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Risk-based area of review estimation in overpressured reservoirs to support injection well storage facility permit requirements for CO 2 storage projects

This paper by the Energy & Environmental Research Center presents a workflow and modeling approach for delineating a risk-based area of review (AOR) to support a U.S. Environmental Protection Agency (EPA) Class VI permit for a carbon dioxide (CO 2 ) storage project. The approach combines semianalytical solutions for estimating formation fluid leakage through a hypothetical leaky wellbore with the results of numerical reservoir simulations to define the AOR. The modeling utilizes 1) semianalytical solutions from the peer-reviewed literature for formation fluid leakage through abandoned wellbores by Raven (1990) and Avci (1994), 2) a FORTRAN model compiled and described in Cihan et al. (2011, 2012) called ASLMA (Analytical Solution for Leakage in Multilayered Aquifers), and 3) a computational framework for estimating a risk-based AOR first proposed by Oldenburg et al. (2014, 2016). Therefore, the approach builds upon well-established research and underlying hydrogeological principles that have been upheld for nearly three decades. Moreover, the ASLMA model has been broadly applied to an array of storage projects. The work presented herein extends these earlier works using a custom wrapper written in the software environment, R (R Core Team, 2020), which was developed to perform multiple runs of the ASLMA model using given ranges for one or more input parameters. In addition, the current work simulates the pressure buildup within the storage reservoir in response to CO 2 injection using a compositional simulator to better accommodate the temporospatial evolution of pressure buildup within the storage reservoir that is more accurately modeled using a heterogeneous geologic model and a compositional simulator that accounts for the multiphase interactions. The workflow is demonstrated using a case study for a 180,000-metric-ton-per-year storage project located in the PCOR (Plains CO 2 Reduction) Partnership region. For the storage project evaluated here, under the scenario where the leaky wellbore is open to a saline aquifer (thief zone) between the overlying seal (cap rock) and the underground sources of drinking water (USDW), the risk-based AOR essentially collapses to the areal extent of the CO 2 plume in the storage reservoir because the pressure buildup in the storage reservoir beyond the CO 2 plume is insufficient to drive formation fluids up a hypothetical leaky wellbore into the USDW. However, even under the conservative assumption that the leaky wellbore is not open to a thief zone, beyond the areal extent of the CO 2 plume, the incremental leakage is less than 400 m 3 over 20 years, which represents ~0.0001% or less of the total volume of water contained within the USDW rock volume. As discussed in the text, the threshold criterion for defining the risk-based AOR is site-specific and should be informed by the results of the sensitivity analysis and available site characterization data. The approach outlined in this paper is designed to be protective of USDWs and, therefore, comply with the Safe Drinking Water Act requirements and provisions for the U.S. EPA Class VI Underground Injection Control (UIC) Program (Class VI Rule) and North Dakota Administrative Code Chapter 43-05-01.

54 ENVIRONMENTAL SCIENCES↗

Height Above Nearest Drainage (HAND) and Hydraulic Property Table for CONUS

The continental flood inundation mapping (CFIM) framework is a high-performance computing (HPC)-based computational framework for the Height Above Nearest Drainage (HAND)-based inundation mapping methodology. Using the 10m Digital Elevation Model (DEM) data produced by U.S. Geological Survey (USGS) 3DEP (the 3-D Elevation Program) and the NHDPlus hydrography dataset produced by USGS and the U.S. Environmental Protection Agency (EPA), a hydrological terrain raster called HAND is computed for HUC6 units in the conterminous U.S. (CONUS). The value of each raster cell in HAND is an approximation of the relative elevation between the cell and its nearest water stream. Derived from HAND, a hydraulic property table is established to calculate river geometry properties for each of the 2.7 million river reaches covered by NHDPlus (5.5 million kilometers in total length). This table is a lookup table for water depth given an input stream flow value. Such lookup is available between water depth 0m and 25m at 1-foot interval. The flood inundation map is then computed by using HAND and this lookup table based on the near real-time water forecast from the National Water Model (NWM) at the National Oceanic and Atmospheric Administration (NOAA). HAND and the Hydraulic Property Table version 0.2. is created to correspond to data updates in the USGS 1/3 arcsec DEM, the USGS National Hydrography Dataset, including its Water Boundary Dataset, and the NHDPlus medium resolution dataset. This dataset comprises 331 HUC6 units for CONUS (excluding the five great lakes units), each is a downloadable zip file. Version 0.1 was computed at the National Center for Supercomputing Applications (NCSA) at the University of Illinois at Urban-Champaign in 2016 and is currently hosted at the Texas Advanced Computing Center (TACC). Please cite this data DOI and the following publications and data DOIs when you use HAND and the hydraulic property table: Liu, Yan Y., David R. Maidment, David G. Tarboton, Xing Zheng, and Shaowen Wang. 'A CyberGIS integration and computation framework for high-resolution continental-scale flood inundation mapping.' JAWRA Journal of the American Water Resources Association 54, no. 4 (2018): 770-784. DOI: 10.1111/1752-1688.12660 Zheng, Xing, David G. Tarboton, David R. Maidment, Yan Y. Liu, and Paola Passalacqua. 'River channel geometry and rating curve estimation using height above the nearest drainage.' JAWRA Journal of the American Water Resources Association 54, no. 4 (2018): 785-806. DOI: 10.1111/1752-1688.12661 Liu, Y. (2018). Height Above Nearest Drainage (HAND) for CONUS - v0.1, HydroShare, https://doi.org/10.4211/hs.69f7d237675c4c73938481904358c789 LICENSE FOR USE -- MAPS AND DATA DISCLAIMER This resource is shared under the Creative Commons Attribution CC BY, http://creativecommons.org/licenses/by/4.0/ MAPS AND DATA DISCLAIMER The Oak Ridge National Laboratory (ORNL) shall not be held liable for improper or incorrect use of the data described or information contained on this map or associated series of maps. The data and related map graphics are not legal, land survey or engineering documents and are not intended to be used as such. ORNL gives no warranty, express or implied, as to the accuracy, reliability, utility or completeness of this information. The user of these maps and data assumes all responsibility and risk for the use of the maps and data. ORNL disclaims all warranties, representations or endorsements either express or implied, with regard to the information contained in this map product, including, but not limited to, all implied warranties of merchantability, fitness for a particular purpose or non-infringement. This preliminary map product is for research and review purposes only. It is not intended to be used for emergency management operational or life safety decisions at the local or regional governmental level or by the general public. Users requiring information regarding hazardous conditions or meteorological conditions for specific geographic areas should consult directly with their city or county emergency management office.

