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At least 631 records · Page 35

Degradation and deforestation increase the sensitivity of the Amazon Forest to climate extremes

About 40% of the Brazilian Amazon has been deforested or suffered changes in forest structure through degradation (selective logging, fires, and fragmentation). The impact of forest degradation on the forest’s sensitivity to climate extremes has not been fully explored because of a lack of data and the complex interplay of forest structure and climate drivers. Here, we combined forest structure data from 545 airborne lidar transects (375 ha each) across the Brazilian Amazon with the Ecosystem Demography Model (ED2). We explore the forest’s functional response to near-present (1981–2019) climate extremes under observed forest structure from lidar ( Control ) and two forest structure change scenarios: (1) forest recovery by excluding all future deforestation and degradation ( Recovery ) and (2) expansion of selective logging and deforestation ( Degradation ). Using the Control simulation, we found a close and positive association between local forest aboveground biomass and the predicted gross primary productivity (GPP) and evapotranspiration (ET). Moreover, both GPP and ET respond negatively to extremes in vapor pressure deficit and downwelling shortwave irradiance in degraded forests in Eastern and Southern Amazon, indicating high sensitivity to droughts. Locally high-biomass forest patches showed little or no negative response of GPP and ET to extreme drought conditions whereas low-biomass forest patches in the same locations—typically degraded forest canopies—responded negatively to higher moisture stress. The results from the Recovery scenario showed similar results to simulations with observed structure; however, under the Degradation scenario, low-biomass forest patches became more abundant, resulting in more regions where GPP and ET are negatively impacted by hot drought conditions according to the ED2 model. Our results suggest that local forest structure is a critical determinant of an ecosystem’s response to climate variability, and that the loss of canopy trees in the Amazon through forest degradation could increase and expand forest vulnerability to droughts.

54 ENVIRONMENTAL SCIENCES↗

Direct Single-Enzyme Biomineralization of Catalytically Active Ceria and Ceria–Zirconia Nanocrystals

Biomineralization is an intriguing approach to the synthesis of functional inorganic materials for energy applications whereby biological systems are engineered to mineralize inorganic materials and control their structure over multiple length scales under mild reaction conditions. Herein we demonstrate a single-enzyme-mediated biomineralization route to synthesize crystalline, catalytically active, quantum-confined ceria (CeO2–x) and ceria–zirconia (Ce1–yZryO2–x) nanocrystals for application as environmental catalysts. In contrast to typical anthropogenic synthesis routes, the crystalline oxide nanoparticles are formed at room temperature from an otherwise inert aqueous solution without the addition of a precipitant or additional reactant. An engineered form of silicatein, rCeSi, as a single enzyme not only catalyzes the direct biomineralization of the nanocrystalline oxides but also serves as a templating agent to control their morphological structure. The biomineralized nanocrystals of less than 3 nm in diameter are catalytically active toward carbon monoxide oxidation following an oxidative annealing step to remove carbonaceous residue. The introduction of zirconia into the nanocrystals leads to an increase in Ce(III) concentration, associated catalytic activity, and the thermal stability of the nanocrystals.

36 MATERIALS SCIENCE↗

Using Ambient Ion Beams to Write Nanostructured Patterns for Surface Enhanced Raman Spectroscopy

Electrolytic spray deposition was used to pattern surfaces with 2D metallic nanostructures. Spots that contain silver nanoparticles (AgNP) were created by landing solvated silver ions at desired locations using electrically floated masks to focus the metal ions to an area as little as 20 mm in diameter. The AgNPs formed are unprotected and their aggregates can be used for surface-enhanced Raman spectroscopy (SERS). The morphology and SERS activity of the NP structures were controlled by the surface coverage of landed silver ions. The NP structures created could be used as substrates onto which SERS samples were deposited or prepared directly on top of predeposited samples of interest. The evenly distributed hot spots in the micron-sized aggregates had an average SERS enhancement factor of 108. The surfaces showed SERS activity when using lasers of different wavelengths (532, 633, and 785 nm) and were stable in air.

