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At least 109 records · Page 6

Illuminating the pathways to carbon liberation: a systems approach to characterizing the consequential unknowns of carbon transformation and loss from thawing permafrost peatlands (Final Report)

The IsoGenie3 Project delivered new systems-level insights into carbon cycling in thawing permafrost landscapes, with an emphasis on methane and carbon dioxide emissions. From >200 samples from the site collected over a decade, co-analyzed for geochemistry and microbiology, the team recovered ~1,500 assembled microbial genomes and ~1,900 viral population genomes, revealing appreciable genetic novelty - from a new highly abundant bacterial phylum, to novel methane consumers and their activities, to rampant viral novelty. IsoGenie3 linked these organisms to carbon compound transformations (which define the cycling of organic matter in soils, and the loss of the greenhouse gases carbon dioxide and methane), and saw that the microbes at each stage of permafrost thaw had different genetic potential to degrade categories of compounds, expressed that genetic potential differently, and actually transformed carbon compounds into greenhouse gases in different ways. IsoGenie 3 identified that some of the thaw-stage differences were due to plant-microbiome relationships; the plant species across the thaw gradient contributed different carbon compounds into the soil, and hosted distinct microbiota (differing among parts of plants as well as species). Lastly, microbes in the saturated post-thaw conditions appeared likely to contribute to the mobilization and toxification of mercury released during thaw. In parallel with ongoing field sampling and analysis, hypotheses arising from field observations were tested via lab incubation experiments. When communities are taken out of their native habitats, they behave differently, and the team first rigorously quantified the magnitude of this effect on microbiome composition and functional capacity, organic matter composition, and gas production; overall the main system processes were maintained in the lab incubations under the conditions tested. Further, the microbial data could inform geochemical reaction network models of those processes. Then, the team ran experiments with additions of compounds, varying temperature, and “live” vs. “dead” peat (the latter having been gamma irradiated, with a few additional variants to control for methodological artifacts). From these, we (a) determined the importance of plant-derived soluble phenolic compounds in bogs’ extraordinary recalcitrance of organic matter, and carbon gas emissions skewed to carbon dioxide; (b) proposed an abiotic ‘tanning’ mechanism, which could contribute to Sphagnum’s inhibitory effect on anaerobic decomposition through alteration of N availability. IsoGenie3 illuminated longer-term and landscape-scale interactions of permafrost thaw and carbon cycling, advancing knowledge of the drivers of methane dynamics not only across in the permafrost-associated peatland (where hydrology and plant communities dictate microbiomes) but also their interconnected lakes (where sediment carbon quality and resident microbiota are determined by position within lake, and lake features). By leveraging observations of site methane dynamics extending well before this project, the team was able to construct a 44-year portrait of the interplay of permafrost thaw, hydrology, vegetation dynamics, and carbon gas emissions, and the doubling of the fully-thawed fens over this time. From the detailed study of this focal site, IsoGenie3 also aimed to improve model representation of these kinds of sites and processes. To improve predictions of methane transformations, we incorporated acetate and isotope dynamics into the ‘DNDC’ biogeochemistry model. In addition, recovered genomes were grouped into ‘functional groups’, i.e. the genomes that perform a specific function of interest, then used to parameterize maximum growth rate and optimum growth temperature (via signatures in their sequence composition) for the BioCrunch model. The BioCrunch model was then in turn used to test the impact of increasing functional resolution of the microbes, on the carbon gas emissions. Lastly for modeling, the ecosys model was parameterized from the microbial and other data, and used to evaluate drivers of e.g. change in methane emissions. Finally, this project also led to the development of a range of new methods and tools, a new metric of organic matter decomposability, as well as a graph-database solution to multidisciplinary data storage and querying. This project’s ongoing analyses at our focal site also contributed to broader advancements in understanding elements of genetic plasticity and methane metabolism, climate change microbiology and community assembly, global peatland geochemistry and Arctic lakes’ roles in climate feedbacks.

