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Efficacy and Costs of Restoring Wetland Breeding Habitat for Imperiled Amphibians in the Southeastern U.S.
Herbaceous isolated wetlands in the North American Southeastern Coastal Plain are important breeding sites for many imperiled amphibians. However, most are degraded from alterations to historic fire disturbance and hydrologic regimes. Without fire, encroaching woody vegetation can transition wetlands to more terrestrial conditions and negatively impact amphibian breeding habitat, yet few studies have experimentally tested the efficacy, cost, or temporal requirement of current methods to restore herbaceous wetland vegetation. Here, we tested the interaction of manipulating wetland canopy and leaf litter/duff to promote herbaceous vegetation within one year (i.e., one breeding season) in degraded herbaceous wetlands in South Carolina. We assessed plant response via herbaceous cover, composition, and species similarity to the wetland seed bank and then related treatment performance to treatment cost. Removing trees combined with burning, disturbing, or removing duff significantly increased herbaceous cover and proportions of wetland plants and graminoids. Removing trees alone did not improve herbaceous cover compared to closed-canopy controls, and manipulating duff alone had limited positive effects on plant cover and composition. The most expensive yet effective treatment was Tree Removal-Duff Removal, while Tree Removal-Duff Disturbance was the most cost-effective. At a minimum, we recommend removing trees and burning to kickstart herbaceous recovery. Promisingly, comparisons of our data with previous seed bank studies from these same wetlands indicate there was limited seed bank attrition during 30 years of woody encroachment. Results from this study should aid practitioners in choosing wetland restoration techniques to better conserve at-risk species in the Southeastern Coastal Plain.
Toward local core outlet temperature monitoring in gas-cooled nuclear reactors using distributed fiber-optic temperature sensors
Gas-cooled nuclear reactors operate at temperatures up to 950 °C with significant spatial variations in power generation and coolant flow through hundreds of parallel flow channels, resulting in complex mixing at the core outlet. The high temperatures and complex mixing can damage downstream components, challenge reactor calorimetry for power determination, and result in significant conservatism in calculated peak fuel temperatures, which ultimately limits the total power output. Directly measuring each gas stream individually is unrealistic using single point thermocouples, requiring more robust sensing techniques. Fiber-optic sensors are resilient to high temperatures (up to 1,000 °C) and radiation damage. Moreover, distributed measurements can be made along the length of one fiber, making them potential candidates for monitoring local core outlet temperatures to improve core calorimetry and identify hot channels. Here, to the authors’ knowledge, this manuscript is the first to report spatially distributed fiber optic temperature measurements to quantify mixing at the outlet of a relevant orifice plate under prototypic temperature and flow regimes to assess the feasibility of using fiber-optic sensors for distributed measurements of coolant temperature in gas-cooled reactors. A single optical fiber captured dynamic changes in local temperatures, whereas the mixed outlet temperature exhibited a muted response and could not identify which channels were responsible for the change in the mixed outlet temperature. The discussion focuses on potential challenges for deploying distributed optical fibers in gas-cooled reactors, including the effects of vibrations, radiation-induced signal attenuation and drift, and routing of the fiber while minimizing flow obstructions.
Multiomic Network Analysis Identifies Dysregulated Neurobiological Pathways in Opioid Addiction
BACKGROUND: Opioid addiction is a worldwide public health crisis. In the United States, for example, opioids cause more drug overdose deaths than any other substance. However, opioid addiction treatments have limited efficacy, meaning that additional treatments are needed. METHODS: To help address this problem, we used network-based machine learning techniques to integrate results from genome-wide association studies of opioid use disorder and problematic prescription opioid misuse with transcriptomic, proteomic, and epigenetic data from the dorsolateral prefrontal cortex of people who died of opioid overdose and control individuals. RESULTS: Here we identified 211 highly interrelated genes identified by genome-wide association studies or dysregulation in the dorsolateral prefrontal cortex of people who died of opioid overdose that implicated the Akt, BDNF (brain-derived neurotrophic factor), and ERK (extracellular signal-regulated kinase) pathways, identifying 414 drugs targeting 48 of these opioid addiction–associated genes. Some of the identified drugs are approved to treat other substance use disorders or depression. CONCLUSIONS: Our synthesis of multiomics using a systems biology approach revealed key gene targets that could contribute to drug repurposing, genetics-informed addiction treatment, and future discovery.
