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At least 937 records · Page 52

Biobased Poly(dodecylene Furanoate) with Inherent Advantages in Performance and Circularity

Biobased polymers are gaining traction toward more sustainable flexible-film packaging, yet overcoming trade-offs between their performance properties and end-of-life (EoL) options still remains a challenge. Here, it is shown that biobased poly(dodecylene 2,5-furanoate) (PDDF), synthesized via both step-growth polycondensation and chain-growth ring-opening polymerization methods, exhibits advantages not only in gas barrier properties but also in EoL options due to its biodegradability and closed-loop chemical circularity. Specifically, PDDF displays significantly lower oxygen and carbon dioxide permeability than commercial poly(butylene adipate-co-terephthalate) (PBAT) and linear low-density polyethylene , alongside a markedly higher modulus (by ≈3 ×) and reduced water vapor transmission rate compared to PBAT. This superior performance is attributed to the inherently rigid, polar, H-bonding furan rings that enhance chain interaction, packing and crystallinity and thus reduce free volume impeding gas diffusion, while the long hydrophobic dodecylene segments inhibit water permeation. Furthermore, PDDF can be recycled back to its cyclic monomer by base-catalyzed depolymerization or diester and diol monomers by simple methanolysis. These superior barrier properties, coupled with biodegradation and closed-loop circularity, highlight the potential of the biobased PDDF as a more sustainable alternative for packaging.

Poly(dodecylene 2,5-furanoate) (PDDF)↗

Soil organic carbon is not just for soil scientists: measurement recommendations for diverse practitioners

Soil organic carbon (SOC) regulates terrestrial ecosystem functioning, provides diverse energy sources for soil microorganisms, governs soil structure, and regulates the availability of organically bound nutrients. Investigators in increasingly diverse disciplines recognize how quantifying SOC attributes can provide insight about ecological states and processes. Today, multiple research networks collect and provide SOC data, and robust, new technologies are available for managing, sharing, and analyzing large data sets. Here, we advocate that the scientific community capitalize on these developments to augment SOC data sets via standardized protocols. We describe why such efforts are important and the breadth of disciplines for which it will be helpful, and outline a tiered approach for standardized sampling of SOC and ancillary variables that ranges from simple to more complex. We target scientists ranging from those with little to no background in soil science to those with more soil-related expertise, and offer examples of the ways in which the resulting data can be organized, shared, and discoverable.

54 ENVIRONMENTAL SCIENCES↗

Male mating season range expansion results from an increase in scale of daily movements for a polygynous–promiscuous bird

Abstract Males of species with promiscuous mating systems are commonly observed to use larger ranges during the mating season relative to non‐mating seasons, which is often attributed to a change in movements related to reproductive activities. However, few studies link seasonal range sizes to variation in daily space use patterns to provide insight into the behavioral mechanisms underlying mating season range expansion. We studied 20 GPS‐tagged male wild turkeys ( Meleagris gallopavo ), a large upland gamebird, during the mating and summer non‐mating seasons to test the hypothesis that larger mating season ranges resulted from male wild turkeys expanding the scale of daily movement activities to locate and court females. We delineated mating and non‐mating seasons based on intensity of gobbling, a vocalization tied to courtship behavior, recorded by autonomous recording units distributed across the study area. Mating season ranges were significantly larger than non‐mating season ranges. Daily ranges were larger in the mating season, as were distances between roost sites used on consecutive nights. Variance in daily range size was greater in the mating season, but low temporal autocorrelation suggested considerable daily variability in both seasons. We found no evidence that male wild turkeys changed how they distributed daily movements within seasonal ranges, or differences in habitat use, suggesting larger mating season ranges result from male wild turkeys increasing the scale of their daily movements, rather than a systematic shift to a nomadic movement strategy. Likely, the distribution of females is more dynamic and ephemeral compared to other resources, prompting males to traverse larger daily ranges during the mating season to locate and court females. Our work illustrates the utility of using daily movement to understand the behavioral process underlying larger space use patterns.

