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DOE OSTI2024

Diverse and unconventional methanogens, methanotrophs, and methylotrophs in metagenome-assembled genomes from subsurface sediments of the Slate River floodplain, Crested Butte, CO, USA

We use metagenome-assembled genomes (MAGs) to understand single-carbon (C1) compound-cycling—particularly methane-cycling—microorganisms in montane riparian floodplain sediments. We generated 1,233 MAGs (>50% completeness and <10% contamination) from 50- to 150-cm depth below the sediment surface capturing the transition between oxic, unsaturated sediments and anoxic, saturated sediments in the Slate River (SR) floodplain (Crested Butte, CO, USA). We recovered genomes of putative methanogens, methanotrophs, and methylotrophs (n = 57). Methanogens, found only in deep, anoxic depths at SR, originate from three different clades (Methanoregulaceae, Methanotrichaceae, and Methanomassiliicoccales), each with a different methanogenesis pathway; putative methanotrophic MAGs originate from within the Archaea (Candidatus Methanoperedens) in anoxic depths and uncultured bacteria (Ca. Binatia) in oxic depths. Genomes for canonical aerobic methanotrophs were not recovered. Ca. Methanoperedens were exceptionally abundant (~1,400× coverage, >50% abundance in the MAG library) in one sample that also contained aceticlastic methanogens, indicating a potential C1/methane-cycling hotspot. Ca. Methylomirabilis MAGs from SR encode pathways for methylotrophy but do not harbor methane monooxygenase or nitrogen reduction genes. Comparative genomic analysis supports that one clade within the Ca. Methylomirabilis genus is not methanotrophic. The genetic potential for methylotrophy was widespread, with over 10% and 19% of SR MAGs encoding a methanol dehydrogenase or substrate-specific methyltransferase, respectively. MAGs from uncultured Thermoplasmata archaea in the Ca. Gimiplasmatales (UBA10834) contain pathways that may allow for anaerobic methylotrophic acetogenesis. Overall, MAGs from SR floodplain sediments reveal a potential for methane production and consumption in the system and a robust potential for methylotrophy.

58 GEOSCIENCES↗

DOE OSTI2020

Mercury methylation potential in a sand dune on Lake Michigan's eastern shoreline

Lake Michigan hosts the largest freshwater sand dune system in the world and is economically important for the fishery industry and tourism. Due to industrial pollution and atmospheric mercury (Hg) deposition, toxic levels of methylmercury (MeHg) have been found in the Lake biota, but little information is known regarding MeHg sources and Hg methylation potential in the shoreline sand dunes. In this study, we conducted anaerobic incubation experiments with beach sands collected from Ludington, Michigan, and examined the effects of organic carbon substrate addition, inorganic nitrogen, and mineral magnetite on Hg methylation. Despite nutrient poor and low-organic carbon conditions, appreciable Hg methylation activity coupled with carbon degradation was observed in the sands. Addition of acetate as a carbon source substantially increased MeHg production from 2 to 380 ng/kg sediment while acetate was rapidly degraded in the first 19 days of incubation. Ammonium addition showed little influence on carbon degradation or Hg methylation, whereas iron oxide addition (~1% dry weight) significantly inhibited both carbon degradation and MeHg production (by up to 90%), highlighting strongly coupled interactions between microbes, carbon substrates, and minerals. This research demonstrates the potential of microbial Hg methylation in the sand dunes, which may play a role in MeHg input and bioaccumulation in the Lake Michigan ecosystem.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Riparian vegetation composition and diversity shows resilience following cessation of livestock grazing in northeastern Oregon, USA

