Tripuhyite (FeSbO4) is an important antimony (Sb)-bearing mineral that controls Sb mobility in contaminated environments, yet its structural stability during microbial reduction remains unresolved. Understanding how FeSbO4 behaves under anoxic conditions is therefore necessary to predict natural Sb cycling. This study examined how an anaerobic microbial community interacts with FeSbO4 and alters its structural and redox behavior. Across all conditions, FeSbO4 released measurable Sb(V), demonstrating that the mineral undergoes partial dissolution in anoxic environment even without microbial activity. However, when extensive microbial Fe(III) reduction occurred in the presence of the electron shuttle anthraquinone-2,6-disulfonate (AQDS), the released Sb was re-immobilized. This indicates that microbial reduction processes modulate Sb mobility. Microbial community analysis showed the enrichment of acetate-utilizing Fe(III)-reducing bacteria as key drivers of Fe reduction. Although secondary Fe minerals were not detected, X-ray absorption fine structure measurements and scanning electron microscopy images revealed the formation of an Sb(III)-bearing phase consistent with valentinite (Sb2O3) in the AQDS-amended treatment. This transformation suggests that AQDS not only enhances Fe(III) reduction but is also linked to Sb(V) reduction, and facilitates the immobilization of reduced Sb(III) as Sb2O3. Overall, this work provides the first evidence that FeSbO4 is susceptible to microbially mediated redox transformations, and that these processes can significantly alter the mobility and speciation of Sb in reducing environments.

Characterizing the solid-phase speciation of antimony (Sb) at contaminated sites is essential for assessing its mobility, bioavailability, and environmental risk. However, comparative field studies across contrasting contamination sources and environments remain limited. To address this gap, we investigated the mineralogy and speciation of Sb-bearing phases in soil and rock samples collected from three distinct sites: an Sb mine, a shooting range, and an Sb refinery, and evaluated their relationships with local biogeochemical parameters. X-ray spectroscopic analyses showed that Sb(V) dominated across all sites, while Sb speciation varied markedly. Tripuhyite (an Sb(V)-ferric mineral) and/or roméite (a Ca-dominant pyrochlore-group Sb(V) oxide) were present at the mine and refinery as oxidation products of Sb(III) phases. In contrast, shooting range soils contained surface-associated Sb(V) immobilized by iron (Fe) phases. Microbial community analysis showed negligible abundance of Sb(III)-oxidizing bacteria and minimal Sb influence on community composition, likely reflecting low Sb bioavailability. Instead, microbial communities consisted of taxa exhibiting metabolic diversity and adaptation to the contaminated environments. Overall, long-term Sb speciation across the three sites is controlled by site-specific contamination sources and abiotic processes, particularly oxidation and stabilization mediated by Fe phases, rather than direct microbial involvement. These findings highlight the importance of comparative field studies for advancing our understanding of Sb behavior in contaminated environments.

The cycling of organic matter in terrestrial soils and sediments is central to a range of biogeochemical processes that regulate nutrient cycling, crop productivity, trace gas emissions, and contaminant transport. Pyrolysis-gas chromatography/mass spectrometry (py-GC/MS) is a powerful tool for characterizing bulk soil organic matter (SOM) at the molecular level. In this study, we used a cryo-focused py-GC/MS system to analyze soil samples from seven diverse ecosystems: vernal pool, prairie pothole, temperate forest, tropical forest, tundra, wildfire-affected boreal forest, and grassland. We addressed a key bottleneck in molecular-level SOM characterization by developing an automated data analysis pipeline to optimize py-GC/MS and complementary evolved gas analysis/mass spectrometry (EGA/MS) methods, incorporating advanced tools for peak deconvolution, developing a custom compound class library, and implementing fragmentation spectrum-based molecular networking for the first time. This improved workflow was applied to soil samples from all seven ecosystems, including multiple depths and density fractions. Our findings demonstrate that ecosystem type plays a dominant role in shaping compositional differences in SOM. We also identified trends in the source of SOM compounds (e.g., microbial vs plant-derived) across soil depth and density fractions, which are critical for understanding persistence and turnover of SOM. Our molecular networking analysis indicated that although many compounds are widespread across ecosystems, others are restricted to specific environments, such as wetlands. This underscores the utility of molecular-level data in elucidating the complexity of SOM composition and the environmental drivers that shape it. Such molecular-level insights can deepen our knowledge of biogeochemical SOM cycles.

