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At least 919 records · Page 51

Surface-Satellite Measurements for Atmospheric Radiative Transfer (SMART)and Chemical, Optical and Microphysical Measurements of In-Situ Troposphere (COMMIT) Research Activities

The GSFC SMART consists of a suite of remote sensing instruments, including many commercially available radiometers, spectrometer, interferometer, and three in-house developed inskuments: micro-pulse lidar (MPL), scanning microwave radiometer (SMiR), and sun-sky-surface photometer (S(sup 3)). SMART cover the spectral range from UV to microwave, and passive to active remote sensing. This is to enrich the EOS-like research activities (i.e., EOS validation, innovative investigations, and long-term local environmental observations). During past years, SMART has been deployed in many NASA supported field campaigns to collocate with satellite nadir overpass for intercomparisons, and for initializing model simulations. Built on the successful experience of SMART, we are currently developing a new ground-based in-situ sampling package, COMMIT, including measurements of trace gases (CO, SO2, NOx, and O3,) concentrations, fine/coarse particle sizers and chemical composition, single- and three-wavelength nephelometers, and surface meteorological probes. COMMIT is built for seeking a relationship between surface in-situ measurements and boundary layer characteristics. This is to enrich EOS-like research on removing boundary layer signal from the entire column from space observation - to deduce the stable (less variability) free-troposphere observations. The COMMIT will try its best to link the chemical, microphysical, and optical properties of the boundary layer with radiation. The next major activities for SMART-COMMIT are scheduled for 2004-2006 in BASE-ASIA and EAST-AIRE. The expected close collaboration of BASE-ASIA with various research projects in Asia (i.e., ABC in South Asia, led by Ramanathan et al.; EAST-AIRE in East Asia, led by Li et al.; and APEX in Northeast Asia, led by Nakajima et al.) will definitely provide a better understanding of the impact of the biomass burning and air pollutants on regional-to-global climate, hydrological and carbon cycles, and tropospheric chemistry in Asia.

Tsay, Si-Chee↗

Electrochemical Capacitance Traces with Interlayer Spacing in Two‐dimensional Conductive Metal–Organic Frameworks

Abstract Electrically conductive metal–organic frameworks (MOFs) are promising candidates for electrochemical capacitors (EC) for fast energy storage due to their high specific surface areas and potential for redox activity. To maximize energy density, traditional inorganic pseudocapacitors have utilized faradaic processes in addition to double‐layer capacitance. Although conductive MOFs are usually comprised of redox active ligands which allow faradaic reactions upon electrochemical polarization, systematic studies providing deeper understanding of the charge storage processes and structure‐function relationships have been scarce. Here, we investigate the charge storage mechanisms of a series of triazatruxene‐based 2D layered conductive MOFs with variable alkyl functional groups, Ni 3 (HIR 3 ‐TAT) 2 (TAT=triazatruxene; R=H, Et, n ‐Bu, n ‐Pent). Functionalization of the triazatruxene core allows for systematic variation of structural parameters while maintaining in‐plane conjugation between ligands and metals. Specifically, R groups modulate interlayer spacing, which in turn shifts the charge storage mechanism from double‐layer capacitance towards pseudocapacitance, leading to an increase in molar specific capacitance from Ni 3 (HIH 3 ‐TAT) 2 to Ni 3 (HIBu 3 ‐TAT) 2 . Partial exfoliation of Ni 3 (HIBu 3 ‐TAT) 2 renders redox active ligand moieties more accessible, and thus increases the dominance of faradaic processes. Our strategy of controlling charge storage mechanism through tuning the accessibility of redox‐active sites may motivate further design and engineering of electrode materials for EC.

