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Understanding the optoelectronic properties of doped 2D organic-inorganic halide perovskite quantum wells: towards efficient quantum well IR photodetectors

Metal halide perovskite (MHP) multiple quantum wells which consist of multilayers of alternate organic and inorganic layers exhibit large exciton binding energies due to the dielectric confinement between the inorganic and organic layers. These naturally formed multiple quantum wells have strong spin-orbit coupling (SOC) due to the presence of heavy elements in their crystal structures. Although the fundamental properties of 2D MHPs are far from being entirely understood, it is widely accepted that their band edge absorption coefficient results from strong exciton interactions. However, studies demonstrating how different exciton interactions and doping effects influence electronic traps and disorder on the band edge absorption coefficient of 2D MHPs have not been demonstrated. Understanding these interactions in MHPs will allow us to access low energy optical transitions for the fabrication of solution processable short-to-mid-wavelength IR photodetectors (1 – 8 μm). Moreover, upon doping, it is possible to move the Fermi energy into the conduction band (CB) to favorably promote the transport of charges in a working device. Herein, we study the development of 2D MHPs having strong SOC, high carrier mobility, and tunable quantum well structures. Our studies shed light on the design and modulation of fundamental physical phenomena by carefully elucidating the role of dopants (n-type and p-type), exciton heterogeneity, orientation, structure, and bias stress effects on the performance of MHPs as potential IR photodetectors.

36 MATERIALS SCIENCE↗

Analysis of incentive policies for phosphorus recovery at livestock facilities in the Great Lakes area

Livestock operations have been highly intensified over the last decades, resulting in the advent of large concentrated animal feeding operations (CAFOs). Intensification decreases production costs but also leads to substantial environmental impacts. Specifically, nutrient runoff from livestock waste results in eutrophication, harmful algal blooms, and hypoxia. The implementation of nutrient recovery systems in CAFOs can abate nutrient releases and negative ecosystem responses, although they might negatively affect the economic performance of CAFOs. We design and analyze potential incentive policies for the deployment of phosphorus recovery technologies at CAFOs considering the geospatial vulnerability to nutrient pollution. The case study demonstration consists of 2217 CAFOs in the U.S. Great Lakes area. The results reveal that phosphorus recovery is more economically viable in the largest CAFOs due to economies of scale, although they also represent the largest eutrophication threats. For small and medium-scale CAFOs, phosphorus credits progressively improve the profitability of nutrient management systems. The integration of biogas production does not improve the economic performance of phosphorus recovery systems at most of CAFOs, as they lack enough size to be cost-effective. Furthermore, phosphorus recovery proves to be economically beneficial by comparing the net costs of nutrient management systems with the negative economic impact derived from phosphorus releases. The incentives necessary for avoiding up to 20.7.10 3 ton/year phosphorus releases and achieve economic neutrality in the Great Lakes area are estimated at $223 million/year. Additionally, the fair distribution of limited incentives is studied using a Nash allocation scheme, determining the break-even point for allocating monetary resources.

54 ENVIRONMENTAL SCIENCES↗

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

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

54 ENVIRONMENTAL SCIENCES↗

Bond Dissociation Energies and Electronic Calculations on the Actinide Halides ThX and UX (X = Cl, Br, I)

Resonant two-photon ionization spectroscopy has been used to locate predissociation thresholds in the spectra of the actinide halides ThX and UX, where X = Cl, Br, and I. These predissociation thresholds are identified as the bond dissociation energies (BDEs) of the molecules. The resulting values show very similar BDEs for the corresponding ThX and UX species, with the thorium molecules being slightly more strongly bound: D 0 (ThCl) = 5.077(6) eV, D 0 (ThBr) = 4.391(4) eV, D 0 (ThI) = 3.537(8) eV, D 0 (UCl) = 4.989(3) eV, D 0 (UBr) = 4.313(3) eV, and D 0 (UI) = 3.449(8) eV. Here, the estimated error limit is given in parentheses in units of the last reported digit. Spinor-based coupled cluster calculations have also been carried out on the halides of this work, including also ThF and UF. Here, the final D 0 values after including contributions due to basis set incompleteness, outer-core-correlation, picture-change, and QED effects are within 0.04 eV of the present experimental values in each case.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impacts of Climate Change on Groundwater Availability and Spring Flows: Observations from the Highly Productive Medicine Lake Highlands/Fall River Springs Aquifer System