54 ENVIRONMENTAL SCIENCES↗

Height Above Nearest Drainage (HAND) and Hydraulic Property Table for CONUS - Version 0.21 (20200601)

The continental flood inundation mapping (CFIM) framework is a high-performance computing (HPC)-based computational framework for the Height Above Nearest Drainage (HAND)-based inundation mapping methodology. Using the 10m Digital Elevation Model (DEM) data produced by U.S. Geological Survey (USGS) 3DEP (the 3-D Elevation Program) and the NHDPlus hydrography dataset produced by USGS and the U.S. Environmental Protection Agency (EPA), a hydrological terrain raster called HAND is computed for HUC6 units in the conterminous U.S. (CONUS). The value of each raster cell in HAND is an approximation of the relative elevation between the cell and its nearest water stream. Derived from HAND, a hydraulic property table is established to calculate river geometry properties for each of the 2.7 million river reaches covered by NHDPlus (5.5 million kilometers in total length). This table is a lookup table for water depth given an input stream flow value. Such lookup is available between water depth 0m and 25m at 1-foot interval. The flood inundation map is then computed by using HAND and this lookup table based on the near real-time water forecast from the National Water Model (NWM) at the National Oceanic and Atmospheric Administration (NOAA). HAND and the Hydraulic Property Table version v0.21 is an upgrade to v0.2. Version 0.21 applies NHD HR etching to DEMs for all HUC6 units before running the HAND workflow. This new version also fixed the issue of void areas along HUC boundary. This dataset comprises 331 HUC6 units for CONUS (excluding the five great lakes units), each is a downloadable zip file. Version 0.1 was computed at the National Center for Supercomputing Applications (NCSA) at the University of Illinois at Urban-Champaign in 2016 and is currently hosted at the Texas Advanced Computing Center (TACC). Please cite this data DOI and the following publications and data DOIs when you use HAND and the hydraulic property table: Liu, Yan Y. Height Above Nearest Drainage (HAND) and Hydraulic Property Table for CONUS - Version 0.2. (20200301). Oak Ridge Leadership Computing Facility. (2020). DOI: 10.13139/ORNLNCCS/1608331 Liu, Yan Y., David R. Maidment, David G. Tarboton, Xing Zheng, and Shaowen Wang. 'A CyberGIS integration and computation framework for high-resolution continental-scale flood inundation mapping.' JAWRA Journal of the American Water Resources Association 54, no. 4 (2018): 770-784. DOI: 10.1111/1752-1688.12660 Zheng, Xing, David G. Tarboton, David R. Maidment, Yan Y. Liu, and Paola Passalacqua. 'River channel geometry and rating curve estimation using height above the nearest drainage.' JAWRA Journal of the American Water Resources Association 54, no. 4 (2018): 785-806. DOI: 10.1111/1752-1688.12661 Liu, Y. (2018). Height Above Nearest Drainage (HAND) for CONUS, HydroShare, https://doi.org/10.4211/hs.69f7d237675c4c73938481904358c789 LICENSE FOR USE -- MAPS AND DATA DISCLAIMER This resource is shared under the Creative Commons Attribution CC BY, http://creativecommons.org/licenses/by/4.0/ MAPS AND DATA DISCLAIMER The Oak Ridge National Laboratory (ORNL) shall not be held liable for improper or incorrect use of the data described or information contained on this map or associated series of maps. The data and related map graphics are not legal, land survey or engineering documents and are not intended to be used as such. ORNL gives no warranty, express or implied, as to the accuracy, reliability, utility or completeness of this information. The user of these maps and data assumes all responsibility and risk for the use of the maps and data. ORNL disclaims all warranties, representations or endorsements either express or implied, with regard to the information contained in this map product, including, but not limited to, all implied warranties of merchantability, fitness for a particular purpose or non-infringement. This preliminary map product is for research and review purposes only. It is not intended to be used for emergency management operational or life safety decisions at the local or regional governmental level or by the general public. Users requiring information regarding hazardous conditions or meteorological conditions for specific geographic areas should consult directly with their city or county emergency management office.

54 ENVIRONMENTAL SCIENCES↗

Managing Subsurface Pressure Buildup and Interference in Commercial-Scale CO 2 Storage Project with Proximal Injection Wells

