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At least 343 records · Page 19

Considering Factors for Ion Concentrations in Precipitation at the Savannah River Site

Precipitation was collected from three different areas on the Savannah River Site during 2021. The precipitation was analyzed for concentrations of 29 different ions and compared with data on factors such as wind speed, wind direction, rain drop sizes, and more. The 2021 ion concentrations were also compared to the ion concentrations from previous years at the site as well as from Santee National Wildlife Refuge which is nearby. The historical ion concentrations data was gathered from the National Atmospheric Deposition Program. Scatter plots and correlation coefficients were used to identify what factors may have the greatest impact on ion concentration in rainwater. The data generally followed the same trends with a few notable outliers. There initially seemed to be a strong correlation between the mean diameter and some ion concentrations as both increased in July. However, ion concentrations in different areas were related to different wind directions, thus spatial variability must be considered. These factors, spatial variability of atmospheric particles and wind direction, impact concentrations of ions in precipitation.

54 ENVIRONMENTAL SCIENCES↗

Engineering Active Sites of Metal/Metal Oxide Catalysts by Oxide Ligand Overlayers

Abstract Engineering sites of supported metal catalysts is essential to enhancing activity and selectivity. Such enhancement is typically achieved by particle size modification, surface alloying, or attaching molecular ligands. Yet, control strategies for complex, multifunctional molecules and catalysts, where selectivity is crucial, are lacking. Here, we demonstrate that submonolayer WO x with tunable coverage preferentially decorates well‐coordinated Pt terrace sites as a stable ligand. By combining experimental kinetics with probe molecules, in situ spectroscopies, and first‐principles modeling, we show that the WO x coverage on Pt modifies the metal‐to‐acid site balance while retaining the acid strength intact and results in optimal reactivity for metal‐acid catalyzed reactions at a specific metal, size, and support‐dependent WO x coverage. The oxide can also alter the reactant adsorption mode, reversing selectivity and pathways from terrace‐ to step‐dominated, as evidenced in furfural decarbonylation and hydrogenation. The insights open avenues for improving metal/metal oxide catalysts beyond the specific system.

Zhou, Jiahua↗

Effects of the method of active site characterization for determining structure-sensitivity in Ag-catalyzed ethylene epoxidation

We report catalysts have been prepared on a low surface area α-Al 2 O 3 support used commercially for previous generation olefin epoxidation catalysts. Prescreening of the low surface area alumina (0.73 m 2 /g) indicated the absence of acid catalyzed isomerization of EO at an evaluation temperature of 210 °C. A 0.1 wt% Ag base material synthesized by incipient wetness impregnation of AgNO 3 was used as a base material for electroless deposition (ED) of additional Ag to increase particle sizes by controlled reduction of Ag + directly onto the preexisting Ag surface to form weight loadings between 0.3 and 5.0 wt% metal. A 12 wt% Ag/α-Al 2 O 3 using Ag 2 C 2 O 4 as the Ag precursor was also prepared to compare performance of the ED samples with a catalyst more typical of industrial formulations. Characterization by SEM, STEM, and hydrogen titration of oxygen precovered Ag characterized before and after catalytic evaluation indicated that microscopy is required to accurately represent distributions of Ag particle sizes, but H 2 titration of O-precovered Ag gives the best representation of active sites since it directly counts the number of Ag surface sites. Larger particles >100 nm are resistant to both Ag sintering and carbon foulant; TOF values were relatively insensitive to particle size with only a 2.2 × difference between the best and worst performing samples. Selectivity, which is not a function of TOF, shows the most significant structure sensitivity effect where particle sizes follow the trend 67 nm ≈ 92 nm (58% EO) < 157 nm (67% EO) < 211–542 nm (73% EO). The lower EO selectivities were also correlated with increased fouling for the smaller Ag sizes, suggesting that more strongly bound EO precursor(s) leads to combustion and CO 2 /H 2 O formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Innovative Deep-Water Mooring Systems for Floating Wind Farms (DeepFarm): Cooperative Research and Development (Final Report)

The DeepFarm project, led by Principle Power Inc (PPI), focused on design, modeling and development of innovative mooring and anchoring systems for semi-submersible floating wind turbine platforms in a deep water, commercial-size wind farm. It explored the possibility of sharing anchors amongst the floating platforms within the farm, and considers site conditions representative of the West Coast and Hawaii, with a variety of water depths, as case studies to ensure that the sensitivity to water depth and park size are well understood. NREL and PPI worked together to develop and apply NREL's computational tools for modeling floating wind farm dynamics and costs.

