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Predictive Flow Simulation with the P2R Model for the 200-IA-1 Preliminary Remediation Goal Saturated Zone Abstraction

In order to develop and evaluate alternatives for remediation of waste sites constituting the 200-IA-1 Operable Unit (OU), a focused feasibility study (FFS) is currently underway. The 200-IA-1 OU FFS requires preliminary remediation goals (PRGs) protective of groundwater be evaluated which includes estimates of fate and transport of contaminants in the groundwater from multiple sources within the Central Plateau Inner Area. This document details the application of the Plateau-to-River (P2R) Model version 8.3 to predict the flow of groundwater on the Central Plateau for the 10,000-year simulation to support the 200-IA-1 OU PRG calculation. The simulated flow field will support the simulation of fate and transport of contaminants for use in estimating peak unit-length concentration as part of the 200-IA-1 OU PRG calculation presented in a separate environmental calculation file (ECF) (ECF-200IA1-20-0108, Determination of Preliminary Remediation Goals for 200-IA-1 Source Operable Unit).

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Sensitivity Analysis of Sediment Coagulations in the Chesapeake Bay

Hydrodynamic models are utilized for fast response to environmental hazards. However, limitations within the models may inhibit their accuracy. A three-dimensional aqueous transport model, ALGE, was developed at the Savannah River National Laboratory (SRNL) as a tool for pollutant dispersion. Recently at SRNL, the capability to account for coagulation and break-up of particles to better account for the fate and transport of materials. A sensitivity analysis was performed to determine a threshold for specified particle parameters that still yield accurate results. Dictating these thresholds advances the development of ALGE to become a product for efficient emergency response.

54 ENVIRONMENTAL SCIENCES↗

Characterization of Iron and Organic Carbon Colloids in Boreal Rivers and Their Fate at High Salinity

Riverine colloids are important carriers of macronutrients, trace metals, and pollutants into marine waters. The aim of the current study was to extend the understanding of iron (Fe) and organic carbon (OC) colloids in boreal rivers and their fate at higher salinities. X-ray absorbance spectroscopy (XAS) and dynamic light scattering (DLS) were combined to explore Fe speciation and colloidal characteristics such as size and surface charge and how these are affected at increasing salinity. XAS confirmed the presence of two Fe phases in the river waters—Fe-organic matter (OM) complexes and Fe(oxy)hydroxides. From DLS measurements on filtered and unfiltered samples, three particle size distributions were identified. The smallest particles (10–40 nm) were positively charged and suggested to consist of essentially bare Fe (oxy)hydroxide nanoparticles. The largest particles (300–900 nm) were dominated by Fe(oxy)hydroxides associated with chromophoric molecular matter. An intermediate size distribution (100–200 nm) with a negative surface charge was presumably dominated by OM and containing Fe-OM complexes. Increasing the salinity resulted in a removal of the smallest distribution. Unexpectedly, both the intermediate and largest size distributions were still detected at high salinity. The collective results suggest that Fe(oxy) hydroxides and Fe-OM complexes are both found across the wide size range studied and that colloidal size does not necessarily reflect either Fe speciation or stability toward salinity-induced aggregation. The findings further demonstrate that also particles beyond the typically studied <0.45-μm size range should be considered to fully understand the riverine transport and fate of macronutrients, trace metals, and pollutants.

54 ENVIRONMENTAL SCIENCES↗

(Project 18-15502) Reducing Uncertainty in Radionuclide Transport Prediction Using Multiple Environmental Tracers (Final Report)