Large-scale decarbonization using carbon capture and storage (CCS) is likely to involve many commercial-scale CO 2 storage projects located in close proximity to each other. This close proximity raises concerns over pressure interference among the storage projects. Pressure interference between injection and storage efforts can reduce the practicable CO 2 storage resource and force wells to inject CO 2 at a lower rate to avoid the fracture pressure thresholds per United States Environmental Protection Agency (EPA) Class VI well regulations to preserve injection and confining zone integrity and potentially mitigate against inducing seismic activity. These analyses employ numerical full-physics reservoir modeling to evaluate how pressure buildup fronts and CO 2 plumes evolve under commercial-scale injection volumes of CO 2 in which multiple storage sites located in close proximity occur in tandem. The simulation models mimic injection at pseudo basin-scale and assume homogeneous saline formation(s) as storage targets with a pair of upper and lower homogeneous seal layer/s. These analyses specifically investigate the efficacy of two basin-wide reservoir pressure management strategies in addressing the technical challenges associated with pressure buildup and CO 2 plume commingling. The strategies explored include: 1) enlarging the area of injection well spacing (WS) and 2) storing CO 2 in a stacked sequence (SSS) of saline formations compared to a single formation. The storage and confining zones properties assumed were held common across the scenarios, unless specified otherwise. Analyses results show that after injecting 4 million tons per year for 30 years using 4 separate wells (each injecting 1 million metric tons per year), the radius of CO 2 plume extends to a mere 3 km or less from injection wells. Meanwhile, the radius of pressure buildup ranges on the order of tens to a few hundreds of kilometers, depending on the magnitude of pressure buildup threshold that one would use to define the front. CO 2 plume commingling from different injection wells appears to occur 50 years post-injection, especially under scenarios with narrowly spaced (i.e., < 5 km apart) injection well locations. Findings from sensitivity cases on the well spacing suggest that storage formations modeled would require different well spacing to avoid fracture pressure thresholds. For instance, modeled storage formations with high fracture gradients (i.e., 0.8 psi/ft) would need less than 5–km well spacing, whereas those with lower fracture gradients (i.e., 0.7 psi/ft) would need approximately 20–km well spacing, based on assumed modeling parameters. Under stacked injection, the pressure challenges (described above) still exist but are more alleviated due to distributing the same injection volume across more available reservoir volume. These analyses demonstrate that stacked-sequence storage can effectively address the challenges, while still providing the same target CO 2 storage volumes and allowing a large number of storage projects to be deployed in the same basin by better utilizing the available storage resource across different reservoir depths. Among cases modeled, the resulting pressure buildup front is most suppressed when each storage project distributes injection volumes over several wells, each of which injects a portion of the total CO 2 across the stacked sequence. This strategy results in the smallest CO 2 aerial footprint amongst scenarios evaluated but also shows the largest reduction in the pressure buildup at the top of perforation at the injection wells (upwards of approximately 42 percent compared to the commercial-scale single-formation storage), the result of which is crucial to maintain caprock integrity. The findings presented by this research draw attention to the importance of greater coordination among storage operators and regulatory stakeholders to foster the upscaling and deployment of CCS. These analyses provide insights into required decision-making when considering multi-project deployment in a shared basin. Because these analyses evaluate a very specific geologic situation, they bear further investigations across other geologic situations.

42 ENGINEERING↗

Performance Criteria for Capture and/or Immobilization Technologies (Revision 1)

The capture and subsequent immobilization of regulated volatile radionuclides from the off-gas streams of a used nuclear fuel (UNF) reprocessing facility has been a topic of substantial research interest for the US Department of Energy and its international counterparts. Removal of specific radionuclides from the plant effluent streams before discharge to the environment is required to meet regulations set forth by the US Environmental Protection Agency. Upon removal, the radionuclides, as well as associated sorbents that cannot be regenerated in a cost-effective manner, are destined for conversion to a waste form. Research in separation and capture methodologies has included a wide range of technology types, and studies of waste forms are correspondingly diverse. In considering the future development and implementation of both sorbents and waste forms, it is necessary to identify benchmark measures of performance to objectively evaluate each sorbent system or waste form. Sets of performance criteria and associated metrics have been developed for sorbent and waste form evaluation. These criteria address physical, radiological, and chemical characteristics, technical practicality, technical maturity, cost, and, for sorbents, system performance. The criteria and metrics appear to be robust and should be applicable despite the eventual waste classification (as either high- or low-level waste). They are flexible enough to address both aqueous reprocessing and electrochemical reprocessing of UNF. These criteria sets can serve as tools to evaluate performance at multiple stages within the development process, and in this revision (Revision 1) they have been used to assess technologies relating to krypton/xenon separations and iodine capture from off-gas streams arising from UNF reprocessing. Assessment of krypton/xenon separations using engineered forms of two zeolite minerals (silver mordenite and hydrogen mordenite in a polyacrylonitrile-based binder [AgZ-PAN/HZ-PAN]) found that the zeolite-based separation is relatively advanced in its development, but several key issues require resolution. First, desorption processes for both krypton and xenon require refinement to provide an understanding of the product purity that can be achieved. Second, adsorption rate data is needed in order to calculate the bed depth required for effective separation. Finally, it is strongly recommended that a technical review of krypton/xenon separation by AgZ-PAN/HZ-PAN be performed to synergize available data and assess the cost savings and operational benefits that may be realized from implementation of this technology. Assessment of metal organic frameworks (MOFs) for their use in the separation of krypton/xenon found that the ideal separation would be performed using a single-column system with a MOF selective for krypton over xenon. A robust research effort should work to identify a krypton-selective MOF designed to operate at temperatures of approximately 0°C or higher, which could be preferred over cryogenic krypton/xenon capture for used fuel reprocessing off-gas streams. In the case of the CaSDB-MOF (the most well-understood xenon sorbent to date), two issues are judged of high importance. First, xenon breakthrough capacity for the CaSDB-MOF in prototypical conditions should be determined. Preliminary research indicates that breakthrough may be near immediate, presenting a substantial obstacle in separative system design. Second, development of desorption methodology should be performed to determine regeneration time, energy requirements, and the product stream composition. Silver-based sorbents (AgZ and AgAero) for use in iodine capture from the dissolver off-gas were evaluated against the established criteria. These sorbents are significantly better understood for this application as a result of research efforts over the past decade. The potential implementation of AgAero at a large scale is hindered by its physical degradation by components of the dissolver off-gas stream. Less is known about the adsorption of iodine by these sorbents from other off-gas streams in the plant. Initial experimental efforts have been closely coordinated in an effort to understand organic iodine (such as would be found in the vessel off-gas) adsorption by AgZ and AgAero. Future work should expand this experimental program, and analysis of other reprocessing facility off-gas streams such as the vitrification off-gas stream should be conducted to better understand other potential applications for iodine sorbents. A review of iodine waste form development shows that this area is diverse and that multiple promising waste forms have been identified for the immobilization of radioactive iodine. Efforts related to the direct conversion of iodine sorbents (including AgZ and AgAero) should be continued because of the advantages of direct conversion in a waste management strategy and other sorbents should continue to be advanced as merited.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

