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interactions between phosphate and various Fe (oxyhydr)oxides are poorly constrained in natural systems. An in-situ incubation experiment was conducted to explore Fe (oxyhydr)oxide transformation and effects on phosphate sorption in soils with contrasting saturation and redox conditions. Synthetic Fe (oxyhydr)oxides (ferrihydrite, goethite and hematite) were coated onto quartz sand and either pre-sorbed with phosphate or left phosphate-free. The oxide-coated sands were mixed with natural organic matter, enclosed in mesh bags, and buried in and around a vernal pond for up to 12 weeks. Redox conditions were stable and oxic in the upland soils surrounding the vernal pond but largely shifted from Fe reducing to Fe oxidizing in the lowland soils within the vernal pond as it dried during the summer. Iron (oxyhydr)oxides lost more Fe (− 41% ± 10%) and P (− 43 ± 11%) when incubated in the redox-dynamic lowlands compared to the uplands (− 18% ± 5% Fe and − 24 ± 8% P). Averaged across both uplands and lowlands, Fe losses from crystalline goethite and hematite (− 38% ± 6%) were unexpectedly higher than losses from short range ordered ferrihydrite (− 12% ± 10%). We attribute losses of Fe and associated P from goethite and hematite to colloid detachment and dispersion but losses from ferrihydrite to reductive dissolution. Iron losses were partially offset by retention of solubilized Fe as organic-bound Fe(III). Iron (oxyhydr)oxides that persisted during the incubation retained or even gained P, indicating low amounts of phosphate sorption from solution. These results demonstrate that hydrologic variability and Fe (oxyhydr)oxide mineralogy impact Fe mobilization pathways that may regulate phosphate bioavailability. 

Vernal ponds are ephemeral landscape features that experience intermittent flooding and drying, leading to variable saturation in underlying soils. Redox potential (E_h) is an important indicator of biogeochemical processes that changes in response to these hydrological shifts; however, high-resolution measurements of E_hin variably inundated environments remain sparse. In this study, the responses of soil E_hto ponding, drying, and rewetting of a vernal pond were investigated over a 5-month period from late spring through early autumn. Soil E_hwas measured at 10-min frequencies and at multiple soil depths (2–48 cm below the soil surface) in shallow and deep sections within the seasonally ponded lowland and in unsaturated soils of the surrounding upland. Over the study period, average E_hin surface soils (0–8 cm) was oxidizing in the upland (753 ± 79 mV) but relatively reducing in the shallow lowland (369 ± 49 mV) and deep lowland (198 ± 37 mV). Reducing conditions (E_h<300 mV) in surface soils prevailed for up to 6 days in the shallow lowland and up to 24 days in the deep lowland after surface water dried out. Intermittent reflooding resulted in multiple shifts between reducing and oxidizing conditions in the shallow lowland while the deep lowland remained reducing following reflooding. Soil E_hin the uplands was consistently oxidizing over the study period with transient increases in response to rain events. Reducing conditions in the lowland resulted in greater Fe-oxide dissolution and release of dissolved Fe and P into porewater than in the surrounding uplands. We determined that change in water depth alone was not a good indicator of soil E_h, and additional factors such as soil saturation and clay composition should be considered when predicting how E_hresponds to surface flooding and drying. These findings highlight the spatial and temporal variability of E_hwithin ponds and have implications for how soil processes and ecosystem function are impacted by shifts in hydrology at terrestrial-aquatic interfaces.