Computational and experimental study of different brines in temperature swing solvent extraction desalination with amine solvents
Rapid global urbanization and high-salinity wastewater disposal from industrial activities have exerted significant pressure on water resources. Over the past few years, temperature swing solvent extraction (TSSE) has been identified as a promising technique to desalinate hypersaline brines. Despite its potential, the TSSE desalination literature has been mainly based on empirical insights, and the limited molecular simulation studies have primarily focused on NaCl brines. Herein, we use molecular dynamics (MD) simulations to study the TSSE desalination of four different brines, namely, KCl, KBr, NaCl, and NaBr using diisopropylamine as the solvent. Based on both bulk and interfacial brine-diisopropylamine MD results, here we investigate the qualitative and quantitative performance of the simulations by benchmarking these results against our experimental evaluations of these same systems. MD results provide satisfactory qualitative agreement with the experimental data of water solubilization in the organic phase and amine solubilization in the aqueous phase for the KBr, KCl, and NaBr brines. Also, the molecular mechanism of solvation of ionic species by water molecules over diisopropylamine suggested by the MD simulations is in agreement with our experimental data. However, larger qualitative and quantitative deviations were observed for the NaCl brines, and this is likely due to polarization and charge transfer effects, as quantified by our quantum chemical calculations.
Molecular beam epitaxy of GaAs templates on water soluble NaCl thin films
Expensive III-V substrates are cost limiting for the adoption of many technologies. Consequently, being able to reuse the original substrate is highly desirable. Existing substrate reuse techniques have significant drawbacks, but this work discusses a new method using molecular beam epitaxy deposition of water soluble NaCl thin films on commonly employed (0 0 1) GaAs substrates. Single-crystal GaAs templates are grown on continuous NaCl layers utilizing careful exposure of the NaCl to an in-situ electron beam and a low temperature nucleation layer. The template layers can be quickly removed from the substrate via dissolution of the NaCl. After liftoff, the original wafer shows an increase in rms surface roughness of only 0.2 nm.
Radiative transition probabilities of neutral and singly ionized Europium estimated by laser-induced breakdown spectroscopy (LIBS)
Laser-induced breakdown spectroscopy (LIBS) is a versatile technique for compositional analysis for solids, liquids, or gasses. LIBS is an asset for the quantitative or qualitative analysis of resource limited materials like actinides and rare earths because it is quasi-nondestructive. Two Eu 2 O 3 pellets were synthesized to be a test and validation set, respectively. Spectral lines identified from the National Institute of Standards and Technology database with fundamental data reported were used to form Saha-Boltzmann plots. The Saha-Boltzmann plots were used to determine the plasma temperatures and electron densities of the laser-induced plasmas for both samples. These Saha-Boltzmann plots were then used to calculate previously unreported transition probabilities associated with identified peaks. Additionally, the transition probabilities presented in this paper provide the capability for calibration free LIBS to be performed more readily on europium samples and the spectroscopic analysis of stellar bodies. Eight previously unreported transition probabilities are presented in this paper; five for Eu I and three for Eu II. The transition probabilities for Eu I ranged from 0.172 to 7.38 × 10 7 s -1 and those for Eu II ranged from 1.56 to 6.75 × 10 7 s -1 .