Riparian ecosystem restoration has been accomplished through exclusion of livestock using corridor fencing along hundreds of kilometers of streams in the western United States, for the benefit of riparian-obligate wildlife and endangered fishes. Yet, there are limited scientific studies that have evaluated more than short-term shifts in vegetation composition and diversity at a single location or handful of locations following grazing. We sampled riparian vegetation composition along 11-paired grazed and ungrazed (exclosed) stream reaches in northeastern Oregon. Exclosure ages ranged from 2 to >30 years and grazing treatments varied from light grazing every one out of three years to heavy season-long grazing. Species richness and diversity was higher in the ungrazed reaches (p = 0.002). The abundance of native sedges ( Carex spp.) and broad-leaved forbs were also significantly (p ≤ 0.05) greater in ungrazed areas. In contrast, exotic species adapted to grazing such as Poa pratensis and Trifolium repens were more abundant in grazed stream reaches. The prevalence of hydrophytic species significantly increased (p ≤ 0.01) in ungrazed reaches, (based on wetland species indicator scores), indicating that wetland-dominated communities within the ungrazed stream reaches were replacing ones adapted to drier environments. The increased abundance of facultative and wetland-obligate species in ungrazed reaches compared to grazed reaches suggests that livestock grazing exacerbates those climate change effects also leading to warmer and drier conditions. Further, riparian-obligate shrub cover along the streambank was higher in 7 of 8 exclosures that were older than 5 years (p = 0.05). As a restoration approach, the inherent resilience of riparian ecosystems exhibited in ungrazed riparian zones suggest positive feedbacks to other beneficial ecosystem processes such as increased species and habitat diversity, increased carbon sequestration, enhanced allochthonous inputs and greater sediment retention, that would affect the aquatic and terrestrial biota, water quality, and stream morphology.

Kauffman, J. Boone (ORCID:0000000290202815)↗

DOE OSTI2026

TEMPEST3 surface runoff water chemistry and organic matter composition

Coastal flooding, driven by storm surges and sea level rise, can mobilize organic matter (OM) via runoff, while introducing compositionally distinct OM (e.g., estuarine OM) into the system. To understand event-scale OM dynamics, we monitored source waters and surface runoff during an ecosystem-scale field manipulation experiment, TEMPEST (Terrestrial Ecosystem Manipulation to Probe the Effects of Storm Treatments), in June 2024. The TEMPEST experiment is part of the COMPASS-FME (Coastal Observations, Mechanisms, and Predictions Across Systems and Scales – Field, Measurements, and Experiments) project and designed to investigate biogeochemical and ecological impacts of freshwater and seawater flooding on coastal terrestrial-aquatic interface ecosystems by simulating freshwater and seawater storm events in two 2000m2 coastal upland forest plots (freshwater and brackish seawater plots). The temporal coverage of this dataset is during the TEMPESTⅢ event (June 11-13, 2024). This dataset contains: - Surface runoff discharge measured by flumes - Sensor data (specific conductivity, salinity, dissolved oxygen, and temperature) - Particle size distribution - Total suspended sediment concentrations (TSS), particulate and dissolved organic carbon (POC, DOC) concentrations, total nitrogen and total dissolved nitrogen (TN, TDN) concentrations - Bulk particulate and dissolved OM compositions (stable C and N isotopes of particulates and optical measurements of chromophoric dissolved OM) - High resolution mass spectrometry analysis data - Water isotope data All data files are plain-text CSV (comma-separated value), and no special software is required to read them.

COMPASS-FME↗

DOE OSTI2025

Particulate organic matter (POM) transport and transformation at the terrestrial-aquatic interface (Final Report)

This project investigates the input, transport, and degradation of particulate organic matter (POM) in near-surface riverbed sediments at the Hanford 300 Area of the Columbia River, a dynamic, regulated river system influenced by upstream dam operations. Riverbed sediments are biogeochemical hot spots where organic carbon inputs stimulate intense microbial activity, affecting nutrient cycling and redox transformations in the hyporheic zone (HZ). While dissolved organic matter (DOM) cycling has been studied extensively, little is known about the infiltration and transformation of POM—particularly under variable flow regimes common in large, regulated rivers.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Local structure and distortions of mixed methane-carbon dioxide hydrates

A vast source of methane is found in gas hydrate deposits, which form naturally dispersed throughout ocean sediments and arctic permafrost. Methane may be obtained from hydrates by exchange with hydrocarbon byproduct carbon dioxide. It is imperative for the development of safe methane extraction and carbon dioxide sequestration to understand how methane and carbon dioxide co-occupy the same hydrate structure. Pair distribution functions (PDFs) provide atomic-scale structural insight into intermolecular interactions in methane and carbon dioxide hydrates. We present experimental neutron PDFs of methane, carbon dioxide and mixed methane-carbon dioxide hydrates at 10 K analyzed with complementing classical molecular dynamics simulations and Reverse Monte Carlo fitting. Mixed hydrate, which forms during the exchange process, is more locally disordered than methane or carbon dioxide hydrates. The behavior of mixed gas species cannot be interpolated from properties of pure compounds, and PDF measurements provide important understanding of how the guest composition impacts overall order in the hydrate structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Evaluating sulfurization as a blue carbon sink in a southern California salt marsh