WIPP PA Sensitivity Studies in Support of CRA-2014 Completeness Determination and Compliance Decision - 18209

The Waste Isolation Pilot Plant (WIPP) has been developed by the U.S. Department of Energy (DOE) for the geologic (deep underground) disposal of transuranic (TRU) waste. Containment of TRU waste at the WIPP is regulated by the U.S. Environmental Protection Agency (EPA). The DOE demonstrates compliance with the containment requirements by means of performance assessment (PA) calculations. WIPP PA calculations estimate the probability and consequence of potential radionuclide releases from the repository to the accessible environment for a regulatory period of 10,000 years after facility closure. Since TRU waste was first received at the WIPP in 1999, compliance recertification applications (CRAs) have been required by the EPA on five-year cycle. The latest CRA (CRA-2014) was submitted by the DOE to the EPA in 2014. As part of the application, a formal set of PA calculations (CRA-2014 PA) was performed and results were documented in detail. The CRA-2014 PA incorporated several parameter updates based on new data, as well as the implementation of a different model for panel closures, barriers planned for the opening of each waste panel. The results presented as part of the CRA-2014 showed via the required complementary cumulative distribution function (CCDF) release curves that the estimated releases were within compliance limits. As part of their process for reviewing the completeness of the CRA-2014 [1], the EPA formally requested that the DOE perform sensitivity studies based on EPA-requested changes to model parameters. The DOE performed and documented the results of three sensitivity studies described below: CRA14-SEN2 [2], CRA14-SEN3 [3], and CRA14-SEN4 [4]. In each case, the new analysis results were compared to CRA- 2014 PA (CRA14) results to determine the impact of the EPA-requested changes. CRA14-SEN2: the application of EPA-requested modified parameters in the operations and experimental (non-waste) areas of the repository to simulate an accelerated (instantaneous) creep closure, the inclusion of capillary pressure effects on relative permeability, and an increase in initial/residual brine saturation and residual gas saturation. The modifications to the repository model resulted in increased pressures and decreased brine saturations in waste areas and increased pressures and brine saturations in the operations and experimental areas. However, the overall effects on total high-probability mean releases from the repository were entirely insignificant. It was concluded that the modeling assumptions associated with the operations and experimental areas of the repository have an insignificant effect on the prediction of total releases from the repository and/or adequacy of the current (CRA14) model to demonstrate compliance with the regulatory limits. CRA14-SEN3: the application of EPA-requested modified parameters in the panel closure areas and operations and experimental (non-waste) areas of the repository to simulate an accelerated (instantaneous) creep closure, the inclusion of capillary pressure effects on relative permeability, and an increase in initial/residual brine saturation and residual gas saturation. The modifications to the repository model predominantly result in increased pressures and decreased brine saturations in waste areas, increased pressures and brine saturations in the operations and experimental areas, and decreased brine and gas flows across all panel closures. The pressure increases in repository waste regions yielded slightly decreased brine saturations (on average) in those areas. However, the overall effects on total high-probability mean releases from the repository are entirely insignificant. It was concluded that the modeling assumptions made for this sensitivity study which were associated with the panel closures and north end areas of the repository have only a small effect on the prediction of total releases from the repository and/or adequacy of the current (CRA14) model to demonstrate compliance with the regulatory limits. CRA14-SEN4: the application of several changes to the current WIPP PA model (CRA14), including: parameter changes, use of an updated code, and a revised computational grid for the BRAGFLO code. The modifications to the repository model resulted in increased releases in all primary release mechanisms. The impacts of each EPA-requested change to CRA14 were analyzed with respect to each release mechanism in the CRA14-SEN4 study. Overall, total high-probability predicted mean releases from the repository were increased by about 15%. Total low-probability predicted mean releases were increased by about 107%. It was concluded that the EPA-requested changes to the CRA14 result in increases to the predicted total releases from the repository. However, releases calculated in the CRA14-SEN4 analysis remained below regulatory limits, demonstrating continued compliance of the WIPP. In January 2017, the EPA determined that CRA-2014 was complete and then began a technical evaluation of CRA-2014 to determine whether the WIPP continued to comply with the radiation protection standards for disposal. During their evaluation, the EPA utilized the sensitivity study results to inform their ultimate determination in July 2017 that the WIPP continues to comply with regulatory standards. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