Entropy-driven melting point depression in fcc HEAs
High Entropy Alloys (HEAs) are an increasingly dominant alloy design paradigm. The premise of entropic stabilization of single-phase alloys has motivated much of the research on HEAs. Chemical complexity may indeed help stabilize single alloy phases relative to other lower-entropy competing solid phases. Paradoxically, this complexity may de-stabilize these alloys against the liquid phase, potentially limiting the application space of HEAs at elevated temperatures. In this work, we carry out a comprehensive investigation of the phase stability in the fcc CoCrFeMnNiV-Al HEA space using a state of the art CALPHAD database. By using modern visualization techniques and statistical analysis we examine the trade-off between chemical complexity and stability against the liquid state and identify a potentially difficult to overcome barrier for development of high temperature alloys, at least within the conventional fcc HEA space. Here, limited experimental data seem to be consistent with this analysis.
Toward Rapid Actinium-225 Purification via Membrane Adsorbers with Covalently Tethered Diglycolamide Ligands
Extractive diglycolamide (DGA) resins are used in several state-of-the-art techniques for purifying 225 Ac, a promising radiometal for targeted alpha therapy. Unfortunately, separation processes that rely on resins are often limited to slow flow rates, high elution volumes, and long processing times. Membrane adsorbers functionalized with DGA ligands are an alternative separation material that may overcome these challenges. This work presents (1) the synthesis of an aminated tetrahexyldiglycolamide ligand, (2) the covalent tethering of the ligand to electrospun poly(vinylbenzyl chloride) fiber mats, and (3) the adsorption and desorption of La(III) and 225 Ac. Chemical and physical characterization supports the covalent tethering of the ligand to the fiber mat, as well as the preservation of the fiber surface area and porosity after functionalization. Equilibrium adsorption experiments were performed with stable La(III) and radioactive 225 Ac. Trends in affinity are consistent between commercial resins and the synthesized membrane adsorbers; however, the Langmuir constants and the maximum binding capacity of the membrane adsorbers were generally lower than the resins. Despite these differences, the modeled selectivity for an equimolar solution of La(III)/ 225 Ac in 10 M nitric acid is 57. Furthermore, 225 Ac is rapidly desorbed from the fibers in 10 M nitric acid (<20 min). The La(III)/ 225 Ac selectivity and rapid 225 Ac desorption indicate this class of materials is promising for rapid radioanalytical separations.
Deciphering Catalyst–Support Interaction via Doping for Highly Active and Durable Oxygen Evolution Catalysis
The design of oxygen evolution reaction (OER) electrocatalysts demands a delicate balance between activity and stability. Here, in this study, we present a rational design approach that leverages catalyst-support interactions to enhance both the intrinsic activity and durability of Ir-based catalysts. Our study reveals that while Mo doping energetically promotes the formation of high-valent Ir species, enhancing intrinsic catalytic activity, it also leads to a reduction in electrical conductivity. These findings emphasize that supporting doping can introduce both beneficial and limiting effects, highlighting the need for a carefully balanced design strategy to optimize the overall OER performance. Simultaneously, in situ analytical techniques and comparative evaluation reveal the crucial role of oxide supports in stabilizing the catalyst. These findings highlight the pivotal role of interface engineering in maintaining catalyst integrity and the need for support materials that balance dopant-driven electronic promotion with structural and electrochemical robustness. These interconnected degradation pathways highlight the need to move beyond a catalyst-centric view and instead adopt a system-level understanding of the stability. Our approach offers a strong foundation for the rational design and evaluation of high-performance OER electrocatalysts for electrochemical energy applications.
Using magnetic dynamics to measure the spin gap in a candidate Kitaev material
Spin-orbit entangled materials have attracted widespread interest due to the novel magnetic phenomena arising from the interplay between spin-orbit coupling and electronic correlations. However, the intricate nature of spin interactions within Kiteav materials complicates the precise measurement of low-energy spin excitations. Using Na 2 Co 2 TeO 6 as an example, we study these low-energy spin excitations using the time-resolved resonant elastic x-ray scattering (tr-REXS). Our observations unveil remarkably slow spin dynamics at the magnetic peak, whose recovery timescale is several nanoseconds. This timescale aligns with the extrapolated spin gap of ~1 μeV, obtained by density matrix renormalization group (DMRG) simulations in the thermodynamic limit. The consistency demonstrates the efficacy of tr-REXS in discerning low-energy spin gaps inaccessible to conventional spectroscopic techniques.