Blue carbon ecosystems such as seagrass meadows, mangrove forests, and salt marshes are important carbon sinks that can store carbon for millennia. Recently, organic matter sulfurization and pyritization have been proposed as mechanisms of net carbon storage in blue carbon ecosystems. At our study site, organic sulfur that is resistant to acid hydrolysis (protokerogen) is an order of magnitude less abundant than pyrite sulfur, suggesting a dominance of pyritization over sulfurization. The C/N ratios and carbon isotope compositions suggest that nearly half of total organic carbon and ≥ 80% of protokerogen is composed of marsh plant material. Sediment protokerogen appears to be sulfurized based on its low δ 34 S values (− 10‰), abundance of disulfides, and higher S/C ratio (~ 1.0%) relative to potential biogenic sulfur sources. However, the interpretation of protokerogen δ 34 S values is complicated by the wide range in sulfur isotope compositions of marsh plants. Evidence for sulfurization occurs within the shallowest sediments across different vegetation zones, yielding consistent products, while pyritization appears to be more sensitive to alterations in sediment redox conditions. Based on organic sulfur and pyrite content, sulfurization may be a more spatially consistent process than pyritization, with implications for carbon storage. The relative abundance of pyrite and protokerogen organic sulfur indicates that pyritization is favored at our study site, but this is likely to vary across the spectrum of blue carbon ecosystems.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Spatial Study 2022: Water Column, Sediment, and Total Ecosystem Respiration Rates across the Yakima River Basin, Washington, USA (v2)

This dataset supports a broader study examining the drivers of spatial variability in sediment respiration rates in the Yakima River Basin and is associated with the manuscript “Sediment-associated processes account for most of the spatial variation in ecosystem respiration in the Yakima River basin” submitted to Nature Communications Earth & Environment (Garayburu-Caruso et al., in review). The dataset provides ecosystem metabolism estimates generated from streamMetabolizer (Appling et al.; 2018) using data collected during the same five-week period at 48 sites within multiple rivers throughout the Yakima River Basin in Washington, USA. Additionally, it includes the scripts used for the analysis and producing the figures in the manuscript. The contents include streamMetabolizer inputs and outputs and additional relevant data needed to generate the main manuscript results. The data included are: total ecosystem respiration, water respiration, calculated sediment-associated respiration, gross primary production outputs from the river corridor model for the Yakima River Basin, median grain size (d50), depth, dissolved oxygen, water temperature, pressure, and annual oxygen consumption. The associated GitHub repository can be found at https://github.com/river-corridors-sfa/SSS_metabolism. Samples collected during this study were labeled as “Second Spatial Study” or “SSS.” Raw time series sensor data, total suspended solids, and depth data from SSS were published at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1969566. A subset of data from the SSS samples were published in the contiguous United States (CONUS)-Scale Model-Sample (CM) study data package available at https://data.ess-dive.lbl.gov/view/doi:10.15485/1923689 that presents data from across the CONUS. They include dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC), total nitrogen (TN), grain size, aerobic sediment respiration, dissolved oxygen (DO), and temperature. Parent IDs and Site IDs are consistent between the SSS and CM data packages, and they can be mapped directly so data across packages can be used together. Field metadata for the samples in this da This dataset is comprised of one main data folder with four subfolders. The main data folder contains of (1) file-level metadata; (2) data dictionary; (3) total/water column/sediment respiration; (4) gross primary production (GPP); (5) median grain size (d50); and (6) annual oxygen consumption. The “Figures” subfolder contains the figures used in the paper and all intermediate files (including geospatial files). The “Published_Data” contains a readme directing the user to download the public data to reproduce analyses and figures. The “Scripts” folder contains all scripts used in the analyses that were not part of running StreamMetabolizer. Lastly, the “Stream_Metabolizer” folder contains all files associated with running StreamMetabolizer including (1) model input files, (2) model output files, (3) processing scripts, (4) histogram plots of the outputs, and (5) an R project. All files are .csv, .pdf, .R, .Rmd, .Rproj, .html, .png, .txt, .qgz, .cpg, .dbf, .prj, .shp, .shp.ea.iso.xml, .shp.iso.xml, .shx, .sbn. ta package can be found at either link. We acknowledge the Yakama Nation as owners and caretakers of the lands where we collected these data. We thank the Confederated Tribes and Bands of the Yakama Nation Tribal Council and Yakama Nation Fisheries for working with us to facilitate sample collection and optimization of data usage according to their values and worldview.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Evaluation of the Change in Uranium Mobility in Sediments from the Hanford 300-FF-5 Stage B Polyphosphate Field Injection