2015 Advanced Site Investigation and Monitoring Report Riverton, Wyoming, Processing Site September 2016

The U.S. Department of Energy conducted initial groundwater characterization of the Riverton, Wyoming, Processing Site in the 1990s. The characterization culminated in a Site Observational Work Plan in 1998 that recommended a natural flushing compliance strategy. Results of verification monitoring indicated that natural flushing was generally progressing as expected until June 2010, when significant increases in contaminant concentrations were measured in several monitoring wells downgradient of the site after the area flooded. In response to the unexpected results following the flood, an enhanced characterization of the surficial aquifer was conducted in 2012, which included installation of 103 boreholes along nine transects with a Geoprobe, collection of 103 water samples and 65 soil samples, laboratory tests on the soil samples, and additional groundwater modeling. This advanced site investigation report summarizes additional investigation in 2015 through the use of backhoe trenching, sonic drilling, multilevel monitoring wells, direct-push drilling, and temporary well points to collect soil and groundwater samples. Additional surface water measurements were made included the installation of a stilling well and the measurement of stream elevation along the Wind River to approximate upgradient groundwater heads. Groundwater sampling included the addition of geochemical constituents and isotopes that have not been sampled in the past to better understand post-flood conditions and the possibility of additional or ongoing contaminant sources. This sampling was performed to (1) better define the contaminant plumes, (2) verify the occurrence of persistent secondary contaminant sources, (3) better understand the reason for the contaminant spikes after a 2010 flood, and (4) assess contaminant plume stagnation near the Little Wind River. This report provides data analyses and interpretations for the 2015 site investigation that addresses these issues and provides recommendations for future efforts. Observations from trenches and sonic drilling indicate the general lithology of the shallow, unconsolidated sediments consists of a silt zone at the surface that ranges from 2.5 to 4.8 feet below ground surface, underlain by sand and gravel, underlain by the top of the weathered bedrock (Wind River Formation). Soil data from trenches and sonic drilling indicate (1) elevated concentrations of several constituents in the silt zone, likely due to the formation of evaporites, (2) uranium is the only measured element that appears to be concentrated in the silt over the groundwater contaminant plume, (3) in the former tailings impoundment area, there may be a thin unsaturated zone with elevated uranium in the native material just below the fill, (4) in the former tailings impoundment area, slightly higher uranium concentrations occur in the underlying saturated sand and gravel, and (5) several bedrock samples have a unique geochemical signature, generally related to a higher silt content. Assessment of groundwater flow included measuring river elevations along the Wind River and installing the temporary well points adjacent to the Little Wind River that provided additional data points to refine contours for water table elevations. These data confirm past interpretations of groundwater flow to the southeast across the site toward the Little Wind River. Hydraulic head elevations between paired surficial and semiconfined aquifer wells indicate variable vertical gradients across the site with the potential for upward and downward flow. Additional direct-push drilling and groundwater sampling confirmed the contaminant plume configuration, but it also revealed a low-sulfate-concentration zone at the edge of the former tailings impoundment. Temporary well points provided better definition of plume concentrations at the bank of the Little Wind River, and data from these wells indicate plume discharge to the river. Additional sampling in an area southwest of the plume that had elevated uranium groundwater concentrations in the past did not have any uranium concentrations above the U.S. Environmental Protection Agency maximum concentration limit for uranium. Results from multilevel monitoring wells indicate some geochemical differences with depth, but overall concentrations are similar to those in nearby conventional monitoring wells in the long-term monitoring program. Geochemistry data from these multilevel monitoring wells confirm the general increase in contaminant concentrations toward the river and toward the plume centerline for chloride, sulfate, and uranium but highlight geochemical controls on calcium. Iron data indicate slightly reducing conditions, especially near water table and bedrock surfaces, with more oxidizing conditions in the middle of the sand and gravel. Uranium activity ratios (234U/238U) confirm the uranium plume in the surficial aquifer as being mill related, and the area to the southwest outside the plume as natural, non-mill related. In the semiconfined aquifer, evidence of aquifer connection and impacts from the mill is inconclusive. Values of δD and δ 18 O suggest water is derived from different sources and tritium data confirm that the semiconfined aquifer water is generally older than the surficial aquifer water. However, these data do indicate some groundwater communication from the surficial aquifer into the semiconfined aquifer, which resulted in δD and δ 18 O and tritium values in the semiconfined aquifer that are more similar to those in the surficial aquifer. Values of δ 34 S sulfate in the semiconfined aquifer combined with sulfate concentrations indicate the potential for some mill- related sulfate in the semiconfined aquifer, albeit limited to an area near and beneath the former tailings impoundment. Uranium and molybdenum concentrations in the semiconfined aquifer are below groundwater standards in all wells. However, the elevated molybdenum concentrations at one semiconfined aquifer well underneath the former tailings impoundment suggests a mill- derived source for the uranium and molybdenum in that well. It is possible that aquifer cross- communication occurred when the tailings impoundment was active and created a higher head. Current cross-communication appears unlikely given the large differences in tritium values and an upward hydraulic head at this location. Nine domestic wells are located within the institutional control boundary (eight in the confined aquifer and one in the semiconfined aquifer). Uranium and molybdenum concentrations in all samples collected from these wells were one or two orders of magnitude below the groundwater standards. Surface water flow in the Little Wind River in September 2015 was low compared to historical averages for that time of year. As a result, the uranium concentration measured in the Little Wind River was at a historical maximum at the sampling location upstream of the site. However, the impact of uranium discharge from the groundwater plume into the Little Wind River was not measureable. Elevated sulfate concentrations were observed in an outfall ditch related to an active sulfuric acid plant. Uranium concentrations in the oxbow lake remain at concentrations above the groundwater standard. Plume contaminant concentrations had returned to levels found prior to the 2010 flood by the end of 2015. However, these concentrations still exceed model predictions for natural flushing, and the current data indicate that natural flushing to achieve remediation goals within the 100-year time period is not likely, especially with the high potential for additional floods in the update to the conceptual site model (CSM), soil data indicate additional contaminant sources, specifically uranium, in evaporites within the silt layer over the uranium plume and in naturally reduced zones (NRZs). Additional zones of slightly elevated uranium concentration are in the native sediments just above the water table but below the fill layer in the former tailings impoundment area. This area also has slightly elevated uranium in the sand and gravel below the water table. Mass balance calculations indicate that small amounts of dissolution in any of these zones with increased uranium in the solid phase can produce groundwater uranium concentrations above the groundwater standard and could account for the post-flood uranium spike. The additional uranium near the former tailings impoundment provides a mechanism for a continuing source for the uranium plume that was not considered in earlier natural flushing models. In addition, uranium released from the silt layer or the NRZs seasonally and during flooding may add uranium to the groundwater plume near the Little Wind River. These mechanisms provide a possible explanation for plume persistence, along with spikes in concentrations during floods, that creates the current plume configuration. Additional updates to the CSM include (1) chloride flushes more rapidly than uranium beneath the former mill site, (2) chloride in the silt layer provides a scenario in which chloride cannot be used as a conservative tracer (especially in areas prone to flooding), (3) uranium concentrations with depth can be variable (especially below NRZs), and (4) calcite and gypsum solubility limits appear to provide important geochemical controls on groundwater geochemistry. The conclusion of this study provides several recommendations for additional work to refine the CSM and continue assessment of the natural flushing compliance strategy. Recommendations for additional work include targeted soil and groundwater sampling to assess geochemical conditions, distribution of contaminants, and groundwater/surface water interaction; additional column tests to provide data for geochemical modeling; and development of an updated groundwater flow model, which will be used in conjunction with a geochemical model to assess the viability of the natural flushing compliance strategy.