54 ENVIRONMENTAL SCIENCES↗

UT-GOM2-2 Preliminary Report: Terrebonne Basin Northern Gulf of Mexico, 30 July-28 September 2023

In the summer and fall of 2023, the Gulf of Mexico Deepwater Hydrate Coring Expedition (UT-GOM2-2) drilled, cored, made downhole measurements, and analyzed samples from the seafloor to the base of the gas hydrate stability zone in one location (Site H, WR313) in the Terrebonne basin, deepwater Gulf of Mexico. Analyses of data and samples from the expedition will inform biological, geochemical, and geomechanical models to constrain the role of gas hydrates in the carbon cycle and the potential for gas hydrates as an energy resource. Pressure and conventional cores were collected continuously to a depth of 155.1 meters below the seafloor (mbsf). At deeper depths, cores were taken periodically from hydrate-bearing sands and their bounding muds to a total depth of 861.3 mbsf. 162.6 m of conventional core and 54.8 m of pressure core were obtained. Twelve temperature measurements were made between 27.1 and 144.5 mbsf to determine the geothermal gradient. At the seafloor, more than 4 m of sandy silt of unknown origin was encountered. Beneath this sand, to a depth of ~200 mbsf, the section was composed of interbedded mud and biogenic carbonate ooze. The biogenic ooze correlated to low density and high porosity intervals observed in the previously acquired logging while drilling (LWD) data and as measured. Calcareous nannofossil biostratigraphy constrains the entire record to the Pleistocene (< 0.91 million years) with a pronounced increase in sedimentation rate with depth. Beneath 200 mbsf, the section was predominantly composed of mud with two thicker, hydrate-bearing coarse-grained intervals, which are commonly known as the Blue and Orange sands. The dissolved gas concentration was quantified from pressure cores. In the shallow section, dissolved methane concentration increased below the sulfate-methane transition zone (SMTZ) and reaches saturation (the limit of solubility for methane) at 147 mbsf. Gas expansion was very common in conventional and depressurized pressure (conventionalized) cores below the SMTZ. At deeper depths, the methane concentration within muds bounding the Blue and Orange reservoirs was generally found to be less than saturation. The dissolved and hydrate gas composition is consistent with a microbial source, containing greater than 99.99% methane and only trace concentrations of ethane, propane, and butane. The methane to ethane ratio (C 1 /C 2 ) and the methane to ethane plus propane (C 1 /(C 2 +C 3 )) decrease with depth down to at least 678 mbsf, mainly driven by the increase in ethane with depth. It is unclear if this trend continues through the Orange sand interval. The δ 13 C isotopic signature of methane ranges between -69.9 and -78.5 ‰ Vienna Pee Dee Belemnite (VPDB). Pressure core recovery of all sandy intervals was poor. However, pressure core logs of the Orange sand show intervals of low density and high velocity, which are indicative of high hydrate saturation. One core from within the Orange sand was composed of interbedded graded sandy silt and mud. The sandy silts from this core are composed of mainly quartz and feldspar with some lithics. Most of the recovered pressure core samples are maintained at near in-situ pressure and temperature (within the hydrate stability field) at the University of Texas Pressure Core Center awaiting analysis. In the shallow section, samples will be used to determine the flux of organic carbon through the basin system, find the rate at which that carbon was consumed, and understand the microbial population responsible for these processes. In the deeper section, samples from in and around the hydrate reservoirs will be used to determine the petrophysical properties of the reservoir and bounding seals in these systems.

03 NATURAL GAS↗

Expedition UT-GOM2-2 Summary

In the summer and fall of 2023, the University of Texas (UT) Deepwater Hydrate Coring Expedition (UT-GOM2-2) drilled, cored, made downhole measurements, and analyzed samples from the seafloor to the base of the gas hydrate stability zone at Site H, in the Walker Ridge Protracted Area Block 313 (Site H, WR313), in the Terrebonne Basin, deepwater Gulf of America (Gulf of Mexico). Analyses of data and samples from the expedition will inform biological, geochemical, and geomechanical models to constrain the role of gas hydrates in the carbon cycle and the potential for gas hydrates as an energy resource.