The purpose of this study was to evaluate the change in uranium mobility in the periodically re-wetted zone (PRZ) and upper unconfined aquifer of the Hanford Site’s 300-FF-5 operable unit as a result of Stage B polyphosphate (PO 4 ) injections. These 300 Area sediments are beneath or near the former North Process Pond, which has previously been shown to contain metatorbernite [Cu(UO 2 ) 2 (PO 4 ) 2 •8H 2 O] and uranophane [Ca(UO 2 ) 2 (SiO 3 OH) 2 •5H 2 O], along with aqueous and adsorbed uranium (U), and small amounts of U in calcite as a result of acidic disposal with a significant number of co-contaminants. Previous laboratory-scale studies have identified multiple mechanisms that decrease uranium mobility with polyphosphate injection: (a) precipitation of a low-solubility uranium-phosphate mineral (autunite); (b) precipitation of a Ca-phosphate solid that incorporates U; (c) precipitation of Ca-phosphate mineral (apatite group minerals) that coats existing uranium phases (i.e., U in calcite, U in Fe-oxides), reducing uranium leaching; and (d) aqueous Ca-U-carbonate species adsorption onto apatite. Given the significant amount of apatite precipitation, other U phases such as carbonates could also coprecipitate with apatite. To quantify differences in solubility, leachability, and phases of uranium between pre- and post-PO 4 -treated sediments, different types of analyses were conducted, including analysis of uranium in (a) a carbonate solution extraction from sediment over 1000 h (41.67 days), (b) six sequential liquid extractions from sediment over approximately 1 week, (c) leaching of uranium from sediments in one dimensional (1-D) column experiments over 2 months, and (d) solid phase characterization of select sediments. An additional extraction and solid phase measurements were conducted to evaluate phosphate precipitate formation. Metals were also analyzed in sequential liquid extractions as indicators of (a) amendment injection delivery, (b) co-contaminant movement, and (c) changes in solid phases. Aqueous and solid phase carbonate measurements were also conducted to evaluate changes in carbonates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

Spatial Study 2022: Surface Water Samples, Cotton Strip Degradation, and Hydrologic Sensor Data across the Yakima River Basin, Washington, USA (v3)