2015 Monitoring Riverton, WY↗

Source Partitioning of Methane Emissions and its Seasonality in the U.S. Midwest

Abstract The methane (CH 4 ) budget and its source partitioning are poorly constrained in the Midwestern United States. We used tall tower (185 m) aerodynamic flux measurements and atmospheric scale factor Bayesian inversions to constrain the monthly budget and to partition the total budget into natural (e.g., wetlands) and anthropogenic (e.g., livestock, waste, and natural gas) sources for the period June 2016 to September 2017. Aerodynamic flux observations indicated that the landscape was a CH 4 source with a mean annual CH 4 flux of +13.7 ± 0.34 nmol m −2 s −1 and was rarely a net sink. The scale factor Bayesian inversion analyses revealed a mean annual source of +12.3 ± 2.1 nmol m −2 s −1 . Flux partitioning revealed that the anthropogenic source (7.8 ± 1.6 Tg CH 4 yr −1 ) was 1.5 times greater than the bottom‐up gridded United States Environmental Protection Agency inventory, in which livestock and oil/gas sources were underestimated by 1.8‐fold and 1.3‐fold, respectively. Wetland emissions (4.0 ± 1.2 Tg CH 4 yr −1 ) were the second largest source, accounting for 34% of the total budget. The temporal variability of total CH 4 emissions was dominated by wetlands with peak emissions occurring in August. In contrast, emissions from oil/gas and other anthropogenic sources showed relatively weak seasonality.

Chen, Zichong↗

Uranium In Situ Electrolytic Deposition with a Reusable Functional Graphene-Foam Electrode

Nuclear fission produces 400 GWe which represents 11% of the global electricity output. Uranium is the essential element as both fission fuel and radioactive waste. Therefore, the recovery of uranium is of great importance. In this study, an in situ electrolytic deposition method to extract uranium from aqueous solution is reported. A functionalized reduced graphene oxide foam (3D-FrGOF) is used as the working electrode, which acts as both a hydrogen evolution reaction catalyst and a uranium deposition substrate. The specific electrolytic deposition capacity for U(VI) ions with the 3D-FrGOF is 4560 mg g –1 without reaching saturation, and the Coulombic efficiency can reach 54%. Moreover, reduction of the uranium concentration in spiked seawater from 3 ppm to 19.9 ppb is achieved, which is lower than the US Environmental Protection Agency uranium limits for drinking water (30 ppb). Furthermore, the collection electrode can be efficiently regenerated and recycled at least nine times without much efficiency fading, by ejecting into 2000 ppm concentrated uranium solution in a second bath with reverse voltage bias. All these findings open new opportunities in using free-standing 3D-FrGOF electrode as an advanced separation technique for water treatment.

36 MATERIALS SCIENCE↗

Challenges in Tracking Waste Reduction Performance Improvement in Manufacturing Plants

The recently released Circularity Gap Report 2023 by the Circle Economy Foundation states that the circularity score for the global economy is declining. The US Environmental Protection Agency (EPA) tracked municipal solid waste from 1960 to 2018 and found that 50% of the waste was destined for landfills. EPA estimates that US industry is responsible for 2.7 Gt of solid nonhazardous waste annually in the US mostly linear economy model. The circular economy framework aims to decouple economic value generation from the extraction of virgin materials from nature. The linear model of material extraction and disposal at the end of life is highly unsustainable. Manufacturing companies are adopting ambitious waste reduction targets to achieve sustainability. Through the Better Plants program, US DOE has established the Waste Reduction Network, which offers technical assistance to partners to achieve their ambitious waste reduction goals. Basic requirements of establishing a target include identifying a baseline, quantifying waste performance, and measuring progress over time. One problem faced by industry is unstandardized metrics for quantifying waste performance that may not be well suited to demonstrate progress. This paper studies traditional methods used to measure waste performance and highlights advantages, disadvantages, and limitations of each method. It also examines the suitability of applying the methods in different manufacturing circumstances. Finally, the paper presents a case study of a large manufacturer that faced inconsistencies in its tracked measurement metric. A solution was proposed and implemented to alter the methodology to enable more accurate waste performance tracking against a baseline.

circular economy↗

Inferring pesticide toxicity to honey bees from a field‐based feeding study using a colony model and Bayesian inference

Abstract Honey bees are crucial pollinators for agricultural crops but are threatened by a multitude of stressors including exposure to pesticides. Linking our understanding of how pesticides affect individual bees to colony‐level responses is challenging because colonies show emergent properties based on complex internal processes and interactions among individual bees. Agent‐based models that simulate honey bee colony dynamics may be a tool for scaling between individual and colony effects of a pesticide. The U.S. Environmental Protection Agency (USEPA) and U.S. Department of Agriculture (USDA) are developing the VarroaPop + Pesticide model, which simulates the dynamics of honey bee colonies and how they respond to multiple stressors, including weather, Varroa mites, and pesticides. To evaluate this model, we used Approximate Bayesian Computation to fit field data from an empirical study where honey bee colonies were fed the insecticide clothianidin. This allowed us to reproduce colony feeding study data by simulating colony demography and mortality from ingestion of contaminated food. We found that VarroaPop + Pesticide was able to fit general trends in colony population size and structure and reproduce colony declines from increasing clothianidin exposure. The model underestimated adverse effects at low exposure (36 µg/kg), however, and overestimated recovery at the highest exposure level (140 µg/kg), for the adult and pupa endpoints, suggesting that mechanisms besides oral toxicity‐induced mortality may have played a role in colony declines. The VarroaPop + Pesticide model estimates an adult oral LD 50 of 18.9 ng/bee (95% CI 10.1–32.6) based on the simulated feeding study data, which falls just above the 95% confidence intervals of values observed in laboratory toxicology studies on individual bees. Overall, our results demonstrate a novel method for analyzing colony‐level data on pesticide effects on bees and making inferences on pesticide toxicity to individual bees.

