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HSQC spectra of lignin isolated from poplar roots

Here we present a curated dataset of two-dimensional heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectra of lignin isolated from roots of a greenhouse grown natural population of an energy crop poplar (Populus trichocarpa). Dormant cuttings of field-grown poplar were grown in 6-liter pots in a peat-based media containing bark, perlite, vermiculite, dolomite lime and a wetting agent in an environmentally controlled greenhouse. Temperatures were between 21 and 23 °C, with supplemental lighting to support a 16-h day length using 1000-watt high-pressure sodium lights in greenhouse. Once established, all plants were cut-back, allowed to regrow and harvested at the same time following an eight-month long growth period. Plants were harvested and the belowground roots were washed off soils, blotted, dried in an oven at 70 °C for 3 days, and Wiley milled (mesh size 20). The roots were Soxhlet-extracted with toluene/ethanol for 24 h to remove extractives. The extracted roots were ball-milled in a Retsch PM100 planetary ball mill using a porcelain jar with ceramic balls at 600 rpm for 2 h (in 5 min on and 5 min off cycles to avoid excessive sample heating). The ball-milled materials were then subjected to enzymatic hydrolysis for 48 h followed by centrifugation and washing with deionized water. The solid residue was extracted twice with 96% (v/v) 1,4-dioxane/water mixture at room temperature overnight. The extracts were combined, rotary evaporated, and freeze-dried to recover lignin. The dry lignin samples were dissolved in deuterated dimethyl sulfoxide (d6) and transferred into a 5 mm tube. 13C–1H HSQC experiments were performed in a Bruker Avance III HD 500 MHz NMR spectrometer operating at a frequency of 125.12 MHz for the 13C nucleus using a standard Bruker pulse sequence on a Prodigy platform cryoprobe. The NMR spectra were acquired under the following acquisition conditions: 220 ppm spectral width in F1 (13C) dimension with 256 data points and 12 ppm spectral width in F2 (1H) dimension with 1024 data points, a 90° pulse, a one bond C–H coupling constant of 145 Hz, a 1.0 s pulse delay, and 64 scans. Spectra were processed using the Bruker TopSpin software. Additional meta data is embedded in the raw spectra figures.

HSQC, lignin, poplar, roots, CBI↗

Carbon flux measurements from chambers collected between April to October 2023 at Old Woman Creek, Huron, Ohio

This dataset contains carbon dioxide and methane gas flux measurements collected via chamber sampling at Old Woman Creek National Estuarine Research Reserve in Huron, OH. These data were generated to understand temporal and vegetation patterns associated with wetland carbon cycling. Specifically, this dataset intends to answer how carbon dioxide and methane fluxes change monthly and hourly across sites with vegetation and without vegetation. Data includes chamber measurements that were measured in both sites with vegetation and without vegetation and that were collected hourly (7 AM to 7 PM or 5 AM to 10 PM and monthly (April to October). The file soilrespiration_data23.csv contains these data, and the metadata file (soilrespiration_chammetadata23.csv) and location metadata file (soilrespiration_locationmetadata23.csv) have information on locations where the chambers were placed and sampled in the wetland. Data processing was done on raw methane fluxes (Flux_CH4) to remove the influence of ebullition (Flux_CH4_ebullition) to get a diffusive flux (Flux_CH4_diffusive).

54 ENVIRONMENTAL SCIENCES↗

Low Count and Background Radionuclides Analysis - 20488

The US Department of Energy (DOE) is often faced with the need to evaluate radionuclides at low concentrations. When site sample data are likely to be close to threshold activity concentrations of interest, then the means by which the radiochemical analysis is performed and reported is critical. This situation can occur when differentiating from zero (presence/absence) for radionuclides that do not occur naturally, close comparison with environmental background for naturally occurring radionuclides, close comparison with a risk- or dose-based threshold concentrations of interest, or even comparisons across studies. There are several analytical issues that are of concern, but the two that appear to cause incorrect decisions to be made most often involve establishing detection limits and subtracting ambient background conditions in the laboratory. These issues are not critical when radionuclide activity concentrations are large relative to thresholds of concern, but they seem to be poorly understood when it matters. When the comparisons are important and are likely to be close to a threshold of interest, then the general contract with the analytical laboratories needs to be changed so that the right or appropriate data are obtained. The concern is that important decisions are made incorrectly more often as greater scrutiny is placed on DoE's radionuclide cleanup or monitoring decisions by the public and other stakeholders. Examples are presented of problems that have been observed for different projects, both within and outside the realm of DOE and NRC remediation and radioactive waste disposal problems, and solutions are offered that should lead to better data from which important decisions need to be made. The first example is from Los Alamos National Laboratory (LANL) and involves radionuclide concentrations in soil and rock beneath LANL's Material Disposal Area (MDA) G. An initial review of the data led to a conclusion that americium and plutonium are a long way present beneath MDA G. A more thorough review of the data that accounted properly for ambient background and the detection limits that had been established led to the opposite conclusion. Another example is from the Nevada National Security Site where tritium results from one of the wells were unexpectedly high. Proper understanding and analysis of ambient background led to the conclusion that the increased concentrations were not so obvious, and that a different contract with the analytical laboratory was needed to provide more appropriate data to support a better determination. Other examples are used from regulatory review of projects in Nevada, where background levels and secular equilibrium for naturally occurring radionuclides are not established correctly because of analytical issues. The same basic issues have also been found to create difficulties analyzing historical data from the West Valley Demonstration Project. There is evidence in the data that the apparent lack of secular equilibrium where it is expected to exist is related to ambient background subtraction or other analytical issues. A final example is presented for analysis of Tc-99 in samples of depleted uranium. In this case, two different studies that were performed only three months apart provide quite different results. The US Environmental Protection Agency (EPA) established the data quality objectives (DQO) process in the mid-1980's to establish decision performance criteria for data collection. EPA guidance (EPA G-4, for example) clearly distinguishes between DQOs and measurement performance objectives (MQOs) that should be addressed for laboratory analysis of samples. The language of DQOs and MQOs has become confused over time it seems, and the subsequent effects seem to include a lack of attention to decision performance and a routine approach to measurement quality. In order to better address radionuclide sample analysis when the concentrations are close to thresholds of concern, which might be zero for some radionuclides, background for others, and risk-based thresholds for yet others, it is important that routine laboratory analysis methods are adjusted, and that the project team and the laboratory work closely together to ensure that the data meets the MQO requirements of laboratory analysis and reporting of results, and that the MQOs effectively support project-specific DQOs. This basic approach will be applied in Los Alamos in the coming year to the collection of moisture data from underneath MDA T that will be analyzed for americium and neptunium isotopes. Proper understanding of the radiochemistry methods and reporting, and of appropriate statistical methods is critical to the success of such projects, ensuring that the right decisions are made. (authors)