Matryoshka phonon twinning in α-GaN
Understanding lattice dynamics is crucial for effective thermal management in electronic devices because phonons dominate thermal transport in most semiconductors. α -GaN has become a focus of interest as one of the most important third-generation power semiconductors, however, the knowledge on its phonon dynamics remains limited. Here we show a Matryoshka phonon dispersion of α -GaN with the complementary inelastic X-ray and neutron scattering techniques and the first-principles calculations. Such Matryoshka twinning throughout the basal plane of the reciprocal space is demonstrated to amplify the anharmonicity of the related phonons through creating abundant three-phonon scattering channels and cutting the lifetime of affected modes by more than 50%. Such phonon topology contributes to reducing the in-plane thermal transport, thus the anisotropic thermal conductivity of α -GaN. The results not only have implications for engineering the thermal performance of α -GaN, but also offer valuable insights on the role of anomalous phonon topology in thermal transport of other technically semiconductors.
The pervasive impact of critical fluctuations in liquid–liquid extraction organic phases
Liquid-liquid extraction is an essential chemical separation technique where polar solutes are extracted from an aqueous phase into a nonpolar organic solvent by amphiphilic extractant molecules. A fundamental limitation to the efficiency of this important technology is third phase formation, wherein the organic phase splits upon sufficient loading of polar solutes. The nanoscale drivers of phase splitting are challenging to understand in the complex hierarchically structured organic phases. In this study, we demonstrate that the organic phase structure and phase behavior are fundamentally connected in a way than can be understood with critical phenomena theory. For a series of binary mixtures of trialkyl phosphate extractants with linear alkane diluents, we combine small angle x-ray scattering and molecular dynamics simulations to demonstrate how the organic phase mesostructure over a wide range of compositions is dominated by critical concentration fluctuations associated with the critical point of the third phase formation phase transition. These findings reconcile many longstanding inconsistencies in the literature where small angle scattering features, also consistent with such critical fluctuations, were interpreted as reverse micellar-like particles. Altogether, this study shows how the organic phase mesostructure and phase behavior are intrinsically linked, deepening our understanding of both and providing a new framework for using molecular structure and thermodynamic variables to control mesostructure and phase behavior in liquid-liquid extraction.
Lack of long-term effect of coarse woody debris dam restoration on ecosystem functioning and water quality in Coastal Plain streams
Coarse woody debris (CWD) addition is a restoration technique that has been used to reduce effects of landscape disturbance on instream habitat. However, efficacy of this technique for improving ecosystem condition is not well established, in part because monitoring designed to evaluate long-term efficacy is rare. We assessed the effectiveness of CWD additions in disturbed Coastal Plain streams at Fort Benning Military Installation, Georgia, USA, 14 y after initial restoration. In October 2003, 4 disturbed streams received CWD additions (restored streams), and 4 streams were left as unrestored controls. Pre-restoration (2001–2003) and post-restoration (2003–2006) monitoring of nutrient uptake, stream metabolism, and water-quality variables revealed 1) minimal change in water-quality variables, 2) increased stream metabolism and nutrient-uptake rates immediately following restoration, and 3) decreased metabolism and uptake over the remainder of the 3-y post-restoration period. We returned to these streams in 2017 and 2018, measured the same variables, and found minimal long-term effects of restoration on water quality, nutrient uptake, and whole-stream metabolism indicators; however, streamwater pH decreased in all streams 14 y after restoration, and there was a weak treatment × period interaction, indicating that CWD additions may decrease pH in the long term. Further, we found few relationships between watershed disturbance and water-quality variables and ecosystem function metrics, although some relationships were apparent during certain seasons and years. Furthermore, our study is one of the few that have assessed the long-term effects of CWD additions, or any other stream-restoration technique, on ecosystem function. These long-term assessments may be necessary to determine if restorations are a good use of limited resources.