In order to successfully site and design a nuclear waste disposal facility, DOE scientists are required to show safe containment of the radioactive waste for up to 1 million years. A significant hurdle to accurately and convincingly demonstrating disposal safety is predicting the fate of radioactive elements once they enter the groundwater system surrounding the repository. These predictions are often made with computer models, which contain accurate physics of groundwater movement and chemical reactions that occur during groundwater flow. As computer power increases, the physics and chemistry of these computer simulators can become more and more realistic and the physically based error decreases. However, the ability of these computer models to provide accurate predictions in a specific place, over long time periods, requires the scientists and engineers to know the subsurface properties of the Earth that control groundwater movement. In particular, groundwater scientists and engineers need to know the groundwater fluid velocity, which can change over time and strongly vary with location within the groundwater system. Because the Earth’s subsurface cannot be directly seen, and can only be sampled at drilling locations, the properties of the groundwater system are never known completely, and computer models of groundwater transport will always have some amount of uncertainty. This project’s principal goal was to use chemicals and isotope “tracers”, which have been introduced to the groundwater system by natural processes over long time periods, to help inform computer models of the groundwater velocity and subsurface properties. The goal was to calculate how much better predictions of groundwater transport were when these “tracers” were used to inform the computer models.

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Application of a Null-Space Monte Carlo Flow Model Set to the Composite Analysis Base Case Fate and Transport Modeling

The Plateau to River Groundwater Model (P2R Model) is a groundwater flow and contaminant fate and transport (F&T) simulation model used to support remedial activities conducted by CH2M HILL Plateau Remediation Company at the Hanford Site in Washington State. Figure 1-1 illustrates the P2R Model extents, discretization, and boundary conditions. The P2R Model is utilized in the Composite Analysis (CA) for the Hanford Site as the computational engine for computing F&T predictions as described in CP-60406, Hanford Site Composite Analysis Technical Approach Description: Groundwater. The model simulates contaminants of concern within the saturated zone of the uppermost aquifer beneath the Central Plateau and downgradient to the Columbia River. CP-57037, Model Package Report for the Plateau to River Model Version 8.3, documents the current version of the P2R Model including a description of the conceptual site model, model development and calibration, and limitations to the model application. The overall objective of the saturated zone modeling effort is to provide a basis for making informed remedial action decisions based on descriptions of current and expected future contaminant concentrations in groundwater at decision points within and downgradient of the Central Plateau of the Hanford Site. Specifically, the purpose of this environmental calculation is to describe the application of the hydraulic property fields and recharge parameters documented in ECF-HANFORD-20-0027, Null Space Monte Carlo Evaluation of the Plateau to River Model, to the CA flow and fate and transport simulation results to quantify the uncertainty in the simulated results due to input parameter selection. Use of numerical groundwater models is always accompanied with uncertainty in the results produced by a model because models are approximations of reality. Thus, by definition, models lack the detail to fully represent observed behavior. Use of numerical techniques, such as a NSMC analysis, can help in identifying and quantifying the potential uncertainties associated with a numerical model such as the P2R Model. The result of NSCM analysis is a set of F&T simulations that provide an estimate of the range of possible outcomes that are used to quantify the uncertainty in simulated concentrations produced using the base case simulations. The simulated concentrations from all simulations will support calculation of the uncertainty of the total dose calculated in a separate calculation.

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Toward polymer upcycling—adding value and tackling circularity

Plastics have revolutionized modern life, but have created a global waste crisis driven by our reliance and demand for low-cost, disposable materials. New approaches are vital to address challenges related to plastics waste heterogeneity, along with the property reductions induced by mechanical recycling. Chemical recycling and upcycling of polymers may enable circularity through separation strategies, chemistries that promote closed-loop recycling inherent to macromolecular design, and transformative processes that shift the life-cycle landscape. Polymer upcycling schemes may enable lower-energy pathways and minimal environmental impacts compared with traditional mechanical and chemical recycling. The emergence of industrial adoption of recycling and upcycling approaches is encouraging, solidifying the critical role for these strategies in addressing the fate of plastics and driving advances in next-generation materials design.