Medicine Lake Highlands/Fall River Springs Aquifer System, located in northeastern California, is home to some of the largest first-order springs in the United States. This work assesses the likely effects of projected climate change on spring flow. Four anticipated climate futures (GFDL A2, GFDL B1, CCSM4 rcp 8.5, CNRM rcp 8.5) for California, which predict a range of conditions (generally warming and transitioning from snow to rain with variable amounts of total precipitation), are postulated to affect groundwater recharge primarily by changing evapotranspiration. The linkages between climate variables and spring flow are evaluated using a water balance model that represents the physics of evapotranspiration and recharge, the Basin Characterization Model. Three of the four climate scenarios (GFDL A2, GFDL B1, CCSM4 rcp 8.5) project that by the year 2100, groundwater recharge (and consequently decreased spring flow) will decrease by 27%, 21%, and 9%, respectively. The fourth scenario (CNRM rcp 8.5) showed an increase in recharge of 32% due to a significant increase in precipitation (27%). Evapotranspiration increases due to a shift in the type of precipitation and a longer growing season. While the likelihood of each scenario is outside the scope of this work, unless total precipitation increases dramatically in the future, increased temperatures and decreasing precipitation will likely result in reduced spring flows, along with warmer water temperatures in downstream habitats.

42 ENGINEERING↗

Discrete quantum geometry and intrinsic spin Hall effect

We show that the quantum geometry of the Fermi surface can be numerically described by a three-dimensional discrete quantum manifold. This approach not only avoids singularities in the Fermi sea, but it also enables the precise computation of the intrinsic Hall conductivity resolved in spin, as well as any other local properties of the Fermi surface. The method assures numerical accuracy when the Fermi level is arbitrarily close to singularities, and it remains robust when Kramers degeneracy is protected by symmetry. Furthermore, the approach is demonstrated by calculating the anomalous Hall and spin Hall conductivities of a two-band lattice model of a Weyl semimetal and a full-band ab initio model of zinc-blende GaAs.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Multimodel simulation of vertical gas transfer in a temperate lake

In recent decades, several lake models of varying complexity have been developed and incorporated in numerical weather prediction systems and climate models. To foster enhanced forecasting ability and verification, improvement of these lake models remains essential. This especially applies to the limited simulation capabilities of biogeochemical processes in lakes and greenhouse gas exchanges with the atmosphere. Here we present multi-model simulations of physical variables and dissolved gas dynamics in a temperate lake (Harp Lake, Canada). The five models (ALBM, FLake, LAKE, LAKEoneD, MTCR-1) considered within this most recent round of the Lake Model Intercomparison Project (LakeMIP) all captured the seasonal temperature variability well. In contrast, none of the models is able to reproduce the exact dates of ice-cover and ice-off, leading to considerable errors in the simulation of eddy diffusivity around those dates.We then conducted an additional modeling experiment with a diffusing passive tracer to isolate the effect of the eddy diffusivity on gas concentration. Remarkably, sophisticated k -" models do not demonstrate a significant difference in the vertical diffusion of a passive tracer compared to models with much simpler turbulence closures. All models simulate less intensive spring overturn compared to autumn. Reduced mixing in the models consequently leads to the accumulation of the passive tracer distribution in the water column. The lake models with a comprehensive biogeochemical module, such as ALBM and LAKE, predict dissolved oxygen dynamics adequate to the observed data. However, for the surface carbon dioxide concentration the correlation between modeled (ALBM, LAKE) and observed data is weak (~0.3). Overall our results indicate the need to improve the representation of physical and biogeochemical processes in lake models, thereby contributing to enhanced weather prediction and climate projection capabilities.