Environmental Molecular Sciences Laboratory↗

Better Catalysts through Microscopy: Mesoscale M1/M2 Intergrowth in Molybdenum–Vanadium Based Complex Oxide Catalysts for Propane Ammoxidation

Catalysis research has transformed from the predominantly empirical field to one where it is possible to control the catalytic properties via characterization and modification of the atomic-scale active centers. Many phenomena in catalysis, such as synergistic effect, however, transcend the atomic scale and also require the knowledge and control of the mesoscale structure of the specimen to harness. Our paper, we use our discovery of atomic-scale epitaxial interfaces in molybdenum vanadium based complex oxide catalysts systems (i.e., MoVMO, M = Ta, Te, Sb, Nb, etc.) to achieve control of the mesoscale structure of this complex mixture of very different active phases. We can now achieve true epitaxial intergrowth between the catalytically critical M1 and M2 phases in the system that are hypothesized to have synergistic interactions, and demonstrate that the resulting catalyst has improved selectivity in the initial studies. Finally, we highlight the crucial role atomic scale characterization and mesoscale structure control play in uncovering the complex underpinnings of the synergistic effect in catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interface properties and built-in potential profile of a LaCr O 3 / SrTi O 3 superlattice determined by standing-wave excited photoemission spectroscopy

LaCrO 3 (LCO)/SrTiO 3 (STO) heterojunctions are intriguing due to a polar discontinuity along [001], exhibiting two distinct and controllable charged interface structures [(LaO) + /(TiO 2 ) 0 and (SrO) 0 /(CrO 2 ) - ] with induced polarization, and a resulting depth-dependent potential. In this study, we have used soft- and hard-x-ray standing-wave excited photoemission spectroscopy (SW-XPS) to quantitatively determine the elemental depth profile, interface properties, and depth distribution of the polarization-induced built-in potentials. We observe an alternating charged interface configuration: a positively charged (LaO) + /(TiO 2 ) 0 intermediate layer at the LCO top /STO bottom interface and a negatively charged (SrO) 0 /(CrO 2 ) - intermediate layer at the STO top /LCO bottom interface. Using core-level SW data, we have determined the depth distribution of species, including through the interfaces, and these results are in excellent agreement with scanning transmission electron microscopy and electron energy-loss spectroscopy mapping of local structure and composition. SW-XPS also enabled deconvolution of the LCO and STO contributions to the valence-band (VB) spectra. Using a two-step analytical approach involving first SW-induced core-level binding-energy shifts and then VB modeling, the variation in potential across the complete superlattice is determined in detail. As a result, this potential is in excellent agreement with density functional theory models, confirming this method as a generally useful tool for interface studies.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

In Situ/Operando Probing of Dynamic Phase Structures of Alumina‐Supported Ultrasmall Copper‐Gold Alloy Nanoparticles Under Reaction Conditions

Abstract The ability to control phase structures and surface sites of ultrasmall alloy nanoparticles under reaction conditions is essential for preparing catalysts by design. This is, however, challenging due to limited understanding of the atomic‐scale phases and their correlation with the ensemble‐averaged structures and activities of catalysts during catalytic reactions. We reveal here a dynamic structural stability of alumina‐supported ultrasmall and equiatomic copper‐gold alloy nanoparticles under reaction conditions as a model system in the in situ/operando study. In situ atomic‐scale morphological tracking under oxygen reveals temperature‐dependent dynamic crystalline‐amorphous dual‐phase structures, showing dynamic stability over an elevated temperature range. This atomic‐scale dynamic phase stability coincides with a “conversion plateau” observed for carbon monoxide oxidation on the catalyst. It is substantiated by the stable lattice ordering/disordering structures and surface sites with oscillatory characteristics shown by operando ensemble‐average structural tracking of the catalyst during the oxidation reaction. The understanding of the atomic‐scale dynamic phase structures in correlation with the ensemble‐average dynamic ordering/disordering phase structures and surface sites provides fresh insights into the unique synergy of the supported alloy nanoparticles. This understanding has implications for the design and structural tuning of active and stable ultrasmall alloy catalysts under elevated temperatures.

Chemistry↗

Scaling impacts on environmental controls and spatial heterogeneity of soil organic carbon stocks