07 ISOTOPE AND RADIATION SOURCES↗

3D Characterization and Time-Lapse Imaging of the Desiccation Treatability Test at the Hanford BC-Cribs and Trenches Site using High Performance Computing applied to Electrical Resistivity Imaging - 12271

Contaminated vadose zone materials are a potential source of long-term groundwater contamination at many sites across the Department of Energy (DOE) complex. Deep vadose zone contamination presents a particularly challenging remedial problem due to the difficultly of locating contaminants and the expense of access and ex situ treatment. In situ remediation techniques, whereby remedial amendments must be delivered to contaminated soils, have been identified as a potential alternative. However, amendment delivery is typically uncertain and post delivery remedial performance is often not well understood due to limited information available from sparsely spaced boreholes. Recent advancements in electrical resistivity tomography (ERT) are being used to address these challenges at the Hanford site by providing remote, three-dimensional images of contaminant distribution and four-dimensional (three spatial dimensions plus the time dimension) images of in-situ vadose zone remediation processes. These capabilities were recently demonstrated with a large scale surface characterization effort and during a smaller scale desiccation treatability test at the Hanford BC-Cribs area. The results of these efforts demonstrate the utility of leveraging high-performance computing resources to process ERT data for 3D reconnaissance mapping of subsurface contaminants and for detailed 3D monitoring of vadose zone remediation efforts. Two examples of ERT imaging at a former waste disposal facility have been demonstrated at different scales; a large scale reconnaissance survey spanning many hundreds of meters and a detailed monitoring application spanning a few tens of meters. Although ERT is applicable at many scales, resolution is generally governed by proximity to electrodes. For instance, the BCCT reconnaissance survey demonstrated herein lost resolution with depth (i.e. away from surface electrodes), and was unable to detect a high conductivity anomaly at approximately 75 m below ground surface in the cribs area; the deep anomalies were detected during highly focused borehole sampling. Conversely, the desiccation site characterization and monitoring demonstrated high resolution at a small scale, but only because of close proximity to survey electrodes. Although proximity to electrodes is not the only factor governing ERT resolution, it is often the primary factor for determining how an ERT system should be effectively deployed for a given application. Regardless of resolution limitations, the utility of ERT for remotely detecting wastes and monitoring subsurface processes is evident. ERT imaging is not a final detection or monitoring solution alone, but provides a necessary capability to remotely detect subsurface conditions and understand subsurface processes. Such a capability can significantly increase the efficacy and reduce the cost of remediation by guiding sampling efforts and informing remedial system design and operation. However, given the computational demands of 3D ERT characterization and monitoring inversions, the full imaging capability enabled by contemporary ERT survey systems can generally only be realized with high performance computing resources, both hardware and software. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

WHONDRS Surface Water Dissolved Organic Carbon and FTICR-MS across Stream Orders in Four United States Watersheds in 2019 and 2020 (v3)

This dataset supports the broader Watershed Rules of Life (WROL) study examining spatial and temporal biogeochemical and microbial relationships across the Connecticut River, Deschutes River, Gunnison River, and Willamette River watersheds. The dataset provides geochemistry and organic matter characterization data generated from surface water collected from August 2019 to September 2020 in Colorado, Connecticut, Oregon, and Vermont. Related data were collected and will be published separately in collaboration with P. A. Raymond and B. C. Crump as part of WROL. This dataset is comprised of one folder containing (1) file-level metadata; (2) data dictionary; (3) readme; (4) field metadata; (5) dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC) data and averages; (6) surface water sampling protocol; (7) methods codes; (8) international generic sample number (IGSN) mapping file; and (9) a folder of high resolution characterization of organic matter via 12 Tesla Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) generated through the Environmental Molecular Sciences Laboratory (EMSL; https://www.pnnl.gov/environmental-molecular-sciences-laboratory). The FTICR folder contains two subfolders, one containing the .xml data files and the other containing instructions for using Formularity (https://omics.pnl.gov/software/formularity) and an R script to process the data based on the user's specific needs. All files are .csv, .pdf, .R, .ref, or .xml. This data package was originally published in October 2022. It was updated in July 2023 (v2) and again in November 2023 (v3). See the change history section in the readme for more details.