17 WIND ENERGY↗

Influence of Domain Size and Support Composition on the Reducibility of SiO 2 and TiO 2 Supported Tungsten Oxide Clusters

Supported tungsten oxides are widely used in a variety of catalytic reactions. Depending on the support, the cluster size, oxidation state, reducibility and speciation of the tungsten oxides can widely differ. When promoted with a platinum group metal, the resulting spillover of hydrogen may facilitate the reduction of supported tungsten oxide species, depending on the support. High resolution scanning transmission electron microscopy imaging showed nanometer scale WO x clusters were synthesized on SiO 2 whereas highly dispersed species were formed on TiO 2 . Results from H 2 -temperature-programmed reduction showed the presence of Pd lowered the initial reduction temperature of SiO 2 -supported WO x species but interestingly did not affect that of TiO 2 -supported WO x . X-ray photoelectron and absorption spectroscopies showed the W atoms in SiO 2 -supported WO x species reduce from a +6 oxidation state to primarily +5 after thermal treatment in 5% H 2 , while the fraction of W in the +5 oxidation state was relatively unaffected by reduction treatment of TiO 2 -supported WO x . The unusual behavior of TiO 2 -supported WO x was explained by quantum chemical calculations that reveal the lack of change in the oxidation state of W is attributed to charge delocalization on the surface atoms of the titania support, which does not occur on silica. Moreover, modeling results at <600 K in the presence of H 2 suggest the formation of Brønsted acid sites, and the absence of Lewis acid sites, on larger aggregates of WO x on silica and all cluster sizes on titania. These results provide experimental and theoretical insights into the nature of supported tungsten oxide clusters under conditions relevant to various catalytic reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Light regulation of light-harvesting antenna size substantially enhances photosynthetic efficiency and biomass yield in green algae

One of the major factors limiting biomass productivity in algae is the low thermodynamic efficiency of photosynthesis. The greatest thermodynamic inefficiencies in photosynthesis occur during the conversion of light into chemical energy. At full sunlight the light-harvesting antenna captures photons at a rate nearly 10 times faster than the rate-limiting step in photosynthetic electron transport. Excess captured energy is dissipated by non-productive pathways including the production of reactive oxygen species. Substantial improvements in photosynthetic efficiency have been achieved by reducing the optical cross-section of the light-harvesting antenna by selectively reducing chlorophyll b levels and peripheral light-harvesting complex subunits. Smaller light-harvesting antenna, however, may not exhibit optimal photosynthetic performance in low or fluctuating light environments. Additionally, we describe a translational control system to dynamically adjust light-harvesting antenna sizes for enhanced photosynthetic performance. Furthermore, by expressing a chlorophyllide a oxygenase (CAO) gene having a 5' mRNA extension encoding a Nab1 translational repressor binding site in a CAO knockout line it was possible to continuously alter chlorophyll b levels and correspondingly light-harvesting antenna sizes by light-activated Nab1 repression of CAO expression as a function of growth light intensity. Significantly, algae having light-regulated antenna sizes had substantially higher photosynthetic rates and two-fold greater biomass productivity than the parental wild-type strains as well as near wild-type ability to carry out state transitions and non-photochemical quenching. These results have broad implications for enhanced algae and plant biomass productivity.

