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Software for High-Resolution Flood Mapping With Sentinel-1 and Sentinel-2 via Misalignment-Robust Cross-Sensor Learning and Generative Despeckling

SF-26-078 This software provides a high-level workflow for satellite-based flood and surface-water mapping using Sentinel-1 SAR and Sentinel-2 multispectral imagery. It supports preparation of remote-sensing data, training and evaluation of deep-learning models, and generation of high-resolution water extent predictions, including methods to improve robustness to SAR speckle noise and cross-sensor image misalignment.

Feinstein, Jeremy [Argonne National Laboratory (AN↗

Topological surface states of semimetal TaSb 2

Topological surface states, protected by the global symmetry of the materials, are the keys to understanding various novel electrical, magnetic, and optical properties. TaSb 2 is a newly discovered topological material with unique transport phenomena, including negative magnetoresistance and resistivity plateau, whose microscopic understanding is yet to be reached. In this study, we investigate the electronic band structure of TaSb 2 using angle-resolved photoemission spectroscopy and density functional theory. Our analyses reveal distinct bulk and surface states in TaSb 2 , providing direct evidence of its topological nature. Notably, surface states predominate the electronic contribution near the Fermi level, while bulk bands are mostly located at higher binding energies. Our study underlines the importance of systematic investigations into the electronic structures of topological materials, offering insights into their fundamental properties and potential applications in future technologies.

36 MATERIALS SCIENCE↗

Confirmatory Survey of the Fuel Oil Tank Area - Humboldt Bay Power Plant, Eureka, California (Final Report)

During the period of February 14 to 15, 2012, ORISE performed radiological confirmatory survey activities for the former Fuel Oil Tank Area (FOTA) and additional radiological surveys of portions of the Humboldt Bay Power Plant site in Eureka, California. The radiological survey results demonstrate that residual surface soil contamination was not present significantly above background levels within the FOTA. Therefore, it is ORISE’s opinion that the radiological conditions for the FOTA surveyed by ORISE are commensurate with the site release criteria for final status surveys as specified in PG&E’s Characterization Survey Planning Worksheet. In addition, the confirmatory results indicated that the ORISE FOTA survey unit Cs-137 mean concentrations results compared favorably with the PG&E FOTA Cs-137 mean concentration results, as determined by ORISE from the PG&E characterization data. The interlaboratory comparison analyses of the three soil samples analyzed by PG&E’s onsite laboratory and the ORISE laboratory indicated good agreement for the sample results and provided confidence in the PG&E analytical procedures and final status survey soil sample data reporting.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Single Molecule Spectroelectrochemistry of Interfacial Charge Transfer Dynamics In Hybrid Organic Solar Cell

Our research under support of this DOE grant is focused on applied and fundamental aspects of model organic solar cell systems. Major accomplishments are: 1) we developed a spectroelectorchemistry technique of single molecule single nanoparticle method to study charge transfer between conjugated polymers and semiconductor at the single molecule level. The fluorescence of individual fluorescent polymers at semiconductor surfaces was shown to exhibit blinking behavior compared to molecules on glass substrates. Single molecule fluorescence excitation anisotropy measurements showed the conformation of the polymer molecules did not differ appreciably between glass and semiconductor substrates. The similarities in molecular conformation suggest that the observed differences in blinking activity are due to charge transfer between fluorescent polymer and semiconductor, which provides additional pathways between states of high and low fluorescence quantum efficiency. Similar spectroelectrochemistry work has been done for small organic dyes for understand their charge transfer dynamics on various substrates and electrochemical environments; 2) We developed a method of transferring semiconductor nanoparticles (NPs) and graphene oxide (GO) nanosheets into organic solvent for a potential electron acceptor in bulk heterojunction organic solar cells which employed polymer semiconductor as the electron donor. Electron transfer from the polymer semiconductor to semiconductor and GO in solutions and thin films was established through fluorescence spectroscopy and electroluminescence measurements. Solar cells containing these materials were constructed and evaluated using transient absorption spectroscopy and dynamic fluorescence techniques to understand the charge carrier generation and recombination events; 3) We invented a spectroelectorchemistry technique using light scattering and electroluminescence for rapid size determination and studying electrochemistry of single NPs in an electrochemical cell. For example, we are able to use this technique to track electroluminescence of single Au NPs, and the electrodeposition of individual Ag NPs in-situ. These metallic NPs are useful to enhance light harvesting in organic photovoltaic systems. The scattering at the surface of an indium tin oxide (ITO) working electrode was measured during a potential sweep. Utilizing Mie scattering theory and high resolution scanning electron microscopy (SEM), the scattering data were used to calculate current-potential curves depicting the electrodeposition of individual Ag NPs. The oxidation of individual presynthesized and electrodeposited Ag NPs was also investigated using fluorescence and DFS microscopies. Our work has produced 1 US provisional patent, 15 published manuscripts, 1 submitted and two additional in-writing manuscripts. 5 graduate students, 1 postdoctoral student, 1 visiting professor, and two undergraduate students have received research training in the area of electrochemistry and optical spectroscopy under support of this award.