Su, Alice Y.↗

Electrochemical Capacitance Traces with Interlayer Spacing in Two‐dimensional Conductive Metal–Organic Frameworks

Abstract Electrically conductive metal–organic frameworks (MOFs) are promising candidates for electrochemical capacitors (EC) for fast energy storage due to their high specific surface areas and potential for redox activity. To maximize energy density, traditional inorganic pseudocapacitors have utilized faradaic processes in addition to double‐layer capacitance. Although conductive MOFs are usually comprised of redox active ligands which allow faradaic reactions upon electrochemical polarization, systematic studies providing deeper understanding of the charge storage processes and structure‐function relationships have been scarce. Here, we investigate the charge storage mechanisms of a series of triazatruxene‐based 2D layered conductive MOFs with variable alkyl functional groups, Ni 3 (HIR 3 ‐TAT) 2 (TAT=triazatruxene; R=H, Et, n ‐Bu, n ‐Pent). Functionalization of the triazatruxene core allows for systematic variation of structural parameters while maintaining in‐plane conjugation between ligands and metals. Specifically, R groups modulate interlayer spacing, which in turn shifts the charge storage mechanism from double‐layer capacitance towards pseudocapacitance, leading to an increase in molar specific capacitance from Ni 3 (HIH 3 ‐TAT) 2 to Ni 3 (HIBu 3 ‐TAT) 2 . Partial exfoliation of Ni 3 (HIBu 3 ‐TAT) 2 renders redox active ligand moieties more accessible, and thus increases the dominance of faradaic processes. Our strategy of controlling charge storage mechanism through tuning the accessibility of redox‐active sites may motivate further design and engineering of electrode materials for EC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

SineKAN: Kolmogorov-Arnold Networks using sinusoidal activation functions

Recent work has established an alternative to traditional multi-layer perceptron neural networks in the form of Kolmogorov-Arnold Networks (KAN). The general KAN framework uses learnable activation functions on the edges of the computational graph followed by summation on nodes. The learnable edge activation functions in the original implementation are basis spline functions (B-Spline). Here, we present a model in which learnable grids of B-Spline activation functions are replaced by grids of re-weighted sine functions (SineKAN). We evaluate numerical performance of our model on a benchmark vision task. We show that our model can perform better than or comparable to B-Spline KAN models and an alternative KAN implementation based on periodic cosine and sine functions representing a Fourier Series. Further, we show that SineKAN has numerical accuracy that could scale comparably to dense neural networks (DNNs). Compared to the two baseline KAN models, SineKAN achieves a substantial speed increase at all hidden layer sizes, batch sizes, and depths. Current advantage of DNNs due to hardware and software optimizations are discussed along with theoretical scaling. Additionally, properties of SineKAN compared to other KAN implementations and current limitations are also discussed.

Reinhardt, Eric↗

On the onset of three-dimensionality and time-dependence in the Goertler vortex problem

The instability of large amplitude Goertler vortices in a growing boundary layer is discussed in the fully nonlinear regime. It is shown that a three-dimensional breakdown to a flow with wavy vortex boundaries similar to that which occurs in the Taylor vortex problem takes place. However, the instability is confined to the thin shear layers which have been shown to trap the region of vortex activity. The disturbance eigenfunctions decay exponentially away from the center of these layers so that the upper and lower shear layers can support independent modes of instability. The structure of the instability, in particular its location and speed of downstream propagation, is found to be entirely consistent with recent experimental results. Furthermore, it is shown that the upper and lower layers support wavy vortex instabilities with quite different frequencies. This result is again consistent with the available experimental observations.

Hall, Philip↗

Unraveling the Synergistic effects of La and Al co-doping on Ni/Co-free P2-type Na 0.67 Mn 0.67 Fe 0.33 O 2 layered oxide cathodes for sodium-ion batteries

Recent developments in high-performance cathodes for sodium-ion batteries (SIBs) tend to mitigate use of critical Ni and Co active species to satisfy sustainability. P2-type layered oxide cathodes based on Mn and Fe promise high capacity, sustainability, and low cost on account of the abundance and multiple redox characteristics of Mn and Fe. However, their commercialization is still challenged due to poor cycling stability caused by phase changes emanating from inherent Jahn-Teller distortions. Herein, we propose a novel strategy of trivalent La and Al co-doping to alleviate the drawbacks, innovating a new cathode of Na 0.67 Mn 0.62 Al 0.05 Fe 0.31 La 0.02 O 2 (AlLa). The co-doped cathode delivers an impressive capacity of 128.7 mAh/g at 1C and 106.5 mAh/g at high rate of 5C with a good capacity retention of 85% after 100 cycles. These are superior to the unmodified material, whose specific capacity was 118.6 mAh/g at 1C and 61.1 mAh/g at 5C with a retention of only 65% after 100 cycles. The synergistic contribution from La and Al associated with their improved oxygen bonding, pillaring, and local electronic structural modification stemming from rigid Lasingle bondO and Alsingle bondO bonding resulted in the observed structural and electrochemical improvement. Overall, this research offers novel strategies for designing high-performance cathode materials for sodium-ion batteries.