59 BASIC BIOLOGICAL SCIENCES↗

Bringing function to structure: Root–soil interactions shaping phosphatase activity throughout a soil profile in Puerto Rico

Abstract Large areas of highly productive tropical forests occur on weathered soils with low concentrations of available phosphorus (P). In such forests, root and microbial production of acid phosphatase enzymes capable of mineralizing organic phosphorus is considered vital to increasing available P for plant uptake. We measured both root and soil phosphatase throughout depth and alongside a variety of root and soil factors to better understand the potential of roots and soil biota to increase P availability and to constrain estimates of the biochemical mineralization within ecosystem models. We measured soil phosphatase down to 1 m, root phosphatase to 30 cm, and collected data on fine‐root mass density, specific root length, soil P, bulk density, and soil texture using soil cores in four tropical forests within the Luquillo Experimental Forest in Puerto Rico. We found that soil phosphatase decreased with soil depth, but not root phosphatase. Furthermore, when both soil and root phosphatase were expressed per soil volume, soil phosphatase was 100‐fold higher that root phosphatase. Both root and soil factors influenced soil and root phosphatase. Soil phosphatase increased with fine‐root mass density and organic P, which together explained over 50% of the variation in soil phosphatase. Over 80% of the variation in root phosphatase per unit root mass was attributed to specific root length (positive correlation) and available (resin) P (negative correlation). Synthesis : Fine‐root traits and soil P data are necessary to understand and represent soil and root phosphatase activity throughout the soil column and across sites with different soil conditions and tree species. These findings can be used to parameterize or benchmark estimates of biochemical mineralization in ecosystem models that contain fine‐root biomass and soil P distributions throughout depth.

59 BASIC BIOLOGICAL SCIENCES↗

Resident and transient coyotes exhibit differential patterns of movement behavior across heterogeneous landscapes in the southeastern United States

Coyotes (Canis latrans) are a highly adaptable canid species whose behavioral plasticity has allowed them to persist in a wide array of habitats throughout North America. As generalists, coyotes can alter movement patterns and change territorial strategies between residency (high site fidelity) and transiency (low site fidelity) to maximize fitness. Uncertainty remains about resident and transient coyote movement patterns and habitat use because research has reached conflicting conclusions regarding patterns of habitat use by both groups. We quantified effects of habitat on resident and transient coyote movement behavior using first passage time (FPT) analysis, which assesses recursive movement along an individual's movement path to delineate where they exhibit area-restricted search (ARS) behaviors relative to habitat attributes. We quantified monthly movement rates for 171 coyotes (76 residents and 53 transients) and then used estimated FPT values in generalized linear mixed models to quantify monthly habitat use for resident and transient coyotes. Transients had greater movement rates than residents across all months except January. Resident FPT values were positively correlated with agricultural land cover during fall and winter, but negatively correlated with agriculture during spring. Resident FPT values were also negatively correlated with developed habitats during May–August, deciduous land cover during June–August, and wetlands during September–January except November. FPT values of transient coyotes were positively correlated with developed areas throughout much of the year and near wetlands during July–September. Transient FPT values were negatively correlated with agriculture during all months except June and July. High FPT values (ARS behavior) of residents and transients were generally correlated with greater densities of edge habitat. Although we observed high individual variation in space use, our study found substantive differences in habitat use between residents and transients, providing further evidence that complexity and plasticity of coyote habitat use is influenced by territorial strategy.

54 ENVIRONMENTAL SCIENCES↗

Estimating carrying capacity for juvenile salmon using quantile random forest models

Abstract Establishing robust methods and metrics to evaluate habitat quality is critical for the recovery of endangered Pacific salmonids ( Oncorhynchus spp.). A variety of modeling approaches are used for status and trend monitoring of anadromous species throughout the Pacific Northwest, USA, but current methods may fail to capture the complex relationship between fish and habitat and are often limited in predictive power beyond specific watersheds. Further, the focus on species distribution and abundance is not easily manipulated to predict carrying capacity and traditional stock‐recruitment analyses are reliant on long‐term data which are not always available. In this study, we developed a quantile random forest model to provide estimates of habitat carrying capacity for Chinook salmon ( O. tshawytscha ) parr during the summer months, at both the site and watershed scale. Quantile random forest models allow for the consideration of noisy data, correlated variables, and non‐linear relationships: common features in fish–habitat datasets. We leveraged Columbia Habitat Monitoring Program data to select habitat co‐variates and predict capacity at those sites. We also identified a set of globally available attributes to extrapolate capacity estimate predictions throughout wadeable streams within the Columbia River basin. Total capacity estimates for watersheds closely matched estimates from alternative fish productivity models. Carrying capacity estimates based on quantile random forest models, like those presented here, provide managers a framework to guide the identification, prioritization, and development of habitat rehabilitation actions to recover salmon populations.