Guseva, Sofya↗

Operation Plumbbob

On June 24, 1957, a thirty-seven kiloton nuclear device, codenamed Priscilla, exploded 700 feet over the Nevada Test Site’s Frenchman dry lake. Below, on the lakebed, was a bank vault designed by the Mosler Safe Company for one of several Federal Civil Defense Administration experiments. The vault was constructed “to evaluate the effectiveness of a reinforced-concrete vault and steel vault door in providing protection against the effects of a nuclear detonation.” Blast damage to the exterior was largely confined to the side walls, whose concrete was stripped off; its steel reinforcing rods bent and twisted. The vault door was essentially undamaged and was opened with minimal difficulty. The vault contents - sandbags, movie camera, and thermometers - were only slightly disturbed. The camera operated as planned, running 40 ft of film. The film, however, was completely fogged. Two clinical type thermometers registered 88°F, and a 24-hr stylus American temperature recorder registered a constant 88°F. Priscilla was the fifth of twenty-nine tests conducted in 1957 as part of Operation Plumbbob, whose stated purpose was to conduct tests “aimed to attain new knowledge important to the defense of the United States and the Free World.” Individual events included “proof tests of air defense and antisubmarine warheads to be stockpiled, development tests of bomb components and mockups, and design tests of smaller and lighter warheads.” One test, John, was that of an air-to-air missile detonated 18,500 feet over the test site.

99 GENERAL AND MISCELLANEOUS↗

U.S. Offshore Wind Energy Noise Reduction Associated with Installation of Fixed-Bottom Foundations: Workshop Report

As offshore wind energy development grows in the United States, solutions are needed to reduce the underwater noise and substrate vibration generated during fixed-bottom turbine installation to help protect marine life. Monopiles are currently the main turbine foundation type installed globally and impact pile driving, the primary installation method, can be a major source of noise and vibration generation during wind farm construction. Opportunities exist to reduce the amount of noise and vibration produced during future offshore wind farm development. The use of alternative foundation types and installation methods, as well as innovative noise abatement technologies, would help reduce the potential detrimental effects on sensitive marine species. To explore these opportunities, the Department of Energy’s Wind Energy Technologies Office, in collaboration with the Bureau of Ocean Energy Management and the National Oceanic and Atmospheric Administration, funded the National Renewable Energy Laboratory and the Pacific Northwest National Laboratory to organize, host, and facilitate a virtual workshop in December 2022. The goal of the workshop was to gather input from the offshore wind energy community on noise reduction strategies for the installation of fixed-bottom offshore wind turbines in U.S. waters across multiple regions, including the U.S. Atlantic Coast, Gulf of Mexico, and Great Lakes to inform recommendations on future research. The joint lab team convened industry representatives, subject matter experts, and regulators to discuss potential pathways to reduce noise and vibration associated with fixed-bottom turbine installation, including the practicality of using alternative foundations and installation methods, the effectiveness of noise abatement technologies, as well as research and monitoring needs. In preparation for the workshop, the team invited experts to be part of a steering committee and worked with its members to help focus activities to meet the workshop goals. Additional pre-workshop activities included developing the invitee list and workshop agenda, reviewing existing Construction and Operations Plans (COP) for proposed offshore wind projects, distributing a brief questionnaire to industry representatives, and drafting the workshop discussion questions and Mural boards. In total, 128 workshop participants provided over 600 comments in response to the 17 group discussion questions used over two workshop sessions. Overarching recommendations highlighted across themes included future investments to provide data sharing, consistency, transparency, and opportunities for sharing best available science, knowledge, and expertise. The joint lab team synthesized the comments and identified four key research and development themes that could help advance the successful implementation of noise and vibration reduction strategies (see report). This report provides an overview of the workshop goals and scope, reviews the pre-workshop activities, presents brief summaries of participant feedback, and concludes with detailed research themes and recommendations for future investments. Appendix A includes the group discussion questions, Appendix B includes the results of the COP review, and Appendix C includes the results of the industry questionnaire. Overall, there was a high level of interest and engagement in the workshop. The sessions provided an opportunity for significant exchange of information between workshop participants from across sectors. Participants identified a variety of opportunities for next steps towards the noise reduction of offshore wind turbine installation in U.S. waters, including recommendations for future investments to provide certainty in the use of new technologies associated with alternative foundation types, noise abatement systems, and efficacy monitoring.