54 ENVIRONMENTAL SCIENCES↗

Microbial community structure and functions differ between native and novel (exotic-dominated) grassland ecosystems in an 8-year experiment

Aims Grasslands dominated by non-native (exotic) species have replaced purely native-dominated areas in many parts of the world forming ‘novel’ ecosystems. It is still poorly understood how soil microbial communities and their functions are affected between these native- and exotic-dominated sites. Methods We sampled 64 experimental grassland plots in central Texas with plant species mixtures of either all native or all exotic species; half with summer irrigation. We tested how native vs. exotic plant species mixtures and summer irrigation affected bacterial and fungal community composition and structure, microbial phylotype co-occurrence, and rates of mineralization across sampling years. Results Plant origin significantly affected fungal community composition and structure, but not diversity, throughout the length of the study, while changes in bacterial communities were limited to certain years. Nitrogen and phosphorus mineralization rates were higher under native plant mixtures, and correlated with changes in particular fungal species. Microbial communities were more structured in exotic than native grassland plots, especially for the fungal community. Conclusions The results indicate that conversion of native to exotic grasslands will more strongly impact fungal than bacterial communities structure. Furthermore, these impacts can alter ecosystem functioning belowground via changes in nitrogen and phosphorus cycling.

54 ENVIRONMENTAL SCIENCES↗

NGEE Arctic Soil Pit and Core Inventory for Samples Collected Between 2016-2019: Locations, Sampling Characteristics, Collection, and Contacts, Seward Peninsula, Alaska, USA

This dataset includes associated information about individual pit and core samples (e.g., location, contact, date, data collected) sampled between 2016 and 2019 from NGEE Arctic sites at Teller (MM 27 and MM47), Kougarok (MM47 and MM56, Hillslope, and vegetation plot areas), and Council (MM71). The inventory is qualitative and excludes those datasets on soil pit cores that included time-series information. The package includes one each *.csv data file, *.kml and *.pdf. All quantitative data is available in the related datasets https://doi.org/10.5440/1417652, https://doi.org/10.5440/1423892, https://doi.org/10.5440/1342956, https://doi.org/10.5440/1854940, https://doi.org/10.5440/1544760, https://doi.org/10.5440/1346200, and https://doi.org/10.5440/1856042. The goal of this dataset is to help modelers understand when, where, and what data was collected with respect to physical soil properties on the Seward Peninsula, AK, USA over the course of NGEE Arctic’s campaigns in the region from 2016-2019. The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

WHONDRS Summer 2019 Sampling Campaign: Global River Corridor Sediment FTICR-MS, Dissolved Organic Carbon, Aerobic Respiration, Elemental Composition, Grain Size, Total Nitrogen and Organic Carbon Content, Bacterial Abundance, and Stable Isotopes (v10)

The WHONDRS Summer 2019 Sampling (S19S) Campaign collected samples in 97 globally distributed river corridor systems between July and September 2019. Surficial streambed sediments were collected at three locations within each site (upstream, midstream, and downstream). Surface water was collected at the downstream site. This dataset includes a portion of the data types produced from the sediment samples and does not include any results from the surface water. Surface water data can be found at https://data.ess-dive.lbl.gov/view/doi:10.15485/1603775. The S19S campaign was designed with the science community to ask questions associated with links among core/transient metabolomes, microbial metabolism, biogeochemical function, and physical properties of watershed and river corridor systems. This data package was originally published in December 2020. It was updated in April 2021 (v2; modified files), May 2022 (v3; new and modified files), November 2022 (v4; new and modified files), January 2023 (v5 and v6; new and modified files), February 2023 (v7; new and modified files), August 2023 (v8; new and modified files), July 2025 (v9; new and modified files), and June 2026 (v10; new and modified files). Version 10 includes major restructuring of the files and their formats. See the change history in the readme for details. In addition to a readme, this data package also includes a file-level metadata (FLMD) file that describes each file and a data dictionary (DD) that describes all column/row headers and variable definitions. This dataset contains (1) readme, (2) data dictionary, (3) file level metadata, (4) sampling protocol, (5) a data checks report, (6) field metadata, (7) international generic sample number (IGSN) mapping file, (8) joint genome institute (JGI) mapping file, (9) a folder of site photos, and (10) a folder of sample data. The sample data folder contains (1) dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC) and FTICR methods; (2) respiration rates and normalized respiration rates calculated from laboratory sediment incubations, (3) X-ray fluorescence (XRF) elemental composition, (4) grain size distribution from the < 2 millimeter fraction of sediment, (5) total organic carbon and total nitrogen content, (6) bacterial abundance flow cytometry data, (7) sediment stable isotopes (C and N), (8) laboratory methods, (9) water and sediment mass and volume used in incubations, (10) a folder with code, inputs, and plots for the respiration rates, (11) a folder containing XRF data, (12) a folder containing unaligned, peak-picked high resolution characterization of dissolved organic matter from sediment via 12 Tesla Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) through the Environmental Molecular Sciences Laboratory (EMSL; https://www.pnnl.gov/environmental-molecular-sciences-laboratory), (12) and a folder containing processed FTICR-MS data. All files are .msa, .txt, .spx, .xml, .csv, .pdf, .txt, .jpg, or .jpeg.