Korley, LaShanda T. J.↗

Understanding Soil Microbial Sources of Nitrous Acid and their Effect on Carbon-Nitrogen Cycle Interactions

Descriptions of soil emissions of reactive nitrogen (NO y ) in climate models are underdeveloped or non-existent, due to the fact that details of the mechanisms leading to nitrous acid (HONO) and nitrogen di-oxide (NO 2 ) formation in soil are lacking. This represents a major gap in our understanding of a significant land-atmosphere interaction that prevents us from scaling these processes from the laboratory scale to the ecosystem and global scales. There is a critical need to include these mechanisms into climate models since NO y controls the oxidative capacity of the atmosphere and the lifetime of greenhouse gases and the rate of secondary aerosol formation that directly and indirectly affect climate. The first objective of this proposal is to conduct laboratory and field measurements of NO y fluxes from diverse soil types and determine the mechanism of biogenic NO y formation. The working hypothesis based on preliminary data is that soil HONO and NO 2 is ultimately derived from ammonia-oxidizing archaea (AOA) and bacteria (AOB) that are widespread, but whose abundance varies across ecosystems. In the case of NO 2 , reactive oxygen species derived from iron-containing minerals and heterotrophic bacteria drive NO-to-NO 2 conversion. The approach is to link soil fluxes of HONO and NO 2 to AOA, AOB, and other heterotrophs using a combination of laboratory and field experiments, isotopic analysis, and molecular techniques to address how variability in land surfaces and edaphic properties impact emissions. In addition, we will determine the effect of HONO and NO 2 on nitrogen immobilization and the photo-oxidative capacity of soil. The working hypothesis is that HONO uptake in soil will be a source of nitrosonium and hydroxyl radical that will lead to thermal- and photodegradation of soil organic matter to CO 2 and CO, and the incorporation of N in soil organic matter. We will use surface-sensitive mass spectrometry techniques and gas phase detection to study N-immobilization in soil and subsequent enhancements in reactivity that lead to decomposition of organic matter. The results will be used to reduce the uncertainty in projections from the Community Earth System Model (CESM) stemming from inaccurate representations of soil NO y emissions. The proposed research is significant because, in addition to demonstrating new mechanisms of NO y formation and loss, it will be a crucial first step towards modeling the land-atmosphere exchange of HONO and NO 2 in the CESM. Improved model treatment of land-air exchange of NO y is key for understanding feedbacks between human activity and climate, and addressing societal concerns about the fate of N and C emitted to the atmosphere.

54 ENVIRONMENTAL SCIENCES↗

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↗

235-F GoldSim Fate and Transport Model: Uncertainty Quantification

Building 235-F was configured with two missions in mind: Actinide Billet Line (ABL) and the fabrication of Pu-238 oxide for space program applications. ABL produced Np-237 billets for use in SRS reactors, whereas the design process, fabrication, and examination of Pu-238 oxide powder occurred within the following areas, respectively: Plutonium Experimental Facility (PEF), Plutonium Fuel Form (PuFF), and Old Metallography Lab (OML). By 1990 production ceased and by 2006 de-inventory occurred; however, assays have shown significant holdup remains within ABL and PuFF. As a result, 235-F is a Category 2 nuclear facility, with plans to undergo deactivation and decommission (D and D) via In-Situ Disposal (ISD). The purpose of this project is to ensure United States Environmental Protection Agency (USEPA) groundwater radiation maximum contaminant level (MCL) and dosage standards are met during the D and D of 235-F by quantifying uncertainty through probabilistic modeling and evaluation of various ISD alternatives. GoldSim is a dynamic modeling software package with a graphical, object-oriented interface capable of capturing the influence of complex system input variability on probabilistic system outcomes. A GoldSim stochastic fate and transport model for 235-F was developed and matched with a PORFLOW deterministic model to simulate probabilistic release and flow of radionuclides from ABL and PuFF into the vadose zone, the Upper Three Runs (UTR) Aquifer, and UTR Creek. The GoldSim model was used to probabilistically evaluate four ISD scenarios against USEPA groundwater radiation MCLs and dosage standards. The deterministic 235-F GoldSim fate and transport model continues to be refined to match the results of the PORFLOW deterministic model to ensure the model accurately represents radionuclide movement through the groundwater system. The stochastic variables that are utilized within the GoldSim model are founded on the most current data; a conservative perspective is taken where needed. Alignment with the PORFLOW deterministic model, coupled with input stochastic variability, allows the probabilistic 235-F GoldSim model to capture the conservative breadth of possible outcomes for radionuclide fate within this particular system. This ensures that the USEPA MCLs and dosage limits hold even in the worst case scenarios.