03 NATURAL GAS↗

Predicting the potential for mineral scale precipitation in unconventional reservoirs due to fluid-rock and fluid mixing geochemical reactions

Mineral precipitation within hydraulically fractured shale may affect fluid flow pathways and impact longterm hydrocarbon production. The ability to predict geochemical reactions that lead to problematic mineral precipitation will lead to active reservoir management strategies to improve overall production. Using the Marcellus Shale as a case study, a combination of laboratory experiments and reaction path modeling was applied to determine which reactions are likely to occur upon introduction of hydraulic fracturing fluid into the shale reservoir. Experimental results indicate that contact between fracturing fluid and shale will result in dissolution of primary minerals (quartz, feldspars, kaolinite, chlorite, pyrite) and secondary mineral precipitation over time periods of less than one week. Precipitation of barite, Fe-oxides, feldspars, amorphous silica and clay is likely to occur within the reservoir during shut in and early flowback due to mixing between fracturing fluid and reservoir brine as based on modeling saturation indices using experimental fluid data. Reaction path modeling of the experimental scenarios corroborates the specific dissolution and precipitation reactions observed experimentally. Comparison of the results to injected and produced waters from a Marcellus Shale well pad in Greene County, PA, USA, shows that the mineral reactions occur during the hydraulic fracturing, shut in, and early flowback periods. The results presented in this paper demonstrate the value in applying experimental approaches to identify mineral precipitation/dissolution reactions that may significantly impact reservoir performance. The good agreement between geochemical models and experimental results provides confidence that numerical models can be applied to screen the potential fluid-mineral and fluid-mixing reactions in unconventional reservoirs that result in undesired mineral scale precipitation.

58 GEOSCIENCES↗

Multi-Scale Modeling Framework for Mercury Biogeochemistry

Multi-Scale modeling of mercury (Hg) geochemical speciation and reactions has been performed by integrating atomistic quantum chemical calculations with continuum scale speciation models. Major progress has been made in the improvement of quantum chemical models to calculate critical thermodynamic data for Hg complexes in aquatic environments. Rapid and reliable quantum chemical approaches have been developed for calculating acid dissociation constants (pK a ) and stability constants (log K), with calculated mean unsigned errors of 0.5 and 1.5 log units, respectively for ligand molecules and Hg complexes. At the continuum scale, systematic analysis of uncertainty propagation in mercury (Hg) speciation modeling has been conducted and was used to identify environmental conditions under which thermodynamic constant uncertainties are significant and recommended to be accounted for. The integrated framework for multi-scale modeling of mercury geochemistry is open to the research community through the web-based multiscale modeling aqueous speciation resource, AQUA-MER. The improved quantum chemical approaches for thermodynamic constant calculations are accessible through AQUA-MER and can be used to provide the missing constants in the continuum scale speciation calculations. In addition to low molecular mass Hg complex speciation, modeling natural aquatic environments also involve the transport of high molecular weight dissolved organic matter (DOM) in reactive flows simultaneously with equilibrium and kinetic reactions. To this end, atomistic MD simulations were performed to capture the details of aggregation, mechanisms and distribution of functional groups in DOM at the molecular level. The elemental composition and calculated bulk properties of the DOM models are in close agreement with experimental measurements. A travel-time based reactive transport model in the hyporheic zone of stream corridors was established for the multicomponent Hg-DOM-S system and implemented through PFLOTRAN.

54 ENVIRONMENTAL SCIENCES↗

Vadose Zone Transport of Tritium and Nitrate under Ponded Water Conditions

Vadose zone transport of tritium and nitrate can be important considerations at radioactive waste sites, landfills, or areas with industrial impacts. These contaminants are of particular concern because they typically have a relatively higher mobility in the subsurface compared to other compounds. Here, we describe a semiarid site with tritium and nitrate contamination involving a manmade ponded water source above a thick unsaturated zone at Los Alamos National Laboratory in New Mexico, USA. This study demonstrates the value of vadose zone flow and transport modeling for the development of field investigation plans (i.e., identifying optimal borehole locations and depths for contaminant characterization), and how a combination of modeling with isotope and geochemical measurements can provide insight into how tritium and nitrate transport in the vadose zone in semiarid environments. Modeling results suggest that at this location, tritium transport is well predicted by classical multiphase theory. Our work expands the demonstrated usefulness of a standard tritium conceptual model to sites with ponded surface conditions and agrees with previous results where a standard model was able to explain the evolution of a tritium plume at an arid waste disposal site. In addition, depth-based analyses of δ 18 O and δ 2 H of pore waters helped confirm the extent of pond infiltration into the vadose zone, and the δ 15 N of nitrate showed that the contaminant release history of the site was different than originally assumed.