14 SOLAR ENERGY↗

Quantification and Controls of Wetland Greenhouse Gas Emissions

Wetlands cover only a small fraction of the Earth’s land surface, but have a disproportionately large influence on global climate. Low oxygen conditions in wetland soils slows down decomposition, leading to net carbon dioxide sequestration over long timescales, while also favoring the production of redox sensitive gases such as nitrous oxide and methane. Freshwater marshes in particular sustain large exchanges of greenhouse gases under temperate or tropical climates and favorable nutrient regimes, yet have rarely been studied, leading to poor constraints on the magnitude of marsh gas sources, and the biogeochemical drivers of flux variability. The Sacramento-San Joaquin Delta in California was once a great expanse of tidal and freshwater marshes but underwent drainage for agriculture during the last two centuries. The resulting landscape is unsustainable with extreme rates of land subsidence and oxidation of peat soils lowering the surface elevation of much of the Delta below sea level. Wetland restoration has been proposed as a means to slow further subsidence and rebuild peat however the balance of greenhouse gas exchange in these novel ecosystems is still poorly described. In this dissertation I first explore oxygen availability as a control on the composition and magnitude of greenhouse gas emissions from drained wetland soils. In two separate experiments I quantify both the temporal dynamics of greenhouse gas emission and the kinetic sensitivity of gas production to a wide range of oxygen concentrations. This work demonstrated the very high sensitivity of carbon dioxide, methane, and nitrous oxide production to oxygen availability, in carbon rich wetland soils. I also found the temporal dynamics of gas production to follow a sequence predicted by thermodynamics and observed spatially in other soil or sediment systems. In the latter part of my dissertation I conduct two field studies to quantify greenhouse gas exchange and understand the carbon sources for decomposition in a 1 km2 restored wetland in the Sacramento Delta. By coupling flux measurements at multiple-scales with remote sensing imagery I showed that large methane emissions produce an overall climate warming effect from the wetland for the next several centuries, despite relatively high productivity. I also used radiocarbon analyses of wetland sediment carbon dioxide and methane to show that both bulk peat and recently fixed carbon contribute to decomposition in the wetland, and that their relative importance is regulated by proximity to, and the phenological cycles of, emergent vegetation.

07 ISOTOPE AND RADIATION SOURCES↗

Lifting Condensation Level Height (LCL Height) Value-Added Product Report

The lifting condensation level height (LCL, m) is determined from continuous surface-air observations of relative humidity and temperature as the altitude where the surface-air moisture equals saturation following a dry-adiabatic ascent. Values are computed from surface meteorological observations for 16 facilities belonging to the U.S. Department of Energy Atmospheric Radiation Measurement (ARM) user facility Southern Great Plains (SGP) atmospheric observatory and for 133 Oklahoma Mesonet (OKM) stations. The LCL Height Value-Added Product (VAP) was developed for use by the Large-Eddy Simulation (LES) ARM Symbiotic Simulation and Observation (LASSO) project (Gustafson et al. 2016, 2017, 2018, 2020).