17 WIND ENERGY↗

Quantifying Uncertainties in Heat Capacity Measurements of Molten Salts Determined Using Differential Scanning Calorimetry

Uncertainty in specific heat capacity values of a molten salt determined by using differential scanning calorimetry (DSC) was assessed based on the precision of replicate measurements of heat flows used in the calculation and effects of corrections that are commonly made to heat flow measurements. The ratio method of determining heat capacity was applied using the results of replicate heat flow measurements made with two empty cells, a sapphire reference material, and three samples of a doped NaCl-UCl 3 salt mixture. Replicate measurements with empty cells were used to quantify the effects of system instabilities and sensitivities on the measured heat flows of sapphire and salt. The combined effects of uncertainties in individual heat flow measurements made with blank cells using this system were quantified to be 2.6 μV based on isothermal holds before and after the scan, with cell placement adding the greatest uncertainty. This value was used as the tolerance for accepting background-corrected heat flows measured with sapphire and salt to calculate the specific heat capacity. The acceptable heat flows measured for sapphire and salt over the temperature range of 540 to 725 °C resulted in calculated specific heat capacity values ranging from 0.53 to 0.91 J g −1 K −1 with an overall average value of 0.70 J g −1 K −1 and an uncertainty of 0.22 J g −1 K −1 at the 99 % confidence level. The combined uncertainty in the specific heat capacity masked detection of any effect of temperature or salt composition that occurred.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Mosler versus the Atom: How safe is a safe?

On June 24, 1957, a thirty-seven kiloton nuclear device, codenamed Priscilla, exploded over the Nevada Test Site’s Frenchman dry lake. Under the direction of the Federal Civil Defense Administration, a bank vault designed by the Mosler Safe Company of San Francisco, was placed at the projected 75 psi line “to evaluate the effectiveness of a reinforced-concrete vault and steel vault door in providing protection against the effects of a nuclear detonation.”

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Field Validation of Thermoelectric Generation System at Holcim Cement Plant in Alpena, Michigan