58 GEOSCIENCES↗

Integrating Tide‐Driven Wetland Soil Redox and Biogeochemical Interactions Into a Land Surface Model

Abstract Redox processes, aqueous and solid‐phase chemistry, and pH dynamics are key drivers of subsurface biogeochemical cycling and methanogenesis in terrestrial and wetland ecosystems but are typically not included in terrestrial carbon cycle models. These omissions may introduce errors when simulating systems where redox interactions and pH fluctuations are important, such as wetlands where saturation of soils can produce anoxic conditions and coastal systems where sulfate inputs from seawater can influence biogeochemistry. Integrating cycling of redox‐sensitive elements could therefore allow models to better represent key elements of carbon cycling and greenhouse gas production. We describe a model framework that couples the Energy Exascale Earth System Model (E3SM) Land Model (ELM) with PFLOTRAN biogeochemistry, allowing geochemical processes and redox interactions to be integrated with land surface model simulations. We implemented a reaction network including aerobic decomposition, fermentation, sulfate reduction, sulfide oxidation, methanogenesis, and methanotrophy as well as pH dynamics along with iron oxide and iron sulfide mineral precipitation and dissolution. We simulated biogeochemical cycling in tidal wetlands subject to either saltwater or freshwater inputs driven by tidal hydrological dynamics. In simulations with saltwater tidal inputs, sulfate reduction led to accumulation of sulfide, higher dissolved inorganic carbon concentrations, lower dissolved organic carbon concentrations, and lower methane emissions than simulations with freshwater tidal inputs. Model simulations compared well with measured porewater concentrations and surface gas emissions from coastal wetlands in the Northeastern United States. These results demonstrate how simulating geochemical reaction networks can improve land surface model simulations of subsurface biogeochemistry and carbon cycling.

54 ENVIRONMENTAL SCIENCES↗

Metabolic skinflint or spendthrift? Insights into ground sloth integument and thermophysiology revealed by biophysical modeling and clumped isotope paleothermometry

Abstract Remains of megatheres have been known since the 18th -century and were among the first megafaunal vertebrates to be studied. While several examples of preserved integument show a thick coverage of fur for smaller ground sloths living in cold climates such as Mylodon and Nothrotheriops , comparatively very little is known about megathere skin. Assuming a typical placental mammal metabolism, it was previously hypothesized that megatheres would have had little-to-no fur as they achieved giant body sizes. Here the “hairless model of integument” is tested using geochemical analyses to estimate body temperature to generate novel models of ground sloth metabolism, fur coverage, and paleoclimate with Niche Mapper software. The simulations assuming metabolic activity akin to those of modern xenarthrans suggest that sparse fur coverage would have resulted in cold stress across most latitudinal ranges inhabited by extinct ground sloths. Specifically, Eremotherium predominantly required dense 10 mm fur with implications for seasonal changes of coat depth in northernmost latitudes and sparse fur in the tropics; Megatherium required dense 30 mm fur year-round in its exclusive range of cooler, drier climates; Mylodon and Nothrotheriops required dense 10–50 mm fur to avoid thermal stress, matching the integument remains of both genera, and further implying the use of behavioral thermoregulation. Moreover, clumped isotope paleothermometry data from the preserved teeth of four genera of ground sloth yielded reconstructed body temperatures lower than those previously reported for large terrestrial mammals (29 ± 2°–32 ± 3° C). This combination of low metabolisms and thick fur allowed ground sloths to inhabit various environments.

