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At least 973 records · Page 54

Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields

We report chamber measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation, where radical concentrations were systematically varied and the molecular composition of semi to low volatility gases and SOA were measured online. Using a detailed chemical mechanism, we find that to explain the behavior of low volatility products and SOA mass yields relative to input H2O2 concentrations, the second generation dihydroxy hydroperoxy peroxy radical (C5H11O6•) must undergo an intra-molecular H-shift with a net forward rate constant of order 0.1 s-1 or higher, consistent with quantum chemical calculations which suggest a net forward rate constant of 0.3-0.9 s-1. Furthermore, these calculations suggest the dominant product of this isomerization is a dihydroxy hydroperoxy epoxide (C5H10O5) which is expected to have a saturation vapor pressure ~2 orders of magnitude higher than the dihydroxy dihydroperoxide, ISOP(OOH)2 (C5H12O6), a major product of the peroxy radical reacting with HO2. These results provide strong constraints on the likely volatility distribution of isoprene oxidation products under atmospheric conditions and thus on the importance of non-reactive gas-particle partitioning of isoprene oxidation products as an SOA source.

D’Ambro, Emma L. (ORCID:0000000230419027)↗

Mechanistic Investigation of the Ce(III) Chloride Photoredox Catalysis System: Understanding the Role of Alcohols as Additives

Photocatalytic C–H activation is an emerging area of research. While cerium chloride photocatalysts have been extensively studied, the role of alcohol additives in these systems remains a subject of ongoing discussion. It was demonstrated that the photocatalyst [NEt 4 ] 2 [Ce IV Cl 6 ] ( 1 ) produces •Cl and added alcohols exhibit zero-order kinetics. Prior studies by other researchers suggested that 1 and alcohols lead to cerium alkoxide [Ce–OR] and alkoxy radical intermediates. Here, to understand these seemingly divergent mechanistic proposals, an expanded investigation comparing cerium(IV) catalyst 1 and cerium(III) complex [NEt 4 ] 3 [Ce III Cl 6 ] ( 2 ), which exhibit markedly different reactivity and C–H selectivity, is disclosed. Our findings reveal that alcohol additives accelerate the conversion of cerium(III) to cerium(IV) catalysts, forming key intermediates such as [NEt 4 ] 2 [Ce III Cl 5 (HOCH 3 )] ( 5 ) and [NEt 4 ] 2 [Ce IV Cl 5 (OCH 3 )] ( 6 ), driven by excited-state di-tert-butyl azodicarboxylate under blue light irradiation. The active complex 6 releases the •OCH 3 radical, in sharp contrast to •Cl radicals initiated by cerium(IV) photoredox catalyst 1 . These different reactivity and selectivity profiles can be understood in the context of complex 5 generation and in situ formation of base to afford complex 6 . Experimental validation shows enhanced selectivity toward C–H bonds with different reactivity with catalyst 1 and methanol upon the addition of base and decreased selectivity with catalyst 2 and methanol upon the addition of acid. These findings unify the previously contrasting observations of cerium halide/alkoxide photocatalytic systems and provide a comprehensive understanding on the essential role of base/acid and alcohol in selectivity and reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex