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Modelling the Sensitivity of Yukon River Biogeochemical Dynamics to Environmental and Chemical Drivers: Implications for Dissolved Organic Carbon

Riverine dissolved organic carbon (DOC) is a critical biogeochemical component that transmits information from Arctic soils to the Arctic Ocean, significantly influencing carbon dynamics in this unique ecosystem. As DOC travels downstream, it undergoes transformations that alter its composition and fate. The Yukon River serves as an effective testbed for modelling these dynamics, offering sufficient scale to capture key biogeochemical processes while having a simpler hydrology than other major Arctic rivers, as well as long-term DOC observational data for model validation. To investigate DOC transformations during transit in the Yukon River, we adapted our Arctic Riverine Organic Macromolecular Model by applying regional-specific parameterisations. Our model simulates the transport and transformation of 15 organic macromolecules, including CDOM (coloured dissolved organic matter), proteins, polysaccharides, lipids, lignin phenols, and humic substances. Initial DOC concentrations were derived from observed soil organic carbon stocks in the surrounding watershed, while chemical transformations and hydrological dynamics were modelled along the river's course. Sensitivity and uncertainty analyses were conducted using a Monte Carlo approach under two experimental setups. Results revealed that variability in DOC and CDOM concentrations at the river mouth were predominantly driven by initial DOC concentration (~70% of variability explained) and dilution at confluence points (~10%). The refractory fraction of DOC explained 21%–88% of the variability in 14 macromolecular concentrations and ranked in the top five sensitive parameters for all outputs when a uniform parameter distribution was assumed. However, when a more likely variability was applied to this parameter, its influence on DOC and CDOM decreased. Given that refractory DOC accounts for ~80% of total DOC in Arctic Rivers, this suggests that most DOC resists degradation and retains its chemical composition during transport to the coastal environment. River velocity, which determines residence time, explained 8%–47% of the variability in protein, polysaccharide, lipid, pigments, and lignin phenols at the river mouth. In contrast, chemical turnover times contributed only 1%–5% to output variability. Our findings underscore the need for improved land-specific headwater observations, including seasonal soil moisture and lateral transport dynamics that control the initial tributary-specific DOC inputs. With accelerated permafrost thaw and increasing river discharge, extending our model to other Arctic River systems and seasons will enhance understanding of Arctic riverine carbon fluxes and their contributions to the Arctic Ocean.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigating the Atmospheric Sources and Sinks of Perfluorooctanoic Acid Using a Global Chemistry Transport Model

Perfluorooctanoic acid, PFOA, is one of the many concerning pollutants in our atmosphere; it is highly resistant to environmental degradation processes, which enables it to accumulate biologically. With direct routes of this chemical to the environment decreasing, as a consequence of the industrial phase out of PFOA, it has become more important to accurately model the effects of indirect production routes, such as environmental degradation of precursors; e.g., fluorotelomer alcohols (FTOHs). The study reported here investigates the chemistry, physical loss and transport of PFOA and its precursors, FTOHs, throughout the troposphere using a 3D global chemical transport model, STOCHEM-CRI. Furthermore, this investigation includes an important loss process of PFOA in the atmosphere via the addition of the stabilised Criegee intermediates, hereby referred to as the “Criegee Field.” Whilst reaction with Criegee intermediates is a significant atmospheric loss process of PFOA, it does not result in its permanent removal from the atmosphere. Additionally, the atmospheric fate of the resultant hydroperoxide product from the reaction of PFOA and Criegee intermediates resulted in a ≈0.04 Gg year-1 increase in the production flux of PFOA. Furthermore, the physical loss of the hydroperoxide product from the atmosphere (i.e., deposition), whilst decreasing the atmospheric concentration, is also likely to result in the reformation of PFOA in environmental aqueous phases, such as clouds, precipitation, oceans and lakes. As such, removal facilitated by the “Criegee Field” is likely to simply result in the acceleration of PFOA transfer to the surface (with an expected decrease in PFOA atmospheric lifetime of ≈10 h, on average from ca. 80 h without Criegee loss to 70 h with Criegee loss).

