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At least 253 records · Page 14

Radio-echo sounding of Crary Ice Rise reveals abundant marine ice in former ice shelf rifts and basal crevasses

Crary Ice Rise formed after the Ross Ice Shelf re-grounded ~1 kyr BP. We present new ice-penetrating radar data from two systems operating at center frequencies of 7 and 750 MHz that confirm the ice rise is composed of a former ice shelf buried by subsequent accumulation. Stacks of englacial diffraction hyperbolas are present almost everywhere across the central ice rise and extend up to ~350 m above the bed. In many cases, bed reflections beneath the diffraction hyperbolas are obscured for distances up to 1 km. Waveform modeling indicates that the diffraction hyperbolas are likely caused by marine ice deposits in former basal crevasses and rifts. The in-filling of rifts and basal crevasses may have strengthened the connection between the ice rise and the surrounding ice shelf, which could have influenced local and regional ice dynamics. Three internal reflection horizons mark the upper limit of disturbed ice and diffraction hyperbolas in different sections of the ice rise, indicating at least three stages of flow stabilization across the ice rise. A surface lineation visible in MODIS imagery corresponds spatially to deepening and strong deformation of these layers, consistent with the characteristics of former grounding lines observed elsewhere in Antarctica.

54 ENVIRONMENTAL SCIENCES↗

Rapid Determination of Uranium Isotopic Abundance from Cotton Swipes: Direct Extraction via a Planar Surface Reader and Coupling to a Microplasma Ionization Source

The collection of solid particulates and liquids from surfaces by the use of cloth swipes is fairly ubiquitous. In such methods, there is a continuous concern regarding the ability to locate and quantitatively sample the analyte species from the material. In this effort, we demonstrate the initial coupling of an Advion Plate Express plate reader to a liquid sampling–atmospheric pressure glow discharge (LS-APGD) microplasma ionization source with an Orbitrap mass spectrometer to perform uranium isotopic analyses of solution residues on cotton swipes. The Plate Express employs a sampling probe head to engage and seal against the swipe surface. Subsequentially, the analyte residues are desorbed and transported within a 2% HNO 3 electrolyte flow to the ionization source. Quantitative recoveries were observed following a single 30 s extraction step, with the absolute mass sampled per extraction being ~100 ng. While the intrasample variability in the analytical responses for triplicate sampling of the same swipe yield ~30% RSD, this lack of precision is offset by the ability to determine isotope ratios for enriched uranium specimens with a precision of better than 10% RSD. Pooled, intersample precision ( n = 9) was found to be <5%RSD across the various sample compositions. Finally, 235 U/ 238 U determinations (ranging from 0.053 to 1.806) were accurate with errors of <10%, absolute. The 234 U- and 236 U-inclusive ratios were determined with similar accuracy in enriched samples. While the driving force for the effort is in the realm of nuclear nonproliferation efforts, the ubiquitous use of cloth swipes across many application areas could benefit from this convenient approach, including the use of versatile, reduced-format mass spectrometer systems.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Oxygen-Vacancy Abundant Nanoporous Ni/NiMnO 3 /MnO 2 @NiMn Electrodes with Ultrahigh Capacitance and Energy Density for Supercapacitors

High-performance energy storage devices (HPEDs) play a critical role in the realization of clean energy and thus enable the overarching pursuit of nonpolluting, green technologies. Supercapacitors are one class of such lucrative HPEDs; however, a serious limiting factor of supercapacitor technology is its sub-par energy density. Here, this report presents hitherto unchartered pathway of physical deformation, chemical dealloying, and microstructure engineering to produce ultrahigh-capacitance, energy-dense NiMn alloy electrodes. The activated electrode delivered an ultrahigh specific-capacitance of 2700 F/cm 3 at 0.5 A/cm 3 . The symmetric device showcased an excellent energy density of 96.94 Wh/L and a remarkable cycle life of 95% retention after 10,000 cycles. Transmission electron microscopy and atom probe tomography studies revealed the evolution of a unique hierarchical microstructure comprising fine Ni/NiMnO 3 nanoligaments within MnO 2 -rich nanoflakes. Theoretical analysis using density functional theory showed semimetallic nature of the nanoscaled oxygen-vacancy-rich NiMnO 3 structure, highlighting enhanced carrier concentration and electronic conductivity of the active region. Furthermore, the geometrical model of NiMnO 3 crystals revealed relatively large voids, likely providing channels for the ion intercalation/de-intercalation. The current processing approach is highly adaptable and can be applied to a wide range of material systems for designing highly efficient electrodes for energy-storage devices.