This dataset supports a broader study examining the drivers of spatial variability in sediment respiration rates in the Yakima River Basin. The dataset provides data and photos generated from sample collection during the same one-week period at 48 sites within multiple rivers throughout the Yakima River Basin in Washington, USA. The contents include surface water geochemistry data; river substrate grain size photos; stream depth data; manual chamber open channel respiration data; and field metadata (including qualitative information on instream and river corridor characteristics). Grain size photos can be used to improve estimates of channel substrate D50 data. The dataset also includes tensile strength and photos from cotton strip field degradation experiments; five-week sensor time series temperature, dissolved oxygen, pressure, pH, specific conductance, chlorophyll A, and turbidity data; plots of the sensor data; and R scripts used to generate the plots. Samples collected during this study were labeled as “Second Spatial Study” or “SSS.” A subset of data from the SSS samples were published in the contiguous United States (CONUS)-Scale Model-Sample (CM) study data package available at https://data.ess-dive.lbl.gov/view/doi:10.15485/1923689 that presents data from across the CONUS. SSS data published in the CM data package were not included in this data package. They include dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC), total nitrogen (TN), grain size, aerobic sediment respiration, dissolved oxygen (DO), and temperature. Parent IDs and Site IDs are consistent between the SSS and CM data packages, and they can be mapped directly so data across packages can be used together. Additionally, sensor data from a similar 2021 spatial study can be found at https://data.ess-dive.lbl.gov/view/doi:10.15485/1892052 and 2021 sample data can be found at https://data.ess-dive.lbl.gov/view/doi:10.15485/1898914. The 2021 spatial study had some sites in common with this 2022 spatial study. This dataset is comprised of three photo folders and one main data folder with six subfolders. The photo folders contain photographs and videos of cotton strip retrieval and sediment quadrats. The main data folder consists of (1) file-level metadata; (2) data dictionary; (3) field metadata; (4) total suspended solids (TSS) data and cotton strip tensile strength data and averages; (5) field protocol; (6) readme; (7) methods codes; (8) international generic sample number (IGSN) mapping file; (9) sensor installation methods summary; (10) stream depth and averages; and (11) Ultrameter data and averages. The Sonar subfolder consists of Sonar time-series depth data and a processing script. The BarotrollAtm, DepthHOBO, MantaRiver, miniDOT, and miniDOTManualChamber subfolders contain time-series data, plots, and summary files. All files are .csv, .pdf, .txt, .R, .Rmd, .jpg, .jpeg, .AVI, .mp4, or .mov. The data package was originally published in April 2023. It was updated in August 2023 (v2; modified files) and September 2024 (v3; modified files). See the change history section in the readme for details. We acknowledge the Yakama Nation as owners and caretakers of the lands where we collected these data. We thank the Confederated Tribes and Bands of the Yakama Nation Tribal Council and Yakama Nation Fisheries for working with us to facilitate sample collection and optimization of data usage according to their values and worldview.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Sink or source? Insights into the behavior of copper and zinc in the sediment porewater of a constructed wetland by peepers

The H-02 free water surface constructed wetland has been applied to remove heavy metals, mainly copper (Cu) and zinc (Zn), from wastewater on the Savannah River Site (Aiken, SC, USA). More and more studies focus on the metal behavior between the sediment and the overlying water, which directly reflects the stability of metals after sedimentation in constructed wetlands. This study focused on the biogeochemical pathways in metal bioavailability and remobilization in the sediment after metals were removed from the overlying water. The dialysis sampling devices (peepers) were used to collect porewater samples from eight depths in the sediment for the measurement of Cu, Zn, dissolved organic carbon (DOC), and major anions (sulfate and chloride). Surface water samples were also collected for the measurement of Cu, Zn, DOC, and anions. Different temporal trends were observed for dissolved Cu between the surface and bottom waters, but not for dissolved Zn. There were no obvious changes in porewater metal concentrations with increasing depths in the sediment. Sediment served as a sink for Cu as only 3% of porewater samples showed higher labile Cu concentrations than the surface water during the entire year. Furthermore, sediment served as a source for Zn in summer and winter as 32% of porewater samples showed higher labile Zn concentrations than the surface water, and these samples were collected at all sediment depths. We think the seasonal changes in the behaviors of Cu and Zn were primarily controlled by the sulfur dynamics and the metal removal processes in the constructed wetland, as well as the different complexing chemistry between Cu and Zn. Also, our study supports that peeper is a powerful tool for studying the biogeochemistry of metals in the sediment.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Critical Minerals and Rare Earth Elements in Powder River Basin Coal and Associated Sediments, Wyoming, USA