54 ENVIRONMENTAL SCIENCES↗

Final Report DE-FE0031785 Mohsen Ahmadian, Ph.D. Demonstration of Proof of Concept of a Multiphysics Approach for Real-Time Remote Monitoring of Dynamic Changes in Pressure and Salinity in Hydraulically Fractured Networks

Hydraulic fracturing has evolved into a multistep process with varying flow rates, carrier fluids (e.g., gel or slickwater), proppant loadings, and proppant grain sizes. As a result, primary recovery from a hydraulically fractured tight-oil reservoir is often a tiny fraction of the original oil in place, ranging between 5 and 10%. As stated in the FOA1990, “part of this problem is due to the inability of current well completion processes to effectively stimulate the entire reservoir volume in contact with the wellbore. Innovative technologies are needed that can help improve the effectiveness of reservoir completion methods, maximize stimulated reservoir volumes, and optimize recovery over the entire producing life span of a well”. We first need to enhance the current fracture diagnostic techniques to improve a well-completion design. However, detecting and delineating a subsurface hydraulic fracture is extremely difficult because the induced fracture network is only fractionally propped, and these propped fractures are generally very thin. Microseismic and tiltmeter monitoring techniques can provide information on the fracture extent but provide little or no information on the movement and final distribution of proppant or production fluids. On the other hand, electromagnetic (EM) imaging has shown the capability to monitor proppant distribution throughout the fracture area, especially in the presence of Electrically Active Proppants (EAPs). A previous EM survey of hydraulic fracturing at the Devine Fracture Pilot Site (DFPS) and subsequent EM code developments demonstrated this survey as a robust technique to remotely interrogate the extent of the EAP-filled hydraulic fracture during its propagation. The objectives of the project were threefold: (1) to capitalize on the material properties of an EAP to demonstrate remote monitoring of relative changes in pressure, pressure, and flow that are commonly encountered during production from a hydraulically fractured reservoir; (2) to evaluate EM imaging tools, to achieve Objective 1 in near real-time; and (3) to develop a multi-physics joint inversion approach to precisely predict flow patterns and physiochemical changes within an EAP-filled fracture network. This research project was built upon our previous work at the Devine Test Site managed by the Bureau of Economic Geology (BEG) at The University of Texas at Austin (UT-Austin). It also leveraged a significant investment from the Advanced Energy Consortium (AEC) to address the DOE's interest in subsurface flow, containment, and characterization by multiple signals. This three-year and three-month project succeeded in demonstrating the feasibility of a real-time dynamic fluid flow mapping technique at Technology Readiness Level 5 (TRL5) by utilizing a commercially available surface-based Controlled-Source Electromagnetic (CSEM) method (Objectives 1, 2). We demonstrated that injections into an EAP-filled fracture could be successfully coupled with real-time electric field measurements on the surface, leading to remote monitoring of dynamic changes within the EAP-filled fracture. Furthermore, the observed electric field in our study is influenced by bottomhole pressure, flow rate, and salinity, which is demonstrated by comparing these parameters with the electrical field potentials. EM simulations solely based on assumptions of fracture conductivity changes during injection did not reproduce the whole measured electric field magnitudes. Preliminary estimates showed that including Streaming Potential (SP) in our geophysical model is likely needed to reduce the simulation misfit.

02 PETROLEUM↗

Evaluation of dynamical downscaling in a fully coupled regional earth system model

A set of decadal simulations has been completed and evaluated for gains using the Regional Arctic System Model (RASM) to dynamically downscale data from a global Earth system model and two atmospheric reanalyses. RASM is a fully coupled atmosphere–land–ocean–sea ice regional Earth system model. Nudging to the forcing data is applied to approximately the top half of the atmospheric domain. RASM simulations were also completed with a modification to the atmospheric physics for evaluating changes to the modeling system. The results show that for the top half of the atmosphere, the RASM simulations follow closely to that of the forcing data, regardless of the forcing data. The results for the lower half of the atmosphere, as well as the surface, show a clustering of atmospheric state and surface fluxes based on the modeling system. At all levels of the atmosphere the imprint of the weather from the forcing data is present as indicated in the pattern of the annual means. Biases, in comparison to reanalyses, are evident in the Earth system model forced simulations for the top half of the atmosphere but are not present in the lower atmosphere. This suggests that bias correction is not needed for fully coupled dynamical downscaling simulations. While the RASM simulations tended to go to the same mean state for the lower atmosphere, there are a differences in the variability and changes of weather patterns across the ensemble of simulations. These differences in the weather result in variances in the sea ice and oceanic states.