13C↗

Data and scripts associated with a manuscript investigating impacts of solid phase extraction on freshwater organic matter optical signatures and mass spectrometry pairing

This data package is associated with the publication “Investigating the impacts of solid phase extraction on dissolved organic matter optical signatures and the pairing with high-resolution mass spectrometry data in a freshwater system” submitted to “Limnology and Oceanography: Methods.” This data is an extension of the River Corridor and Watershed Biogeochemistry SFA’s Spatial Study 2021 (https://doi.org/10.15485/1898914). Other associated data and field metadata can be found at the link provided. The goal of this manuscript is to assess the impact of solid phase extraction (SPE) on the ability to pair ultra-high resolution mass spectrometry data collected from SPE extracts with optical properties collected on ambient stream samples. Forty-seven samples collected from within the Yakima River Basin, Washington were analyzed dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC), absorbance, and fluorescence. Samples were subsequently concentrated with SPE and reanalyzed for each measurement. The extraction efficiency for the DOC and common optical indices were calculated. In addition, SPE samples were subject to ultra-high resolution mass spectrometry and compared with the ambient and SPE generated optical data. Finally, in addition to this cross-platform inter-comparison, we further performed and intra-comparison among the high-resolution mass spectrometry data to determine the impact of sample preparation on the interpretability of results. Here, the SPE samples were prepared at 40 milligrams per liter (mg/L) based on the known DOC extraction efficiency of the samples (ranging from ~30 to ~75%) compared to the common practice of assuming the DOC extraction efficiency of freshwater samples at 60%. This data package folder consists of one main data folder with one subfolder (Data_Input). The main data folder contains (1) readme; (2) data dictionary (dd); (3) file-level metadata (flmd); (4) final data summary output from processing script; and (5) the processing script. The R-markdown processing script (SPE_Manuscript_Rmarkdown_Data_Package.rmd) contains all code needed to reproduce manuscript statistics and figures (with the exception of that stated below). The Data_Input folder has two subfolders: (1) FTICR and (2) Optics. Additionally, the Data_Input folder contains dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC) data (SPS_NPOC_Summary.csv) and relevant supporting Solid Phase Extraction Volume information (SPS_SPE_Volumes.csv). Methods information for the optical and FTICR data is embedded in the header rows of SPS_EEMs_Methods.csv and SPS_FTICR_Methods.csv, respectively. In addition, the data dictionary (SPS_SPE_dd.csv), file level metadata (SPS_SPE_flmd.csv), and methods codes (SPS_SPE_Methods_codes.csv) are provided. The FTICR subfolder contains all raw FTICR data as well as instructions for processing. In addition, post processed FTICR molecular information (Processed_FTICRMS_Mol.csv) and sample data (Processed_FTICRMS_Data.csv) is provided that can be directly read into R with the associated R-markdown file. The Optics subfolder contains all Absorbance and Fluorescence Spectra. Fluorescence spectra have been blank corrected, inner filter corrected, and undergone scatter removal. In addition, this folder contains Matlab code used to make a portion of Figure 1 within the manuscript, derive various spectral parameters used within the manuscript, and used for parallel factor analysis (PARAFAC) modeling. Spectral indices (SPS_SpectralIndices.csv) and PARAFAC outputs (SPS_PARAFAC_Model_Loadings.csv and SPS_PARAFAC_Sample_Scores.csv) are directly read into the associated R-markdown file. We acknowledge the Yakama Nation as owners and caretakers of the lands where we collected some of 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↗

Subsurface Uranium Fate and Transport: Integrated Experiments and Modeling of Coupled Biogeochemical Mechanisms of Nanocrystalline Uraninite Oxidation by Fe(III)-(hydr)oxides - Project Final Report