The demand for Rare Earth Elements (REE) and other critical minerals (CM) required for consumer products, defense-related applications, and low-carbon energy technology is increasing rapidly. Unconventional sources of REE/CM, such as coal and associated sediments, could prove very important in building resilient and ethical energy supply chains. Utilization of existing infrastructure and the highly trained energy workforce in traditionally coal-producing regions in emerging REE/CM industries could provide an economic boost to coal communities. The Powder River Basin (PRB) of Wyoming and Montana, USA, is a prime candidate to investigate the feasibility of extracting REE/CM from coal and associated sediments. The PRB hosts thick (>50 ft) coal seams that are mined at the surface and more than 40% of the coal produced in the US comes from the PRB. Geochemical data from multiple locations in PRB coal systems show REE enrichments at the top and bottom margins and at internal partings in coal seams. This trend is exhibited in two cores drilled at Peabody’s North Antelope Rochelle mine in the east central PRB, the largest coal mine in the world. The two cores include the Wyodak Anderson coal zone as well as the over- and underlying shale units. The Wyodak Anderson coal zone is part of the Paleocene Tongue River Member of the Fort Union Formation in which most of the coal resources in the PRB reside. To understand REE/CM enrichment, a total of 188 samples were analyzed for their major and trace element chemistry from both cores, sampled at one foot or smaller intervals. The two cores show distinct REE enrichments in the uppermost and lowermost 3 to 12 feet of the Wyodak Anderson coal zone, as well as enrichments in bounding carbonaceous shale units. Total REE+Y (REY) concentrations as high as 2510 ppm (all concentrations reported on an ash basis), or 15 times average upper continental crust values (Taylor and McLennan, 1995), were identified in the coal. Partings within the coal zone also show relative REE enrichment, with concentrations up to 485 ppm REY. The remaining interior portions of the coal zone contain lower concentrations of REE, resulting in an average REY for all samples from both cores of 288 ppm. The proportion of high-value critical REE (Nd, Eu, Tb, Dy, Er, Y) compared to REY averages 36%, which is higher than the critical REE proportion in average upper continental crust of 33%. This finding highlights the relative enrichment of middle REE compared to light REE, in contrast to many conventional REE deposits. Other critical trace elements that show enrichments above average upper continental crust include Ga, Nb, and V. Within this sample suite, Ga concentrations range from 2.8 to 213 ppm, with an average of 29 ppm; Nb from 2.9 to 166 ppm with an average of 26 ppm; and V from 27 to 1695 ppm with an average of 188 ppm. None of these trace elements exhibit the same distinct pattern of enrichment as REE in the upper and lower bounding layers and internal partings of the coal zone. Major element chemistry indicates CaO concentrations averaging ~25% in the coal samples from both cores, which has important implications for the extractability of REE from coal. Calcium-rich PRB coal has been shown to be more amenable to REE extraction than lower calcium coals by some methods (Stuckman et al., 2019; Taggart et al., 2016), highlighting the importance of REE extractability in addition to REE concentration in assessing the value of potential feedstocks. The original coal resource in the PRB is estimated at 1.16 trillion short tons (Luppens et al., 2015). Thus, the PRB represents an important potential unconventional source for REE and other CM. Ongoing research to fully characterize the REE/CM resource, identify enrichment mechanisms, and further develop and scale extraction technologies is necessary to understand the full potential of this resource.

Phillips, Erin↗

DOE OSTI2023

Chemodiversity of riverine dissolved organic matter: Effects of local environments and watershed characteristics

Riverine dissolved organic matter (DOM) is crucial to global carbon cycling and aquatic ecosystems. However, the geographical patterns and environmental correlates of DOM chemodiversity remain elusive especially in surface waters and sediments of global rivers. Here, we systematically analyzed DOM molecular diversity and composition in surface waters and sediments across 97 globally distributed rivers using data from the Worldwide Hydrobiogeochemistry Observation Network for Dynamic River Systems (WHONDRS) consortium. Here, we further examined the associations of molecular richness and composition with geographical, climatic, physicochemical variables, as well as the watershed characteristics. We found that molecular richness significantly decreased toward higher latitudes, but only in sediments (r = -0.24, P < 0.001). The environmental variables like precipitation and non-purgeable organic carbon showed strong associations with DOM molecular richness and composition. Interestingly, we identified that less-documented factors like watershed characteristics were also related to DOM molecular richness and composition, and were stronger in waters than sediments. Such associations were further supported by the fact that 11 out of 13 watershed characteristics (e.g., land cover variables) showed more positive than negative correlations with molecular abundance especially in waters. The molecules positively and negatively correlated with specific watershed characteristics had distinct traits, such as stoichiometric ratios and aromaticity. Land covers shifted from natural (e.g., forests) to human-modified (e.g., impervious area) were associated with systematic changes in DOM molecular chemistry. Our findings imply that it may be possible to use a small set of broadly available data types to predict DOM molecular richness and composition across diverse river systems. Elucidation of mechanisms underlying these relationships will provide further enhancements to such predictions, especially when extrapolating to unsampled systems.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Biogeochemistry simulations for the Salt Marsh Accretion Response to Temperature eXperiment (SMARTX)