Executive Summary Project Background The Industrial Technology Validation (ITV) program aims to identify and demonstrate the performance of new, emerging, and underutilized energy-saving technologies in the industrial sector to help inform decisions to help accelerate their commercialization and deployment, as well as to help make industries more competitive. This ITV demonstration evaluated a thermoelectric generation (TEG) technology at a cement plant, aiming to reduce energy demand in the cement industry. A median cement plant consumes 5.73 million British thermal units per ton of clinker production (resulting in 0.838 metric tons of carbon dioxide [CO₂] emissions per ton of clinker) (Boyd and Zhang 2011, EPA 2021), equivalent to approximately 6.9 trillion British thermal units (TBtu) per year in energy consumption at a cement plant producing 3,300 tons of clinker per day.¹ Collaborating with Holcim, Advanced Thermovoltaic Systems (ATS) developed and deployed a pilot-scale thermoelectric power system to efficiently capture and convert waste heat to electricity. The system leverages the Seebeck effect to convert temperature differences on two sides of semiconductor cartridges into electrical power (ScienceDirect, n.d.). This generation is realized with minimal moving parts compared to existing waste-heat-to-generation solutions and allows capture from heat sources with temperatures as low as 150°C. This project aimed to validate a scalable solution applicable for capturing medium-temperature waste heat, including ambient losses from other high-temperature processes, and high-temperature sources less suitable for other waste-heat-to-power solutions. By recovering this otherwise wasted heat, this project intends to validate improvements to overall process efficiency through reduction in purchased electricity, thereby reducing operational costs while enhancing resiliency and competitiveness. Description and Scope This study evaluated the performance of a TEG system from ATS as a solution to convert waste heat into useful power at a Holcim cement plant in Alpena, Michigan. This plant is a fully integrated cement plant that has been operating since 1907. The facility operates continuously (24/7/365) with approximately 250 employees and five long dry kilns, yielding a total production capacity of 7,852 tons of cement per day (EPA 2023). Currently, the Alpena plant uses waste heat boilers to convert waste heat from the exhaust of each kiln into steam, which drives steam turbine generators. The ATS TEG is being evaluated for its potential to supplement the steam turbines by capturing the remaining lower grade heat. This technology is also being considered for other Holcim plants where steam turbines are not a viable option. ATS installed a pilot-scale TEG unit with an array of 582 individual thermoelectric semiconductor cartridges, of which 573 were operational. The cartridges are sandwiched between 48 hot plates and 49 cold plates. Each cartridge is designed to generate 20 watts (W) of gross power at a hot-side temperature of 240°C and cold-side temperature of 20°C. As such, the total gross generation capacity of the installed system is 11.5 kilowatts (kW) at design conditions. The system configuration for the evaluation was designed to prioritize convenience of installation and minimize disruption to production at the site, while ensuring that the heat required can be obtained for evaluating the TEG system at various operational conditions. To accomplish this, a portion of the steam supplied to Alpena’s steam turbine generation system was diverted to be used as the heat source for the TEG system, while water was supplied to the cold side of the system from nearby Lake Huron. This configuration was designed for the evaluation of the pilot-scale system to assess the performance at different conditions. A commercial-scale system will likely vary from the pilot system depending on typical configurations, including both scale and application. Future commercial applications of the ATS system would involve integrating the system into the exhaust from kiln preheaters, clinker coolers, or radiant heat capture from kiln shells for the heat source. For the cold source, a range of cooling solutions can be considered, including a mechanical cooling system, depending on the location and the application. To increase the generation capacity for commercial applications, the technology provider is working toward developing a commercial-scale TEG system, which would combine multiple TEG units (each similar in design to the pilot system) together. The scope of this evaluation includes the pilot-scale TEG system and all impacted equipment including pumps, controllers, and power handling equipment. Study Objectives The evaluation's goal was to assess the potential of the ATS TEG system to generate useful electrical power by capturing waste heat from cement production kilns. The objectives of this study are to evaluate and verify the following claims made by ATS regarding the pilot-scale system installed at the Holcim Alpena plant. The following design parameters and claims are also outlined in Table ES- 1 and Table ES- 2: • Gross Power: The thermoelectric system converts heat into power to create gross power, the total measured power generated by the system. The 573 active cartridge pilot-scale system is expected to generate 11.5 kW of gross power at the designed hot-side temperature of 240°C and cold-side temperature of 20°C. Power production is dependent on the temperature difference between the heat source (ultimately from the waste heat) and cold temperature supply source. • Net Power: The net power is the total usable power provided to the site by the TEG system after deducting parasitic power loads from the gross generated power. Supplementary equipment is required to operate the TEG system including pumps, controllers, and, in certain anticipated applications, mechanical cooling, which introduce parasitic loads to system operation. After deducting the parasitic loads from the gross power generation, ATS anticipates achieving a net power generation of 7.5 kW from the pilot-scale system. • Thermal Efficiency: The thermal efficiency is the percent of the total heat transferred to the TEG system that is converted to gross power. Historically, TEGs have a thermal efficiency of 2%–5% (DOE 2008). Prior industrial-scale TEG systems, such as the E1 TEG offered by Alphabet Energy, operated at an efficiency of 2.5% (Lamonica, 2014). ATS anticipates achieving an average efficiency of 4.8% or higher in converting heat energy to usable electricity. • Cartridge Performance: The TEG system comprises 573 active individual semiconductor cartridges, each of which generates a portion of the total power. Cartridge optimization and selection is an important design consideration for potential future TEG system design performance. Therefore, understanding the distribution of gross power and efficiency within the pilot system is vital to understanding what is achievable. At a design hot-side temperature of 240°C and cold-side temperature of 20°C, ATS anticipates a cartridge performance of 20 W of gross power per cartridge at an efficiency of 4.8% per cartridge. In addition to evaluating the claimed performance of the TEG pilot-scale unit, the study estimated the potential annual impacts of a scaled-up commercial system used to capture kiln waste heat over annual operations. The evaluation estimated the gross and net annual electric generation achievable by capturing heat from the two proposed tap-in points: the kiln exhaust and the clinker cooler exhaust; see Section 2.1 for details. Two use cases were examined: • Holcim Alpena: The Holcim Alpena site consists of long dry kilns with superheater boilers, which differs from the rest of Holcim’s cement plant portfolio and results in lower waste heat temperatures. The study estimates