Subsurface bacteria including sulfate reducing bacteria (SRB) reduce soluble U(VI) to insoluble U(IV) with subsequent precipitation of UO 2 . We have shown that SRB reduce U(VI) to nanometer-sized UO 2 particles (1-5 nm) which are both intra- and extracellular, with UO 2 inside the cell likely physically shielded from subsequent oxidation processes. We evaluated the UO 2 nanoparticles produced by Desulfovibrio desulfuricans G20 under growth and non-growth conditions in the presence of lactate or pyruvate and sulfate, thiosulfate, or fumarate, using ultrafiltration and HR-TEM. Results showed that a significant mass fraction of bioreduced U (35-60%) existed as a mobile phase when the initial concentration of U(VI) was 160 µM. Further experiments with different initial U(VI) concentrations (25 - 900 M) in MTM with PIPES or bicarbonate buffers indicated that aggregation of uraninite depended on the initial concentrations of U(VI) and type of buffer. It is known that under some conditions SRB-mediated UO 2 nanocrystals can be reoxidized (and thus remobilized) by Fe(III)-(hydr)oxides, common constituents of soils and sediments. To elucidate the mechanism of UO 2 reoxidation by Fe(III) (hydr)oxides, we studied the impact of Fe and U chelating compounds (citrate, NTA, and EDTA) on reoxidation rates. Experiments were conducted in anaerobic batch systems in PIPES buffer. Results showed EDTA significantly accelerated UO 2 reoxidation with an initial rate of 9.5 M day-1 for ferrihydrite. In all cases, bicarbonate increased the rate and extent of UO 2 reoxidation with ferrihydrite. The highest rate of UO 2 reoxidation occurred when the chelator promoted UO 2 and Fe(III) (hydr)oxide dissolution as demonstrated with EDTA. When UO 2 dissolution did not occur, UO 2 reoxidation likely proceeded through an aqueous Fe(III) intermediate as observed for both NTA and citrate. To complement to these laboratory studies, we collected U-bearing samples from a surface seep at the Rifle field site and have measured elevated U concentrations in oxic iron-rich sediments. To translate experimental results into numerical analysis of U fate and transport, a reaction network was developed based on Sani et al. (2004) to simulate U(VI) bioreduction with concomitant UO 2 reoxidation in the presence of hematite or ferrihydrite. The reduction phase considers SRB reduction (using lactate) with the reductive dissolution of Fe(III) solids, which is set to be microbially mediated as well as abiotically driven by sulfide. Model results show the oxidation of HS– by Fe(III) directly competes with UO 2 reoxidation as Fe(III) oxidizes HS– preferentially over UO 2 . The majority of Fe reduction is predicted to be abiotic, with ferrihydrite becoming fully consumed by reaction with sulfide. Predicted total dissolved carbonate concentrations from the degradation of lactate are elevated (log(pCO 2 ) ~ –1) and, in the hematite system, yield close to two orders-of-magnitude higher U(VI) concentrations than under initial carbonate concentrations of 3 mM. Modeling of U(VI) bioreduction with concomitant reoxidation of UO 2 in the presence of ferrihydrite was also extended to a two-dimensional field-scale groundwater flow and biogeochemically reactive transport model for the South Oyster site in eastern Virginia. This model was developed to simulate the field-scale immobilization and subsequent reoxidation of U by a biologically mediated reaction network.

54 ENVIRONMENTAL SCIENCES↗

Controls on Soil Organic Matter Degradation and Subsequent Greenhouse Gas Emissions Across a Permafrost Thaw Gradient in Northern Sweden

Warming-induced permafrost thaw could enhance microbial decomposition of previously stored soil organic matter (SOM) to carbon dioxide (CO 2 ) and methane (CH 4 ), one of the most significant potential feedbacks from terrestrial ecosystems to the atmosphere in a changing climate. The environmental parameters regulating microbe-organic matter interactions and greenhouse gas (GHG) emissions in northern permafrost peatlands are however still largely unknown. The objective of this work is to understand controls on SOM degradation and its impact on porewater GHG concentrations across the Stordalen Mire, a thawing peat plateau in Northern Sweden. Here, we applied high-resolution mass spectrometry to characterize SOM molecular composition in peat soil samples from the active layers of a Sphagnum-dominated bog and rich fen sites in the Mire. Microbe-organic matter interactions and porewater GHG concentrations across the thaw gradient were controlled by aboveground vegetation and soil pH. An increasingly high abundance of reduced organic compounds experiencing greater humification rates due to enhanced microbial activity were observed with increasing thaw, in parallel with higher CH 4 and CO 2 porewater concentrations. Bog SOM however contained more Sphagnum-derived phenolics, simple carbohydrates, and organic- acids. The low degradation of bog SOM by microbial communities, the enhanced SOM transformation by potentially abiotic mechanisms, and the accumulation of simple carbohydrates in the bog sites could be attributed in part to the low pH conditions of the system associated with Sphagnum mosses. We show that Gibbs free energy of C half reactions based on C oxidation state for OM can be used as a quantifiable measure for OM decomposability and quality to enhance current biogeochemical models to predict C decomposition rates. We found a direct association between OM chemical diversity and δ 13 C-CH 4 in peat porewater; where higher substrate diversity was positively correlated with enriched δ 13 C-CH 4 in fen sites. Oxidized sulfur-containing compounds, produced by Sphagnum, were further hypothesized to control GHG emissions by acting as electron acceptors for a sulfate-reducing electron transport chain, inhibiting methanogenesis in peat bogs. These results suggest that warming-induced permafrost thaw might increase organic matter lability, in subset of sites that become wetlands, and shift biogeochemical processes toward faster decomposition with an increasing proportion of carbon released as CH 4 .