Coastal ecosystems have been largely ignored in Earth system models but are important zones for carbon and nutrient processing. Interactions between water, microbes, soil, sediments, and vegetation are important for mechanistic representation of coastal processes and ecosystem function. To investigate the role of these feedbacks, we used a reactive transport model (PFLOTRAN) that has the capability to be connected to the Energy Exascale Earth System Model (E3SM). PFLOTRAN was used to incorporate redox reactions and track chemical species important for coastal ecosystems as well as define simple representations of vegetation dynamics. Our goal was to incorporate oxygen flux, salinity, pH, sulfur cycling, and methane production along with plant-mediated transport of gases and tidal flux. Using porewater profile and incubation data for model calibration and evaluation, we were able to create depth-resolved biogeochemical soil profiles for saltmarsh habitat and use this updated representation to simulate direct and indirect effects of elevated CO2 and temperature on subsurface biogeochemical cycling. We found that simply changing the partial pressure of CO2 or increasing temperature in the model did not fully reproduce observed changes in the porewater profile, but the inclusion of plant or microbial responses to CO2 and temperature manipulations was more accurate in representing porewater concentrations. This indicates the importance of characterizing tightly coupled vegetation-subsurface processes for developing predictive understanding and the need for measurement of plant-soil interactions on the same time scale to understand how hotspots or moments are generated.Included in this data package are PFLOTRAN input (PFLOTRAN input files and chemical database) files for simulating single column biogeochemistry, root, and tide interactions at the Global Change Research Wetland (Kirkpatrick Marsh; Edgewater, MD). The biogeochemical network includes soil organic matter decomposition, nitrogen, iron, and sulfur cycling, and methanogenesis. Reduced species can be oxidized and plant processes include oxygen and nutrient priming, methane release, and nutrient uptake.Inputs:TAI_database.dat - geochemical database for reactions, more information on database structure and variables can be found here https://www.pflotran.org/documentation/user_guide/cards/pages/geochemical_database.htmlswamp.in - input file for biogeochemical network in PFLOTRANswamp_eCO2.in - input file for biogeochemical network in PFLOTRAN with input gas partial pressures/concentrations adjusted for elevated CO2 treatmentsOutputs:swamp_obs_0.tec - hourly porewater concentrations from from multiple depths in the soil columnswamp_eCO2_obs_0.tec - hourly porewater concentrations from multiple depths in the soil column for elevated CO2 treatmentsPFLOTRAN code access: https://github.com/fmyuan/pflotran-elm-interface.git

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Developing a Redox Network for Coastal Saltmarsh Systems in the PFLOTRAN Reaction Model

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

129 I, 99 Tc, And U Distribution Coefficients of Subsurface Sediments Collected from the Proposed Site of the Environmental Management Disposal Facility