gross and net annual generation using the superheater boiler exhaust and clinker cooler exhaust, based on 2023 operational data. • Typical Installation: Common cement plants have preheater kilns with higher exhaust temperatures than Holcim Alpena across a range of production rates. The study estimates gross and net annual generation using the preheater exhaust and clinker cooler exhaust, with a sensitivity analysis to account for the typical range of preheater exhaust temperatures, clinker cooler exhaust temperatures, and clinker production rates. Methodology The evaluation methodology followed a measurement and verification (M&V) strategy based on the International Performance Measurement and Verification Protocol Option B through comprehensive measurements and analyses of the affected systems. Evaluation data was collected from March 9 to March 11, 2024, the test period of the pilot TEG system. During the test period, in coordination with the ITV team, the ATS team adjusted system operations to capture the range of variability expected for each of the variables pertinent to performance of the system. The methodology consisted of two parts: evaluating the performance of the pilot unit's TEG system and estimating the annual TEG impact in terms of gross and net power based on a given waste heat profile. First, the evaluation of the thermoelectric generation performance of the pilot unit relative to the claims was performed by analyzing the collected test data. Gross power of the pilot TEG system was directly measured. Net power was determined by deducting the measured parasitic power from the gross power. The gross power generation was compared to heat transferred to the system by the working fluid (which was heated by steam generated from the kiln waste heat) to calculate the thermal efficiency achieved by the system. Performance of individual semiconductor cartridges within the pilot array was also assessed in terms of measured gross cartridge power and calculated cartridge thermal efficiency. The second part of the evaluation estimated the annual TEG impacts in terms of gross power and net power (calculated from the difference between gross power and parasitic power). This analysis comprised development of mathematical regression models for gross power and parasitic power, with assessment of each model’s goodness-of-fit characteristics to ensure satisfaction of statistical requirements. The models predicted the gross power generation, the parasitic load based on the temperature difference between the hot working fluid and the cold-side fluid (cold water from Lake Huron) entering the system, the volumetric flow rate of the cold-side fluid at the inlet, and the volumetric flow rate of the hot working fluid at the inlet. The annual impact analysis considered a theoretical commercial-scale system sized to capture the available waste heat at a cement plant, consisting of linked pilot-scale units that receive heat from a theoretical gas-to-working-fluid heat exchanger. To estimate annual impacts at the Alpena plant, the gross power and parasitic power regression models were applied to the arrays in the theoretical commercial-scale system. The heat supplied to the unit was calculated based on the kiln run time, annual production, kiln exhaust waste heat, and clinker cooler waste heat derived from 2023 Holcim Alpena kiln operational data. Net power impacts were calculated by deducting the resulting parasitic power from the estimated gross power. Inputs for the model were generated from a combination of hourly data, assumed design considerations for TEG system scale-up from the pilot-scale unit, and assumptions regarding TEG system operations. This analysis was then used as the basis for estimating annual impacts of typical TEG installation at cement plants, by applying sensitivity analyses to key kiln operational characteristics including kiln preheater exhaust temperatures, cooler clinker exhaust temperatures, and plant daily production rates across a range of expected values. Project Results/Findings Table ES- 2 and Table ES- 2 provide a summary of the operating conditions and evaluation results compared to the stated claims from the technology provider. Key takeaways include: • Gross Power: The peak gross power achieved during the testing period was 10.0 kW, compared to the 11.5 kW expected for 573 active cartridges. The claimed gross power was associated with a target hot side of 240°C; however, the system only received a maximum hot-side mean plate temperature of 212°C during the testing period. • Net Power: The pilot-scale unit exceeded the claims for net power, achieving a peak of 7.7 kW net compared to a claim of 7.5 kW. One factor contributing to the higher achieved net power is the relatively high water pressure available through Lake Huron. The pilot TEG system did not require cold-side pumps during the test, whereas most installations would. This reduced the parasitic loads on the system, ultimately contributing to higher net power relative to the gross power. • Thermal Efficiency: The pilot-scale unit outperformed the claimed efficiency, achieving a peak system efficiency of 5.0% thermal efficiency compared to the stated 4.8%. • Cartridge Performance: To compare cartridge performance against claims, the study focused on the third day of testing, which aimed for conditions closest to the design specifications, with a hot side of 240°C and cold-side exit temperature of 6.4°–30°C. On this day, the mean gross power observed in the cartridges within the TEG array was 18.1 W/cartridge, and the peak performance was 34.7 W/cartridge. The estimated mean cartridge efficiency was 5.2%, and the estimated efficiency at peak gross cartridge power was 10%. The regression models developed for gross power generation and parasitic loads were used to estimate the generation impact for given heat input to the TEG from the working fluid (captured from the waste heat) and from the cold loop (Lake Huron) on an hourly basis for a year of operation. Based on this analysis, installation of a commercial-scale TEG system at the Holcim cement plant in Alpena, Michigan, with a waste heat exchanger of 0.85 effectiveness, would generate up to 391 kW of net power, translating to between 920,000 and 1,800,000 kilowatt-hours (kWh) in net electricity per year. Based on typical grid emissions for Alpena, this would avoid estimated net emissions by 752 metric tons of CO₂ annually.² The sensitivity analysis estimated that typical TEG system installations at cement plants could generate an average of 56–1,040 kW of net power, or between 488,000 and 9,110,000 kWh of net energy. This generation potential is most significantly affected by plant production rates and also influenced by preheater and clinker cooler exhaust temperatures. Applying the national average emission rate, typical commercial-scale installations at Holcim plants are projected to avoid between 182 and 3,401 metric tons of CO₂ annually per site. Table ES- 3 shows a summary of the estimated annual impacts.³ While parasitic loads are significant and vary by application, this analysis assumed the use of heating loop pumps and access to Lake Huron as a cold sink. This setup assumed no need for cooling loop pumps due to the available water pressure at the test site. Applications that require cooling towers or additional equipment are likely to experience higher parasitic loads. Therefore, the study’s estimates are most applicable to scenarios with similar parasitic load configurations—namely, access to a high-pressure cold sink. Applicability to other locations may be limited, as differing conditions could necessitate additional pumps and cooling systems, potentially impacting performance significantly.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Lithium's low-temperature phase transitions: Insights into quantum lattice dynamics and superconductivity