54 ENVIRONMENTAL SCIENCES↗

Use of Stable Mercury Isotopes to Assess Mercury and Methylmercury Transformation and Transport across Critical Interfaces from the Molecular to the Watershed Scale (Final Report)

This project titled “Use of Stable Mercury Isotopes to Assess Mercury and Methylmercury Transformation and Transport across Critical Interfaces from the Molecular to the Watershed Scale” represents a collaborative effort between the University of Michigan (Jason Demers, PI) and Oak Ridge National Laboratory (Scott Brooks, co-I). Much has been learned about mercury (Hg) cycling in stream ecosystems, and East Fork Poplar Creek (EFPC) in particular, through decades of previous research. Nevertheless, some of the most fundamental questions regarding the sources of bioavailable Hg and its transformation to toxic methylmercury (MeHg) have remained unanswered. These fundamental questions include: (1) what are the sources and biogeochemical processes that lead to the input of dissolved Hg to stream water across critical subsurface interfaces within stream ecosystems, and EFPC in particular? and (2) what are the sources and biogeochemical processes that control the production and fate of bioaccumulative MeHg within stream ecosystems, and in EFPC in particular? To address these fundamental questions, our project aimed to couple laboratory experiments and field observations, both utilizing natural abundance Hg stable isotope techniques, to identify the processes responsible for generating mobile, bioavailable dissolved Hg from recalcitrant legacy sources within critical subsurface zones (e.g., streambed hyporheic zone, riparian floodplain subsurface). We used the isotopic signature of this bioavailable dissolved Hg to track its mobilization across these critical interfaces in order to link diffuse subsurface sources of dissolved Hg with increases in surface water dissolved Hg flux measured at the watershed scale. Additionally, our research aimed to determine the isotopic composition of MeHg within these same critical subsurface zones. We directly assessed the isotopic composition of MeHg within biota in order to gain insight into which subsurface sources of inorganic Hg and toxic MeHg are available for bioaccumulation within the EFPC ecosystem. Net fluxes of dissolved Hg along the flow path of EFPC were shown to vary spatially and temporally. In the Upper EFPC, within the Y12 boundary, stream water flux of dissolved Hg consistently decreased between the outfall and the downstream boundary of Y12 (57% ± 29%, 1SD). Within the Upper EFPC, an assessment of Hg isotopic composition suggested that losses were strongly reaction-driven, although isotopic diagnostics did not conform to any known processes. Downstream of Y12, in the upper reach of the Lower EFPC, dissolved Hg fluxes tended to increase during the dormant season (net gain of 11-120%), and decrease during the growing season (net loss of 23% +/- 18%, 1SD). In the downstream-most reach of Lower EFPC, dissolved Hg fluxes increased by 12-108% in 9 out of 10 monthly assessments. Overall, diffuse fluxes from the non-Y12 watershed accounted for 34% (+/- 17%, 1SD) of all dissolved Hg exported during base flow. Within Lower EFPC, an assessment of Hg isotopic composition was consistent with the contribution of diffuse Hg inputs from high-concentration hotspots within riparian floodplains and streambed hyporheic pore water. To investigate remobilization of recalcitrant Hg from legacy sediment sources, we developed procedures that coupled isotopic analysis with sequential extractions of streambed sediment. We found that the proportion of weakly-bound Hg within EFPC streambed sediment was relatively small, but could still account for a large proportion of the annual flux of dissolved Hg from EFPC. These sequential extractions also showed that this weakly-bound Hg fraction could be replenished from the much larger fraction of recalcitrant Hg in sediment. The isotopic composition of these weakly-bound and remobilized recalcitrant Hg fractions within the sediment was consistent with high-concentration dissolved Hg hotspots within hyporheic pore water. Thus, this research provided novel evidence that legacy mercury sources within streambed sediment could provide an ongoing contribution of dissolved Hg to surface waters. Finally, we developed new methods for the direct determination of the MeHg isotopic composition of organisms, which allowed a more direct evaluation of inorganic Hg and MeHg sources accumulating in the food web. We found that fish and aquatic invertebrates in both EFPC and a regional background site obtained inorganic Hg and MeHg from multiple isotopically distinct sources, including sediment, suspended particulates, and periphyton. Photodemethylation was found to be an important reaction influencing MeHg dynamics at both sites. However, the balance of microbial methylation and demethylation processes differed between the two streams, with fractionation resulting from methylation and demethylation processes being relatively in balance within the regional background site, whereas microbial methylation appeared to be dominant over microbial demethylation within the EFPC ecosystem. Broadly, the application of Hg isotopic analysis in this study led to numerous novel insights regarding the biogeochemical cycling of Hg in stream ecosystems. This research project promoted the development of two new approaches, including the coupling of sequential extractions with Hg isotopic analysis to assess remobilization of recalcitrant Hg within sediments, and a new method for the isotopic analysis of MeHg isolated from environmental samples. Both of these efforts represent advances in capacity for the field of mercury isotopic analysis and environmental assessment. Overall, this study demonstrates that the application of Hg stable isotope techniques continues to provide new insights into the biogeochemical cycling of Hg in complex aquatic environments, both within the EFPC and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mercury Remediation Technology Development for Lower East Fork Poplar Creek (FY2020 Update)