Carbon dioxide (CO2) sequestration has garnered widespread attention as a key strategy for mitigating CO2 emissions and combating the greenhouse effect. However, the mechanisms underlying the interactions between CO2, widespread siliceous minerals and biological processes remain unclear. The present study explored the potential impacts of different CO2 concentrations on microbial activity, environmental conditions and their feedback on the fate of CO2. A total of 20 experimental conditions was created, with the variables including different natural and synthetic siliceous minerals (e.g., quartz sand and a type of commercial glass beads), the presence or absence of the iron-reducing microorganism Orenia metallireducens (strain Z6) and varying CO2 concentrations (0%, 20%, 50%, 100%) in the presence of ferrihydrite and pyruvate. Geochemical, microbial and mineralogical analyses revealed that elevated CO2 concentrations significantly inhibited microbial Fe(III) reduction and pyruvate metabolism. Interestingly, compared to cultures without mineral amendments or those with glass beads alone, the addition of quartz sand enabled strain Z6 to better withstand the environmental stress caused by elevated CO2, promoting pyruvate fermentation and iron reduction. In addition to an increased pH, the formation of siderite, hematite and vivianite was also observed in the bioactive systems. Although both glass beads and quartz sand were primarily composed of silica, differences in the mineral structure, elemental composition and acid neutralization capacity rendered quartz sand more chemically active and unexpectedly led to greater CO2 sequestration.

Suspended solids can be the primary vector for transporting contaminants in streams. The objective of this study was to determine whether changes in the properties of suspended solids during rain events impacted contaminant transport. Stream water was collected during five episodic events downstream from a U-contaminated wetland located in South Carolina, USA. The suspended particles were initially composed of Fe-flocs (particles formed in situ prior to the rain event) that had significantly greater Fe, Mn, organic-C, and U content than particles collected later during a sampling rain event. XANES and EXAFS revealed that U in the Fe-flocs was U(VI) and that it was not incorporated in a mineral structure but existed as inner- or outer-sphere adsorbed uranyl species associated with organic matter and Fe-oxides. The uranyl had an extraordinarily high affinity for the suspended solids, with solid to liquid U ratios of >72,000 (μg/kg)/(μg/L). After the initial flush of Fe-flocs, a greater fraction of the suspended solids had lower organic-C, Fe, Mn, and amorphous phases and were composed of more quartz, kaolinite, and gibbsite, resulting in lower U concentrations than those in the solids collected earlier in the rain event. This study highlights the importance of understanding suspended solids as transport vectors and their potential dynamic nature during rain events.