See, Kevin E.↗

Hyperspectral leaf reflectance of grasses varies with evolutionary lineage more than with site

Abstract To predict ecological responses at broad environmental scales, grass species are commonly grouped into two broad functional types based on photosynthetic pathway. However, closely related species may have distinctive anatomical and physiological attributes that influence ecological responses, beyond those related to photosynthetic pathway alone. Hyperspectral leaf reflectance can provide an integrated measure of covarying leaf traits that may result from phylogenetic trait conservatism and/or environmental conditions. Understanding whether spectra‐trait relationships are lineage specific or reflect environmental variation across sites is necessary for using hyperspectral reflectance to predict plant responses to environmental changes across spatial scales. We measured hyperspectral leaf reflectance (400–2400 nm) and 12 structural, biochemical, and physiological leaf traits from five grass‐dominated sites spanning the Great Plains of North America. We assessed if variation in leaf reflectance spectra among grass species is explained more by evolutionary lineage (as captured by tribes or subfamilies), photosynthetic pathway (C 3 or C 4 ), or site differences. We then determined whether leaf spectra can be used to predict leaf traits within and across lineages. Our results using redundancy analysis ordination (RDA) show that grass tribe identity explained more variation in leaf spectra (adjusted R 2 = 0.12) than photosynthetic pathway, which explained little variation in leaf spectra (adjusted R 2 = 0.00). Furthermore, leaf reflectance from the same tribe across multiple sites was more similar than leaf reflectance from the same site across tribes (adjusted R 2 = 0.12 and 0.08, respectively). Across all sites and species, trait predictions based on spectra ranged considerably in predictive accuracies ( R 2 = 0.65 to <0.01), but R 2 was >0.80 for certain lineages and sites. The relationship between Vc max , a measure of photosynthetic capacity, and spectra was particularly promising. Chloridoideae, a lineage more common at drier sites, appears to have distinct spectra‐trait relationships compared with other lineages. Overall, our results show that evolutionary relatedness explains more variation in grass leaf spectra than photosynthetic pathway or site, but consideration of lineage‐ and site‐specific trait relationships is needed to interpret spectral variation across large environmental gradients.

Pau, Stephanie [Department of Geography University↗

All the light we cannot see: Climate manipulations leave short and long‐term imprints in spectral reflectance of trees

Abstract Anthropogenic climate change, particularly changes in temperature and precipitation, affects plants in multiple ways. Because plants respond dynamically to stress and acclimate to changes in growing conditions, diagnosing quantitative plant‐environment relationships is a major challenge. One approach to this problem is to quantify leaf responses using spectral reflectance, which provides rapid, inexpensive, and nondestructive measurements that capture a wealth of information about genotype as well as phenotypic responses to the environment. However, it is unclear how warming and drought affect spectra. To address this gap, we used an open‐air field experiment that manipulates temperature and rainfall in 36 plots at two sites in the boreal‐temperate ecotone of northern Minnesota, USA. We collected leaf spectral reflectance (400–2400 nm) at the peak of the growing season for three consecutive years on juveniles (two to six years old) of five tree species planted within the experiment. We hypothesized that these mid‐season measurements of spectral reflectance capture a snapshot of the leaf phenotype encompassing a suite of physiological, structural, and biochemical responses to both long‐ and short‐time scale environmental conditions. We show that the imprint of environmental conditions experienced by plants hours to weeks before spectral measurements is linked to regions in the spectrum associated with stress, namely the water absorption regions of the near‐infrared and short‐wave infrared. In contrast, the environmental conditions plants experience during leaf development leave lasting imprints on the spectral profiles of leaves, attributable to leaf structure and chemistry (e.g., pigment content and associated ratios). Our analyses show that after accounting for baseline species spectral differences, spectral responses to the environment do not differ among the species. This suggests that building a general framework for understanding forest responses to climate change through spectral metrics may be possible, likely having broader implications if the common responses among species detected here represent a widespread phenomenon. Consequently, these results demonstrate that examining the entire spectrum of leaf reflectance for environmental imprints in contrast to single features (e.g., indices and traits) improves inferences about plant‐environment relationships, which is particularly important in times of unprecedented climate change.

