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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↗

A Materials Perspective on Direct Recycling of Lithium-Ion Batteries: Principles, Challenges and Opportunities

As the dominant means of energy storage technology today, the widespread deployment of lithium-ion batteries (LIBs) would inevitably generate countless spent batteries at their end of life. From the perspectives of environmental protection and resource sustainability, recycling is a necessary strategy to manage end-of-life LIBs. Compared with traditional hydrometallurgical and pyrometallurgical recycling methods, the emerging direct recycling technology, rejuvenating spent electrode materials via a non-destructive way, has attracted rising attention due to its energy efficient processes along with increased economic return and reduced CO 2 footprint. This review investigates the state-of-the-art direct recycling technologies based on effective relithiation through solid-state, aqueous, eutectic solution and ionic liquid mediums and thoroughly discusses the underlying regeneration mechanism of each method regarding different battery chemistries. It is concluded that direct regeneration can be a more energy-efficient, cost-effective, and sustainable way to recycle spent LIBs compared with traditional approaches. Additionally, it is also identified that the direct recycling technology is still in its infancy with several fundamental and technological hurdles such as efficient separation, binder removal and electrolyte recovery. Finally, in addressing these remaining challenges, this review proposes an outlook on potential technical avenues to accelerate the development of direct recycling toward industrial applications.

25 ENERGY STORAGE↗

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↗

Effects of Dissolved Organic Carbon on Copper Toxicity to Embryos of Mytilus galloprovincialis as Measured by Diffusive Gradient in Thin Films

Diffusive Gradient in Thin-film (DGT), a passive sampling method, has the potential to better quantify the bioavailable fraction of Cu in seawater, when determining toxicological endpoints, versus grab samples evaluated for total or dissolved Cu. In the present study, laboratory exposure of DGTs and Mediterranean mussel (M. galloprovincialis) embryos at varying concentrations of dissolved organic carbon (DOC) and Cu were performed to resolve the degree to which mimicry of toxicity-buffering occurs in passive sampler quantification. Studies were performed in water collected from Sequim Bay, Washington, USA, spiked with Suwannee River Natural Organic Matter (SRNOM) and Cu(II)SO4. The results provide preliminary EC50s ranging from 4.8 to 11.5 µg/L as CDGT Cu over the span of 0.892 to 8.28 mg/L DOC. M. galloprovincialis was selected as the relevant organism for this correlation based on current consensus for deriving water criteria values, which are based solely from Mytilus spp. toxicological study final acute values, maintaining the intent of protecting environmental and commercial interests to the fauna regarded as most sensitive to Cu input in the marine environment. The present study provides an initial DGT response by which coastal DOC pools with varying functional binding group mixtures can be compared to discern the applicability of broad use for quantifying biological effects at time scales integrated to account for pulsed-input to marine waters.

copper, Bioavailability, Diffusive Gradient in Thi↗

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.↗

Performance of Wrought Superalloys in Extreme Environments

As power generation systems move towards higher efficiency operation above 700 °C, wrought superalloys are the leading structural alloy candidates, including precipitation strengthened (PS) alloys 740 and 282 for the highest temperatures. To evaluate the performance of these alloys for these applications, a range of 500–5000 h evaluations have been conducted in environments including steam, supercritical CO2 (sCO2) and simulated combustion exhaust with H2O and/or SO2 at 700–800 °C and compared to baseline exposures in laboratory air and 1 bar CO2. These alloys primarily rely on the formation of an external Cr-rich oxide layer or scale for environmental protection and the reaction rates in all of these conditions are similar and relatively low. However, compared to a conventional solid solution strengthened alloy, like 625, the mass gains are higher for PS alloys due to the internal oxidation of the γ' forming additions, Al and Ti. Post-exposure characterization has quantified the reaction products and the depth of internal oxidation is not a concern and does not appear to increase above the baseline behavior in laboratory air. Likewise, there is no indication of internal carburization in the sCO2 environment at 750 °C/300 bar. The addition of 0.1% SO2 in CO2-10% H2O at 800 °C actually suppressed the internal oxidation at 1 bar but SO2 may be a concern when the total pressure is higher.

Pint, Bruce A.↗

Experimental Validation of the Horikx Theory to be Used in the Rubber Devulcanization Analysis

The waste rubber and end-of-life tires management has become a serious environmental problem. It is well known that the best way to carry out the disposal of these wastes is through recycling by devulcanization. Therefore, in the last decades, many methods have been developed to perform this treatment. Nevertheless, the degree and quality of the achieved devulcanization is still difficult to evaluate. The Horikx theory is an approach often used for this purpose. Hence, in this work, the validity of this theory was experimentally checked. The theoretical curve that represents crosslink scission was experimentally built for sulfur-cured natural rubber, sulfur-cured natural rubber reinforced with carbon black, sulfur-cured ethylene propylene diene monomer rubber and peroxide-cured ethylene propylene diene monomer rubber. Several samples with vulcanization (or devulcanization) degree ranging from 0 to 100% were processed, and the corresponding soluble fractions and crosslink densities were measured by the swelling test. The experimental results were in good agreement with the theoretical predictions, independently of the studied material, fact that confirms the validity of the Horikx approach. This finding will contribute to improve the waste rubber devulcanization, and therefore to progress in the environmental protection.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Finite Element Modeling of the Phase Change in Thermally-Grown SiO 2 in SiC Systems for Gas Turbines