Synthetic strategies to glean molecular complexes of high-valent lanthanides, other than the ubiquitous Ce 4+ ion, are exceptionally rare, and thorough, detailed characterization in these systems is limited by complex lifetime and reaction and isolation conditions. The synthesis of high-symmetry complexes in high purity with significant lifetimes in solution and the solid state is essential for determining the role of ligand-field splitting, multiconfigurational behavior, and covalency in governing the reactivity and physical properties of these potentially technologically transformative tetravalent ions. We report the synthesis and physical characterization of an S 4 symmetric, four-coordinate tetravalent terbium complex, [Tb(NP(1,2-bis- t Bu-diamidoethane)(NEt 2 )) 4 ] (where Et is ethyl and t Bu is tert-butyl). The ligand field in this complex is weak and the metal–ligand bonds sufficiently covalent so that the tetravalent terbium ion is stable and accessible via a mild oxidant from the anionic, trivalent, terbium precursor, [(Et 2 O)K][Tb(NP(1,2-bis- t Bu-diamidoethane)(NEt 2 )) 4 ]. The crucial stability of the tetravalent complex enables its thorough characterization. The stepwise development of the supporting ligand points to key ligand control elements for further extending the known tetravalent lanthanide ions in molecular complexes. Magnetic susceptibility, electron paramagnetic resonance (EPR) spectroscopy, X-ray absorption near-edge spectroscopy (XANES), and density functional theory studies indicate a 4ƒ 7 ground state for [Tb(NP(1,2-bis- t Bu-diamidoethane)(NEt 2 )) 4 ] with considerable zero-field splitting, demonstrating that magnetic, tetravalent lanthanide ions engage in covalent metal–ligand bonds. This result has significant implications for the use of tetravalent lanthanide ions in magnetic applications since the observed zero-field splitting is intermediate between that observed for the trivalent lanthanides and for the transition metals. The similarity of the multiconfigurational behavior in the ground state of [Tb(NP(1,2-bis- t Bu-diamidoethane)(NEt 2 )) 4 ] (measured by Tb L 3 -edge XAS) to that observed in TbO 2 implicates ligand control of multiconfigurational behavior as a key component of the stability of the complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

What Limits Predictive Certainty of Long-Term Carbon Uptake?

Terrestrial biosphere models can help identify physical processes that control carbon dynamics, including land-atmosphere CO 2 fluxes, and have the potential to project the terrestrial ecosystem response to changing climate. It is important to identify ecosystem processes most responsible for model predictive uncertainty and design improved model representation and observational system studies to reduce that uncertainty. Here we identified model parameters that contribute the most uncertainty to long-term (~100 years) projections of net ecosystem exchange, net primary production, and aboveground biomass within a mechanistic terrestrial biosphere model (Ecosystem Demography, version 2.1) ED2. An uncertainty analysis identified parameters that represent the quantum efficiency of light to photosynthetic conversion, leaf respiration and soil-plant water transfer as the highest contributors to model uncertainty regardless of time frame (annual, decadal, and centennial) and output (e.g., net ecosystem exchange, net primary production, aboveground biomass). Contrary to expectations, the contribution of successional processes related to reproduction, competition, and mortality did not increase as the time scale increased. These findings suggest that uncertainty in the parameters governing short-term ecosystem processes remains the most significant bottleneck to reducing predictive uncertainty. Key actions to reduce parameter uncertainty include more leaf-level trait measurements across multiple sites for quantum efficiency and leaf respiration rate. Further, the empirical representation of soil-plant water transfer should be replaced with a mechanistic, hydraulic representation of water flow, which can be constrained with direct measurements. This analysis focused on aboveground ecosystem processes. The impact of belowground carbon cycling, initial conditions, and meteorological forcing should be addressed in future studies.

54 ENVIRONMENTAL SCIENCES↗

Are Land‐Use Change Emissions in Southeast Asia Decreasing or Increasing?

Abstract Southeast Asia is a region known for active land‐use changes (LUC) over the past 60 years; yet, how trends in net CO 2 uptake and release resulting from LUC activities (net LUC flux) have changed through past decades remains uncertain. The level of uncertainty in net LUC flux from process‐based models is so high that it cannot be concluded that newer estimates are necessarily more reliable than older ones. Here, we examined net LUC flux estimates of Southeast Asia for the 1980s−2010s from older and newer sets of Dynamic Global Vegetation Model simulations (TRENDY v2 and v7, respectively), and forcing data used for running those simulations, along with two book‐keeping estimates (H&N and BLUE). These estimates yielded two contrasting historical LUC transitions, such that TRENDY v2 and H&N showed a transition from increased emissions from the 1980s to 1990s to declining emissions in the 2000s, while TRENDY v7 and BLUE showed the opposite transition. We found that these contrasting transitions originated in the update of LUC forcing data, which reduced the loss of forest area during the 1990s. Further evaluation of remote sensing studies, atmospheric inversions, and the history of forestry and environmental policies in Southeast Asia supported the occurrence of peak emissions in the 1990s and declining thereafter. However, whether LUC emissions continue to decline in Southeast Asia remains uncertain as key processes in recent years, such as conversion of peat forest to oil‐palm plantation, are yet to be represented in the forcing data, suggesting a need for further revision.