The large lattice dynamics of lithium, driven by its low atomic mass, results in energetically similar structures and significant isotope effects under pressure, posing challenges to current theoretical models. Above 20 GPa and at low temperatures, lithium's electronic properties deviate from simple metallic behavior, with superconductivity emerging in a complex, pressure-dependent manner, alongside an unusual isotope effect. The structural phases of 7 Li reported under these conditions are inconsistent across studies, and the structures of 6 Li remain unexamined. These gaps limit our understanding of the effects of pressure on lithium's electronic properties and the role of quantum lattice effects on its structural behavior under pressure. Here, we integrate experimental and theoretical approaches to investigate the low-temperature structural phase boundaries in lithium isotopes. We map the structural phase diagram of 7 Li from 5 to 55 GPa and 15–75 K, identifying the sequence fcc → ℎ⁡R⁢1 → cI16. A pronounced isotope effect is observed, with 6 Li shifting the fcc → ℎ⁡R⁢1 phase boundary to lower pressures at 15 K. Density functional theory calculations further clarify how these structural changes affect superconducting properties, particularly emphasizing the role of the fcc → ℎ⁡R⁢1 transition in lithium's superconductivity. Furthermore, our findings offer insights into the unique behavior of lithium isotopes under pressure.

36 MATERIALS SCIENCE↗

Why Seeding Works When Nucleation Barriers Vanish

This paper explains why seeds can speed up crystallization even when the formation of new crystal nuclei is not the slow step. In zeolite synthesis, local crystalline order can form relatively early, but the material may still appear poorly crystalline by X-ray diffraction because many small crystallites are misoriented and lack long-range coherence. Using coarse-grained molecular simulations, the study showed that seeds help solve this coherence problem. Rather than primarily lowering a nucleation barrier, seeds impose a common orientation on nearby growing crystallites, allowing them to merge into larger, better aligned domains. This accelerates the development of X-ray-detectable crystallinity even if the total amount of locally ordered material has not changed much. The work changes how induction times in zeolite synthesis should be interpreted: the delay before X-ray crystallinity appears can reflect the time needed to build long-range structural coherence, not simply the time needed to form crystalline material. This provides a new explanation for why seeding is effective in growth-limited crystallization and offers design principles for controlling crystallization rate and crystal quality.

36 MATERIALS SCIENCE↗

Statistical Steady-State Stability Analysis for Transmission System Planning for Offshore Wind Power Plant Integration

This paper presents a statistical steady-state stability analysis for transmission system planning studies in order to identify operational issues inherent in the integration of offshore wind power plants. It includes normal and contingency operation. This study considers the integration of a 1000-MW offshore wind power plant into the FirstEnergy/PJM service territory in the U.S. Great Lakes region as a case study and uses a realistic computer model of the U.S. Eastern Interconnection, a 63,000-bus test system. The results show the utility of this statistical analysis tool and its effectiveness in identification of the operational impacts as a result of the integration of offshore wind power plant.