The spatial heterogeneity of land surfaces affects energy, moisture, and greenhouse gas exchanges with the atmosphere. However, representing heterogeneity of terrestrial hydrological and biogeochemical processes in earth system models (ESMs) remains a critical scientific challenge. We report the impact of spatial scaling on environmental controls, spatial structure, and statistical properties of soil organic carbon (SOC) stocks across the US state of Alaska. We used soil profile observations and environmental factors such as topography, climate, land cover types, and surficial geology to predict the SOC stocks at a 50 m spatial scale. These spatially heterogeneous estimates provide a dataset with reasonable fidelity to the observations at a sufficiently high resolution to examine the environmental controls on the spatial structure of SOC stocks. We upscaled both the predicted SOC stocks and environmental variables from finer to coarser spatial scales ( s = 100, 200, 500 m, 1, 2, 5, 10 km) and generated various statistical properties of SOC stock estimates. We found different environmental factors to be statistically significant predictors at different spatial scales. Only elevation, temperature, potential evapotranspiration, and scrub land cover types were significant predictors at all scales. The strengths of control (the median value of geographically weighted regression coefficients) of these four environmental variables on SOC stocks decreased with increasing scale and were accurately represented using mathematical functions ( R 2 = 0.83–0.97). The spatial structure of SOC stocks across Alaska changed with spatial scale. Although the variance (sill) and unstructured variability (nugget) of the calculated variograms of SOC stocks decreased exponentially with scale, the correlation length (range) remained relatively constant across scale. The variance of predicted SOC stocks decreased with spatial scale over the range of 50 to ~ 500 m, and remained constant beyond this scale. The fitted exponential function accounted for 98% of variability in the variance of SOC stocks. We found moderately-accurate linear relationships between mean and higher-order moments of predicted SOC stocks ( R 2 ~ 0.55–0.63). Current ESMs operate at coarse spatial scales (50–100 km), and are therefore unable to represent environmental controllers and spatial heterogeneity of high-latitude SOC stocks consistent with observations. We conclude that improved understanding of the scaling behavior of environmental controls and statistical properties of SOC stocks can improve ESM land model benchmarking and perhaps allow representation of spatial heterogeneity of biogeochemistry at scales finer than those currently resolved by ESMs.

54 ENVIRONMENTAL SCIENCES↗

Scaling impacts on environmental controls and spatial heterogeneity of soil organic carbon stocks

The spatial heterogeneity of land surfaces affects energy, moisture, and greenhouse gas exchanges with the atmosphere. However, representing the heterogeneity of terrestrial hydrological and biogeochemical processes in Earth system models (ESMs) remains a critical scientific challenge. We report the impact of spatial scaling on environmental controls, spatial structure, and statistical properties of soil organic carbon (SOC) stocks across the US state of Alaska. We used soil profile observations and environmental factors such as topography, climate, land cover types, and surficial geology to predict the SOC stocks at a 50 m spatial scale. These spatially heterogeneous estimates provide a data set with reasonable fidelity to the observations at a sufficiently high resolution to examine the environmental controls on the spatial structure of SOC stocks. We upscaled both the predicted SOC stocks and environmental variables from finer to coarser spatial scales ( s = 100, 200, and 500 m and 1, 2, 5, and 10 km) and generated various statistical properties of SOC stock estimates. We found different environmental factors to be statistically significant predictors at different spatial scales. Only elevation, temperature, potential evapotranspiration, and scrub land cover types were significant predictors at all scales. The strengths of control (the median value of geographically weighted regression coefficients) of these four environmental variables on SOC stocks decreased with increasing scale and were accurately represented using mathematical functions ( R 2 = 0.83–0.97). The spatial structure of SOC stocks across Alaska changed with spatial scale. Although the variance (sill) and unstructured variability (nugget) of the calculated variograms of SOC stocks decreased exponentially with scale, the correlation length (range) remained relatively constant across scale. The variance of predicted SOC stocks decreased with spatial scale over the range of 50 m to ~ 500 m, and remained constant beyond this scale. The fitted exponential function accounted for 98 % of variability in the variance of SOC stocks. We found moderately accurate linear relationships between mean and higher-order moments of predicted SOC stocks ( R 2 ∼ 0.55–0.63). Current ESMs operate at coarse spatial scales (50–100 km), and are therefore unable to represent environmental controllers and spatial heterogeneity of high-latitude SOC stocks consistent with observations. We conclude that improved understanding of the scaling behavior of environmental controls and statistical properties of SOC stocks could improve ESM land model benchmarking and perhaps allow representation of spatial heterogeneity of biogeochemistry at scales finer than those currently resolved by ESMs.

54 ENVIRONMENTAL SCIENCES↗

Efficacy of vibro-impact energy harvesting absorbers on controlling dynamical systems under vortex-induced vibrations and base excitation

Here this study investigates improving the efficacy of an energy harvesting absorber's ability to control a structure under vortex-induced vibrations, base excitation, and a combination of the two by including mechanical amplitude stoppers. The nonlinear reduced-order model is developed through modifying trilinear spring models to represent the impact forces, a modified van der Pol oscillator to represent the forcing due to the vortex-induced vibrations and using the Euler-Lagrange principle to express the equations of motion. It is seen that a soft stopper stiffness and a 5mm gap performs the most effectively of increasing the power generated from the absorber while still greatly reducing the primary structure's amplitude. By changing the stopper's location towards the middle of the energy harvesting absorber, the large effects of the impact forces are reduced and improves the efficacy of medium and hard stopper stiffnesses to generate near the amount of power the soft stopper does, while greatly improving the control of the primary structure. When the system is under combined loadings, the large oscillations of the synchronization region cause the effective configuration to be that of a 27.5 mm gap with soft stiffnesses. The results shows that medium stiffness stoppers with small gaps generate large aperiodic regions due to the high impact force. When the oscillations are close to the stoppers, the beating phenomenon is observed and is not overpowered by the vibro-impact force.