Stefanski, Artur [Department of Forest Resources U↗

Free‐Standing α‐MoO 3 / Ti 3 C 2 MXene Hybrid Electrode in Water‐in‐Salt Electrolytes

While transition‐metal oxides such as α‐MoO 3 provide high capacity, their use is limited by modest electronic conductivity and electrochemical instability in aqueous electrolytes. Two‐dimensional (2D) MXenes, offer metallic conductivity, but their capacitance is limited in aqueous electrolytes. Insertion of partially solvated cations into Ti 3 C 2 MXene from lithium‐based water‐in‐salt (WIS) electrolytes enables charge storage at positive potentials, allowing a wider potential window and higher capacitance. Herein, we demonstrate that α‐MoO 3 /Ti 3 C 2 hybrids combine the high capacity of α‐MoO 3 and conductivity of Ti 3 C 2 in WIS (19.8 m LiCl) electrolyte in a wide 1.8 V voltage window. Cyclic voltammograms reveal multiple redox peaks from α‐MoO 3 in addition to the well‐separated peaks of Ti 3 C 2 in the hybrid electrode. This leads to a higher specific charge and a higher rate capability compared to a carbon and binder containing α‐MoO 3 electrode. These results demonstrate that the addition of MXene to less conductive oxides eliminates the need for conductive carbon additives and binders, leads to a larger amount of charge stored, and increases redox capacity at higher rates. In addition, MXene encapsulated α‐MoO 3 showed improved electrochemical stability, which was attributed to the suppressed dissolution of α‐MoO 3 . The work suggests that oxide/MXene hybrids are promising for energy storage.

36 MATERIALS SCIENCE↗

Enhancing Direct Electrochemical CO 2 Electrolysis by Introducing A-Site Deficiency for the Dual-Phase Pr(Ca)Fe(Ni)O 3-δ Cathode

High-temperature CO 2 electrolysis via solid oxide electrolysis cells (CO 2 –SOECs) has drawn special attention due to the high energy convention efficiency, fast electrode kinetics, and great potential in carbon cycling. However, the development of cathode materials with high catalytic activity and chemical stability for pure CO 2 electrolysis is still a great challenge. In this work, A-site cation deficient dual-phase material, namely (Pr 0.4 Ca 0.6 ) x Fe 0.8 Ni 0.2 O 3-δ (PCFN, x = 1, 0.95, and 0.9), has been designed as the fuel electrode for a pure CO 2 –SOEC, which presents superior electrochemical performance. Among all these compositions, (Pr 0.4 Ca 0.6 ) 0.95 Fe 0.8 Ni 0.2 O 3-δ (PCFN95) exhibited the lowest polarization resistance of 0.458 Ω cm 2 at open-circuit voltage and 800 °C. The application of PCFN95 as the cathode in a single cell yields an impressive electrolysis current density of 1.76 A cm -2 at 1.5 V and 800 °C, which is 76% higher than that of single cells with stoichiometric Pr 0.4 Ca 0.6 Fe 0.8 Ni 0.2 O 3-δ (PCFN100) cathode. The effects of A-site deficiency on materials' phase structure and physicochemical properties are also systematically investigated. Such an enhancement in electrochemical performance is attributed to the promotion of effective CO 2 adsorption, as well as the improved electrode kinetics resulting from the A-site deficiency.

30 DIRECT ENERGY CONVERSION↗

Modeling Heterogeneity in UO 2 Nanoparticles Using X‐ray Absorption Spectroscopy

Abstract EXAFS provides the capability to interrogate nanoparticle (NP) structure in atomistic detail without relying on long‐range crystallinity. There is a limitation in that EXAFS provides averaged structural information, making it difficult to separate a small amount of heterogeneous structure from bulk. In this work, models were developed to extract surface‐specific information from conventional EXAFS measurements collected on UO 2 NPs of varying size. Specifically, the surface terminating species of UO 2 NPs was determined from comparison of coordination numbers with geometric models while the origin of static disorder was interrogated from user‐defined simulations. Results show that the degree of oxygenation on the NP surface does not significantly deviate from bulk surface and that static disorder is highly enhanced in NP surface layers but cannot be attributed to surface relaxation effects alone. The approach described herein has the potential to be adapted to a range of inorganic NP systems to interrogate surface structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Potential dependent spectroelectrochemistry of electrofluorogenic dyes on indium–tin oxide

