverine phosphorus and iron species during hot transport moments: impacts of land cover and seasonality

Spring runoff often comprises the majority of annual discharge and riverine phosphorus (P) export due to sustained high flow, and the magnitude of spring runoff can be a strong predictor of receiving water summer harmful algal bloom severity. Yet the loading of reactive forms of P during this time period remains poorly-characterized in time, space and geochemical partitioning. Here, we explore the hypothesis that riverine dissolved and suspended sediment P loads during spring runoff have a particularly high proportion of potentially reactive species due to unique hydrologic pathways and P association with iron (Fe).The concentration, distribution and temporal dynamics of dissolved P (DP), dissolved and colloidal Fe, and redox sensitive suspended sediment P (RSP) and Fe during spring runoff and summer storms were compared in forested and agricultural catchments of the same watershed. The dominant carrier of RSP was Fe (oxy)hydroxides across land cover and season, but Fe (oxy)hydroxide particles and colloids in agricultural catchments were strongly enriched in RSP and DP during spring runoff and summer storms, particularly at the onset of snowmelt. In 2014, 83% of DP and 74% of RSP were delivered to Missisquoi Bay during spring runoff. Suspended sediment was significantly more redox sensitive than typically input to limnological models, suggesting that the reactivity of this load may be systematically underestimated. Changes in the timing, provenance
and severity of spring runoff associated with climate or land cover change will have dramatic impacts on total riverine P loads and their potential reactivity in receiving water ecosystems.