25 ENERGY STORAGE↗

Possible radio emission mechanism for pulsars

A mathematical model is presented and discussed as a possible mechanism to describe radio emission from pulsars. The model determines that the magnetic field in the neutron proton electron (npe) layer of a neutron star results from a quasistationary eddy current of superconducting and normal protons relative to normal electrons, which generates radio emission by the Josephson effect. The radiation propagates in the magnetically active medium, from the optically thick npe layer to the magnetosphere through breaks in the crust. As a result, hot radio spots form on the surface of the star, and a radiation pattern forms near the magnetic poles, the cross section of which gives the observed pulse structure. Due to the specific properties of the mechanism, variations of the quasistationary current are converted to amplitude frequency variations of the radiation spectrum. Variations of the fine structure of the spectrum pulse amplitude and spectral index, as well as their correlation are discussed.

Kovalev, Y. A.↗

Solar activity: The Sun as an X-ray star

The existence and constant activity of the Sun's outer atmosphere are thought to be due to the continual emergence of magnetic fields from the Solar interior and the stressing of these fields at or near the surface layers of the Sun. The structure and activity of the corona are thus symptomatic of the underlying magnetic dynamo and the existence of an outer turbulent convective zone on the Sun. A sufficient condition for the existence of coronal activity on other stars would be the existence of a magnetic dynamo and an outer convective zone. The theoretical relationship between magnetic fields and coronal activity can be tested by Solar observations, for which the individual loop structures can be resolved. A number of parameters however, which enter into the alternative theoretical formulations remain fixed in all Solar observations. To determine whether these are truly parameters of the theory observations need to be extended to nearby stars on which suitable conditions may occur.

Golub, L.↗

Role of mixed conducting Pr 0.1 Gd 0.1 Ce 0.8 O 1.9-δ barrier layer on the promotion of SOFC performance

The cathode activity in a solid oxide fuel cell can be promoted by introducing various catalysts to reduce its polarization resistance towards oxygen reduction, and thus improve cell performance. Here, in this work, the La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF) cathode surface is modified by the infiltration of Pr 6 O 11 and the power density at 0.8 V and 750 °C is improved by 21%. Moreover, by replacing the traditional barrier layer Gd 0.2 Ce 0.8 O 1.9 with mixed conducting Pr 0.1 Gd 0.1 Ce 0.8 O 1.9 (PGCO), the power density increases by 38%. The ohmic resistance is dramatically reduced by applying the PGCO interlayer. The distribution of relaxation time was used to analyze the mechanism for which the polarization resistance was decreased, attributing to the mixed conduction nature in PrO x . An increase of power density, ~0.358 W/cm 2 (71%) at 0.8 V, is achieved with the implementation of both surface modification and buffer layer engineering.

08 HYDROGEN↗

Sodium trithiocarbonate cathode for high-performance sodium–sulfur batteries

The high abundance and low cost of sodium and sulfur make room-temperature sodium-sulfur (RT Na-S) batteries an attractive technology compared to the current lithium-ion batteries for large-scale grid-storage applications. However, the commercialization of RT Na-S batteries is impeded by the slow kinetics of Na-S chemistry, severe sodium polysulfide shuttling, and uncontrollable growth of dendritic Na. Herein, sodium trithiocarbonate (Na 2 CS 3 ) is applied as a cathode material to facilitate concurrent improvement in both electrodes, leading to a high-rate performance with extended cycle life. The conductive characteristic of the carbon-sulfur resonance bond provides fast ion and electron transfer throughout the cathode, resulting in superior electrochemical reactivity. At the cathode, the presence of Na2CS3 forms an oligomer-structured layer to suppress the dissolution and shuttling of active materials. Meanwhile, when small portions of Na 2 CS 3 intermediates migrate to the anode, a stable solid electrolyte interphase (SEI) layer with uniform Na-ion flux is formed, enabling improved Na stripping and plating performance. A series of electrochemical and materials characterization, accompanied by density functional theory calculations demonstrate that Na 2 CS 3 is a promising candidate to realize high-rate performance long cycle life RT Na-S batteries.