16 TIDAL AND WAVE POWER↗

Role of Complexation Strength on the Photophysical and Transport Properties of Semiconducting Charged Polymer Complexes

The high polymer fraction in complexes of conjugated and insulating polyelectrolytes offers unique opportunities for the fabrication of conductive thick films and bulk structures. The electrostatic interactions in these systems further provide a handle for controlling their structure and properties. The impact of charge-mediated complexation strength on the photophysical and electronic transport properties in blends of conjugated polyelectrolytes (CPEs) with oppositely charged polymeric ionic liquids (PILs) was examined. Complexes were formed with varying frequency of charged repeat units, from 50 to 100%, on an anionic polythiophene-based CPE and a complimentary cationic PIL. In highly charged complexes, the intimate mixing between the CPE and the PIL reduced the structural disorder along the CPE backbone, enhancing its intrachain conjugation and interchain stacking. In weakly charged complexes (<90%), these chain planarization effects were absent and microphase separation occurred. At all charge fractions examined, the electrical conductivity of an acid-doped complex was higher than that of the unblended constituent CPE. Further, the highest electrical conductivity, near 1 S cm –1 , was found for a charge fraction of 100%. These results demonstrate the potential for designing effective polymeric conductors using electrostatic complexation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NORM in Building Materials: A Case Study in Releasing and Disposing of Building Debris within the DOE System - 18123

In 2013, the Office of Management and Budget issued Memorandum 2013-02, clarifying its 'Freeze the Footprint' policy. Memorandum 2013-02 requires that all federal agencies maintain or reduce their total square footage, within each subsequent year, from a FY2012 baseline. Memorandum 2013-02 also requires that total square footage remain constant with respect to the type/intended use of a building. At Los Alamos National Laboratory (LANL), this means that new construction cannot occur without demolition of equivalent (both in type and square footage) building(s). Since 2013, decommissioning and demolition of aging, unused facilities at LANL has increased. In 2016, the TA16-280 building complex was scheduled for demolition. TA16-280 is a former high explosives (HE) processing facility that consists of six buildings connected to each other via weatherproof walkways. It was constructed in the 1950's and has been subsequently used for HE shipping, receiving, and storage. Interviews with radiation protection staff suggest that some of the buildings within the complex may have been used to store depleted uranium metal parts in a non-dispersible form. It is LANL policy to conduct decommissioning surveys for radioactive materials when building history cannot confirm that a structure is radiologically non-impacted. LANL follows the Multi-Agency Radiation Survey and Assessment of Materials and Equipment (MARSAME) process to develop its surveys and clear structures from radiological control. After clearance, a structure may be dispositioned as non-regulated waste, at a significant cost savings compared to regulated disposition pathways such as low-level waste. MARSAME measurements conducted in the 16-280 complex were elevated compared to reference measurements of surrogate materials, and a majority of the survey units failed to pass indistinguishable from background (IFB), which is LANL's unregulated clearance criteria. Further measurements conducted both in situ and in the laboratory indicated the presence of naturally-occurring thorium in several building materials including: poured concrete, the glaze atop ceramic blast tiles, and the porcelain enamel on the exterior of blast-proof ceiling lamps. Other than naturally-occurring thorium, there were no elevated radionuclide concentrations detected in building materials. It should be noted that there was no history of thorium use in the 16-280 complex, and the material in question was in all cases fixed to and within the building materials in question. Except in certain specific cases, such material is exempt from regulation under the Atomic Energy Act of 1954 [3], as amended, and is therefore exempt from regulation under the Nuclear Regulatory Commission, the Department of Energy, and agreement state regulatory frameworks. Despite this regulatory exemption, disposition of material from the 16-280 complex proved to be challenging, principally because local industrial landfills stipulate 'No radioactive material' in their Waste Acceptance Criteria. This disconnect between what is regulated and what is disposable creates a situation where some DOE sites find it easier to disposition property as Low Level Waste in lieu of pursuing a non-regulated disposition pathway. This presentation will explore the specifics of the 16-280 decommissioning project as well as the implications of the release/disposition disconnect for naturally occurring radioactive material and project planning at LANL. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

High Efficiency Structural Flowthrough Rotor with Active Flap Control: Volume Three: Market & Team

The Zimitar one-piece rotor primary structure is integrated, so balanced thrust and gravity loads flow through the hub region without transferring out of its composite material. Large inner rotor geometry is used since there is no need to neck down to a blade root region and pitch bearing. Rotor control is provided by a highly redundant, five flap system on each blade, sized so that easily handled standard electric linear actuators are sufficient.