Deak, Michael D.↗

Offshore application of landslide susceptibility mapping using gradient-boosted decision trees: a Gulf of Mexico case study

Abstract Among natural hazards occurring offshore, submarine landslides pose a significant risk to offshore infrastructure installations attached to the seafloor. With the offshore being important for current and future energy production, there is a need to anticipate where future landslide events are likely to occur to support planning and development projects. Using the northern Gulf of Mexico (GoM) as a case study, this paper performs Landslide Susceptibility Mapping (LSM) using a gradient-boosted decision tree (GBDT) model to characterize the spatial patterns of submarine landslide probability over the United States Exclusive Economic Zone (EEZ) where water depths are greater than 120 m. With known spatial extents of historic submarine landslides and a Geographic Information System (GIS) database of known topographical, geomorphological, geological, and geochemical factors, the resulting model was capable of accurately forecasting potential locations of sediment instability. Results of a permutation modelling approach indicated that LSM accuracy is sensitive to the number of unique training locations with model accuracy becoming more stable as the number of training regions was increased. The influence that each input feature had on predicting landslide susceptibility was evaluated using the SHapely Additive exPlanations (SHAP) feature attribution method. Areas of high and very high susceptibility were associated with steep terrain including salt basins and escarpments. This case study serves as an initial assessment of the machine learning (ML) capabilities for producing accurate submarine landslide susceptibility maps given the current state of available natural hazard-related datasets and conveys both successes and limitations.

Dyer, Alec S. (ORCID:0000000219813904)↗

Controls on Barite (BaSO 4 ) Precipitation in Unconventional Reservoirs

Barite (BaSO 4 ) precipitation is one of the most ubiquitous examples of secondary sulfate mineral scaling in shale oil and gas reservoirs. Often, a suite of chemical additives is used during fracturing operations to inhibit the accumulation of mineral scales, though their efficacy is widely varied and poorly understood. This study combines experimental data and multi-component numerical reactive transport modeling to offer a more comprehensive understanding of the geochemical behavior of barite accumulation in shale matrices under conditions typical of fracturing operations. A variety of additives and conditions are individually tested in batch reactor experiments to identify the factors controlling barite precipitation. Our experimental results demonstrate a pH dependence in the rate of barite precipitation, which we use to develop a predictive model including a pH-dependent term that satisfactorily reproduces our observations. Further, this model is then extended to consider the behavior of three major shale samples of highly variable mineralogy (Eagle Ford, Marcellus, and Barnett). This data-validated model offers a reliable tool to predict and ultimately mitigate against secondary mineral accumulation in unconventional shale reservoirs.

54 ENVIRONMENTAL SCIENCES↗

Flow Directions and Ages of Subsurface Water in a Salt Marsh System Constrained by Isotope Tracing

Salt marshes are dynamic hydrologic systems where terrestrial groundwater, terrestrial surface water, and seawater mix due to bi-directional flows and pressure gradients. Due to the counteracting terrestrial and marine forcings that control these environments, we do not comprehensively understand water fluxes in these complex coastal systems. To understand the water sources, flow directions, and velocities in salt marsh porewater, we employed a combination of geochemical tracers and analytical models across a hillslope-to-salt marsh continuum in a salt marsh experiencing daily inundation of estuarine surface water (SW) from tides and mixing of fresh seasonal groundwater. We used tritium ( 3 H) as a hydrologic tracer to assess porewater ages and stable water isotope ($\delta$ 2 H and $\delta$ 18 O) analyses to separate isotopically distinct estuarine and terrestrial groundwater across different depths and landscape positions in the study transect. We employed electrical conductivity to constrain the role of source mixing and evapotranspiration in salt marsh hydrology. Salinity and stable isotopes revealed that transpiration, rather than evaporation, increased subsurface water salinity to concentrations above estuarine SW during summer. Elevated salinity at depth indicated that salt marsh subsurface water is recharged during the dry growing season. Seasonal recharge patterns drive long-term deep subsurface water dynamics across the salt marsh, with 3 H ages of 3–7 years, and daily tidal cycles drive short-term shallow porewater dynamics with 3 H ages of 0 ± 3.6 years. Furthermore, our conceptual understanding of the spatiotemporal changes in SW-subsurface water interactions at the terrestrial-marine interface quantifies the hydrological constraints we are missing to improve our understanding of biogeochemical cycles within the salt marsh.