Coastal environments are dynamic interfaces that mediate carbon and nutrient exchanges between terrestrial landscapes and open waters, and understanding the biogeochemical factors controlling these exchanges, particularly iron (Fe) redox transformations, is crucial for predicting coastal ecosystem functions. Here, we investigated the mechanisms controlling Fe speciation changes across upland-to-shoreline gradients in freshwater and estuarine soils using Fe K-edge X-ray absorption spectroscopy, solid and porewater composition analysis, and 16S rRNA sequencing analysis. We show that Fe transformations depend primarily on inundation patterns. In unsaturated uplands, Fe occurs as Fe(III) oxyhydroxides, mainly goethite (9-35 %), Fe(II,III)-phyllosilicates (39-89 %), and Fe(III)-organic species (0-61 %). Soils influenced by estuarine waters exhibit porewater sulfide concentrations reaching up to 221 μM, Fe- and S-cycling bacteria, and up to 81 % pyrite (FeS2), indicating that sulfur-driven redox dynamics control Fe transformations. In lacustrine wetlands, Fe(III) reduction is indicated by porewater Fe(II) concentrations increasing to 1.0-2.1 mM, and ~10-15 % of Fe as Fe(II,III)-(hydr)oxides (green rust), vivianite (Fe3(PO4)2·8H2O), and/or adsorbed Fe(II) species. EXAFS data also indicate reduction of structural Fe(III) to Fe(II) in phyllosilicates. The presence of Fe- and S-cycling bacteria, as well as sulfide (0-10 μM), suggests that Fe-cycling is microbially driven and potentially coupled with cryptic S-cycling. Fe(II) oxidation was indicated above/near the water table by the presence of Fe(III) oxyhydroxides (ferrihydrite, lepidocrocite). Furthermore, negligible Fe(III) or sulfate reduction was observed at some water-saturated sites located at the upland-wetland transition, likely due to oxic (sub-)surface water inputs. Overall, our results highlight the importance of considering both Fe-speciation and hydro-biogeochemical dynamics when predicting Fe-cycling at coastal interfaces.

Antimony (Sb) is a toxic metalloid that poses environmental risks in terrestrial and aquatic systems. The fate of the Sb(V) oxyanion, Sb(OH)(6)(-), is governed by complex biogeochemical processes, including immobilization by ferric (Fe(III)) oxides, reduction by sulfide, and the less-explored competitive adsorption with other anions such as phosphate (PO43-). This study investigates the interplay between such mechanisms in controlling the behavior of Sb(V) associated with ferrihydrite (Fh) under Fe(III)- and sulfate-reducing conditions, with a particular emphasis on the role of phosphate in influencing Sb(V) mobility and transformation. Anoxic reactors that contained Sb(V)-coprecipitated Fh, varying PO43- concentrations (0, 0.2, and 2 mM), and sulfate, were inoculated with a microbial community sourced from Sb-contaminated soil. Additionally, abiotic reactors with either Sb(V)adsorbed or Sb(V)-coprecipitated Fh and different PO43- loadings (0-100 mM) were created to investigate the competitive adsorption mechanisms in the absence of microbial activity. Results from the abiotic reactors suggest that Sb(V) is likely incorporated into the Fh structure, with only minor amounts remaining surface-bound and extractable by PO43-. In the biotic reactors, microbial Fe(III) and sulfate reduction were more extensive in the presence of PO43-. At 0.2 mM PO43-, microbial activity transformed Fh into siderite and led to the complete reduction of Sb(V) to Sb(III) as stibnite (Sb2S3). At 2 mM PO43-, the greater coverage by PO43- stabilized Fh and decreased the extent of both Fe(III) and Sb(V) reduction, and shifted the reduced products to mackinawite and Sb (III) adsorbed onto Fh, in addition to stibnite formation. This study demonstrates that while PO43- may not directly compete with Sb(V) for sorption sites, it can influence Sb mobility in Fe(III)- and sulfate-reducing environments by enhancing microbial activity and altering the mineralization pathways.