Indium-tin oxide (ITO) is used in a variety of applications due to its electrical conductivity and optical transparency. Moreover, ITO-coated glass is a common working electrode for spectroelectrochemistry. Thus, the ITO substrates should exhibit well-understood spectroscopic characteristics. Here, we report anomalous potential-dependent luminescence emission from three structurally dissimilar electrofluorogenic probe on ITO-coated glass. The three probes, flavin mononucleotide, resorufin, and Nile blue, show the expected fluorescence modulation between their oxidized, emissive forms and their reduced, nonfluorescent forms at low laser irradiance and/or high concentrations. However, at high irradiance and/or low concentration, the emission intensity increases at reducing potentials, contrary to expectations. In addition, a strong interplay between probe molecule concentration and laser irradiance is observed. We attribute the anomalous behavior to a combination of (1) irradiance-dependent ITO carrier dynamics, and (2) interaction of the fluorescent probe with ITO at reducing potentials resulting in a charge transfer state with altered emission behavior. Thus, the potential- and irradiance-dependent behavior of ITO and the resulting charge transfer state may not only interfere with the observation of potential-dependent fluorescence from redox probes but can completely reverse the polarity of the potential-dependent luminescence, especially at high irradiance and low concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fast and Scalable Synthesis of LiNi 0.5 Mn 1.5 O 4 Cathode by Sol–Gel-Assisted Microwave Sintering

High-voltage spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) is a promising cathode material for high-energy-density and high-power-density lithium-ion batteries (LIBs). The high cost of the currently available LIBs needs to be addressed urgently for wide application in the transport sector (electric vehicles, buses) and large-scale energy storage systems (ESS). Of significance, herein, novel fast and scalable microwave-assisted synthesis of LNMO is reported, which leads to a production cost cut. X-ray diffraction (XRD) analysis confirms the formation of the desired phase with high crystallinity. Field emission scanning (FE-SEM) and transmission electron microscopy (TEM) analyses indicate that the synthesized phase is of nanometric size (50–150 nm) due to an extremely short sintering time (20 min). The material synthesized at 750 °C shows a higher initial discharge capacity (130 mA h g -1 ) than that synthesized at 650 °C (115 mA h g -1 ). The materials heat treated at higher temperatures show better electrochemical performance in terms of initial capacity, rate capability, and improved cycling. The improved electrochemical performance of LNMO at 750 °C is attributed to the formation of a stable crystal structure, low charge transfer resistance at the electrode/electrolyte interface, high electrical conductivity due to the presence of a disorder structure, and improved ionic diffusivity.

25 ENERGY STORAGE↗

Quantification of modeling uncertainty in the Rayleigh damping model

Understanding and accurately characterizing energy dissipation mechanisms in civil structures during earthquakes is an important element of seismic assessment and design. The most commonly used model is attributed to Rayleigh. This paper proposes a systematic approach to quantify the uncertainty associated with Rayleigh's damping model. Bayesian calibration with embedded model error is employed to treat the coefficients of the Rayleigh model as random variables using modal damping ratios. Through a numerical example, we illustrate how this approach works and how the calibrated model can address modeling uncertainty associated with the Rayleigh damping model.

42 ENGINEERING↗

Impact of specimen preparation method on photovoltaic backsheet degradation during accelerated aging test