54 ENVIRONMENTAL SCIENCES↗

Feasibility of enhancing carbon sequestration and stock capacity in temperate and boreal European forests via changes to management regimes

Forest management practices might act as nature-based methods to remove CO 2 from the atmosphere and slow anthropogenic climate change and thus support an EU forest-based climate change mitigation strategy. However, the extent to which diversified management actions could lead to quantitatively important changes in carbon sequestration and stocking capacity at the tree level remains to be thoroughly assessed. To that end, we used a state-of-the-science bio-geochemically based forest growth model to simulate effects of multiple forest management scenarios on net primary productivity (NPP) and potential carbon woody stocks (pCWS) under twenty scenarios of climate change in a suite of observed and virtual forest stands in temperate and boreal European forests. Previous modelling experiments indicated that the capacity of forests to assimilate and store atmospheric CO 2 in woody biomass is already being attained under business-as-usual forest management practices across a range of climate change scenarios. Nevertheless, we find that on the long-term, with increasing atmospheric CO 2 concentration and warming, managed forests show both higher productivity capacity and a larger potential pool size of stored carbon than unmanaged forests as long as thinning and tree harvesting are of moderate intensity.

54 ENVIRONMENTAL SCIENCES↗

Dynamic Surface Incorporation of Pb 2+ Ions at the Actively Dissolving Calcite (104) Surface

The reaction of dissolved Pb 2+ with calcite surfaces at near-equilibrium conditions involves adsorption of Pb 2+ and precipitation of secondary heteroepitaxial Pb-carbonate minerals. A more complex behavior is observed under far-from-equilibrium conditions, including strong inhibition of calcite dissolution, development of microtopography, and near-surface incorporation of multiple monolayers (ML) of Pb 2+ without precipitation of secondary phases [where 1 ML ≡ 1 Ca/20.2 Å 2 , the crystallographic site density of the calcite (104) lattice plane]. However, the mechanistic controls governing far-from-equilibrium reactivity are not well understood. Here, in this study, we observe the interfacial incorporation of dissolved Pb 2+ during the dissolution of calcite (104) surfaces at pH ~3.7 in a flow-through reaction cell, revealing the formation of a ~1 nm thick Pb-rich calcite layer with a total Pb coverage of ~1.4 ML. These observations of the sorbed Pb distribution used resonant anomalous X-ray reflectivity, X-ray fluorescence, and nanoinfrared atomic force microscopy. We propose that this altered surface layer represents a novel sorption mode that is stabilized by conditions of sustained disequilibrium. This behavior may significantly impact the transport of dissolved metals during disequilibrium processes occurring in acid mine drainage and subsurface CO 2 injection and, if appropriately accounted for, could improve the predictive capability of geochemical reactive-transport models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigating the Roughness and Advance Rate of the Weathering Interface (Final Report)

To understand geological systems that are important to our national well-being -- such as nuclear waste repositories or hydraulically fractured rocks -- requires the ability to make quantitative projections of the evolution of rock-water systems forward in time. A fundamental goal of much of our geochemical research was focused on development of numerical models of reactive transport to simulate the evolution of natural water-rock systems. The geochemical community has provided such models and they are rapidly being improved with field-model cross-testing. This project was especially impactful in field-model testing for well-constrained weathering systems to provide new conceptual understanding of how these systems function.

04 OIL SHALES AND TAR SANDS↗

Integration of Omics into a New Comprehensive Rate Law for Competitive Terminal Electron-Accepting Processes in Reactive Transport Models: Application to N, Fe, S, and Contaminant Transformations in Stream and Wetland Sediments