59 BASIC BIOLOGICAL SCIENCES↗

The use of tetragnathid spiders as bioindicators of metal exposure at a coal ASH spill site

Abstract On 22 December 2008, a dike containing coal fly ash from the Tennessee Valley Authority Kingston Fossil Fuel Plant (TN, USA) failed, resulting in the largest coal ash spill in US history. The present study was designed to determine sediment metal concentrations at multiple site locations and to determine whether site-specific bioaccumulation of metals existed in tetragnathid spiders. Selenium and nickel were the only 2 metals to exceed the US Environmental Protection Agency sediment screening levels. Selenium concentrations in spiders were significantly higher at ash-affected sites than in those from reference sites. The ratio of methylmercury to total mercury in spiders was found to be similar to that in other organisms (65–75%), which highlights the potential use of tetragnathid spiders as an indicator species for tracing contaminant transfer between the aquatic and terrestrial ecosystems. Environ Toxicol Chem 2013;32:2065–2068. © 2013 SETAC

Otter, Ryan R.↗

Integrating Mercury Concentrations in American Alligators ( Alligator mississippiensis ) with Hunter Consumption Surveys to Estimate Exposure Risk

Mercury is a naturally occurring element but is also considered a widespread contaminant due to global anthropogenic activity. Even in moderate amounts, mercury (Hg) is an established neurotoxin and is associated with a range of adverse outcomes both in humans and wildlife. Humans in the United States are most commonly exposed to Hg through contaminated food or drinking water, and the consumption of game species, particularly those occupying higher trophic levels, has the potential to expose hunters to high concentrations of Hg. In the present study, we determined Hg concentrations in tail muscle and blood from American alligators (Alligator mississippiensis) inhabiting a region (Savannah River Site, SC, USA) with known Hg contamination. We then integrated these data with alligator harvest records and previously published surveys of alligator meat consumption patterns to estimate potential exposure risk. We found that the average Hg concentrations in tail muscle (1.34 mg/kg, wet wt) from sampled alligators exceeded the recommended threshold for Hg exposure based on the World Health Organization's guidelines (0.5mg/kg, wet wt). In addition, based on regional consumption patterns reported for both adults and children, we estimated Hg exposures (x¯ Adult = 0.419 μg/kg/day, x¯ Child = 2.24 μg/kg/day) occurring well above the US Environmental Protection Agency methylmercury reference dose of 0.1 μg/kg/day. Although the two reservoirs sampled in the present study are not currently open to alligator hunting, they are connected to waters that are publicly accessible, and the extent of alligator mobility across these sites is not known. Together, the findings reported in the present study further demonstrate the need for active monitoring of Hg concentrations in game species, which can convey substantial exposure risks to the public.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A phased workflow to define permit‐ready locations for large volume CO 2 injection and storage

Abstract To‐date, only two UIC Class VI permits have been issued by the US Environmental Protection Agency. We illustrate a four‐phase workflow to first identify regional storage resources and then down‐select sites to yield permit‐ready locations that can accept and store large volumes of CO 2 . Specific permit requirements should guide objectives and define deliverables of respective workflow phases. In the first phase we used available regional data and screened structure and injection zones to locate resources that match CO 2 volumes planned to be captured. Available data were also used to assess presence and depth of usable groundwater, the key resource being protected via permitting. We then used advanced, closed‐form, analytical solutions (EASiTool) to estimate CO 2 injectivity into each hydrologically connected injection compartment. In the second phase we acquired and conditioned additional wireline logs and leased available seismic datasets. We interpreted the depositional systems from wireline well‐log character and mapped sandbody geometry to interpolate injection and confining‐zone distribution. Using available data, we mapped faults and locations of freshwater and overpressure (or other capacity‐limiting geologic parameters) in more detail. In the third phase, we used the augmented geologic data to develop a static model for the selected area, extracted the areas of highest interest, and generated and ran dynamic (flow) models. In a fourth phase, we reduced major uncertainties identified in earlier phases. Our case study indicates that to complete preparation of a permit application requires (1) improved lithologic characterization information (thicknesses and horizontal and vertical connectivity) and (2) better definition of poorly defined local faults. © 2023 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.

58 GEOSCIENCES↗

Total Recoverable Aluminum: Not Totally Relevant for Water Quality Standards

Abstract A large water quality data set, representing more than 100 surface-water locations sampled from 2007 to 2017 in the Los Alamos area of New Mexico, USA's Pajarito Plateau, was assembled to evaluate Al concentrations in unfiltered and filtered samples. Aluminum concentrations often exceeded United States Environmental Protection Agency (USEPA) and New Mexico ambient water quality criteria (AWQC), regardless of filter size and sample location. However, AWQC are based on laboratory toxicity studies using soluble Al salts and do not reflect natural conditions in Pajarito Plateau surface waters. The plateau is predominately covered by glassy and recrystallized volcanic ashes (e.g., Bandelier Tuff) containing colloidal to sand-sized aluminosilicates. Samples from natural background drainages and areas downstream of developed regions exhibited similar Al concentrations, suggesting that AWQC exceedances are caused by naturally elevated Al concentrations. Solubility calculations indicated that most samples were oversaturated with respect to amorphous Al(OH)3(s). Therefore, AWQC exceedances are likely artifacts of the “total recoverable” sample preparation, which includes acidification and partial digestion, thereby liberating nonbioavailable Al from aluminosilicates. Accordingly, Al concentrations were strongly associated with suspended sediment concentrations (SSCs), implying that aluminosilicates in suspended sediment contributed to AWQC exceedances and Al oversaturation. Solid-phase particle characterization, using X-ray diffraction (XRD) and scanning electron microscopy with electron dispersive spectroscopy (SEM/EDS) did not identify potentially bioavailable amorphous Al(OH)3(s) in any sample tested. Thus, current sample collection and analysis protocols should not be used to evaluate attainment of Al AWQC on the Pajarito Plateau or locations where aluminosilicates are substantial contributors to total recoverable Al. A sample preparation method (e.g., pH 4 extraction) capable of differentiating nonbioavailable and bioavailable forms of Al is recommended. Otherwise, current New Mexico and USEPA sample preparation approaches will continue to generate artifactual AWQC exceedances in surface waters that contain aluminosilicates. Integr Environ Assess Manag 2019;00:1–14. © 2019 SETAC