The operating lifetimes of SiC-based components in combustion environments are directly linked to the adhesion of the protective environmental barrier coating (EBC) layer. One of the major known failure modes for EBCs is the formation of a thick SiO 2 thermally grown oxide (TGO), which decreases coating adhesion and encourages eventual coating spallation. The effect of the TGO thickness under Yb 2 Si 2 O 7 EBCs on silicon carbide was investigated using finite element models (FEMs) with various interfacial architectures and SiO 2 TGO thicknesses. Further, the FEMs incorporated a user-defined material to simulate the volume contraction of the TGO during the silica phase transformation from β-cristobalite to α-cristobalite upon cooling from the stress-free state at 1350°C to room temperature. Systems with and without a silicon bond coating intermediary layer were assessed. It was shown that the TGO phase transformation stress (1.6–1.7 GPa) dominated the increase in stress in the TGO and EBC layers. Furthermore, it was found that stress increase in the TGO was independent of TGO thickness and interface geometry. These results indicate that stabilization of the TGO to mitigate the phase transformation could dramatically improve the performance of SiC-base components with EBCs.

36 MATERIALS SCIENCE↗

A statistical and simulation-informed model for estimating permeability from pore size distribution in saturated geomaterials

Accurate permeability estimation is essential across subsurface engineering applications but remains challenging due to the complex pore structures of natural geomaterials. Traditional empirical methods and simplified theoretical models often inadequately capture the role of pore size distribution and connectivity. Here, this study develops a statistical and simulation-informed permeability model that collapses pore-scale complexity into a compact scaling of the form k = αϕμ d 2 , where ϕ is porosity, μ d is mean pore size, and α is a weakly varying coefficient. By combining pore network simulations with statistical analysis of unimodal and bimodal pore size distributions, we identify three key findings: (i) permeability is much more sensitive to mean pore size than to porosity; (ii) across extensive datasets, the ratio σ d /μ d (standard deviation to mean) clusters around a characteristic value ∼0.4, allowing the effects of the full pore size distribution to be represented by μ d and a narrowly varying α ≈ 0.05; and (iii) for bimodal systems, there exists a critical fraction of small pores ∼0.78 above which flow becomes small-pore dominated, enabling the definition of an effective flow-controlling pore population and facilitating simplified permeability estimation for such systems. The resulting model, which requires only porosity and a representative mean pore size as inputs, is validated against comprehensive experimental datasets (>1700 samples) spanning diverse soils and rocks and achieves good predictive accuracy. Overall, this work provides a physically grounded yet practically simple permeability estimator suitable for subsurface engineering, environmental protection, and resource management applications.

Permeability↗

ZIF-67 incorporated with carbon derived from pomelo peels: A highly efficient bifunctional catalyst for oxygen reduction/evolution reactions

Developing carbon catalyst materials using natural, abundant and renewable resources as precursors plays an increasingly important role in clean energy generation and environmental protection. In this work, N-doped pomelo-peel-derived carbon (NPC) materials were prepared using a widely available food waste-pomelo peels and melamine. The synthetic NPC exhibits well-defined porosities and a highly doped-N content (e.g. 6.38 at% for NPC-2), therefore affords excellent oxygen reduction reaction (ORR) catalytic activities in alkaline electrolytes. NPC was further integrated with ZIF-67 to form ZIF-67@NPC hybrids through solvothermal reactions. The hybrid catalysts show substantially enhanced ORR catalytic activities comparable to that of commercial 20 wa Pt/C. Furthermore, the catalysts also exhibit excellent oxygen evolution reaction (OER) catalytic activities. Among all prepared ZIF-67@NPC hybrids, the optimal composition with ZIF-67 to NPC ratio of 2:1 exhibits the best ORR and OER bifunctional catalytic performance and the smallest Delta E (E-OER@10 mA cm(-2)-E-ORR@-1 mA cm(-2)) value of 0.79 V. The catalyst also demonstrated desirable 4-electron transfer pathways and superior catalytic stabilities. The Co-N-4 in ZIF-67, electrochemical active surface area, and the strong interactions between ZIF-67 and NPC are attributed as the main contributors to the bifunctional catalytic activities. These factors act synergistically, resulting in substantially enhanced bifunctional catalytic activities and stabilities; consequently, this hybrid catalyst is among the best of the reported bifunctional electrocatalysts and is promising for use in metal-air batteries and fuel cells. (C) 2016 Elsevier B.V. All rights reserved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

Nth-plant scenario for forest resources and short rotation woody crops: Biorefineries and depots in the contiguous US

Estimating the US potential of woody material is of vital importance to ensure cost-effective supply logistics and develop a sustainable bioenergy and bioproducts industry. We analyzed a mature conversion technology for woody resources for the contiguous US that takes advantage of economies of scale: the nth-plant. Here, we developed a database to quantify the total accessible woody biomass within a distributed network of preprocessing depots and biorefineries considering both quality specifications for conversion and a target cost to compete with fossil fuels. We considered two categories of woody biomass: 1) forest residues from trees, tops and limbs produced from conventional thinning and timber harvesting operations as well as non-timber tree removal; and 2) short rotation woody crops such as poplar, willow, pine, and eucalyptus. A mixed integer linear programming model was developed to analyze scenarios with woody feedstock blends at variable biomass ash contents and cost targets at the biorefinery. When considering a target cost of 85.51 dollars/dry ton (2016$) at the biorefinery, the maximum accessible biomass from forest residues in 2040 remained constant at 106 million dry tons regardless of ash targets. Including short rotation woody crops as part of the blend increased the total accessible biomass to 153 and 195 million dry tons at ash targets of 1% and 1.75%, respectively. We concluded from our analysis that woody resources could address about 55% of EPA’s (Environmental Protection Agency) target of 16 billion gallons of cellulosic biofuel.

09 BIOMASS FUELS↗