Surface waters represent important sources of alternate energy and drinking water in the United States, and characterizing the biogeochemical processes that affect surface water quality is relevant to the DOE-BER mission. Sediment biogeochemical processes regulate the release of carbon (C), nutrients, and contaminants to surface waters and thus influence water quality. Sediment biogeochemical processes are dynamic and affected by the deposition and remobilization of solid material and changes in environmental conditions driven by water discharge variations. Wetlands are important natural filters of surface waters which may either trap, metabolize, or mobilize nutrients and contaminants. Despite their importance, biogeochemical processes regulating nutrient and contaminant release and C transformation in stream and wetland sediments cannot be predicted accurately by current mathematical models. These reactive transport models largely rely on detectable changes in geochemical conditions to activate metabolic processes, do not accurately account for the competition between microbial processes, and poorly constrain effects of hydrological perturbations on biogeochemical processes. In this BER-SBR exploratory project, metagenomic and geochemical signatures were combined to identify microbially-mediated redox processes in anaerobic stream and wetland sediments from the Savannah River Site (SRS, ANL SFA) and East Fork Poplar Creek (EFPC, ORNL SFA) that play important roles in C, uranium (U), and mercury (Hg) transformations. In addition, sediment incubations were conducted to examine the competition between anaerobic respiration processes Finally, new rate laws were developed for reactive transport models that rely on complementary metagenomic and geochemical signatures to identify the underlying anaerobic microbial processes in stream and wetland sediments, describe the competition between the dominant metabolic processes involved in nutrient release and U and Hg mobilization, and more accurately quantify carbon transformation and the response of microbial processes to changes in redox conditions associated with hydrological forcing. These rate laws were optimized in batch reactors with SRS wetland sediments, where iron and sulfate reduction dominate. Anaerobic carbon remineralization processes followed the expected thermodynamic sequence of microbial respiration with depth in both sediments, except that geochemical signals indicated that sulfate reduction was inactive in EFPC sediments and moderate in SRS wetland sediments. Estimates indicated that microbial iron reduction contributed to at least half of the production of reduced iron in these sediments. Incubations demonstrated that nitrate reduction, denitrification, and dissimilatory nitrate reduction to ammonium were active in the natural EFPC sediment and activated upon nitrate amendment in these nitrate-rich sediments. In turn, these processes were outcompeted by the addition of either iron oxides or sulfate as alternative terminal electron acceptors. Although geochemical products of sulfate reduction were not detected in the incubations, the abundance of sulfate reduction genes increased with depth in the sediment and was equally more pronounced in treatments amended with either iron oxides or sulfate. Simultaneously, anaerobic sulfide oxidizing bacteria coupling sulfide oxidation to DNRA (and not conventional denitrification) were apparently enriched over time, regardless of the treatments. These findings indicate that sulfate reduction is important in freshwater stream sediments and probably catalyzed by a cryptic sulfur cycle involving nitrogen species, in which the sulfur products from sulfate reduction are immediately removed by side reactions and not detectable by geochemical measurements alone. Similar experiments in SRS sediments, however, demonstrated little interaction between nitrogen and sulfur cycling microorganisms. Sulfate reduction was impacted by the addition of more thermodynamically favorable electron acceptors, suggesting either that iron-reducing microorganisms outcompeted sulfate-reducing microorganisms for organic substrate, depleting the stock of electron donor available for sulfate reduction, or that the cryptic sulfur cycle was shunted by the precipitation of FeS generated as a result of the abiotic reduction of iron oxides by dissolved sulfide. A diagnostic modeling exercise was conducted to further investigate the competition between terminal electron accepting processes. As conventional kinetic models typically do not account for cryptic cycles and used inaccurate formulations to describe competition between microbial communities, new metabolic rate laws were developed that explicitly express the electron acceptor-specific enzyme of each energetically favorable metabolic process based on gene abundance detected in the incubations. The model was tested with the sediment slurry incubation data to determine whether substrate competition could explain the decrease in sulfate reduction observed in the presence of iron oxide competitor. The model was able to reproduce geochemical concentrations really well in each treatment once the model was calibrated with the unamended control, suggesting that microbial competition was indeed driven by thermodynamic considerations. Overall, carbon remineralization processes and rates will be reproduced much more realistically with the new metabolic rate laws.