54 ENVIRONMENTAL SCIENCES↗

Concentration-Discharge Relationships in the Six Largest Arctic Rivers, 2003-2019

This dataset provides the results of the analysis of the relationship of dissolved analyte concentrations and river discharges in the six largest Arctic rivers across the global panarctic region (see Figure 1 in documentation file *.pdf). Long-term measurements of dissolved analyte concentrations and river discharge have been collected for each of the Kolyma, Lena, Mackenzie, Ob, Yenisey, and Yukon rivers by the Arctic Great Rivers Observatory (ArcticGRO) project from ~2003-present (Shiklomanov, 2021). The relationship of dissolved analyte concentrations and discharges in each river was characterized by statistical analysis of the slope of the log(concentration) vs log(discharge) (b), the coefficient of variation ratio (CVc/CVq), the 2.5% and 97.5% confidence intervals of b, and assigning a chemostatic, flushing, diluting, or non-systematic behavior category according to Koger (2018). The summary of these analyses for all six rivers is provided in one .csv file. The concentrations of 20 dissolved analytes and discharge measurement data for the individual Kolyma, Lena, Mackenzie, Ob, Yenisey, and Yukon rivers are also provided with this dataset. There are seven *.csv files; one for each river plus the statistical summary. These public ArcticGRO data at "https://www.arcticgreatrivers.org" (Shiklomanov, 2021) were downloaded on Feb 13, 2020, but each river has different measurement dates over the sampling and analysis period. The ArcticGRO metadata document (*.pdf) downloaded on Feb 13, 2020 is also included in this dataset. The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

Occurrence and Stabilization of Colloidal and Nanoparticulate Mercury Sulfides (Final Technical Report)

Mercury contaminates the soils at several DOE sites, including facilities at Oak Ridge, Hanford, and the Savannah River site. This contamination poses a hazard to surrounding ecosystems because the metal continuously leaches to local streams and rivers and is converted to methylmercury, a neurotoxic and highly bioaccumulative form of mercury. Anaerobic microorganisms such as sulfate-reducing and iron-reducing bacteria are primarily responsible for methylmercury production in the environment. The remediation of mercury-contaminated ecosystems is difficult because we lack a poor understanding of the factors that control mercury mobilization and methylation in sediments. The objective of this project was to investigate the forms of mercury that are bioavailable to methylating bacteria. This project specifically focused on mercury-sulfide-organic matter geochemistry and the persistence of nanoparticulate HgS that are intermediates of metal sulfide precipitation reactions occurring in the presence of natural organic matter (NOM). This work involved two specific aims: 1) Investigate environmental processes that facilitate the occurrence and stabilization of nanoparticulate HgS and other metal sulfides; and (2) Investigate the occurrence of nanoparticulate HgS in sediments of the East Fork Poplar Creek, located in near a DOE facility in Oak Ridge, TN. For specific aim #1, laboratory experiments were performed to simulate metal sulfide precipitation processes in environmental systems. A key experimental variable was the type and concentration of NOM that was used in the experiments simulating metal sulfide precipitation. The characteristics of the metal sulfide nanoparticles were analyzed using a suite of analytical techniques that included X-ray based methods at DOE synchrotron facilities (National Synchrotron Light Source and Advanced Photon Source). Field sampling in Oak Ridge was performed in collaboration with colleague at the Oak Ridge National Laboratory. The experimental results demonstrated that a combination of photon scattering and spectroscopic tools can be used to characterize nanoscale structures that form during heterogeneous metal-sulfide-NOM precipitation. ZnS precipitation experiments with a low molecular weight thiol indicated the importance of specific metal-ligand binding for altering the kinetics of ZnS nanoparticle aggregation and monomer growth. However, NOM consists of macromolecular structures that may interact with nano-HgS in non-specific ways (e.g. electrosteric surface interactions. The methylation potential of nano-HgS in sediments may depend on size and crystallinity of nanoparticles and interactions with NOM. For specific aim #2, sediment core samples were collected in three separate locations along the East Fork Poplar Creek in Oak Ridge, TN in June 2011. Analysis of the sediment samples indicated that more than 90% of the Hg in the porewater is associated with colloidal material. These results highlight the importance of small particles for dominating Hg speciation in sediment porewater. Overall, this project highlights the importance of nanoscale phases for mercury speciation. Nanoparticulate HgS will be of particular importance in the anaerobic habitats of methylating microorganisms. In previous models for Hg bioavailability, nanoparticles of Hg are presumed to be unavailable for methylating bacteria. However, recent work shows that nanoparticles contribute to bioavailable Hg that greatly exceeds the contribution from larger HgS microparticles (Zhang et al., 2012). The work performed for this exploratory project lays the groundwork for further study on nanoscale mercury sulfide geochemistry and contributes to an improved understanding of Hg bioavailability and methylation potential.