17 WIND ENERGY↗

Preparation of dendritic-like Ag crystals using monocrystalline silicon as template

Research highlights: {yields} Template-assisted method for synthesis of dendritic silver. {yields} Unique dendritic silver structure with stems, branches, and leaves. {yields} The morphology of silver depends on silicon surface roughness. {yields} Both diffusion and oriented attachment dominating the dendritic structure formation. -- Abstract: Symmetric dendritic silver structures with controlled morphology were successfully synthesized by a solvothermal method with the assistance of monocrystalline silicon. The morphology and structure of the dendritic silver were characterized by transmission electron microscopy (TEM), powder X-ray diffraction (XRD), and scanning electron microscopy (SEM). It was found that the architecture of silver crystals could be controlled via simply adjusting the experiment parameters: AgNO{sub 3} concentration, reaction time and temperature. Moreover, structural characterizations suggested that the dendritic silver structures preferentially grew along (1 1 1) and (2 0 0) directions, leading to the formation of dendritic structures with 1-2 {mu}m in stem diameter and 10-50 {mu}m in length. Additionally, the formation process of the dendritic silver structures was studied, and a possible formation mechanism was proposed based on the experimental results.

36 MATERIALS SCIENCE↗

Entanglement entropy and the colored Jones polynomial

We study the multi-party entanglement structure of states in Chern-Simons theory created by performing the path integral on 3-manifolds with linked torus boundaries, called link complements. For gauge group SU(2), the wavefunctions of these states (in a particular basis) are the colored Jones polynomials of the corresponding links. We first review the case of U(1) Chern-Simons theory where these are stabilizer states, a fact we use to re-derive an explicit formula for the entanglement entropy across a general link bipartition. We then present the following results for SU(2) Chern-Simons theory: (i) The entanglement entropy for a bipartition of a link gives a lower bound on the genus of surfaces in the ambient S3 separating the two sublinks. (ii) All torus links (namely, links which can be drawn on the surface of a torus) have a GHZ-like entanglement structure — i.e., partial traces leave a separable state. By contrast, through explicit computation, we test in many examples that hyperbolic links (namely, links whose complements admit hyperbolic structures) have W-like entanglement — i.e., partial traces leave a non-separable state. (iii) Finally, we consider hyperbolic links in the complexified SL(2,C) Chern-Simons theory, which is closely related to 3d Einstein gravity with a negative cosmological constant. In the limit of small Newton constant, we discuss how the entanglement structure is controlled by the Neumann-Zagier potential on the moduli space of hyperbolic structures on the link complement.

't Hooft and Polyakov loops↗

Finely tunable dynamical coloration using bicontinuous micrometer-domains

Nanostructures similar to those found in the vividly blue wings of Morpho butterflies and colorful photonic crystals enable structural color through constructive interference of light waves. Different from commonly studied structure-colored materials using periodic structures to manipulate optical properties, we report a previously unrecognized approach to precisely control the structural color and light transmission via a novel photonic colloidal gel without long-range order. Nanoparticles in this gel form micrometer-sized bicontinuous domains driven by the microphase separation of binary solvents. This approach enables dynamic coloration with a precise wavelength selectivity over a broad range of wavelengths extended well beyond the visible light that is not achievable with traditional methods. The dynamic wavelength selectivity is thermally tunable, reversible, and the material fabrication is easily scalable.

42 ENGINEERING↗

High Efficiency Structural Flowthrough Rotor with Active Flap Control: Volume One: Preliminary Design Report

The Zimitar one-piece rotor primary structure is integrated, so balanced thrust and gravity loads flow through the hub region without transferring out of its composite material. Large inner rotor geometry is used since there is no need to neck down to a blade root region and pitch bearing. Rotor control is provided by a highly redundant, five flap system on each blade, sized so that easily handled standard electric linear actuators are sufficient.

17 WIND ENERGY↗