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Smith, Chelsea

Publications and source records attributed to Smith, Chelsea.

Iron transformation mediates phosphate retention across a permafrost thaw gradient

Phosphorus limits primary productivity in many (Sub-)Arctic ecosystems and may constrain biological carbon sequestration. Iron (III) oxides strongly bind phosphate in soils but can dissolve under flooded, reducing conditions induced by permafrost thaw and ground collapse. The ability for iron to regulate phosphate storage and solubility in thawing permafrost landscapes remains unclear. Here, iron-rich sediments containing iron oxides and organic-bound iron were incubated with or without added phosphate in soils along a permafrost thaw gradient to evaluate how iron-phosphate associations respond to thaw-induced redox shifts. Iron oxides partially dissolved and released sorbed phosphate when incubated in soils underlain by degraded permafrost. Iron complexed by organic matter remained stable but provided no phosphate binding capacity. Phosphate addition enhanced iron oxide dissolution and phosphorus concentrations in associated microbial biomass. Our study demonstrates that the capacity for iron oxides to immobilize and retain phosphate in permafrost peatlands decreases with permafrost thaw.

54 ENVIRONMENTAL SCIENCES↗

Changes in inundation drive carbon dioxide and methane fluxes in a temperate wetland

Wetlands cycle carbon by being net sinks for carbon dioxide (CO 2 ) and net sources of methane (CH 4 ). Daily and seasonal temporal patterns, dissolved oxygen (DO) availability, inundation status (flooded or dry/partially flooded), water depth, and vegetation can affect the magnitude of carbon uptake or emissions, but the extent and interactive effects of these variables on carbon gas fluxes are poorly understood. We characterized the linkages between carbon fluxes and these environmental and temporal drivers at the Old Woman Creek National Estuarine Research Reserve (OWC), OH. We measured diurnal gas flux patterns in an upstream side channel (called the cove) using chamber measurements at six sites (three vegetated and three non-vegetated). We sampled hourly from 7 AM to 7 PM and monthly from July to October 2022. DO concentrations and water levels were measured monthly. Water inundation status had the most influential effect on carbon fluxes with flooded conditions supporting higher CH 4 fluxes (0.39 μmol CH 4 m –2 s –1 ; –1.23 μmol CO 2 m –2 s –1 ) and drier conditions supporting higher CO 2 fluxes (0.03 μmol CH 4 m –2 s –1 ; 0.86 μmol CO 2 m –2 s –1 ). When flooded, the wetland was a net CO 2 sink; however, it became a source for both CH 4 and CO 2 when water levels were low. We compared chamber-based gas fluxes from the cove in flooded (July) and dry (August) months to fluxes measured with an eddy covariance tower whose footprint covers flooded portions of the wetland. The diurnal pattern of carbon fluxes at the tower did not vary with changing water levels but remained a CO 2 sink and a CH 4 source even when the cove where we performed the chamber measurements dried out. Furthermore, these results emphasize the role of inundation status on wetland carbon cycling and highlight the importance of fluctuating hydrologic patterns, especially hydrologic drawdowns, under changing climatic conditions.

54 ENVIRONMENTAL SCIENCES↗

Influence of contrasting redox conditions on iron (oxyhydr)oxide transformation and associated phosphate sorption

Iron (oxyhydr)oxides strongly adsorb phosphate and limit its bioavailability, but 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. In conclusion, these results demonstrate that hydrologic variability and Fe (oxyhydr)oxide mineralogy impact Fe mobilization pathways that may regulate phosphate bioavailability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Variability in soil redox response to seasonal flooding in a vernal pond

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 h in variably inundated environments remain sparse. In this study, the responses of soil E h to ponding, drying, and rewetting of a vernal pond were investigated over a 5-month period from late spring through early autumn. Soil E h was 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 h in 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 h in 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 h responds to surface flooding and drying. These findings highlight the spatial and temporal variability of E h within ponds and have implications for how soil processes and ecosystem function are impacted by shifts in hydrology at terrestrial-aquatic interfaces.

54 ENVIRONMENTAL SCIENCES↗