54 ENVIRONMENTAL SCIENCES↗

Data for "Soil carbon dynamics during drying vs. rewetting: Importance of antecedent moisture conditions"

This dataset contains data used for the paper "Soil carbon dynamics during drying vs. rewetting: importance of antecedent moisture conditions". The Related References field will be updated with a full citation when available.Soil moisture influences soil carbon dynamics, including microbial growth and respiration. The response of such ‘soil respiration’ to moisture changes is generally assumed to be linear and reversible, i.e. to depend only on the current moisture state. Current models thus do not account for antecedent soil moisture conditions when determining soil respiration or the available substrate pool. We conducted a laboratory incubation to determine how the antecedent conditions of drought and flood influenced soil organic matter (SOM) chemistry, bioavailability, and respiration. We sampled soils from an upland coastal forest, Beaver Creek, WA USA, and subjected them to drying and rewetting treatments. For the drying treatment, field moist soils were saturated and then dried to 75, 50, 35, and 5 % saturation. In the rewetting treatment, field moist soils were air-dried and then rewet to 35, 50, 75, and 100 % saturation. We measured respiration and water extractable organic carbon (WEOC) concentrations and used 1H-NMR and FT-ICR-MS to characterize the WEOC pool across the treatments. The drying vs. wetting treatment strongly influenced SOM bioavailability, as rewet soils (with antecedent drought) had greater WEOC concentrations and respiration fluxes compared to the drying soils (with antecedent flood). In addition, air-dry soils had the highest WEOC concentrations, and the NMR-resolved peaks showed a strong contribution of protein groups in these soils. Both NMR and FT-ICR-MS analyses indicated increased contribution of complex aromatic groups/molecules in the rewet soils, compared to the drying soils. We suggest that drying introduced organic matter into the WEOC pool via desorption of aromatic molecules and/or by microbial cell lysis, and this stimulated microbial mineralization rates. Our work indicates that even short-term shifts in antecedent moisture conditions can strongly influence soil C dynamics at the core scale. The predictive uncertainties in current soil models may be reduced by a more accurate representation of soil water and C persistence that includes a mechanistic and quantitative understanding of the impact of antecedent moisture conditions.This dataset contains a compressed (.zip) archive of the data and R scripts used for this manuscript. The dataset includes files in .csv and .txt format, which can be accessed and processed using MS Excel or R. NMR data are provided as raw output data (accessed in Bruker TopSpin or MestreNova) as well as the MestreNova-processed files. This archive can also be accessed on GitHub at https://github.com/kaizadp/hysteresis_and_soil_carbon (DOI: 10.5281/zenodo.4432885).

1H-NMR↗

Uranium Sequestration - Field Test to Remedial Action - 17151

The Hanford Site historical nuclear weapons production has resulted in legacy soil and groundwater contamination and is now one of the nation's largest superfund sites. The 300 Area of the Hanford Site is adjacent to the Columbia River close to the city of Richland, Washington. It contained facilities and waste disposal sites that supported uranium fuel production and research and development activities. Contaminated liquid waste discharged to the waste disposal sites caused persistent uranium contamination within the underlying groundwater, which flows into the Columbia River. The DOE performed field scale treatability studies in the 300 Area to assess the use of phosphate to sequester uranium as a potential remediation strategy. The Record of Decision was issued in November 2013 and requires DOE to use phosphate to sequester uranium over a 1.2 hectare area by applying phosphate to the highest uranium concentration areas of the vadose zone and the periodically re-wetted zone using a combination of surface infiltration, periodically re-wetted zone injection, and shallow aquifer injection. Due to the inherent difficulties in scale-up from a limited field test to a full-scale remedial action, it was determined that uranium sequestration would occur in two sequential stages: Stage A and Stage B. Stage A would treat a 0.3 hectare area, while Stage B would treat the remaining 0.9 hectare area. The purpose of Stage A was to test the remediation approach on a smaller area, refine the process based on the results, and then implement it in a larger area. Stage A of the phosphate application to sequester uranium was implemented in November 2015. This paper includes a description of the Stage A uranium sequestration process (objectives, observations, and conclusions), the sampling and monitoring approach, the physical sequestration system, and recommended changes for Stage B. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Progress Report on the ISCR Pilot Test Conducted at the Former CCC/USDA Grain Storage Facility in Montgomery City, Missouri, as of April 2013