In this study, we highlight some important factors in the specimen preparation methods for evaluating photovoltaic backsheet properties after accelerated aging. Two different sequences are considered: Method (I) cut-then-age: cut into 1-cm wide strips and then expose to stress, and Method (II) age-then-cut: expose a larger sheet to stress and then cut into 1-cm widths for mechanical property measurements. We also compare the effect of three cutting methods, (a) tensile specimen punch, (b) paper cutter, and (c) fresh razor blade. Several commercial backsheets were evaluated, with stress exposures including (a) pressure cooker test (PCT), (b) dry ultraviolet (UV) radiation exposure, and (c) UV combined damp heat tests. Fourier transform infrared spectrometer (FTIR) and intrinsic viscosity (IV) were used to analyze the materials on unstressed materials and samples exposed to PCT. The results show that both the cutting method and the time of cutting have an impact on the backsheet mechanical properties. Additionally, under UV exposure, Method II, age-then-cut, generally resulted in a higher average value, with more variation than Method I; however, if the side strips from Method II were excluded, the variation dropped to the same level. This is because the specimens at the sides of the sheet get additional damage from UV light from the exposed sides of the sample. In contrast to UV exposure, PCT specimens prepared by Method II result in lower average values and higher variability. This is attributed to embrittlement through the bulk of the sample where the cutting of embrittled specimens appears to result in more edge defects which can then initiate a break at smaller strains. The data suggest that for UV exposures, the specimens should be cut after aging and the exposed side specimens discarded, and that for PCT exposures, the specimens should be cut before the exposure.

14 SOLAR ENERGY↗

Rational optimization of substituted α–MnO 2 cathode for aqueous zinc–ion battery

Density functional theory (DFT) is utilized to explore the effects of increasing concentrations of vanadium (V) and chromium (Cr) substitution on the discharge of α-MnO 2 cathode in hydrated zinc-ion batteries (ZIBs). During H + -intercalation and Zn 2+ -intercalation, Cr-substitution proves to be more effective than V-substitution in promoting discharge behaviors. Transitioning from Mn 0.875 Cr 0.125 O 2 , Mn 0.75 Cr 0.25 O 2 to Mn 0.625 Cr 0.375 O 2 is found to consistently enhance the discharge voltage, along with improved tunnel structure retention and volume expansion suppression. In comparison, the promoting effect of increasing V-substitution is relatively small at initial discharge stages and leads to degradation at later stages, primarily due to an increased concentration of unstable Mn 2+ ion. The superior effect of Cr-substitution is attributed to the unique atomic and electronic structures of substituted Cr 4+ and reduced Cr 3+ ions during discharge. These ions serve as active electron acceptors to limit the formation of Mn 3+ and Mn 2+ ions, and as anchors to stabilize the α-MnO 2 framework and intercalated H + /Zn 2+ ions, respectively. Finally, our study highlights fine-tuning through substitution to enhance the performance of α-MnO 2 -based cathode materials in ZIBs.

25 ENERGY STORAGE↗

Effects of different pretreatment methods on the drying characteristics and quality of potatoes

Abstract The effects of different pretreatments on the vitamin C content of peeled fresh potato, the drying characteristics, and several quality attributes of dehydrated potatoes were investigated. Citric acid pretreatment (0.1%–0.3%, 10–30 min), steam blanching (100ºC, 1–2 min), and water blanching (95°C, 1–2 min) were found to have no obvious effect on the drying rate of potatoes, whereas temperature was the main influencing factor. In terms of quality of dehydrated diced potato, 20 min of citric acid pretreatment resulted in the highest vitamin C retention and better color. Furthermore, dehydrated potato pretreated with citric acid all showed similar dynamic moisture adsorption curves, namely type II sorption isotherm. The moisture adsorption curves can be well fitted using the Guggenheim–Anderson–deBoer model with R 2 higher than .97.

Sun, Xiangfeng↗

A Data Library of Liquid Clouds Modelled With a Large Eddy Simulation Framework

We describe a library of atmospheric large eddy simulations (LES) of liquid-phase boundary layer clouds constructed to enable aerosol–cloud–turbulence interaction studies, support parameterization evaluation and development, and provide training data for machine learning applications. The simulations use a modern LES framework designed for high numerical accuracy, coupled to a detailed spectral bin microphysical scheme. Case studies are configured to represent observed conditions in four key global cloud regions—the Northeastern Atlantic, Northeastern Pacific, Continental United States and Southern Ocean—following a semi-idealised approach. The library also includes aerosol concentration halving and doubling experiments to expose the sensitivities of the case studies to aerosol perturbations. Simulation results are compared to observations on a case-by-case basis, then the library's coverage is evaluated in terms of spreads in meteorological factors and atmospheric boundary layer attributes.

aerosol↗