Ryan, Adam C.↗

Improving the Assessment and Valuation of Climate Change Impacts for Policy and Regulatory Analysis

The social cost of carbon (SCC) is a monetized metric for evaluating the benefits associated with marginal reductions in carbon dioxide (CO2) emissions. It represents the expected welfare loss from the future damages caused by the release of one tonne of CO2 in a given year, expressed in consumption equivalent terms. It is intended to be a comprehensive measure, taking into account changes in agricultural productivity, human health risks, loss of ecosystem services and biodiversity, and the frequency and severity of flooding and storms, among other possible impacts. Estimating the SCC requires long-term modeling of global economic activity, the climate system, and the linkages between the two through anthropogenic greenhouse gas (GHG) emissions and the effects of changing climatic conditions on economic activity and human well-being. The United States government currently uses the SCC in regulatory benefit-cost analyses to assess the welfare effects of changes in CO2 emissions. Consistent application of the SCC to federal rulemaking analyses began in 2009-2010 with the development of a set of global SCC estimates that employed three prominent integrated assessment models (IAMs) -- DICE, FUND, and PAGE. The U.S. government report identified a number of limitations associated with SCC estimates in general and its own assumptions in particular: an incomplete treatment of damages, including potential “catastrophic” impacts; uncertainty regarding the extrapolation of damage functions to high temperatures; incomplete treatment of adaptation and technological change; and the evaluation of uncertain outcomes in a risk-neutral fashion. External experts have identified other potential issues, including how best to model long-term socio-economic and emissions pathways, oversimplified physical climate and carbon cycle modeling within the IAMs, and an inconsistency between non-constant economic growth scenarios and constant discount rates. The U.S. government has committed to updating the estimates regularly as modeling capabilities and scientific and economic knowledge improves. To help foster further improvements in estimating the SCC, the U.S. Environmental Protection Agency and the U.S. Department of Energy hosted a pair of workshops on “Improving the Assessment and Valuation of Climate Change Impacts for Policy and Regulatory Analysis.” The first focused on conceptual and methodological issues related to integrated assessment modeling and the second brought together natural and social scientists to explore methods for improving damage assessment for multiple sectors. These two workshops provide the basis for the 13 papers in this special issue.

Climate Change↗

Effect of CO on alcohol oxidation over commercial oxidation catalysts for control of emissions from lean-burn engines

For commercialization, alcohol-based net-zero carbon fuels in diesel-driven internal combustion engines must meet emissions standards set by the U.S. Environmental Protection Agency. Here, a series of aged commercial oxidation catalysts, Pt diesel oxidation catalyst (DOC), Pd+Pt DOC, and Pt oxidation catalyst (Pt OC), were studied using an automated flow reactor and in situ DRIFTS techniques to investigate the impact of CO on alcohol oxidation. Surface formate and acetate intermediates were formed due to partial oxidation of methanol and ethanol, respectively. Sequential introduction of alcohol and CO experiments using in situ DRIFTS on all three catalysts showed that CO inhibited low temperature methanol oxidation. Mutual inhibition effects between CO and ethanol were observed during co-oxidation. Acetate species shifted CO oxidation to higher temperatures on Pt DOC and Pt OC, whereas CO pre-exposure inhibited acetate formation. CO oxidation occurred at lower temperatures during ethanol and CO co-oxidation on Pd+Pt DOC.

33 ADVANCED PROPULSION SYSTEMS↗

Using facility-level emissions data to estimate the technical potential of alternative thermal sources to meet industrial heat demand

Industry is frequently highlighted as the world's largest energy-using end-use sector. More specifically, the demand for heat drives much of the demand for energy and fossil fuels in the industrial sector. We conduct a top-down analysis to characterize historical energy and fossil fuel use in 14 top-GHG-emitting industries in the United States, their heat demand requirements, and the potential to substitute heat from geothermal, solar thermal (including concentrating technologies), and small modular nuclear reactors to meet these needs while reducing fossil-fuel use and greenhouse gas (GHG) emissions. We base this analysis on publicly-available facility-level GHG emissions and fuel-combustion data, in addition to assumed requirements for process temperature, to demonstrate the potential value to industry energy analysts of the U.S. Environmental Protection Agency's Greenhouse Gas Reporting Program data. We estimate on a county level that the adoption of these alternative heat sources could have reduced 2015 fossil-fuel use by approximately 31% and combustion GHG emissions by approximately 24%. The most extensive substitution opportunities are in the ethyl alcohol manufacturing and wet corn-milling industries; petroleum refining represents the largest absolute emissions mitigation potential. This initial top-down analysis of substitution potential does not consider more detailed technical factors, including resource availability that will influence the actual deployment of alternative energy technologies. The analysis also does not consider the economic or market factors, including the expected cost to build and operate these generators. We do assume process byproducts that are extensively used for combustion fuels would not be good candidates for substitution for alternative energy generators. Based on these caveats, our analysis could be considered a top-range estimate for this mix of heat generators and industry heat demands. Any subsequent analysis of these alternate energy sources should increase the level of technical, economic, and policy detail.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