Mercury (Hg) remediation is a high priority for the US Department of Energy (DOE) Oak Ridge Office of Environmental Management. Mercury contamination in the environment can be found at all three DOE facilities in Oak Ridge, but probably the greatest environmental risk concern relative to Hg on the Oak Ridge Reservation is associated with historical Hg losses at and near the Y-12 National Security Complex (Y-12). Water and fish from East Fork Poplar Creek (EFPC) downstream of Y-12 exceed regulatory thresholds. Because of the complexities of Hg transport and fate in the aquatic environment, conventional remedial options for EFPC are highly uncertain. DOE is using a phased adaptive management approach to Hg remediation at Y-12 with a focus in the next few years on construction of the Mercury Treatment Facility (MTF) to treat the most contaminated Y-12 outfall entering EFPC (DOE 2017a; DOE 2017b). Once operational, the MTF will provide additional protection against inadvertent releases of Hg into the stream from decontamination and decommissioning of Y-12 Hg-use buildings. Although the MTF is anticipated to substantially decrease Hg water concentrations and flux in the upper part of EFPC, research and technology development are needed to develop appropriate and long-term remedial solutions for the downstream environment. Since late 2014, the Oak Ridge Office of Environmental Management and URS | CH2M Oak Ridge LLC/Restoration Services, Inc. have supported DOE’s Oak Ridge National Laboratory (ORNL) Environmental Sciences Division staff in conducting field and laboratory studies to develop Hg remedial technology solutions for lower EFPC (LEFPC). A technology development strategy for LEFPC was developed in 2014 that was consistent with the adaptive management paradigm and DOE’s technology readiness level (TRL) guidelines (Peterson et al. 2015). Initially, a thorough review of the literature was conducted and site-specific information was collected to develop a broad number of potential technologies that might be applied in LEFPC. An adaptive management approach was then used to focus on technologies that might have the most promise and potential remediation benefit. Field and laboratory studies conducted from 2014 to 2020 have identified the major drivers of Hg flux and bioaccumulation in EFPC and narrowed the list of high-merit technologies that might be of use in remediating the downstream environment.