09 BIOMASS FUELS↗

Assessing Spatial Representativeness of Global Flux Tower Eddy-Covariance Measurements Using Data from FLUXNET2015

Large datasets of carbon dioxide, energy, and water fluxes were measured with the eddy-covariance (EC) technique, such as FLUXNET2015. These datasets are widely used to validate remote-sensing products and benchmark models. One of the major challenges in utilizing EC-flux data is determining the spatial extent to which measurements taken at individual EC towers reflect model-grid or remote sensing pixels. To minimize the potential biases caused by the footprint-to-target area mismatch, it is important to use flux datasets with awareness of the footprint. This study analyze the spatial representativeness of global EC measurements based on the open-source FLUXNET2015 data, using the published flux footprint model (SAFE-f). The calculated annual cumulative footprint climatology (ACFC) was overlaid on land cover and vegetation index maps to create a spatial representativeness dataset of global flux towers. The dataset includes the following components: (1) the ACFC contour (ACFCC) data and areas representing 50%, 60%, 70%, and 80% ACFCC of each site, (2) the proportion of each land cover type weighted by the 80% ACFC (ACFCW), (3) the semivariogram calculated using Normalized Difference Vegetation Index (NDVI) considering the 80% ACFCW, and (4) the sensor location bias (SLB) between the 80% ACFCW and designated areas (e.g. 80% ACFCC and window sizes) proxied by NDVI. Finally, we conducted a comprehensive evaluation of the representativeness of each site from three aspects: (1) the underlying surface cover, (2) the semivariogram, and (3) the SLB between 80% ACFCW and 80% ACFCC, and categorized them into 3 levels. The goal of creating this dataset is to provide data quality guidance for international researchers to effectively utilize the FLUXNET2015 dataset in the future.

54 ENVIRONMENTAL SCIENCES↗

Implications from Monitoring Gopher Tortoises at Two Spatial Scales

A problem that conservation biologists face is how to monitor species, given both resource limitations and the inherent challenges of assessing long-term demographic processes. We assessed gopher tortoise (Gopherus polyphemus) abundance at a landscape scale and at the scale of 3 local populations within the Conecuh National Forest (CNF).USA between 1991 and 2017. Landscape-level data were collected 26 from line transect distance sampling arranged uniformly across the CNF and collected during a single season (2011); data for local populations were generated from long-term mark-recapture of individuals at three sites selected based on prior knowledge of high density at each. At a landscape scale, we estimated 5,242 (95% CI = 3,538-7,768) tortoises occurred across the approximately 34,000-ha forest, yielding a density of 0.14-0.32 tortoises/ ha. These low densities across the landscape suggest that, on average, management activities across the property have not allowed tortoise populations to retain social structure needed for long-term persistence. The three local populations, however, contained 25-60 individuals and densities of 1.9–6.9 tortoises/ha. Over the study period, populations at two sites were stable and the third experienced significant population growth. Mean annual survival of individuals was 0.89 and invariant across size classes. Altogether, line transect distance sampling is important for assessing landscape-scale abundance of tortoises but may fail to detect local clusters of high-density sites important for population persistence. Our mark-recapture efforts at the local scale revealed that small populations on these high-density sites can exhibit long-term stability or growth even though they do not meet current established criteria for viability. Improved models that incorporate immigration and emigration and better reflect dynamics of peripheral populations would assist in determining how such populations best contribute to species recovery and regional conservation targets.

59 BASIC BIOLOGICAL SCIENCES↗

Aerosol Activation in Radiation Fog at the Atmospheric Radiation Program Southern Great Plains Site

Environmental supersaturation is a key parameter in the formation of fog and clouds, yet it cannot be measured directly and must be inferred. Calculating the ambient supersaturation in fog requires knowledge of the aerosol hygroscopicity as well as particle size distribution, and relatively few values have been reported in the literature. Here we use κ-Köhler theory to derive aerosol activation properties based on particle hygroscopicity and dry particle size distributions, and then estimate the effective peak supersaturation during eight cases of radiative fog at the Southern Great Plains site in rural north-central Oklahoma, USA. The mean hygroscopicity parameter κ of particles likely to act as cloud condensation nuclei varied from 0.14 to 0.43. Ambient effective peak supersaturation during the fog episodes was between 0.01%–0.07%, with most values below 0.04%. Furthermore, the minimum 50% dry activation diameter generally ranged between 300–400 nm with little activation of particles with diameters below 300 nm.