In many aquatic and terrestrial ecosystems, iron (Fe) reduction by microorganisms is a key part of biogeochemical cycling and energy flux. The presence of redox-active electron shuttles in the environment potentially enables a phylogenetically diverse group of microbes to use insoluble iron as a terminal electron acceptor. We investigated the impact that different electron shuttles had on respiration, microbial physiology, and microbial ecology. We tested eight different electron shuttles, seven quinones and riboflavin, with redox potentials between 0.217 and -0.340 V. Fe(III) reduction coupled with acetate oxidation was observed with all shuttles. Once Fe(III) reduction began to plateau, a rapid increase in acetate consumption was observed and coincided with the onset of methane production, except in the incubations with the shuttle 9,10-anthraquinone-2-carboxylic acid (AQC). The rates of iron reduction, acetate consumption, methanogenesis, and the microbial communities varied significantly across the different shuttles independent of redox potential. In general, shuttles appeared to reduce the overall diversity of the community compared to no shuttle controls, but certain shuttles were exceptions to this trend. Geobacteraceae were the predominant taxonomic family in all enrichments except in the presence of AQC or 1,2-dihydroxyanthraquinone (AQZ), but each shuttle enriched a unique community significantly different from the no shuttle control conditions. This suggests that the presence of different redox-active electron shuttles can have a large influence on the microbial ecology and total carbon flux in the environment.IMPORTANCEIron is the fourth most abundant element in the Earth's crust, and the reduction of iron by microbes is an important component of global biogeochemical cycles. A phylogenetically diverse group of microbes is capable of conserving energy with oxidized iron as a terminal electron acceptor, but the environmental conditions favoring certain taxonomic clades in iron-reducing environments are unclear. One complicating factor often overlooked in small-scale enrichments is the influence of soluble, redox-active electron shuttles on the rate and microbial ecology of iron reduction. We tested the effects of eight different electron shuttles on microbial physiology and ecology in iron-reducing enrichments derived from a local wetland. Each electron shuttle varied the microbial activity and enriched for a microbial community distinct from the no shuttle control condition. Therefore, in complex subsurface environments with many redox-active compounds present, we propose electron shuttles as a reason for the coexistence of multiple clades of iron-reducing bacteria.

Coastal soils are a significant but highly uncertain component of global biogeochemical cycles. These systems experience spatial and temporal variability in biogeochemical processes, driven by marsh-to-upland gradients and hydrological fluctuations. These fluctuations make it difficult to understand and predict biogeochemical processes in these highly dynamic systems. We studied coastal soil biogeochemistry and its variability (a) at regional scales and (b) across transects from upland forest to marsh, in two contrasting regions-Lake Erie, a freshwater lacustrine system, and Chesapeake Bay, a saltwater estuarine system. Salinity-related analytes were a key source of variability in soil biogeochemistry, not just in the saltwater system, but surprisingly, also in the freshwater system. We had hypothesized linear trends in biogeochemical parameters along the TAI-however, contrary to expectations, transition soils were not consistently intermediate between upland and marsh endmembers; the non-monotonic trends of C, P, Fe along our transects suggest that these do not behave as expected and may be difficult to model and predict-thus these are key analytes to study in our regions. Rapidly changing soil factors across coastal gradients (e.g., Ca, K, CEC, and TS) may act as precursors to ecosystem shifts. Our comprehensive soil characterization represents a snapshot of a single timepoint of surface soils and provides essential data for mechanistic modeling of ecosystem dynamics across coastal transects.

The reduction of Hg-II to Hg-I or Hg-0 can lead to significant changes in Hg toxicity and mobility in the environment. Photochemical reduction is the primary process for the reduction of Hg-II to Hg-0 in sunlit environments; however, dark reduction of Hg-II can occur via microbial metabolic processes and/or reduction by reduced natural organic matter, Fe-II mineral phases, Fe-II sorbed to minerals, or aqueous Fe-II. Here, we demonstrate a novel Hg-II reduction pathway involving another environmentally relevant reductant, Mn-II. Abiotic reduction of (HgO)-O-II by Mn-II was studied as a function of pH and anion environment (perchlorate, sulfate, chloride) using X-ray absorption spectroscopy to characterize the solid-phase Hg and Mn species. At circumneutral pH of 7.5, about 70% of Hg-II was reduced to elemental Hg-0 within 2 h. In contrast, 12 h were needed to achieve the same extent of reduction at pH 6.9. In the presence of sulfate and chloride, Hg-I species were formed. Hg-II reduction was initially rapid and coupled with the oxidation of soluble Mn-II-oxides to insoluble Mn-IV-oxides, followed by a significantly slower reduction of Hg-II during the Mn-II-catalyzed transformation of the Mn-IV-oxides to hydroxide and oxyhydroxide minerals. The observed reduction of Hg-II by Mn-II at circumneutral pH could be an important transformation pathway for environmental Hg, affecting its bioavailability and mobility under mildly reducing conditions.