25 ENERGY STORAGE↗

Cold plasma heating in the plasma sheet boundary layer - Theory and simulations

Satellite observations in recent years have confirmed that the plasma sheet boundary layer is a permanent feature of the earth's magnetotail located between the lobe and central plasma sheet during both quiet and active magnetic periods. Distinct features of the boundary layer include field aligned ion beams and intense electrostatic emissions known as broadband electrostatic noise. Since the plasma sheet boundary layer is a spatial feature of the magnetotail, within it will occur thermal mixing of the resident warm boundary layer plasma with inflowing (convecting) cold ionospheric plasma. A theoretical study involving linear theory and nonlinear numerical particle simulations is presented which examines ion beam instabilities in the presence of a thermally mixed hot and cold background plasma. It is found that the free energy in the ion beams can heat the cool ionospheric plasma to ambient plasma sheet boundary layer temperatures via broadband electrostatic noise. These results, along with recent observational reports that ionospheric outflow can account for measured plasma sheet densities, suggest that the ionospheric role in plasma sheet dynamics and content may be as large as the solar wind.

Schriver, David↗

Enhancing the Reaction Kinetics and Stability of Co‐Free Li‐Rich Cathode Materials via a Multifunctional Strategy

Co-free Li-rich layered oxides (CFLLOs) with anionic redox activity are among the most promising cathode materials for high-energy-density and low-cost lithium-ion batteries (LIBs). However, irreversible oxygen release often causes severe structural deterioration, electrolyte decomposition, and the formation of unstable cathode-electrolyte interface (CEI) film with high impedance. Additionally, the elimination of cobalt elements further deteriorates the reaction kinetics, leading to reduced capacity and poor rate performance. Here, in this study, a multifunctional strategy is proposed, incorporating Li 2 MnO 3 phase content regulation, micro-nano structure design, and heteroatom substitution. The increased content of Li 2 MnO 3 phase enhances the capacity through oxygen redox. The smaller nanoscale primary particles induce greater tensile strain and introduce more grain boundaries, thereby improving the reaction kinetics and reactivity, while the larger micron-sized secondary particles help to reduce interfacial side reactions. Furthermore, Na⁺ doping modulates the local coordination environment of oxygen, stabilizing both the anion framework and the crystal structure. As a result, the designed cathode exhibits enhanced rate performance, delivering a capacity of 158 mAh g⁻¹ at 5.0 C and improved cyclic stability, with a high capacity retention of 99% after 400 cycles at 1.0 C. This multifunctional strategy holds great promise for advancing the practical application of CFLLOs in next-generation LIBs.

Co-free Li-rich layered oxide↗

New Insights on the 7[superscript]Be Cycle in the Ocean

The cosmogenic radionuclide 7[superscript]Be has been applied as a tracer of dynamical processes in the upper ocean and of atmospheric deposition of trace elements at the sea surface. These applications usually assume that 7[superscript]Be is entirely in the dissolved form, and that scavenging and downward export of 7[superscript]Be by settling particles can be neglected. In this work, we explore these assumptions and more generally assess the significance of the 7[superscript]Be activity in the particulate fraction, through the generation of vertical profiles of particulate 7[superscript]Be in the open ocean. From detailed measurements obtained from low-background gamma spectrometers placed in underground facilities, we report vertical profiles of 7[superscript]Be activity in suspended particles (7[superscript]Bep[subscript]) collected in various oceanic regions: the Mediterranean Sea (DYFAMED station), the Indian Sector of the Southern Ocean (station A3-2 from the KEOPS2 cruise), the Sargasso Sea (OFP station), and the subpolar North Atlantic Ocean (GEOVIDE cruise). We find that, in each oceanic region, 7[superscript]Bep[subscript] activities are generally higher in the mixed layer than in the thermocline. They vary in the mixed layer from 3.0 dpm/m3 at DYFAMED to 33.1dpm/m3 at GEOVIDE cross-over station 51/60, i.e., within a range consistent with previous 7[superscript]Bep[subscript] measurements for the open ocean. For the GEOVIDE cruise, the 7[superscript]Bep[subscript] activities measured on different filter types at different depths are corrected for filter offsets derived from multiple 7[superscript]Bep[subscript] measurements at a near-coastal station in the western Mediterranean Sea. We then combine measurements of total 7[superscript]Be activity (Shelley et al., 2017) with our measurements of 7[superscript]Bep[subscript] activity to estimate the solid/solution partitioning of 7[superscript]Be. On average, the particulate fraction would represent 6% of total 7[superscript]Be activity at 5-m water depth (n = 6), 22% at 20 m (n = 2) and 9% at 70 m (n = 3). At GEOVIDE stations, 7[superscript]Bep[subscript] inventories range from 5% to 19% of the total 7[superscript]Be inventories. In the Labrador Sea, the measured 7[superscript]Bep[subscript] inventories are lower than the dry 7[superscript]Be deposition fluxes estimated from aerosol samples collected during GEOVIDE, suggesting that a significant portion of 7[superscript]Bep[subscript] may be removed by sinking particles. The distribution coefficient Kd for 7Be increases with depth, with log10Kd averaging 5.2 ± 0.1 at 5 m to 6.1 ± 0.1 between 70 and 150 m, suggesting that scavenging of dissolved 7[superscript]Be by particles is more pronounced in the thermocline than in the mixed layer when differences in particle concentrations are taken into account. Overall, our study suggests that, at least in some oceanic regions, the removal of 7[superscript]Be by marine particles may be significant and that it may need to be considered in applications of 7[superscript]Be as a tracer of oceanic processes and atmospheric deposition.