54 ENVIRONMENTAL SCIENCES↗

Impact of Snow Darkening by Deposition of Light-Absorbing Aerosols on Snow Cover in the Himalayas–Tibetan Plateau and Influence on the Asian Summer Monsoon: A Possible Mechanism for the Blanford Hypothesis

The impact of snow darkening by deposition of light-absorbing aerosols (LAAs) on snow cover over the Himalayas–Tibetan Plateau (HTP) and the influence on the Asian summer monsoon were investigated using the NASA Goddard Earth Observing System Model Version 5 (GEOS-5). The authors found that during April–May–June, the deposition of LAAs on snow led to a reduction in surface albedo, initiating a sequence of feedback processes, starting with increased net surface solar radiation, rapid snowmelt in the HTP and warming of the surface and upper troposphere, followed by enhanced low-level southwesterlies and increased dust loading over the Himalayas–Indo-Gangetic Plain. The warming was amplified by increased dust aerosol heating, and subsequently amplified by latent heating from enhanced precipitation over the Himalayan foothills and northern India, via the elevated heat pump (EHP) effect during June–July–August. The reduced snow cover in the HTP anchored the enhanced heating over the Tibetan Plateau and its southern slopes, in conjunction with an enhancement of the Tibetan Anticyclone, and the development of an anomalous Rossby wave train over East Asia, leading to a weakening of the subtropical westerly jet, and northward displacement and intensification of the Mei-Yu rain belt. The authors’ results suggest that the atmosphere-land heating induced by LAAs, particularly desert dust, plays a fundamental role in physical processes underpinning the snow–monsoon relationship proposed by Blanford more than a century ago.

54 ENVIRONMENTAL SCIENCES↗

IceCube Constraints on the Fermi Bubbles

We analyze the IceCube four-year neutrino data in search of a signal from the Fermi bubbles. No signal is found from the bubbles or from their dense shell, even when taking into account the softer background. This imposes a conservative ξ {sub i} < 8% upper limit on the cosmic-ray ion (CRI) acceleration efficiency, and an η ≡ ξ {sub e} / ξ {sub i} ≳ 0.006 lower limit on the electron-to-ion ratio of acceleration efficiencies (at the 2 σ confidence level). For typical ξ {sub i} , a signal should surface once the number of IceCube neutrinos increases by ∼an order of magnitude, unless there is a <PeV cutoff on the CRI spectrum.

79 ASTRONOMY AND ASTROPHYSICS↗

Thermal Performance of Uninsulated and Partially Filled Wall Cavities

Wall cavities are widely present in the construction of low rise homes since wood framing is the most common type of construction for residential buildings in the United States. The primary function of such wall construction is to provide a stable frame to which interior and exterior wall coverings can be attached and by which a roof can be supported. The existence of wall cavities increases the thermal resistance of the enclosure, particularly when they are filled with insulating material. Several design guides provide data for prediction of the thermal resistance of uninsulated wall cavities of varying internal geometries. However, U-value coefficients provided in these guides do not account for partially insulated cavities or for variations in aspect ratio. Whole building energy simulation tools, like DOE2 or Energy Plus, use simplified, 1-D characterization of building envelopes. For the most part, this characterization assumes a fixed thermal resistance over the range of temperatures experienced by the enclosure. In reality, the thermal resistance is dominated by convection and radiation and is a function of several parameters, including the temperatures and emissivities of the cavity surfaces and the aspect ratio of the cavity. This study describes detailed CFD modeling to evaluate the thermal performance of uninsulated or partially filled wall cavities accounting for conduction through framing, convection, and radiation. The resulting correlations can serve as input for DOE2 and Energy Plus modeling of older homes, where the walls are either uninsulated or partially insulated due to the settling of the insulating material. Parameters of the study are the ambient temperature outdoors, emissivity of the cavity surfaces, cavity aspect ratio, and height of the insulation level. The outcomes of this study provide: An understanding of the thermal performance of uninsulated or partially insulated wall cavities, which is an essential aspect of energy conservation in residential buildings. Accurate input for whole building simulations models like DOE2 and Energy Plus in various climate zones. Recommendations on retrofit measures.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Measurements of impurity concentrations and transport in the Lithium Tokamak Experiment