54 ENVIRONMENTAL SCIENCES↗

Standardized Data to Improve Understanding and Modeling of Soil Nitrogen at Continental Scale

Abstract Nitrogen (N) is a key limiting nutrient in terrestrial ecosystems, but there remain critical gaps in our ability to predict and model controls on soil N cycling. This may be in part due to lack of standardized sampling across broad spatial–temporal scales. Here, we introduce a continentally distributed, publicly available data set collected by the National Ecological Observatory Network (NEON) that can help fill these gaps. First, we detail the sampling design and methods used to collect and analyze soil inorganic N pool and net flux rate data from 47 terrestrial sites. We address methodological challenges in generating a standardized data set, even for a network using uniform protocols. Then, we evaluate sources of variation within the sampling design and compare measured net N mineralization to simulated fluxes from the Community Earth System Model 2 (CESM2). We observed wide spatiotemporal variation in inorganic N pool sizes and net transformation rates. Site explained the most variation in NEON’s stratified sampling design, followed by plots within sites. Organic horizons had larger pools and net N transformation rates than mineral horizons on a sample weight basis. The majority of sites showed some degree of seasonality in N dynamics, but overall these temporal patterns were not matched by CESM2, leading to poor correspondence between observed and modeled data. Looking forward, these data can reveal new insights into controls on soil N cycling, especially in the context of other environmental data sets provided by NEON, and should be leveraged to improve predictive modeling of the soil N cycle.

54 ENVIRONMENTAL SCIENCES↗

Tuning the interfacial spin-orbit coupling with ferroelectricity

Detection and manipulation of spin current lie in the core of spintronics. Here we report an active control of a net spin Hall angle, θ SHE (net), in Pt at an interface with a ferroelectric material PZT (PbZr 0.2 Ti 0.8 O 3 ), using its ferroelectric polarization. The spin Hall angle in the ultra-thin Pt layer is measured using the inverse spin Hall effect with a pulsed tunneling current from a ferromagnetic La 0.67 Sr 0.33 MnO 3 electrode. The effect of the ferroelectric polarization on θ SHE (net) is enhanced when the thickness of the Pt layer is reduced. When the Pt layer is thinner than 6 nm, switching the ferroelectric polarization even changes the sign of θ SHE (net). This is attributed to the reversed polarity of the spin Hall angle in the 1 st -layer Pt at the PZT/Pt interface when the ferroelectric polarization is inverted, as supported by the first-principles calculations. These findings suggest a route for designing future energy efficient spin-orbitronic devices using ferroelectric control.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

North American boreal forests are a large carbon source due to wildfires from 1986 to 2016

Wildfires are a major disturbance to forest carbon (C) balance through both immediate combustion emissions and post-fire ecosystem dynamics. Here we used a process-based biogeochemistry model, the Terrestrial Ecosystem Model (TEM), to simulate C budget in Alaska and Canada during 1986–2016, as impacted by fire disturbances. We extracted the data of difference Normalized Burn Ratio (dNBR) for fires from Landsat TM/ETM imagery and estimated the proportion of vegetation and soil C combustion. We observed that the region was a C source of 2.74 Pg C during the 31-year period. The observed C loss, 57.1 Tg C year -1 , was attributed to fire emissions, overwhelming the net ecosystem production (1.9 Tg C year -1 ) in the region. Our simulated direct emissions for Alaska and Canada are within the range of field measurements and other model estimates. As burn severity increased, combustion emission tended to switch from vegetation origin towards soil origin. When dNBR is below 300, fires increase soil temperature and decrease soil moisture and thus, enhance soil respiration. However, the post-fire soil respiration decreases for moderate or high burn severity. The proportion of post-fire soil emission in total emissions increased with burn severity. Net nitrogen mineralization gradually recovered after fire, enhancing net primary production. Net ecosystem production recovered fast under higher burn severities. The impact of fire disturbance on the C balance of northern ecosystems and the associated uncertainties can be better characterized with long-term, prior-, during- and post-disturbance data across the geospatial spectrum. Our findings suggest that the regional source of carbon to the atmosphere will persist if the observed forest wildfire occurrence and severity continues into the future.