Beryllium-7↗

From Langmuir isotherm to Brunauer–Emmett–Teller isotherm

Abstract Developed for multilayer adsorption, the Brunauer–Emmett–Teller ( BET) isotherm considers the adsorption of the first layer as an equilibrium chemical reaction between adsorbate molecules and adsorption sites and the adsorption of the second and subsequent layers as a condensation–evaporation process. Following the recent development of an activity‐based formulation for the Langmuir isotherm for monolayer adsorption, we present an activity‐based formulation for the BET isotherm in which species concentrations are replaced with species activities. Capturing the adsorbent surface heterogeneity for the adsorption of the first layer, the resulting thermodynamic BET isotherm is shown to accurately represent pure component adsorption isotherms over the relative pressure range of zero to unity or prior to the onset of capillary condensation. The thermodynamic BET isotherm should facilitate accurate estimation of monolayer adsorption capacity and the corresponding adsorbent surface area.

Vyawahare, Pradeep↗

Super-porous Pt/CuO/Pt hybrid platform for ultra-sensitive and selective H 2 O 2 detection

A super-porous Pt/CuO/Pt hybrid electrode is demonstrated with extremely high sensing performance parameters for the hydrogen peroxide (H 2 O 2 ) detection. A unique physiochemical approach is adapted for the fabrication of 3-D super-porous Pt/CuO/Pt sensing platform. Here, the super-porous Pt/CuO/Pt hybrid platform demonstrates a superior sensitivity of 16,694 µA mM -1 cm -2 with a limit of detection of 2.91 nM (S/N = 3). It also demonstrates an excellent selectivity against the interfering molecules such as NaCl, fructose, ascorbic acid, citric acid, dopamine and glucose with a wide linear range. The demonstrated performance ranks the Pt/CuO/Pt hybrid platform as one of the best H 2 O 2 sensors as summarized in the Table 2. The super-porous CuO layer is fabricated by a dynamic hydrogen bubbling technique of electrochemical deposition and metallic Pt NP decoration is achieved by the physical vapor deposition (PVD) and post-annealing. The super-porous CuO layer offers a drastically improved electrochemical active surface area, and the Pt NP decoration offers a significantly improved conductivity and improved charge accumulation for the H 2 O 2 reduction. The DFT simulations confirm the predominance of CuO over Cu 2 O and Pt over Pd for the H 2 O 2 detection based on the adsorption energy, density of states and charge accumulation calculations.