This thesis presents new measurements of core impurity concentrations and transport in plasmas with lithium coatings on all-metal plasma facing components (PFCs) in the Lithium Tokamak Experiment (LTX). LTX is a modest-sized spherical tokamak uniquely capable of operating with large area solid and/or liquid lithium coatings essentially surrounding the entire plasma (as opposed to just the divertor or limiter region in other devices). Lithium (Li) wall-coatings have improved plasma performance and confinement in several tokamaks with carbon (C) PFCs, including the National Spherical Torus Experiment (NSTX). In NSTX, contamination of the core plasma with Li impurities was very low (<0.1%) despite extensive divertor coatings. Low Li levels in NSTX were found to be largely due to neoclassical forces from the high level of C impurities. Studying impurity levels and transport with Li coatings on stainless steel surfaces in LTX is relevant to future devices (including future enhancements to NSTX-Upgrade) with all-metal PFCs. The new measurements in this thesis were enabled by a refurbished Thomson scattering system and improved impurity spectroscopy, primarily using a novel visible spectrometer monitoring several Li, C, and oxygen (O) emission lines. A simple model was used to account for impurities in unmeasured charge states, assuming constant density in the plasma core and constant concentration in the edge. In discharges with solid Li coatings, volume averaged impurity concentrations were low but non-negligible, with~2-4% Li, ~0.6-2% C, ~0.4-0.7% O, and Z_eff<1.2. Transport was assessed using the TRANSP, NCLASS, and MIST codes. Collisions with the main H ions dominated the neoclassical impurity transport, unlike in NSTX, where collisions with C dominated. Furthermore, neoclassical transport coefficients calculated with NCLASS were similar across all impurity species and differed no more than a factor of two, in contrast to NSTX where they differed by an order of magnitude. However, time-independent simulations with MIST indicated that unlike NSTX, neoclassical theory did not fully capture the impurity transport and anomalous transport likely played a significant role in determining impurity profiles.

Lithium plasma facing components↗

Licensing of the national repository for LILW waste in Bulgaria - 15609

Radioactive waste arises from the operation and decommissioning of the Bulgarian nuclear power plants and from other sources in research, medical applications and industry. The need for building the National Disposal Facility (NDF) is recognized by the Bulgarian government, and described and justified in the Environment Impact Assessment Decision. The Bulgarian State Enterprise for Radioactive Waste Management (SERAW) is endeavoring to build a near-surface repository for short-lived low and intermediate level radioactive waste (SL-LILW). The European Union finances the establishment of the NDF through the Kozloduy International Decommissioning Support Fund. The Bulgarian government has defined the NDF as a Project of National Importance. At the conclusion of an international tendering process, SERAW awarded the contract for development of the NDF design, including Intermediate Safety Analysis Report (ISAR), to the Consortium of Westinghouse Electric Spain S.A.U, DBE Technology GmbH of Germany, and ENRESA, the Spanish National Waste Management Agency. Two Bulgarian companies also participate in the project as subcontractors;KK-Project and EQE-Bulgaria. The project 'Technical Design and ISAR Preparation for the National Disposal Facility at Bulgaria' is identified within SERAW as 'R-Project 5'. Since obtaining SERAW's approval for the preferred repository design variant, R Project 5 has focused on the development of the Technical Design and on preparation of the ISAR, which demonstrates the safety and suitability of the proposed NDF design. The Consortium submitted to SERAW the Technical Design for revision on March 2013. SERAW's experts immediately started the review of the design. In addition, SERAW invited independent, highly qualified Bulgarian experts and scientists to participate in the review. In November 2013, SERAW approved the Technical Design. The Consortium submitted the Intermediate Safety Analysis Report to SERAW for review following a similar process in July 2014. Both documents were meanwhile handed over to the appropriate Bulgarian licensing authorities. SERAW's goal is to receive a license for construction of the NDF in early 2015. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Design and Construction of a Loess-Cement Cushion as an Integral Component of an SL-LILW Repository - 16077