Performance Assessment calculations were completed in 2020 to evaluate the Environmental Management Disposal Facility (EMDF), a proposed new low-level radioactive waste (LLW) disposal facility on the U.S. Department of Energy’s Oak Ridge Reservation (ORR). Among the large number of input parameters needed for such calculations, are distribution coefficients (K d values; radionuclide concentration solid:liquid ratio) that provide a measure of the tendency of radionuclides to bind to sediments. The objective of this study was to measure K d values of three radionuclides that may pose a disproportionately large amount of risk, U, 129 I and 99 Tc. The average I K d value for the 14 geological materials recovered from the proposed EMDF site was 37.8 mL/g and ranged from -1.8 to 140.9 mL/g. These values were consistent, but somewhat larger than previous measurements made with ORR sediments and were about an order of magnitude greater than those used in previous EMDF PA calculations. The median Tc K d value was 365.7 mL/g, much greater than previously reported using ORR geological materials. Five of the 14 tested geological materials sorbed large quantities of Tc, suggesting that the weakly sorbing Tc(VII) species had been reduced to the sparingly soluble Tc(IV) species. The five strongly sorbing sediments had apparent Tc solubility values of approximately <10 -8 mol/L. The median U K d value was 5,726 mL/g. All of the tested geological materials had large K d values, ranging from 625 to >10,208 mL/g. Among the sediment samples that exhibited strong U binding, the apparent solubility value was approximately <10 -9 mol/L. Based on sediment properties and general ORR geological considerations, it was proposed that much of the I and Tc retention could be attributed to the site materials exhibiting low pH (average pH = 4.94), low redox status, and/or the elevated levels of iron oxides, manganese oxides, and natural organic matter. Similarly, the extremely high U binding measured in these sediments may also be attributed to the low conditions of carbonates, which can complex and therefore solubilize uranyl in these tests due to the low pH, and also the relatively high concentrations of iron and organic coatings on these samples. An implication of this study is that the areas of the EMDF subsurface environment may have natural properties for attenuating I, Tc, and U movement, and potentially other radionuclides, thereby possibly reducing risk posed by burial of LLW at this site. This document is a revision of SRNL-STI-2021-00404, Revision 0 that includes new data describing U K d values and new I and Tc K d values for four Nolichucky sediments. These new results were integrated into the data presented in the original document.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2021

Biogeochemistry of Pond B (Savannah River Site, South Carolina, USA): Water column and Sediments

Pond B at Savannah River Site (SRS, South Carolina) is a monomictic reservoir that received SRS R reactor cooling water from 1961–1964. Previous studies conducted between the 1980s–1990s on the water column and sediments of Pond B measured trace amounts of Pu (33 MBq 238Pu and 430 MBq 239,240Pu), 241Am, and 137Cs. Since then, the pond has been relatively isolated and the radionuclide concentrations have not been monitored over time. Herein, about 30 years after the last publication on Pond B, we are re-evaluating the geochemistry and radionuclide distribution within Pond B at five locations along a horizontal transect from the inlet to outlet. In addition, we are conducting the first analysis of the microbial community composition. This data package consists of water column measurements (1) using a multi-probe sonde, (2) plutonium isotopes and total concentrations, (3) total organic/inorganic carbon concentrations, (4) trace metals and major ions concentrations, and (6) microbial community composition. Sediment measurements include (1) plutonium isotopes and total concentrations and (2) microbial community composition.For sediment core and porewater, please see other Pond B data package (ess-dive-60d2352a4495472-20200615T203925174).The data in this package will be submitted for peer review in 2023.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Climate and atmospheric deposition drive the inter-annual variability and long-term trend of dissolved organic carbon flux in the conterminous United States

The lateral flux of dissolved organic carbon (DOC) from soils to inland waters and ultimately to the ocean represents a fundamental component of the global carbon cycle. To estimate the DOC flux, we developed an empirical terrestrial-aquatic DOC fluxes model (TAF-DOC). TAF-DOC incorporates various environmental factors (e.g., meteorology, sulfur, and nitrogen deposition) that to-date have not been comprehensively considered or well-represented in existing modeling frameworks. TAF-DOC was applied to estimate spatial-temporal patterns of DOC flux and potential fates across the conterminous United States during the 1985 to 2018 time period. Our results suggest that TAF-DOC successfully characterized spatial-temporal of DOC flux. As expected, the interannual pattern of DOC flux was strongly regulated by precipitation, but the long-term trend was significantly influenced by the rate of atmospheric wet sulfur deposition. From 1985 to 2018, TAF-DOC estimated DOC loading from terrestrial to aquatic ecosystems in the conterminous United States to be 33.5 ± 2.2 TgC per year, which was roughly 0.39–0.49% of total soil organic carbon stock estimates. The dominant fate of terrestrially-derived DOC was delivery to the coastal ocean in riverine export (41%), with another 21% buried in sediment and the remaining 12.8 ± 0.4 TgC per year (38%) returned to the atmosphere through outgassing from inland waters. Finally, assuming the quantities of DOC sediment burial and export to the ocean as an annual sink of terrestrially-derived carbon, budget inventories and models that do not account for DOC flux in the conterminous United States will underestimate the net annual carbon sink by as much as 5.5–6.4%.

54 ENVIRONMENTAL SCIENCES↗