25 ENERGY STORAGE↗

Chemical and Electrochemical O 2 Reduction on Earth-Abundant M-N-C Catalysts and Implications for Mediated Electrolysis

M-N-C catalysts, incorporating non-precious-metal ions (e.g. M = Fe, Co) within a nitrogen-doped carbon support, have been the focus of broad interest for electrochemical O 2 reduction and aerobic oxidation reactions. The present study explores the mechanistic relationship between the O 2 reduction mechanism under electrochemical and chemical conditions. In this work, chemical O 2 reduction is investigated via the aerobic oxidation of a hydroquinone, in which the O–H bonds supply the protons and electrons needed for O 2 reduction to water. Mechanistic studies have been conducted to elucidate whether the M-N-C catalyst couples two independent half-reactions (IHR), similar to electrode-mediated processes, or mediates a direct inner-sphere reaction (ISR) between O 2 and the organic molecule. Kinetic data support the latter ISR pathway. This conclusion is reinforced by rate/potential correlations that reveal significantly different Tafel slopes, implicating different mechanisms for chemical and electrochemical O 2 reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Future Hurricanes Will Increase Palm Abundance and Decrease Aboveground Biomass in a Tropical Forest

Hurricanes are expected to intensify throughout the 21st century, yet the impact of frequent major hurricanes on tropical ecosystems remains unknown. To investigate tropical forest damage and recovery under different hurricane regimes, we generate a suite of scenarios based on Coupled Model Intercomparison Project Phase 6 climate projections and increased hurricane recurrence and intensity for the Luquillo Experimental Forest, Puerto Rico. We then use the Ecosystem Demography model to predict changes in carbon stocks, forest structure and composition. In this work, our results indicate that frequent hurricane disturbances in the future would decrease the overall aboveground biomass, decrease the dominance of late-successional species, but increase the dominance of palm species. Warmer climates with increased CO 2 would have little effect on the functional-type composition but increase the aboveground biomass. However, the predicted climate and CO 2 fertilization effects would not compensate for the biomass loss due to more frequent severe-hurricane disturbances.

54 ENVIRONMENTAL SCIENCES↗

Abundant Nitrate and Nitric Acid Aerosol in the Upper Troposphere and Lower Stratosphere

The tropospheric and stratospheric nitrate aerosol is simulated by a sectional aerosol model coupled to the Community Earth System Model. The simulated nitrate mass fractional contribution to aerosols is significantly higher in the upper troposphere and lower stratosphere (UTLS) than that at the surface. Both in situ measurements and simulations show that nitrate aerosol accounts for about 30%–40% of the aerosol mass at the tropopause of the Asian summer monsoon (ASM) region. Furthermore, simulated condensed nitric acid particles account for ~20% of the annual mean aerosol mass at the tropical tropopause, and over 95% in the UTLS at the South Pole in June-July-August. Here, our study suggests that the extremely cold ambient conditions in the UTLS of the tropics, ASM and polar regions thermodynamically favor the condensation of ammonia and nitric acid. The widely distributed nitrate aerosol in the global UTLS may be overlooked by climate models.

54 ENVIRONMENTAL SCIENCES↗

WACCM6 Projections of Polar Mesospheric Cloud Abundance Over the 21st Century

Polar mesospheric clouds (PMC), or noctilucent clouds, can be observed over high latitudes with the naked eye from the ground or from space near the summer solstice. PMC are considered a direct and sensitive indicator of climate change and have been reported to appear more frequently in recent decades. How PMC will change in the future under the influence of natural variability and anthropogenic forcing is uncertain. In this study, we utilize model output from the Whole Atmosphere Community Climate Model under several shared socioeconomic pathway (SSP) scenarios and input the water vapor, temperature, and pressure information into a 0-d PMC model to project the trend and variation of PMC over the 21st century, and their relationship to future changes of temperature, water vapor, and the solar cycle. The 0-d model calculations indicate that PMC ice water content (IWC) will increase and PMC will extend to lower latitudes under high SSP scenarios. Under these scenarios, more mesospheric water vapor leads to an increased IWC of PMC over the polar region, and colder mesopause temperature leads to more PMC over the mid-latitudes. There is a significant anti-correlation between the solar cycle and PMC IWC over the 21st century, but the anti-correlation is not always significant on the decadal scale. Finally, methane oxidation in the stratosphere and water vapor entering from the troposphere are both responsible for future changes in mesospheric water vapor and thus PMC.

54 ENVIRONMENTAL SCIENCES↗