The microbial reduction of Fe(III) is a major component of Fe cycling in terrestrial and aquatic environments and is affected by the Fe(III) mineralogy of the system. The majority of the research examining the bioreduction of Fe(III) oxides by Fe(III)-reducing bacteria (IRB) has focused on the reduction of poorly crystalline Fe(III) phases, primarily ferrihydrite; however, crystalline Fe(III) oxides like goethite (α-FeOOH) and hematite (α-Fe 2 O 3 ) comprise the majority of Fe(III) oxides in soils. This study examined the bioreduction of goethite and hematite of geogenic and synthetic origin by Shewanella putrefaciens CN2, a well-studied model IRB, in laboratory incubations. Overall, the rate and extent of Fe(II) production were greater for goethite than for hematite, and for geogenic Fe(III) oxides relative to their synthetic analogs. Although there was substantial production of Fe(II) (i.e., > 5 mM Fe(II)) in many of the systems, X-ray diffraction analysis of the solids at the end of the incubation did not indicate the formation of any Fe(II)-bearing secondary minerals (e.g., magnetite, siderite, green rust, etc.). The results of this study demonstrate the variability in the extent of bioreduction of geogenic goethite and hematite, and furthermore, that synthetic goethite and hematite may not be good analogs for the biogeochemical behavior of Fe(III) oxides in aquatic and terrestrial environments.

Rhenium (Re) is an extremely rare element, with a crustal abundance of approximately 0.4 parts per billion (ppb) and a sea water concentration of 8.3 parts per trillion (ppt). However, Re concentrations in anoxic marine sediments range from 2 to 184 ppb, which is attributed to reduction of the highly soluble perrhenate ion (Re(VII)O4−) to insoluble Re(IV) species. Anoxic sediments typically contain Fe(II) and sulfide species, which could potentially reduce Re(VII) to Re(IV). In this study, we examined the interactions of KReO4 with magnetite (Fe3O4), siderite (FeCO3), vivianite (Fe3(PO4)2•8H2O), green rust (mixed Fe(II)/Fe(III) layered double hydroxide), mackinawite (FeS), and chemically reduced nontronite (NAu-1) using X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy to determine the valence state and speciation of Re. Uptake of Re by green rust was rapid, with ~50% associated with the solids within 2 days. In contrast, there was <10% uptake by the other Fe(II) phases over 48 days. Reduction of Re(VII) to Re(IV) was only observed in the presence of green rust, producing clusters of bidentate-coordinated Re(IV)O6 octahedra.. These results suggest that except for green rust, the potential for other Fe(II)-bearing minerals to act as reductants for ReO4− in sedimentary environments requires further investigation.

Uranium (U) and nickel (Ni) released 50 years ago have been immobilized in the Tims Branch wetlands located on the Savannah River Site in the United States. Sediments were collected from seven locations to identify the factors responsible for this attenuation. Ni and U contents in the solids were significantly correlated, suggesting that depositional as opposed to chemical processes contributed to their spatial distribution. Based on sequential extractions, 63 ± 16% of the U was partitioned into the organic fraction, whereas Ni was distributed between several sediment fractions. An inverse pH-organic matter (OM) correlation and positive correlations of OM with total U and organic-bound U/Ni suggest that increased OM preservation and binding to the mineral surfaces were likely responsible for Ni- and especially U-sediment retention (Tims Branch pH = 4.84 ± 0.68). EXAFS analysis indicated the predominance of U(VI) coordinated with clay minerals (~65%), together with ~35% coordinated to either OM (in areas with elevated OM levels) or iron oxides. The desorption-Kd coefficients of U (3972 ± 1370 L/kg) and Ni (30 ± 8 L/kg) indicate that dissolved Ni poses a greater long-term risk than dissolved U for migrating downstream. This study suggests that a delicate balance of geochemical properties controls whether wetlands behave as sinks or sources of contaminants.