54 ENVIRONMENTAL SCIENCES↗

Mercury Remediation Technology Development for Lower East Fork Poplar Creek—FY 2021 Update

Mercury remediation is a high priority for the US Department of Energy (DOE) Oak Ridge Office of Environmental Management. Mercury contamination in the environment can be found at all three DOE facilities in Oak Ridge, Tennessee, but the greatest environmental risk concern relative to Hg on the Oak Ridge Reservation is likely associated with historical Hg losses at and near the Y-12 National Security Complex (Y-12). Mercury in water and fish from East Fork Poplar Creek (EFPC) downstream of Y-12 exceeds regulatory thresholds. Because of the complexities of Hg transport and fate in the aquatic environment, conventional remedial options for EFPC are highly uncertain. DOE is using a phased adaptive management approach to Hg remediation at Y-12, with a focus in the next few years on construction of the Mercury Treatment Facility (MTF) to treat the most contaminated Y-12 outfall entering EFPC (DOE 2017a; DOE 2017b). Once operational, the MTF will provide additional protection against inadvertent releases of Hg into the stream from decontamination and decommissioning of Y-12 Hg-use buildings. Although the MTF is anticipated to substantially decrease Hg water concentrations and flux in upper EFPC (UEFPC), research and technology development are needed to develop appropriate and longer-term remedial solutions for the downstream environment. Since late 2014, the Oak Ridge Office of Environmental Management and URS | CH2M Oak Ridge LLC/Restoration Services Inc. have supported DOE’s Oak Ridge National Laboratory (ORNL) Environmental Sciences Division staff in conducting field and laboratory studies to develop Hg remedial technology solutions for lower EFPC (LEFPC). Whereas previous annual reporting updates for Hg remediation technology development for LEFPC have focused on presenting detailed results from the previous fiscal year, this FY 2021 update takes a comprehensive, higher-level approach to the research and technology development activities conducted since 2014. The report is organized to be consistent with the three tasks defined in the LEFPC strategic plan

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Escaping the fate of Sisyphus: assessing resistome hybridization baits for antimicrobial resistance gene capture

Finding, characterizing and monitoring reservoirs for antimicrobial resistance (AMR) is vital to protecting public health. Hybridization capture baits are an accurate, sensitive and cost-effective technique used to enrich and characterize DNA sequences of interest, including antimicrobial resistance genes (ARGs), in complex environmental samples. We demonstrate the continued utility of a set of 19 933 hybridization capture baits designed from the Comprehensive Antibiotic Resistance Database (CARD)v1.1.2 and Pathogenicity Island Database (PAIDB)v2.0, targeting 3565 unique nucleotide sequences that confer resistance. We demonstrate the efficiency of our bait set on a custom-made resistance mock community and complex environmental samples to increase the proportion of on-target reads as much as >200-fold. However, keeping pace with newly discovered ARGs poses a challenge when studying AMR, because novel ARGs are continually being identified and would not be included in bait sets designed prior to discovery. Here we provide imperative information on how our bait set performs against CARDv3.3.1, as well as a generalizable approach for deciding when and how to update hybridization capture bait sets. This research encapsulates the full life cycle of baits for hybridization capture of the resistome from design and validation (both in silico and in vitro) to utilization and forecasting updates and retirement.

59 BASIC BIOLOGICAL SCIENCES↗

Choosing the Best Modeling Platform for Radiological Risk Assessment Models - 20468