54 ENVIRONMENTAL SCIENCES↗

Patch-Based Convolutional Neural Networks for Multiple Microstructural Features Detection in FIB-SEM Micrographs of Irradiated Nuclear Fuel

Focused ion beam scanning electron microscopy (FIB-SEM) tomography has increasingly been utilized for acquiring three-dimensional (3D) microstructure features at the sub-micron scale in irradiated nuclear materials. This technique involves sequential ion beam slicing followed by electron beam imaging and compositional mapping using energy dispersive spectroscopy (EDS). Despite its growing use, several challenges persist. These include the time-intensive nature of data collection of EDS data, difficulties in distinguishing between various microstructures, and issues with image alignment. These challenges currently limit the broader application of FIB-SEM tomography in the field. To overcome these limitations, we propose using convolutional neural networks (CNNs) to automate microstructure identification in SEM images. Our study introduces a new framework for identifying microstructures in irradiated U-10Zr (wt. %) metallic fuel with limited annotated data. The framework includes the creation of a reliable annotated dataset with paired SEM and ground truth data from EDS maps, the applications of CNNs for microstructure identification, and the validation of model performance. Specifically, we employed the Segment Anything Model (SAM) to align SEM images with corresponding EDS maps and focused ion beam (FIB) tomography SEM data. We evaluate several models, including Patch-based U-Net, Attention U-Net, and Residual U-Net, finding that patch-based U-Net exhibits superior segmentation performance and consistency. This approach reduces reliance on EDS detectors and aids in accelerating nuclear material analysis process, highlighting the potential of advanced deep learning techniques to improve microstructural understanding in nuclear material. This is the first framework to integrate SAM and Patch-based CNN models for semantic segmentation of irradiated nuclear materials, with potential applicability to other tomography datasets.

36 - MATERIALS SCIENCE↗

Cloud radiative effect dominates variabilities of surface energy budget in the dark Arctic

Climate models simulate a wide range of temperatures in the Arctic. Here we investigate one of the main drivers of changes in surface temperature: the net surface heat flux in the models. We show that in the winter months of the dark Arctic, there is a more than two-fold difference in the net surface heat fluxes among the models, and this difference is dominated by the downward infrared radiation from clouds. Owing to the small amount of water vapor in the winter Arctic, infrared radiation from clouds transmits more easily to the surface in the Arctic than at other latitudes, resulting in large cloud radiative effect at the surface. The dominant role of the cloud effect is also found in the transient variability of the net surface heat flux. Results demonstrate that accurate simulation of clouds is crucial for determining the net surface heat flux, which in turn affects surface temperature and sea ice properties in the Arctic.

54 ENVIRONMENTAL SCIENCES↗

Applying equity principles leads to higher carbon removal obligations in Canada

Despite net-zero pledges, consensus on national responsibilities for carbon dioxide removal (CDR) strategies is lacking. Here, we use integrated assessment modeling to examine equity-informed estimates of Canada’s remaining carbon budgets, exploring CDR’s role at net-zero and beyond. Gigaton-scale CDR efforts post-2050 are needed to address Canada’s carbon debt under various burden-sharing principles. Cumulative negative emissions (2050-2100) could increase from 7.5 GtCO 2 in the Net-Zero scenario to 20.3 GtCO 2 in equity-informed scenarios. By 2100, a CDR portfolio, including bioenergy with carbon capture and storage, direct air capture, and enhanced weathering could contribute up to ~500 MtCO 2 /year of removals. The projected average CDR growth rates, 2.8%-16%/year, align with the historical adoption rates of ammonia synthesis and biomass consumption in Canada, underscoring the importance of drawing lessons from past successes. Socio-economic and technological sensitivity analysis highlights that, despite variations in the role of individual CDR technologies, CDR remains essential for Canada’s post-net-zero commitments.