Antimony (Sb), a non-essential metalloid, can be released into the environment through various industrial activities. Sb(III) is considered more toxic than Sb(V), but Sb(III) can be immobilized through the precipitation of insoluble Sb2S3 or Sb2O3. In the subsurface, Sb redox chemistry is largely controlled by microorganisms; however, the exact mechanisms of Sb(V) reduction to Sb(III) are still unclear. In this study, a new strain of Sb(V)-reducing bacterium, designated as strain YZ-1, that can respire Sb(V) as a terminal electron acceptor was isolated from Sb-contaminated soils. 16S-rRNA gene sequencing of YZ-1 revealed high similarity to a known Fe(III)-reducer, Rhodoferax ferrireducens. XRD and XAFS analyses revealed that bioreduction of Sb(V) to Sb(III) proceed through a transition from amorphous valentinite to crystalline senarmontite (allotropes of Sb2O3). Genomic DNA sequencing found that YZ-1 possesses arsenic (As) metabolism genes, including As(V) reductase arsC. The qPCR analysis showed that arsC was highly expressed during Sb(V)-reduction by YZ-1, and thus is proposed as the potential Sb(V) reductase in YZ-1. This study provides new insight into the pathways and products of microbial Sb(V) reduction and demonstrates the potential of a newly isolated bacterium for Sb bioremediation.

As global change processes modify the extent and functions of terrestrial-aquatic interfaces, the variability of critical and dynamic transitional zones between wetlands and uplands increases. However, it is still unclear how fluctuating water levels at these dynamic boundaries alter groundwater biogeochemical cycling. Here, we used high-temporal resolution data along gradients from wetlands to uplands and during fluctuating water levels at freshwater coastal areas to capture spatiotemporal patterns of groundwater redox potential (E-h). We observed that topography influences groundwater E-h that is higher in uplands than in wetlands; however, the high variability within TAI zones challenged the establishment of distinct redox zonation. Declining water levels generally decreased E-h, but most locations exhibited significant E-h variability, which is associated with rare instances of short-term water level fluctuations, introducing oxygen. The E-h-oxygen relationship showed distinct hysteresis patterns, reflecting redox poising capacity at higher E-h, maintaining more oxidizing states longer than the dissolved oxygen presence. Surprisingly, we observed more frequent oxidizing states in transitional areas and wetlands than in uplands. We infer that occasional oxygen entering specific wetland-upland boundaries acts as critical biogeochemical control points. High-resolution data can capture such rare yet significant biogeochemical instances, supporting redox-informed models and advancing the predictability of climate change feedback.

Construction and demolition wastes (CDWs) have become a significant environmental concern due to urbanization. CDWs in landfill sites can generate high-pH leachate and various constituents (e.g., acetate and sulfate) following the dissolution of cement material, which may affect subsurface biogeochemical properties. However, the impact of CDW leachate on microbial reactions and community compositions in subsurface environments remains unclear. Therefore, we created columns composed of layers of concrete debris containing-soil (CDS) and underlying CDW-free soil, and fed them artificial groundwater with or without acetate and/or sulfate. In all columns, the initial pH 5.6 of the underlying soil layer rapidly increased to 10.8 (without acetate and sulfate), 10.1 (with sulfate), 10.1 (with acetate), and 8.3 (with acetate and sulfate) within 35 days. Alkaliphilic or alkaline-resistant microbes including Hydrogenophaga, Silanimonas, Algoriphagus, and/or Dethiobacter were dominant throughout the incubation in all columns, and their relative abundance was highest in the column without acetate and sulfate (50.7-86.6%). Fe(III) and sulfate reduction did not occur in the underlying soil layer without acetate. However, in the column with acetate alone, pH was decreased to 9.9 after day 85 and Fe(II) was produced with an increase in the relative abundance of Fe(III)-reducing bacteria up to 9.1%, followed by an increase in the methanogenic archaea Methanosarcina, suggestive of methanogenesis. In the column with both acetate and sulfate, Fe(III) and sulfate reduction occurred along with an increase in both Fe(III)- and sulfate-reducing bacteria (19.1 and 17.7%, respectively), while Methanosarcina appeared later. The results demonstrate that microbial Fe(III)- and sulfate-reduction and acetoclastic methanogenesis can occur even in soils with highly alkaline pH resulting from the dissolution of concrete debris.