54 ENVIRONMENTAL SCIENCES↗

Revealing the structure of a catalytic combustion active-site ensemble combining uniform nanocrystal catalysts and theory insights

Supported metal catalysts are extensively used in industrial and environmental applications. To improve their performance, it is crucial to identify the most active sites. This identification is, however, made challenging by the presence of a large number of potential surface structures that complicate such an assignment. Often, the active site is formed by an ensemble of atoms, thus introducing further complications in its identification. Being able to produce uniform structures and identify the ones that are responsible for the catalyst performance is a crucial goal. Here, we utilize a combination of uniform Pd/Pt nanocrystal catalysts and theory to reveal the catalytic active-site ensemble in highly active propene combustion materials. Using colloidal chemistry to exquisitely control nanoparticle size, we find that intrinsic rates for propene combustion in the presence of water increase monotonically with particle size on Pt-rich catalysts, suggesting that the reaction is structure dependent. We also reveal that water has a near-zero or mildly positive reaction rate order over Pd/Pt catalysts. Theory insights allow us to determine that the interaction of water with extended terraces present in large particles leads to the formation of step sites on metallic surfaces. These specific step-edge sites are responsible for the efficient combustion of propene at low temperature. This work reveals an elusive geometric ensemble, thus clearly identifying the active site in alkene combustion catalysts. These insights demonstrate how the combination of uniform catalysts and theory can provide a much deeper understanding of active-site geometry for many applications

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Artificial Soiling Replication of Field Losses on Commercial Photovoltaic Modules

Here, this study demonstrates the capabilities of an indoor artificial soiling approach developed to closely replicate the natural, cyclic soil accumulation processes in the field-dust suspension, deposition, and sedimentation/cementation-for a subtropical climate. In this work, a near-field environment is replicated in an artificial soiling cubic chamber through controlled regulation of humidity, temperature, dust type, and dust concentration, based on site-specific historical climate data. Two different models (MA and MB) of full-size commercial photovoltaic modules from a single manufacturer, installed side by side in the mid-Atlantic United States, were retrieved and subjected to artificial soiling experiments and various characterization measurements, including short-circuit current, colorimetry, reflectance, X-ray fluorescence, laser diffraction, and optical microscopy. Both in the field and in our improved field-representative artificial soiling tests, the MA model experienced roughly twice the soiling loss as the MB model. To closely replicate the field soiling losses for a site-specific climate, it is critical to include: 1) The use of field-collected dust with identical dust chemistry and particle distribution instead of standardized ISO 12103 Arizona Road dusts, 2) the use of only a small amount of field-collected dust inside the chamber during the deposition process (e.g., 0.15 g), and 3) the preconditioning of the surface coating for the partial/full dose of UV stress as experienced in the field during sunlight exposure and the abrasion as experienced in the field during regular module cleaning activities, if/as needed. The field-representative artificial soiling method developed here could potentially be adopted for rank ordering of various antisoiling coatings developed by researchers and industry stakeholders.

14 SOLAR ENERGY↗

Highly efficient libraries design for saturation mutagenesis

Abstract Saturation mutagenesis is a semi-rational approach for protein engineering where sites are saturated either entirely or partially to include amino acids of interest. We previously reported on a codon compression algorithm, where a set of minimal degenerate codons are selected according to user-defined parameters such as the target organism, type of saturation and usage levels. Here, we communicate an addition to our web tool that considers the distance between the wild-type codon and the library, depending on its purpose. These forms of restricted collections further reduce library size, lowering downstream screening efforts or, in turn, allowing more comprehensive saturation of multiple sites. The library design tool can be accessed via http://www.dynamcc.com/dynamcc_d/. Graphical Abstract

59 BASIC BIOLOGICAL SCIENCES↗

Real-time dynamics of the Schwinger model as an open quantum system with Neural Density Operators

Ab-initio simulations of multiple heavy quarks propagating in a Quark-Gluon Plasma are computationally difficult to perform due to the large dimension of the space of density matrices. This work develops machine learning algorithms to overcome this difficulty by approximating exact quantum states with neural network parametrisations, specifically Neural Density Operators. As a proof of principle demonstration in a QCD-like theory, the approach is applied to solve the Lindblad master equation in the 1 + 1d lattice Schwinger Model as an open quantum system. Neural Density Operators enable the study of in-medium dynamics on large lattice volumes, where multiple-string interactions and their effects on string-breaking and recombination phenomena can be studied. Thermal properties of the system at equilibrium can also be probed with these methods by variationally constructing the steady state of the Lindblad master equation. Scaling of this approach with system size is studied, and numerical demonstrations on up to 32 spatial lattice sites and with up to 3 interacting strings are performed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Magnetic field effects on the quantum spin liquid behaviors of NaYbS 2