54 ENVIRONMENTAL SCIENCES↗

Tracing baryon and electric charge transport in isobar collisions

It is of fundamental interest to understand the carrier of conserved quantum charges within protons and nuclei at high energy. Preliminary data from isobar collisions at RHIC reveal a scaled net-baryon to net-electric charge ratio (B/ΔQ × ΔZ/A) at midrapidity between 1.2 and 2, consistent with string junction model predictions. Here, we compute the initial stage scaled net baryon to net-electric charge ratio for isobar collisions. Our model incorporates a realization of the string junction model and models the nuclear structure. Our predictions identify the baseline expectations for such measurement and quantify the impact of the nuclear structure.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

A fuel for sub-critical fast reactor

Along with the problem of the nuclear waste transmutation, the problem of minimization of waste production is of current interest. It is not possible to eliminate production of waste at a nuclear power plant, but, as is shown in this report, it is in principle possible to arrange a fuel composition with no net production of transuranic elements. The idea is to find the transuranic elements composition to which the depleted uranium is continuously supplied during frequent reprocessing, and amount of each other transuranic fuel component remains unchanged in time. For each transuranic component, the balance is achieved by equating burnup and production rates. The production is due to neutron capture by the neighboring lighter isotope and subsequent beta-decay. The burnup includes fission, neutron capture and decays. For the calculations a simplified burnup model which accounts for 9 isotopes of uranium, neptunium, plutonium and americium is used. The calculated fuel composition consists mainly of uranium with minority of plutonium isotopes. Such a fuel, after usage in a sub-critical fast reactor, should be reprocessed. The fission product content increases during burnup, representing a net production of waste, while the transuranic elements and {sup 238}U should be recycled into a new fuel. For such a fuel cycle, the net consumption is only for 238U, and the net waste production is just fission products.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Evaluating the performance of two neutron spectrum unfolding codes based on iterative procedures and artificial neural networks

In this work the performance of two neutron spectrum unfolding codes based on iterative procedures and artificial neural networks is evaluated. The first one code based on traditional iterative procedures and called Neutron spectrometry and dosimetry from the Universidad Autonoma de Zacatecas (NSDUAZ) use the SPUNIT iterative algorithm and was designed to unfold neutron spectrum and calculate 15 dosimetric quantities and 7 IAEA survey meters. The main feature of this code is the automated selection of the initial guess spectrum trough a compendium of neutron spectrum compiled by the IAEA. The second one code known as Neutron spectrometry and dosimetry with artificial neural networks (NDSann) is a code designed using neural nets technology. The artificial intelligence approach of neural net does not solve mathematical equations. By using the knowledge stored at synaptic weights on a neural net properly trained, the code is capable to unfold neutron spectrum and to simultaneously calculate 15 dosimetric quantities, needing as entrance data, only the rate counts measured with a Bonner spheres system. Similarities of both NSDUAZ and NSDann codes are: they follow the same easy and intuitive user's philosophy and were designed in a graphical interface under the LabVIEW programming environment. Both codes unfold the neutron spectrum expressed in 60 energy bins, calculate 15 dosimetric quantities and generate a full report in HTML format. Differences of these codes are: NSDUAZ code was designed using classical iterative approaches and needs an initial guess spectrum in order to initiate the iterative procedure. In NSDUAZ, a programming routine was designed to calculate 7 IAEA instrument survey meters using the fluence-dose conversion coefficients. NSDann code use artificial neural networks for solving the ill-conditioned equation system of neutron spectrometry problem through synaptic weights of a properly trained neural network. Contrary to iterative procedures, in neural net approach it is possible to reduce the rate counts used to unfold the neutron spectrum. To evaluate these codes a computer tool called Neutron Spectrometry and dosimetry computer tool was designed. The results obtained with this package are showed. The codes here mentioned are freely available upon request to the authors.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