Sajadi, Amirhossein↗

Evaluating SWAT + model uncertainties for human and natural outcomes: Application in a Great Lakes agricultural watershed

Nutrient exports from agricultural lands in the Great Lakes Region pose significant threats to water quality and ecological health through eutrophication, hypoxia, and harmful algal blooms. Climate change and agricultural adaptation practices complicate future nutrient loading due to intensified hydrologic cycles and land use decisions. Our research focuses on evaluating the Soil and Water Assessment Tool (SWAT) plus model parametric uncertainties for human and natural outcomes across different scales. These factors are integral to ensuring a balance between productive agricultural practices and maintaining the health of watershed hydrology. However, uncertainties in modeling such complex interactions pose significant challenges, limiting our ability to precisely determine critical factors that influence crop yield and soil moisture. Our analysis employs Sobol global sensitivity analysis to evaluate first-order, second order, and total-order indices for SWAT crop growth parameter, ensuring comprehensive assessment of individual and interactive effects on model outputs. The objective is to identify the parameters that significantly affect model outputs for crop yield and soil moisture and improve our understanding of their interactions at the basin and hydrological response unit (HRU) scale. Our case study, the Portage River Watershed, which drains into Lake Erie, is chosen to better capture finer scale interactions crucial for predicting nutrient loading under future climate scenarios. This foundational work is aimed at setting the stage for the future development of an agent-based model (ABM). The ABM model would incorporate SWAT outputs to dynamically simulate decision-making processes.

Bunyon, Enock↗

Copper transformation, speciation, and detoxification in anoxic and suboxic freshwater sediments

The complex chemistry of copper (Cu) in freshwater sediments at low concentrations is not well understood. We evaluated the transformation processes of Cu added to freshwater sediments under suboxic and anoxic conditions. Freshwater sediments from three sources in Michigan with different characteristics (Spring Creek, River Raisin, and Maple Lake) were spiked with 30 or 60 mg kg -1 Cu and incubated under a nitrogen atmosphere. After 28-d, each treatment subset was amended with organic matter (OM) to promote anoxic conditions and evaluate its effects on Cu speciation. OM addition triggered a shift from suboxic to anoxic conditions, and sequential extractions showed that Cu accordingly shifted from acid-soluble to oxidizable fractions. Extended X-ray absorption fine-structure (EXAFS) spectroscopy revealed that Cu sulfides dominated all anoxic samples except for Spring Creek 30 mg kg -1 , where Cu(I) was predominantly complexed to thiol groups of OM. Covellite and chalcopyrite (CuFeS 2 ) were the predominant Cu species in nearly all anoxic samples, as determined by Raman spectroscopy, scanning electron microscopy, and X-ray absorption near-edge structure (XANES) spectroscopy. Copper reduction also occurred under suboxic conditions: for two of three sediments, around 80% had been reduced to Cu(I), while the remaining 20% persisted as Cu(II) complexed to OM. However, in the third coarsest (i.e., Spring Creek), around 50% of the Cu had been reduced, forming Cu(I)-OM complexes, while the remainder was Cu(II)-OM complexes. Toxicity tests showed that survival of H. azteca and D. magna were significantly lower in suboxic treatments. Anoxic sediments triggered a near-complete transformation of Cu to sulfide minerals, reducing its toxicity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanisms of SARS-CoV-2 neutralization by shark variable new antigen receptors elucidated through X-ray crystallography

Single-domain Variable New Antigen Receptors (VNARs) from the immune system of sharks are the smallest naturally occurring binding domains found in nature. Possessing flexible paratopes that can recognize protein motifs inaccessible to classical antibodies, VNARs have yet to be exploited for the development of SARS-CoV-2 therapeutics. Here, we detail the identification of a series of VNARs from a VNAR phage display library screened against the SARS-CoV-2 receptor binding domain (RBD). The ability of the VNARs to neutralize pseudotype and authentic live SARS-CoV-2 virus rivalled or exceeded that of full-length immunoglobulins and other single-domain antibodies. Crystallographic analysis of two VNARs found that they recognized separate epitopes on the RBD and had distinctly different mechanisms of virus neutralization unique to VNARs. Structural and biochemical data suggest that VNARs would be effective therapeutic agents against emerging SARS-CoV-2 mutants, including the Delta variant, and coronaviruses across multiple phylogenetic lineages. This study highlights the utility of VNARs as effective therapeutics against coronaviruses and may serve as a critical milestone for nearing a paradigm shift of the greater biologic landscape.

60 APPLIED LIFE SCIENCES↗