The Bulgarian State Enterprise for Radioactive Waste Management (SERAW) is planning the construction of a near-surface repository for short-lived low and intermediate level radioactive waste, the National Disposal Facility (NDF), adjacent to the Kozloduy Nuclear Power Plant (KNPP). The NDF will be constructed as a reinforced concrete vault-type repository system, where prefabricated cubic waste packages (2 m on a side) will be emplaced in large reinforced concrete disposal cells. Waste emplacement operations will be conducted in three phases over a total of 60 years of operations. After the last waste packages have been disposed, an engineered multilayer cover will be installed over the site to further isolate the waste from the accessible environment. The Radiana Site where the NDF will be constructed is a sloping area located between the second and sixth loess terraces above the River Danube with elevations ranging from approximately +40 m to elevation +95 m. The unsaturated zone at the location selected for waste disposal ranges from 13 m to 16 m in thickness. After construction, the unsaturated zone will consist of a 5 m thick, engineered loess-cement cushion installed over naturally occurring Pliocene clays and sandy clayey sediments of the Brusarci Formation with a thickness above the top of groundwater ranging from 8 m to 11 m. The loess-cement cushion is a key component of the 'engineered fill' barrier as identified in the Intermediate Safety Assessment Report (ISAR) for the NDF. This barrier consists of engineered fill both below the disposal cells, i.e., the loess-cement cushion, and above the disposal cells, i.e. the final multilayer cover to be installed at closure of the facility. The loess-cement cushion component of this barrier will act to provide a geo-technically stable foundation for the disposal system. In addition, the barrier will raise the base of the disposal cells and increases the unsaturated zone thickness above the top of the groundwater table, as well as to serve as a chemical barrier that will act to sorb radionuclides thereby retarding their migration to the underlying groundwater. In addition to its assigned barrier functions the loess cement cushion also houses key embedded components required as part of the overall NDF safety concept, including systems necessary for operational and post-closure performance monitoring as well as the support foundation structures required for the mobile roofs, which are designed to handle and protect the waste during emplacement operations. The post-closure monitoring period, i.e., the period of institutional control, is given by as 300 years. While similar although less massive cushions have been previously constructed as foundations for various structures at the KNPP, the loess-cement cushion planned for construction at the NDF including the embedded structures will represent a first of its kind construction in terms of both its physical dimensioning as well as its requirements for long-term performance. This paper describes the design of the cushion, its functions and its construction as planned for the NDF as an integral component of the site safety concept. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Computational Fluid Dynamics Simulations of Glass Vitrification Refractory Coupon Tests

The Waste Treatment and Immobilization Plant (WTP) at the Hanford site is nearing the start of the Direct-Feed Low-Activity Waste (DFLAW) operations. DFLAW is destined to convert a pretreated low activity waste portion of the 56 million gallons of tank waste into a stable solid glass. In the subsequent decade completion of the high-level waste (HLW) facility is anticipated. Sustained operational missions of both LAW and HLW melter facilities are expected over multiple decades. In high-temperature glass melters, the refractory lining corrodes over time, which could potentially be an issue for longer term operations, this refractory corrosion is higher at the level of the glass-air interface due to surface tension driven flow. The glass viscosity, melt pool temperature, and glass chemical composition can impact the rate at which the refractory corrodes. This rate is important to quantify for the various waste glasses to be produced at the WTP since the integrity of the refractory should not be a limiting factor affecting the lifetime of the melter. To this end, a series of glasses representative of the first batches of waste glass produced by the WTP will be melted in small-scale crucibles with Monofrax® K-3 coupons inserted. The corrosion of the K-3 will be measured in the melt and at the meltline (or neckline). A model for the corrosion rate will be constructed and implemented into a previously developed framework for a computational fluid dynamics (CFD) model of the full-scale WTP. To assist with experimental design and validate the implementation of the model in the full-scale melter, CFD simulations of the small-scale crucible tests were performed. The bubbling that occurs in the small-scale crucible is initially validated here with a model that uses silicone oil at room temperature. The viscosity of the oil ranges from 1 to 100 Pa•s, which corresponds to operating glass pool temperatures near 1150 °C down to idling temperatures near 950 °C. The simulation results show good agreement with the bubble sizes that form during experiments. CFD modeling of the crucible setup was used to determine bubbling characteristics to match the range of near-wall velocities expected in the full-scale WTP. This study presents the initial CFD modeling results, corrosion testing plan, and some preliminary corrosion samples with an outline for the next steps for the development of the corrosion model.