36 MATERIALS SCIENCE↗

Molecular Determination of Organic Adsorption Sites on Smectite during Fe Redox Processes Using ToF-SIMS Analysis

Turnover of soil organic carbon (SOC) is strongly affected by a balance between mineral protection and microbial degradation. However, the mechanisms controlling the heterogeneous and preferential adsorption of different types of SOC remain elusive, especially for humic substrates (HSs) and microbial carbon (MC), two hotly-debated forms of SOC prevalent in soils. In this work, the heterogeneous adsorption of HSs and MC on a clay mineral (nontronite NAu-2) during microbial-mediated Fe redox cycling was determined with the use of time-of-flight secondary ion mass spectrometry (ToF-SIMS). The results revealed that HSs pre-adsorbed on NAu-2 would partially inhibit the microbial Fe(III) reduction and structural modification of NAu-2, thus retarding the subsequent adsorption of MC. In contrast, NAu-2 without pre-coated HSs was adsorbed by a significant amount of MC from microbial polysaccharides as a result of Fe(III) reduction. This was attributed to the deposition of a thin Al-rich layer on clay surface, which provided active sites for MC adsorption. This study provides direct and detailed molecular evidence for the first time to explain the preferential adsorption of MC over HSs on the surface of clay minerals in the iron redox processes, which could be critical for the preservation of MC in soil. The results also indicate that ToF-SIMS is a unique tool for understanding complex organic-mineral-microbe interactions.

54 ENVIRONMENTAL SCIENCES↗

Rapid Identification of X-ray Diffraction Patterns Based on Very Limited Data by Interpretable Convolutional Neural Networks

Large volumes of data from material characterizations call for rapid and automatic data analysis to accelerate materials discovery. Herein, we report a convolutional neural network (CNN) that was trained based on theoretical data and very limited experimental data for fast identification of experimental X-ray diffraction (XRD) patterns of metal–organic frameworks (MOFs). To augment the data for training the model, noise was extracted from experimental data and shuffled; then it was merged with the main peaks that were extracted from theoretical spectra to synthesize new spectra. For the first time, one-to-one material identification was achieved. Theoretical MOFs patterns (1012) were augmented to a whole data set of 72 864 samples. It was then randomly shuffled and split into training (58 292 samples) and validation (14 572 samples) data sets at a ratio of 4:1. For the task of discriminating, the optimized model showed the highest identification accuracy of 96.7% for the top 5 ranking on a test data set of 30 hold-out samples. Neighborhood component analysis (NCA) on the experimental XRD samples shows that the samples from the same material are clustered in groups in the NCA map. Analysis on the class activation maps of the last CNN layer further discloses the mechanism by which the CNN model successfully identifies individual MOFs from the XRD patterns. Furthermore, this CNN model trained by the data augmentation technique would not only open numerous potential applications for identifying XRD patterns for different materials, but also pave avenues to autonomously analyze data by other characterization tools such as FTIR, Raman, and NMR spectroscopies.

36 MATERIALS SCIENCE↗

Environmental Factors Associated With Fall Phytoplankton Blooms in the Northern Bering and Chukchi Seas

This study investigates environmental drivers of fall phytoplankton blooms in the Arctic, focusing on the northern Bering and Chukchi seas. Random Forests models were used to analyze covariates of fall phytoplankton blooms from 2013 to 2018, incorporating shipboard, remote sensing, and modeled environmental properties. Four regional models and one comprehensive all-station model considered fall as well as midsummer conditions. Midsummer properties included suspended particulate matter, chlorophyll-a, and the proportion of degraded pheophytin to chlorophyll-a used as a proxy for bloom stage. Open water duration was one of the highest ranked factors in predicting fall blooms. Open water duration also influences the stage of midsummer (July) blooms as indicated by pheophytin proportions, which in turn were the highest-ranked factor for predicting fall bloom events in the Chirikov Basin (northern Bering Sea between St. Lawrence Island and the Bering Strait) and the Chukchi Sea. Wind direction, specifically easterly winds, was an important predictor in the northern Bering Sea. Maximum wind speed ranked highly at stations located within the nutrient-poor Alaska Coastal Current in the Chukchi Sea. However, stormy days, average and maximum wind speeds generally ranked low in importance as a predictor of fall bloom events. Other parameters, including photosynthetic active radiation, modeled nutrient concentrations, mixed layer depth, and time since sea ice breakup date showed strong but regionally varying relationships with fall blooms. Altogether, results from these Random Forests models suggest that high wind events and storms in the absence of sea ice provide an incomplete narrative for initiating fall bloom events.

Gaffey, C. B. [Clark University, Worcester, MA (Un↗