Spin-orbit coupling is an important ingredient to regulate the many-body physics, especially for many spin liquid candidate materials such as rare-earth magnets and Kitaev materials. The rare-earth chalcogenides NaYbCh 2 (Ch = O, S, Se) is a congenital frustrating system to exhibit the intrinsic landmark of spin liquid by eliminating both the site disorders between Na + and Yb 3+ ions with the big ionic size difference and the Dzyaloshinskii-Moriya interaction with the perfect triangular lattice of the Yb 3+ ions. The temperature versus magnetic-field phase diagram is established by the magnetization, specific heat, and neutron-scattering measurements. Notably, the neutron diffraction spectra and the magnetization curve might provide microscopic evidence for a series of spin configuration for in-plane fields, which include the disordered spin liquid state, 120° antiferromagnet, and one-half magnetization state. Furthermore, the ground state is suggested to be a gapless spin liquid from inelastic neutron scattering, and the magnetic field adjusts the spin orbit coupling. Therefore, the strong spin-orbit coupling in the frustrated quantum magnet substantially enriches low-energy spin physics. This rare-earth family could offer a good platform for exploring the quantum spin liquid ground state and quantum magnetic transitions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Hydrogen Bonding Stiffens Peptide Amphiphile Supramolecular Filaments by Aza-Glycine Residues

Peptide amphiphiles (PAs) are a class of molecules comprised of short amino acid sequences conjugated to hydrophobic moieties that may exhibit self-assembly in water into supramolecular structures. Here, we investigate here how mechanical properties of hydrogels formed by PA supramolecular nanofibers are affected by hydrogen bond densities within their internal structure by substituting glycine for aza-glycine (azaG) residues. We found that increasing the number of PA molecules that contain azaG up to 5 mol% in PA supramolecular nanofibers increases their persistence length fivefold and decreases their diffusion coefficients as measured by fluorescence recovery after photobleaching. When these PAs are used to create hydrogels, their bulk storage modulus (G') was found to increase as azaG PA content in the supramolecular assemblies increases up to a value of 10 mol% and beyond this value a decrease was observed, likely due to diminished levels of nanofiber entanglement in the hydrogels as a direct result of increased supramolecular rigidity. Interestingly, we found that the bioactivity of the scaffolds toward dopaminergic neurons derived from induced pluripotent stem cells can be enhanced directly by persistence length independently of storage modulus. We hypothesize that this is due to interactions between the cells and the extracellular environment across different size scales: from filopodia adhering to individual nanofiber bundles to cell adhesion sites that interact with the hydrogel as a bulk substrate. Fine tuning of hydrogen bond density in self-assembling peptide biomaterials such as PAs provides an approach to control nanoscale stiffness as part of an overall strategy to optimize bioactivity in these supramolecular systems. supramolecular biomaterials.

36 MATERIALS SCIENCE↗

Pore-Scale Transport Effects in Electrochemical CO 2 Reduction on Gold via Coupled Microkinetic-Transport Modeling

A pore-resolved modeling framework is developed to quantify how pore-scale transport affects the intrinsic microkinetics of CO 2 -to-CO on Au. A DFT-informed microkinetic model is coupled self-consistently to a Generalized-Modified Poisson–Nernst–Planck (GMPNP) transport description in a single, electrolyte-filled cylindrical pore, allowing local concentrations and potential to feed back into site-specific reaction rates. FIB-SEM is used to determine pore sizes within realistic electrode materials. Across pore diameters, d p = 10–6000 nm, the surface-averaged CO 2 reduction rate is systematically reduced relative to the ideal microkinetic baseline where mass transport is not accounted for; the effectiveness factor 𝜂 𝑠,CO 2 , which quantifies this ratio, decreases rapidly at more negative potentials and is about 1% near −1.0 V vs SHE due to reactant depletion. Spatial maps reveal pore-bulk alkalization that emerges at higher cathodic bias, with a small, near-wall pH dip due to electrostatic repulsion of hydroxide at the cathode interface. For a fixed aspect ratio L p /d p , narrower pores exhibit larger 𝜂 𝑠,CO 2 by shortening diffusion paths, whereas variations in the aspect ratio L p /d p play a secondary role. A dimensionless analysis (surface/bulk Damköhler numbers) delineates operating regimes. In conclusion, this work offers a concept for incorporating microkinetic models into homogenized porous-electrode models through effectiveness factors and pore-size distribution.