The Commodity Credit Corporation of the U.S. Department of Agriculture (CCC/USDA) is conducting an environmental investigation at the former CCC/USDA grain storage facility on the county fairgrounds in Montgomery City, Missouri, to evaluate contamination associated with the former use of grain fumigants containing carbon tetrachloride at the site. The CCC/USDA studies have identified carbon tetrachloride in the soils (primarily unconsolidated glacial tills) at concentrations that exceed the U.S. Environmental Protection Agency (EPA) regional screening level (RSL) values for this compound in residential soils (610 μg/kg) but are below the corresponding RSL for industrial soils (3,000 μg/kg). Concentrations of carbon tetrachloride greater than the EPA maximum contaminant level (MCL; 5.0 μg/L) for this contaminant in drinking water were also identified in the shallow groundwater (Argonne 2012). On the basis of these findings, remedial actions are considered necessary to mitigate the present and potential future impacts of the contamination. In cooperation with the Missouri Department of Natural Resources (MDNR), the CCC/USDA has initiated a field-scale pilot test to evaluate an in situ technology for treatment of the carbon tetrachloride contamination. In this approach, a chemical amendment consisting primarily of slow-release organic matter and zero-valent iron is employed to induce oxygen-depleted, chemically reducing conditions in the subsurface. These conditions foster the in situ chemical reduction (ISCR) of carbon tetrachloride and its degradation products (chloroform, methylene chloride, and chloromethane) via both inorganic and biologically mediated processes. The chemical amendment being used, EHC™, was developed by the Adventus Group, Freeport, Illinois, and is now manufactured and distributed by FMC Environmental Solutions, Philadelphia, Pennsylvania. With the approval of the MDNR (2012), the ISCR technology is being tested in two target areas interpreted to represent contaminant source areas. The pilot test is being implemented on behalf of the CCC/USDA by Argonne National Laboratory. Approximately 80,000 lb of the EHC material was injected by using direct-push techniques at 99 locations in the target areas, from November 9 to December 15, 2012 (Argonne 2012). To determine the geochemical effects of the pilot injections and their impact on the levels of contamination in the test areas, an extended monitoring program (Argonne 2012) is being implemented. The program includes an initial “baseline” sampling event to document pre-treatment conditions and periodic post-injection monitoring events, approximately 1, 2, 4, 6, 9, and 12 months after the completion of the injection program (Argonne 2012). This report provides a brief summary of the specific activities conducted, with a compilation of the monitoring data obtained, during the baseline sampling event (October 2012) and the first, second, and third post-injection monitoring events (in January, February, and April 2013).

54 ENVIRONMENTAL SCIENCES↗

Dynamic Responses of Trace Metal Bioaccessibility to Fluctuating Redox Conditions in Wetland Soils and Stream Sediments

Natural aquatic systems undergo fluctuating redox conditions due to microbial activity, varying water saturation levels, and nutrients dynamics. With fluctuating redox conditions, trace metals can mobilize or sequester in response to changes in iron and sulfur speciation and the concentrations and lability of organic carbon. This study examined the effect of redox fluctuations on trace metal mobility in samples collected from two different natural aquatic systems: riparian wetlands and a stream. The wetland soils contained low sulfur and total Fe contents as compared to stream sediments. The mineral composition at both sites was dominated by quartz. We incubated water-saturated soils under three cycles of anoxic-oxic conditions (τanoxic:τoxic = 3) spanning 24 days and monitored the change in dissolved and bioavailable metal concentrations. For both natural systems, reduction of iron oxides under anoxic conditions caused Co and Zn release. In contrast, oxidation of sulfides mobilized Cu under oxic conditions in both sites. In wetland soils, dissolution of Fe (hydr)oxides increased Ni solubility; however, in stream sediments, Ni release occurred when sulfides or organic matter were oxidized. For stream sediments, each subsequent redox cycle increased the bioavailability of trace metals. Redox fluctuations in wetland soils increased bioavailable Zn and Cu and decreased bioavailable Ni and Co. This study illustrates that different trace metals display distinct bioavailability patterns during redox fluctuations in natural environments. The biogeochemical cycling of nutrients in systems with redox fluctuations may be influenced by these trace metal availability patterns in addition to the availability of electron donors and acceptors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydraulic Conductivity Measurements, Utqiagvik (Barrow), Alaska, 2014

Six individual ice cores were collected from the Barrow Environmental Observatory in Barrow, Alaska, in May of 2013 as part of the Next Generation Ecosystem Experiment (NGEE). Each core was drilled at a different location to varying depths. After drilling, the cores were stored in coolers packed with dry ice and flown to Lawrence Berkeley National Laboratory (LBNL) in Berkeley, CA. 3-dimensional images of the cores were constructed using medical X-ray computed tomography (CT) scanner at 120kV. Hydraulic conductivity samples were extracted from these cores at LBNL Richmond Field Station in Richmond, CA, in February 2014 by cutting 5 to 8 inch segments using a chop saw. Samples were packed individually and stored at -20C freezing temperatures to minimize any changes in structure or loss of ice content prior to analysis. Hydraulic conductivity was determined through falling head tests using a permeameter [ELE International, Model #: K-770B] (Appendix A). Samples were placed in a latex membrane via a membrane stretcher while frozen. Use of a membrane stretcher made the membranes easier to secure and minimized contact with the sample. A clear polycarbonate sleeve, fabricated with a stainless steel ring at the bottom to keep the sleeve from floating, was placed around the sample inside the permeameter to minimize deformation during analysis. The permeameter was filled with water and 1.0 PSI of air was applied for confining pressure during sample defrost. Outflow valves were left open to allow for incremental thawing and samples were left to thaw for approximately 12 hours. After approximately 12 hours of thaw, initial falling head tests were performed. When the flow was significantly too fast or too slow, the analysis was stopped and the burette size was adjusted accordingly (i.e. a larger diameter burette was used for flows that were faster than desired or a smaller diameter burette was used for flows that were slower than desired). Two to four measurements were collected on each sample and collection stopped when the applied head load exceeded 25% change from the original load. Analyses were performed between 2 to 3 times for each sample. The final hydraulic conductivity calculations were computed using methodology of Das et al., 1985.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a 15-year research effort (2012-2027) to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