Topological nodal point superconductivity in checkerboard magnet-superconductor hybrid systems
Here, we demonstrate that checkerboard magnet-superconductor hybrid (MSH) systems possess a rich phase diagram exhibiting both strong topological superconducting (STSC) and topological nodal point superconducting (TNPSC) phases. We show that TNPSC phases exist both for ferromagnetic and antiferromagnetic systems, yielding a plethora of qualitatively different edge mode structures. Checkerboard MSH systems also facilitate the emergence of STSC phases, which can be induced even in the limit of vanishing magnetization. Our results provide a new path for the quantum engineering of topological superconducting phases using atomic manipulation techniques.
Foreground-immune CMB lensing reconstruction with polarization
Extragalactic foregrounds are known to generate significant biases in temperature based CMB lensing reconstruction. Several techniques, which include "source hardening'" and "shear-only estimators'' have been proposed to mitigate contamination and have been shown to be very effective at reducing foreground-induced biases. Here we extend both techniques to polarization, which will be an essential component of CMB lensing reconstruction for future experiments and investigate the "large lens'' limit analytically to gain insight on the origin and scaling of foreground biases, as well as the sensitivity to their profiles. Furthermore, using simulations of polarized point sources, we estimate the expected bias to both Simons Observatory and CMB-S4 like (polarization-based) lensing reconstruction, finding that biases to the former are minuscule while those to the latter are potentially non-negligible at small scales ($L$ ~ $1000-2000$). In particular, we show that for a CMB-S4 like experiment, an optimal linear combination of point-source hardened estimators can reduce the (point-source induced) bias to the CMB lensing power spectrum by up to two orders of magnitude, at a ~ 4% noise cost relative to the global minimum variance estimator.
Picosecond carrier dynamics in InAs and GaAs revealed by ultrafast electron microscopy
Understanding the limits of spatiotemporal carrier dynamics, especially in III-V semiconductors, is key to designing ultrafast and ultrasmall optoelectronic components. However, identifying such limits and the properties controlling them has been elusive. Here, using scanning ultrafast electron microscopy, in bulk n-GaAs and p-InAs, we simultaneously measure picosecond carrier dynamics along with three related quantities: subsurface band bending, above-surface vacuum potentials, and surface trap densities. We make two unexpected observations. First, we uncover a negative-time contrast in secondary electrons resulting from an interplay among these quantities. Second, despite dopant concentrations and surface state densities differing by many orders of magnitude between the two materials, their carrier dynamics, measured by photoexcited band bending and filling of surface states, occur at a seemingly common timescale of about 100 ps. This observation may indicate fundamental kinetic limits tied to a multitude of material and surface properties of optoelectronic III-V semiconductors and highlights the need for techniques that simultaneously measure electro-optical kinetic properties.
Methods—Analyzing Electrochemical Kinetic Parameters in Deep Eutectic Solvents Using an Extended Butler-Volmer Equation
Deep eutectic solvents (DESs) are promising electrolytes for electrochemical redox reactions, which can be used in redox flow batteries (RFBs). However, in some systems like the Fe 2+/3+ redox reaction in ethaline, traditional Tafel-based kinetic analysis generates unreasonable kinetic parameters (i.e., large anodic/cathodic charge transfer coefficients ( α a , α c ) along with low exchange current densities ( i 0 )). This hinders a comprehensive kinetic and kinetic mechanism study. Here, we perform a detailed investigation of the Tafel analysis using a series of synthetic rotating disk electrode (RDE) data. We find the Tafel analysis only works well when i 0 < 0.57 i lim (limiting current density) in our scenario and leads to abnormal kinetic values once i 0 exceeds this limiting value. Thus, we propose an extended Butler-Volmer (ex-BV) analysis based on modern non-linear fitting techniques to obtain the actual kinetic parameters for such systems. The results show that this method fits the RDE data closely and generates reliable α a , α c and i 0 values, demonstrating that it is a good replacement for traditional Tafel analysis for kinetic studies in high-viscosity electrolytes such as DES systems.