Abboud, Alexander W. [Idaho National Lab]↗

Dissolved pyrogenic carbon leaching in soil: Effects of soil depth and pyrolysis temperature

We report Pyrogenic organic carbon (PyC) is found in soils as a heterogeneous mixture of thermally altered plant residues that range in their susceptibility to losses via mineralization, leaching, and erosion. Leaching of PyC as DOC (DPyC) within the soil profile is likely influenced by the chemical composition of solid PyC and the dominant soil processes and properties at a particular depth. Here we report the results of a 2-year laboratory decomposition and leaching study designed to investigate the interactive effects of pyrolysis temperature levels (no pyrolysis, 300 °C, and 450 °C) and soil depth (surface soil, 0–10 cm depth; subsurface soil, 50–70 cm depth) on losses of 13 C-labeled jack pine (Pinus banksiana) wood, wood pyrolyzed at 300 °C (PyC300) and wood pyrolyzed at 450 °C (PyC450) as dissolved organic carbon (DOC). Losses of wood and PyC in the 13 C- DOC pool were measured in leachates drained from soils once a month over the course of 1 year, and at one single leaching event after 2 years. We found that pyrolysis temperature levels interacted with time and soil depth to affect losses of wood and PyC as DOC throughout the 1-year incubation and leaching study, with greater DOC losses from wood in surface soil (0.73 ± 0.076% of added C) than in subsurface soil (0.40 ± 0.063% of added C) averaged across sampling time. Monthly DOC losses from PyC were not affected by soil depth. Cumulative data indicated a small contribution of wood (2.86 ± 0.07%), PyC300 (0.40 ± 0.04%), and PyC450 (0.16 ± 0.01%) to total DOC leached from soils. DOC losses from wood and PyC300 (as a proportion of added C) were greater in surface soil than in subsurface soil, whereas DOC losses from PyC450 were unaffected by differences between surface and subsurface soil. Losses of DOC were greater from PyC300 than from PyC450 in surface soil, with no significant differences in DOC losses between PyC300 and PyC450 in subsurface soil. One single leaching event at the end of the 2-year decomposition study resulted in higher DOC losses from wood in subsurface soil than in surface soil likely due to desorption, and no differences in DOC losses between PyC300 and PyC450 regardless of soil depth. Our results suggest strong interactions between the initial physicochemical composition of organic C inputs and soil properties (soil depth as a proxy) that control the mobility and transport of PyC and should be better represented in Earth system models.

54 ENVIRONMENTAL SCIENCES↗

Influence of Surface Ligands on Energetics at FASnI 3 /C 60 Interfaces and Their Impact on Photovoltaic Performance

Interfacial chemistry and energetics significantly impact the performance of photovoltaic devices. In the case of Pb-containing organic metal halide perovskites, photoelectron spectroscopy has been used to determine the energetic alignment of frontier electronic energy levels at various interfaces present in the photovoltaic device. For the Sn-containing analogues, which are less toxic, no such measurements have been made. Through a combination of ultraviolet, inverse, and X-ray photoelectron spectroscopy (UPS, IPES, and XPS, respectively) measurements taken at varying thickness increments during stepwise deposition of C 60 on FASnI 3 , we present the first direct measurements of the frontier electronic energy levels across the FASnI 3 /C 60 interface. The results show band bending in both materials and transport gap widening in FASnI 3 at the interface with C 60 . The XPS results show that iodide diffuses into C 60 and results in n-doping of C 60 . This iodide diffusion out of FASnI 3 impacts the valence and conduction band energies of FASnI 3 more than the core levels, with the core level shifts displaying a different trend than the valence and conduction bands. Surface treatment of FASnI 3 with carboxylic acids and bulky ammonium substituted surface ligands results in slight alterations in the interfacial energetics, and all surface ligands result in similar or improved PV performance relative to the untreated devices. Finally, the greatest PV stability results from treatment with a fluorinated carboxylic acid derivative; however, iodide diffusion is still observed to occur with this surface ligand.

interfacial energetics↗

Lifetimes of electronic excitations in unoccupied surface states and the image potential states on Pd(110)

The contribution of inelastic electron-electron scattering to the decay rate of excitations in the surface states and first two image potential states at the Y-bar point on the surface is calculated in the GW approximation, and the quasi-momentum dependence of the corresponding contribution for the surface states is analyzed. The mechanisms of electron scattering in these states are studied, and the temperature dependence of the excitation lifetime is analyzed with allowance for the contribution of the electron-phonon interaction calculated earlier.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