Radiological risk assessments, in the form of performance or safety assessments, are often required under regulations or guidance for remediation of contaminated land, decommissioning of contaminated buildings or structures, and radioactive waste disposal. These risk assessments are usually supported by fate and transport models that address decay and ingrowth of radionuclides, as well as their movement through engineered systems and the natural environment. These models are often projected thousands, or more, years into the future, largely because the radioactive species change through decay and ingrowth, and hence the magnitude of the radioactive effect changes with time. There are many computer codes that are available to address this type of modeling. They range from addressing specific pathways or processes such as infiltration of water, groundwater, surface water, air, biota, diffusion and advection of water and gases, to those that try to couple all processes together to evaluate the impact of fate and transport through the entire system to places in space and time to which access is assumed. These different types of codes are sometimes separated with the monikers process-level and systems-level codes, although it is often not clear that this separation does justice to the capabilities of the many codes that are available to evaluate fate and transport of radionuclides. The focus of this paper is the latter group of modeling codes. Several systems level modeling codes exist and are used. There are differences between these codes in terms of utility, flexibility, complexity and cost. The purpose of this paper is to compare a few of these codes in the context of work currently being performed by the International Atomic Energy Agency (IAEA) Modeling and Data for Radiological Impact Assessments (MODARIA) II Working Group 1 (WG1). The MODARIA II WG1's main focus is how stakeholder engaged decision analysis can, or should, be applied to radiological contamination problems so that better, longstanding, sustainable, solutions are reached. However, the WG1 also recognizes the potential impact of the modeling tools that are chosen to address radiological risk, which is often a primary objective of decision making for radiological problems. Other objectives might also be important, such as constraining costs, obtaining financing, minimizing impact on ecosystems, saving cultural resources, saving jobs, farmland, environmental justice, etc., in a full decision analysis for a given radiological contamination problem, but none of these other objectives have the same types of complex modeling needs as minimize radiological dose. Consequently, a further focus of WG1 is to evaluate the potential impacts on decision making of the choice of fate and transport, and risk assessment, modeling codes that are used to support decision making. The WG1 will produce a report at the end of 2020 that will focus on an approach to effective decision making and stakeholder engagement. The report will also consider the role that performance assessment modeling should play in the decision-making process, including the impact of the choice of modeling tools or computer codes on risk-informed decision making. Several sites around the World have been made available by Member States for these model comparisons, and several modeling tools have been considered. However, the focus of this paper is on two of the sites, one in Belgium and one in Ukraine, and on three of the tools: NORMALYSA (NORM And Legacy Site Assessment); GoldSim{sup C}, and AMBER{sup C}. The final report from this working group will also cover other modeling tools, including RESRAD, and PC-Cream{sup R}. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Titanium dioxide and table sugar enhance the leaching of silver out of nanosilver packaging

We manufactured laboratory-scale food packages containing 2.57 ± 0.18 × 10 –3 wt% silver nanoparticles (AgNPs) and used them to show that table sugar (sucrose) and microcrystalline titanium dioxide (μTiO 2 ) enhance Ag migration from these packages and into aqueous food simulants. Ag migration into purified water was detected but was below the limit of ICP-MS quantitation, giving a range of potential Ag migration between 0.059 and 0.082 ng cm –2 packaging surface area. Ag migration into 9 wt% aqueous sucrose solution was 0.547 ± 0.084 ng cm –2 and migration into 9 wt% sucrose solution containing 0.01 wt% μTiO 2 was 0.724 ± 0.032 ng cm –2 . Total Ag migration into a 0.01 wt% μTiO 2 aqueous dispersion without sucrose was between 0.122 and 0.162 ng cm –2 , with upper and lower limits defined by the detectability of Ag in the supernatant phase of the simulant. If the midpoint of this range is taken as a baseline, these results imply that, compared to purified water, Ag migration was increased by approximately 10.3 times when the water simulant contained μTiO 2 and sucrose at commercially-relevant concentrations. Notably, the Ag migrated into water containing both ingredients exceeded the total Ag migrated into either of the single-ingredient simulants, pointing to a potential cooperative relationship between sucrose and μTiO 2 that possibly derives from binding and redox interactions between these two ingredients. Sucrose and μTiO 2 also both reduced a portion of migrated Ag + back into AgNPs, and μTiO 2 particles efficiently captured (>25% by mass) migrated Ag on their surfaces. Similar effects on migration were observed with nanocrystalline TiO 2 . Furthermore, these experiments are the first to show that TiO 2 particles exert a strong influence on the quantity and form of Ag that could migrate from AgNP-enabled packaging, suggesting that food formulations and interactions between individual food components may be important to consider when evaluating the fate of nanoparticles in these consumer applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