Au-catalyst↗

Optimization of La 2 NiO 4+δ Electrolysis Cell Oxygen Electrode through Surfactant-Enabled LaCoO 3±δ Nanocatalyst Deposition

Lanthanum nickelate (LNO) has shown promise as a Cr-resistant air electrode material for SOECs but has suboptimal surface oxygen exchange properties. Nanocoating of the LNO surface with lanthanum cobaltite (LCO) was chosen to improve cell performance as a surface oxygen conductor. The work focused on the implementation of a two-step nano-LCO film deposition utilizing catechol molecules in a porous LNO electrode. The subgoals of the work were to maintain nanosized LCO particles/ grains to increase active surface area and to control the regularity/ homogeneity of the coating across the microstructure. To achieve these goals, a novel surfactant-enhanced liquid infiltration method was utilized, where nucleation sites were spread across the electrode structure to control the location and size of LCO particles. Various catechol surfactant compositions were evaluated for their ability to control the kinetics of nanoparticle deposition and the homogeneity of the coating. Chelated LCO was characterized by X-ray diffraction (XRD), which found a substantial improvement in LCO formation with surfactant addition and determined polymerized norepinephrine to be the best-performing surfactant, with 88.4% pure LCO formed at low temperature. X-ray photoelectron spectroscopy (XPS) confirmed LCO nanostructures formed by the two-step infiltration process, showing no impurities and a stable perovskite structure. Deposition kinetics were analyzed using atomic force microscopy (AFM), correlating infiltration times and solution molarity to nanoparticle size and distribution, the results of which were confirmed in symmetrical cell samples by scanning electron microscopy (SEM). Electrochemical impedance spectroscopy (EIS) testing demonstrated substantial improvements in polarization resistance, where the nanocoating reduced the resistance by ∼55% to 0.152 Ω·cm 2 at 700 °C and 0.039 Ω·cm 2 at 800 °C. Electrical conductivity relaxation (ECR) at this temperature confirmed an improved surface oxygen exchange coefficient of the LCO + LNO heterostructure predicted by the Bode data from EIS, alongside a reduction in activation energy by about 30%.

Deposition↗

Controlling saturation to improve per- and polyfluoroalkyl substance (PFAS) removal in biochar-amended stormwater bioretention systems

Black carbon-amended bioretention systems are an increasingly popular strategy for the removal of organic contaminants, including poly- and perfluoroalkyl substances (PFASs) and other trace organic contaminants (TOrCs), from urban stormwater. Many PFASs preferentially accumulate at the air–water interface, but detention time requirements for stormwater bioretention systems typically result in full saturation of the bioretention systems, effectively removing their air–water interfaces. This study assessed the effect of bioretention system saturation on removal of PFASs, metals, and hydrophilic TOrCs. A field-aged mixture of 40% v/v sand, 30% v/v zeolite, and 30% v/v biochar was packed into columns which were operated with hydraulic controls to remain unsaturated or fully saturated throughout the duration of the experiment. Twenty-four storm events sized to a 95th percentile storm at a California, United States military site were simulated using synthetic stormwater fortified with aqueous film forming foam-derived PFASs, TOrCs, and metals to mimic real-world conditions. Unsaturated conditions outperformed saturated conditions for removal of all PFASs analyzed. A simulated inadvertent system perturbation (i.e. flooding event) in the unsaturated columns did not result in significantly greater mobilization of PFAS mass, suggesting that more sorption to the biochar occurred as a result of the transient retention of PFASs at the air–water interface reducing kinetic sorption limitations. Overall, maintaining unsaturated conditions in a biofilter may extend the sorptive filter lifetime for PFASs by up to 83%. The results have implications for bioretention system application and design for PFAS removal in contaminated catchment areas.

13 HYDRO ENERGY↗