Lead contamination in soils and sediments is a major threat to water quality. In surface and near-surface environments, Pb is not redox active; however, common Pb hosts, including Fe(III)-(hydr)oxides and sulfides, dissolve and precipitate as redox conditions change. Dissolution of Pb hosts may release Pb to porewater, leading to spikes in dissolved Pb concentrations and potential transport into surface or groundwater. Here, we examine the impacts of hydrologically coupled redox transitions on Pb partitioning in contaminated floodplain soils. We find that the affinity of Pb for particulate organic matter (POM), inclusive of mineral-associated organic matter, ensures that across redox transitions Pb is retained in the solid phase, despite host-phase (Fe(III)-(hydr)oxide and sulfide) dissolution. As seasonal hydrologic dynamics shift porewater redox conditions, Pb-bearing Fe(III)-(hydr)oxides (Pb-HFO) and sulfides (PbS) are dissolved and (re)precipitated. However, despite these shifts in redox conditions and associated host-phase transformations, Pb retention on POM, coupled with the formation of PbS and Pb-HFO, maintains dissolved Pb concentrations below 17 μg L −1 . Importantly, the predominance of Pb adsorbed on POM alongside low dissolved Pb concentrations indicates that Pb released from HFO and PbS is retained by POM. Thus, despite host-phase dissolution during redox transitions, partitioning of Pb to the aqueous phase is minimal and, therefore, transport of dissolved Pb is unlikely.

Mountain floodplain soils often show spatiotemporal variations in redox conditions that arise due to changing hydrology and resulting biogeochemistry. Under oxygen-depleted conditions, solid phase terminal electron acceptors (TEAs) can be used in anaerobic respiration. However, it remains unclear to what degree the redox properties of solid phases limit respiration rates and hence organic matter degradation. Here, we assess such limitations in soils collected across a gradient in native redox states from the Slate River floodplain (Colorado, U.S.A.). We incubated soils under anoxic conditions and quantified CO 2 production and microbial Fe(III) reduction, the main microbial metabolic pathway, as well as the reactivity of whole-soil solid phase TEAs toward mediated electrochemical reduction. Fe(III) reduction occurred together with CO 2 production in native oxic soils, while neither Fe(II) nor CO 2 production was observed in native anoxic soils. Initial CO 2 production rates increased with increasing TEA redox reactivity toward mediated electrochemical reduction across all soil depths. Low TEA redox reactivity appears to be caused by elevated Fe(II) concentrations rather than crystallinity of Fe(III) phases. Our findings illustrate that the buildup of Fe(II) in systems with long residence times limits the thermodynamic viability of dissimilatory Fe(III) reduction and thereby limits the mineralization of organic carbon.

Reaction conditions and mechanisms promoting or inhibiting U reduction exert a central control on U solubility and, therefore, U transport and its associated risks. Here, we vary and track common aqueous uranium species to show that a kinetic restriction inhibits homogeneous reduction of the calcium-uranyl-carbonato species (CaUO2(CO3)3 2– and Ca2UO2(CO3)3) by Fe­(II)(aq), while ferrihydrite surface-catalyzed reduction of all aqueous uranyl by Fe­(II) proceeds. Using U L3 high energy resolution fluorescence detection (HERFD) X-ray absorption near edge structure (XANES) spectroscopy, U L3 extended X-ray absorption fine structure (EXAFS) spectroscopy, and transmission electron microscopy (TEM), we also show that U­(V) is generated and incorporated into ferrihydrite formed from homogeneous U­(VI) reduction by Fe­(II)(aq). Through elucidation of the mechanisms that inhibit reduction of the calcium-uranyl-carbonato species and promote stabilization of U­(V), we advance our understanding of the controls on U solubility and thus improve prediction of U transport in surface and subsurface systems.

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Hydrologic extremes dominate chemical exports from riparian zones and dictate water quality in major river systems. Yet, changes in land use and ecosystem services alongside growing climate variability are altering hydrologic extremes and their coupled impacts on riverine water quality. In the western U.S., warming temperatures and intensified aridification are increasingly paired with the expanding range of the American beaver—and their dams, which transform hydrologic and biogeochemical cycles in riparian systems. Here, we show that beaver dams overshadow climatic hydrologic extremes in their effects on water residence time and oxygen and nitrogen fluxes in the riparian subsurface. In a mountainous watershed in Colorado, U.S.A., we find that the increase in riparian hydraulic gradients imposed by a beaver dam is 10.7–13.3 times greater than seasonal hydrologic extremes. The massive hydraulic gradient increases hyporheic nitrate removal by 44.2% relative to seasonal extremes alone. A drier, hotter climate in the western U.S. will further expand the range of beavers and magnify their impacts on watershed hydrology and biogeochemistry, illustrating that ecosystem feedbacks to climate change will alter water quality in river systems.