54 ENVIRONMENTAL SCIENCES↗

Chromium isotope fractionation during reduction of Chromium(VI) by Iron(II/III)-bearing clay minerals

Chromium stable isotope ratios are used to trace the reduction of Cr(VI) to Cr(III) in both ancient and modern systems. However, quantitative interpretation of Cr isotopic signatures has been stymied by the large variability in isotopic fractionation factors for Cr(VI) reduction by different reductants. Here we determine Cr isotope fractionation factors during Cr(VI) reduction by Fe(II/III)-bearing clay minerals, which are abundant in subsurface environments. Several variables were tested: pH, total Fe content of the clay, and the fraction of reduced Fe within the clay (Fe(II)/Fe(total)). The latter controls the standard reduction potential of the clay. Our results demonstrate that neither pH nor total Fe content of the clay have major effects on isotopic fractionation. In contrast, as the effective standard reduction potential of the clay and thus the standard free energy of Cr(VI) reduction become more negative, Cr isotope fractionation factors decrease in magnitude from - 4.9 to -1.3‰ according to a linear free energy relationship. This linear free energy relationship can be predicted from Marcus electron transfer theory and allows first-order predictions of Cr isotope fractionation factors to be made from the standard reduction potential or Fe(II)/Fe(total) of a clay, potentially improving our ability to model Cr isotope signatures in geochemical systems. Chromium is the first isotope system to show such a linear free energy relationship over a diverse range of reductants, including both aqueous and solid-phase reductants, and may provide a model for determining other redox-driven kinetic isotope effects in environmentally important isotope systems.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Conceptual Model Update of Mercury Sources and Flux at Y-12 and Upper East Fork Poplar Creek, Oak Ridge,Tennessee

The interactions between the key processes that control the fate and transport of mercury (Hg) in the sediments, groundwater, and stream water within the Y-12 National Security Complex (Y-12) in Oak Ridge, Tennessee are complex, and many aspects are not well understood. In contaminated environments such as Y-12, conceptual models are frequently developed to aid in visualizing and understanding the dynamic nature of the hydrologic, geochemical, and physical environment. These conceptual models integrate data in an internally consistent manner to understand processes that control the fate and transport of contaminants. Over the past few decades of environmental investigation at Y-12, a number of conceptual models have been developed to identify and define various technical processes at various scales. The main purpose of the activities described in this report is to update the 2011 conceptual model for Upper East Fork Poplar Creek using the most recent Hg concentration and flux data and informed scientific interpretation. Emphasis was placed on improving the previous model by implementing a more detailed spatial and temporal approach to visualize transport pathways in the watershed and trends in flux and concentration over time, and to compare baseflow and stormflow system dynamics. Detailed descriptions of historical and current Hg sources and transport pathways are also provided for the east and west ends of the facility. This conceptual model will allow the US Department of Energy to evaluate past and present remedial activities and provide a strong technical basis for prioritizing and optimizing remedial responses in a cost-effective and efficient manner. Twenty years ago, Hg flux from Outfall (OF) 200 at the headwaters of East Fork Poplar Creek represented approximately 20% of the overall flux leaving Y-12. By the time of the 2011 conceptual model report, that percentage had increased to 70%–80%. Flux estimates compiled for this report using data from 2009 to 2018 show that OF200 accounted for roughly 60% of the flux leaving Y-12. The relative role of the four storm drain conduits to OF200 appeared similar to 2011, with OF163 being the greatest contributor to downstream flux. An increase in Hg concentrations and flux occurred throughout and downstream of west end storm drains in 2011 in response to a storm drain cleanout. Leading up to the 2011 storm drain cleanout, annual baseflow flux was higher at OF200A6 than at Station 17. From 2011 to 2018, the trend reversed with concentrations and flux being higher at Station 17 than at OF200A6. A spike in concentrations occurred in July 2018, potentially due to a one-time influx of Hg that occurred during COLEX decontamination and decommissioning activities at Y-12. This report includes recommendations for improving our conceptual understanding of Hg sources, transport pathways, and flux at Y-12. Important recommendations include further evaluation of transport pathways, concurrent measurement of Hg concentration and flux under baseflow and stormflow conditions at multiple sites, and research to understand the connections among periphyton and methylmercury concentration, bioavailability, and bioaccumulation. Ongoing facility decontamination and decommissioning efforts, site characterization, remedial actions, and research are facilitating the collection of new Hg data at Y-12. The conceptual model update provided herein takes advantage of the extensive recent Hg sampling to provide an updated assessment of Hg mass balance and support a refined understanding of Hg behavior at or near Y-12. This assessment should assist in future environmental management decisions and in mitigating the impacts of Hg on the surrounding environment.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