An assessment of global Ocean Thermal Energy Conversion resources under broad geographical constraints

Rates of Ocean Thermal Energy Conversion (OTEC) are assessed with a high-resolution ocean general circulation model when broad geographical restrictions are imposed on the OTEC implementation area. This may correspond to practical or legal limitations, such as the cost of long submarine power cables or the extent of Exclusive Economic Zones. Because some environmental effects predicted under large-scale OTEC scenarios exhibit a strong asymmetry among major oceanic basins, numerical experiments where the OTEC domain is restricted to such specific areas are also conducted. Results suggest that in all cases, a rate of about 0.2 TW per Sverdrup of OTEC deep cold seawater is sustained when overall OTEC net power peaks. At that juncture, temperature profiles in the OTEC implementation areas are affected in similar ways, while the strength of the Thermohaline Circulation roughly doubles. Overall geographical constraints simply defined by distance to shore, given the model’s 1° horizontal resolution, produce global OTEC net power maxima of 12–14 TW. In such cases, OTEC net power density approximately increases in inverse proportion to the OTEC implementation area. Limiting OTEC development to the Indo-Pacific yields results similar to the global case with a maximum proportional to the implementation area (12 TW), but simulations restricted to the Atlantic behave quite differently. In the latter case, OTEC net power peaks a little over 5 TW. In conclusion, it is estimated that producing half the predicted power maxima would substantially limit large-scale environmental temperature changes in each case.

13 HYDRO ENERGY↗

Note: Calibration of EBT3 radiochromic film for measuring solar ultraviolet radiation

Solar (UVA + UVB) exposure was assessed using the Gafchromic EBT3 film. The coloration change was represented by the net reflective optical density (Net ROD). Through calibrations against a UV-tube lamp, operational relationships were obtained between Net ROD and the (UVA + UVB) exposures (in J cm⁻²p or J m⁻²). The useful range was from ~0.2 to ~30 J cm⁻². The uniformity of UV irradiation was crucial for an accurate calibration. For solar exposures ranging from 2 to 11 J cm⁻², the predicted Net ROD agreed with the recorded values within 9%, while the predicted exposures agreed with the recorded values within 15%.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Formation of a new archetypal Metal-Organic Framework from a simple monatomic liquid

We report a molecular-dynamics simulation of a single-component system of particles interacting via a spherically symmetric potential that is found to form, upon cooling from a liquid state, a low-density porous crystalline phase. Its structure analysis demonstrates that the crystal can be described by a net with a topology that belongs to the class of topologies characteristic of the Metal-Organic Frameworks (MOFs). The observed net is new, and it is now included in the Reticular Chemistry Structure Resource database. The observation that a net topology characteristic of MOF crystals, which are known to be formed by a coordination-driven self-assembly process, can be reproduced by a thermodynamically stable configuration of a simple single-component system of particles opens a possibility of using these models in studies of MOF nets. It also indicates that structures with MOF topology, as well as other low-density porous crystalline structures can possibly be produced in colloidal systems of spherical particles, with an appropriate tuning of interparticle interaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Roughness effects in uncompensated antiferromagnets

Monte Carlo simulations show that roughness in uncompensated antiferromagnets decreases not just the surface magnetization but also the net magnetization and particularly strongly affects the temperature dependence. In films with step-type roughness, each step creates a new compensation front that decreases the global net magnetization. The saturation magnetization decreases non-monotonically with increasing roughness and does not scale with the surface area. Roughness in the form of surface vacancies changes the temperature-dependence of the magnetization; when only one surface has vacancies, the saturation magnetization will decrease linearly with surface occupancy, whereas when both surfaces have vacancies, the magnetization is negative and exhibits a compensation point at finite temperature, which can be tuned by controlling the occupancy. Roughness also affects the spin-texture of the surfaces due to long-range dipolar interactions and generates non-collinear spin configurations that could be used in devices to produce locally modified exchange bias. These results explain the strongly reduced magnetization found in magnetometry experiments and furthers our understanding of the temperature-dependence of exchange bias.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