The objective of this study was to determine if U sediment concentrations in a U-contaminated wetland located within the Savannah River Site, South Carolina, were greater in the rhizosphere than in the nonrhizosphere. U concentrations were as much as 1100% greater in the rhizosphere than in the nonrhizosphere fractions; however and importantly, not all paired samples followed this trend. Iron (but not C, N, or S) concentrations were significantly enriched in the rhizosphere. XAS analyses showed that in both sediment fractions, U existed as UO22+ coordinated with iron(III)-oxides and organic matter. A key difference between the two sediment fractions was that a larger proportion of U was adsorbed to Fe(III)-oxides, not organic matter, in the rhizosphere, where significantly greater total Fe concentrations and greater proportions of ferrihydrite and goethite existed. Based on 16S rRNA analyses, most bacterial sequences in both paired samples were heterotrophs, and population differences were consistent with the generally more oxidizing conditions in the rhizosphere. Finally, U was very strongly bound to the whole (unfractionated) sediments, with an average desorption Kd value (Usediment/Uaqueous) of 3972 ± 1370 (mg-U/kg)/(mg-U/L). Together, these results indicate that the rhizosphere can greatly enrich U especially in wetland areas, where roots promote the formation of reactive Fe(III)-oxides.

A nuclear fuel fabrication facility released 43,500 kg of uranium into a riparian wetland located on the Savannah River Site between 1955 and 1988. Studies were undertaken to evaluate hydrological and geochemical processes influencing uranium accumulation in the wetland. Gamma-radiation-mapping surveys were conducted by systematically walking over the contaminated wetland with backpacks equipped with global positioning systems and NaI gamma detectors. Based on maps compiled from >700,000 gamma spectra and eight sediment uranium depth profiles, it was determined that 94% of the released uranium remained in the wetland. The uranium in the wetland is concentrated in five multi-hectare areas along the stream, accounting for similar to 11% of the land area adjacent to the stream. While land type (upland or wetland) and topography provided a reasonable first approximation of where much of the uranium was deposited, hydrological watershed modeling revealed that the stream velocity was especially slow through many of the hot spots. Using autoradiography combined with SEM/ EDX measurements of contaminated sediments, surprisingly few hot particles were detected. Instead, uranium was evenly distributed throughout the sampled sediment, suggesting that dissolved uranium had bound to sediment particles that became suspended and later deposited in low energy (low flow velocity) portions of the stream. EXAFS suggested that U atoms were present as individual ions in disordered complexes within the sediment. Furthermore, linear combination analyses suggested that the predominant component of the U(VI) was adsorbed to sediment minerals (similar to 70%) and a minor component (similar to 30%) was associated with organic matter phases. These studies show that wetlands can be extraordinarily effective at binding and retaining uranium, thereby providing a natural barrier to the transport of uranium out of a watershed. However, significant anthropogenic or climatic changes to wetlands, such as those associated with flooding, forest fires, or land use, may disrupt the complex hydrological and biogeochemical balance necessary to maintain long-term immobilization of uranium.