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At least 937 records · Page 52

Exponential Water Uptake in Ionomer Membranes Results from Polymer Plasticization

Water content is the most influential factor in the performance of ion-exchange membranes (IEMs), controlling their mechanical rigidity, ionic conductivity, and degradation rates. Membranes absorb water exponentially at high water activity (a w ), making that region of the sorption isotherm the most influential on membrane properties. Plasticization of the polymer by water has been proposed to cause this exponential uptake at high a w . However, an integrated microscopic picture of the structure, thermodynamic, and mechanical properties of IEMs as a function of a w has remained elusive. In this work, we use large-scale molecular simulations validated with experimental measurements to compute the sorption isotherms, Young’s modulus, polymer dynamics, and structure of IEMs. The simulations unveil that the exponential increase in water uptake (WU) coincides in all cases with the glass to rubber transition of the membrane, as measured through its Young’s modulus and segmental polymer dynamics. Functionalization of the polymer with alkyl groups further contributes to its plasticization, increasing the WU at a given a w and ion-exchange capacity (IEC). The alkyl chains act synergistically with water to plasticize the polymer matrix and allow water penetration in the membrane. The simulations reveal that the width of the water channels depends on the ratio λ of water to ions in the polymer but is independent of its IEC. We conclude that differences in the polymer matrix–not the water channels–are responsible for the distinct uptake response of IEMs to the thermodynamic driving force of water activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Feedback regulation of crystal growth by buffering monomer concentration

Abstract Crystallization is a ubiquitous means of self-assembly that can organize matter over length scales orders of magnitude larger than those of the monomer units. Yet crystallization is notoriously difficult to control because it is exquisitely sensitive to monomer concentration, which changes as monomers are depleted during growth. Living cells control crystallization using chemical reaction networks that offset depletion by synthesizing or activating monomers to regulate monomer concentration, stabilizing growth conditions even as depletion rates change, and thus reliably yielding desired products. Using DNA nanotubes as a model system, here we show that coupling a generic reversible bimolecular monomer buffering reaction to a crystallization process leads to reliable growth of large, uniformly sized crystals even when crystal growth rates change over time. Buffering could be applied broadly as a simple means to regulate and sustain batch crystallization and could facilitate the self-assembly of complex, hierarchical synthetic structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal–bicarbonate ion pairing in alkaline aqueous solutions from multilevel embedded correlated wavefunction theory and molecular dynamics

In this work, we examine ion-pairing mechanisms of bicarbonates in alkaline aqueous solutions with the divalent metal ions most abundantly present in seawater, namely, Ca 2+ and Mg 2+ . We employ a rare-event enhanced sampling approach within first-principles molecular dynamics to explore regions of phase space spanning solvent-shared to contact ion pairs. Second-order Møller–Plesset perturbation theory (MP2) corrections are subsequently applied in an embedding framework (EMB) to refine the electronic structure of stationary states and associated reaction barriers along the free-energy profiles while retaining the extended solvent effects at the density functional theory (DFT) level. Ca 2+ –HCO 3 − was previously hypothesized to exist in a solvent-shared ion pair (SSHIP) by DFT studies with an endergonic contact ion pair (CIP) formation; however, our EMB-MP2 refinement of the DFT ion-pairing pathways reveals that Ca 2+ and HCO 3 − form a virtually barrier-free CIP in alkaline solutions, with even more energetic ease than the widely studied Ca–CO 3 ion pair. We find qualitative agreement between DFT and EMB-MP2 for Mg 2+ —unlike Ca 2+ , Mg 2+ refuses to shed its strong hydration shell, thereby preferring a SSHIP state with a significant activation barrier to crossover to the CIP forms—a trait reminiscent of ion pairing in Mg–CO 3 and closely related to the kinetic limitations underlying the famous subject of the dolomite problem. Our study highlights the importance of improved electronic structure descriptions of liquids, modeled as a condensed phase of matter lacking in long-range crystalline order. It also strongly suggests that Ca 2+ –HCO 3 − CIPs are likely precursors involved in prenucleation of CaCO 3 mineral formation in seawater.

Sharma, Vidushi [Princeton Plasma Physics Laborato↗

Major outburst of periodic Comet Halley at a heliocentric distance of 14 AU

The properties and evolution of the major outburst experienced by Comet Halley at 14 AU during February-March 1991 are studied. It is found that the observed halo is a segment of a conical surface populated by solid particles ejected from a localized, temporarily activated region on the sunlit hemisphere of the spinning nucleus. The total mass of the ejecta was at least 10 exp 12 g and CO was probably the prime driver, accelerating the smallest grains to a terminal velocity of about 45 m/s. The mass loading of the gas flow by particulate matter is enormous, with the mass production rate exceeding the expected production rate of CO by a factor of several tens.

Sekanina, Z.↗

Ocean liming effect on a North Atlantic microbial community: changes in composition and rates

The ongoing rise in atmospheric CO 2 levels and the consequent global warming make it increasingly difficult to maintain the global temperature within the 1.5 - 2°C target set by the Paris Agreement. Therefore, strategies to remove carbon dioxide from the atmosphere are being developed, with ocean alkalinity enhancement (OAE) gaining most attention. Within OAE, ocean liming- the addition of quicklime (CaO) or hydrated lime (Ca(OH) 2 )- can not only remove CO 2 from the atmosphere but potentially counteract the effects of ocean acidification. Although quite attractive, these technologies have yet to be tested regarding ecological safety and efficacy. Here we report the impacts of ocean liming on the abundance, composition and extracellular enzymatic activity (EEA) rates of a North Atlantic planktonic community. The results demonstrate that OAE led to a decreased phytoplankton development, mainly diatoms. The bacterial response to OAE was community-specific, with a consistent increase in the relative abundance of the order Oceanospirillales. OAE also led to increased EEA rates, especially within the bacterial community. These findings suggest that while initial effects on phytoplankton may be limited, the specific impacts on bacterial groups suggest that OAE could influence the remineralization of organic matter. If our results apply to other communities, OAE might initially affect marine microbial dynamics, but further studies are needed to determine if these effects are long-term.

16S↗

Long-range Transport of Siberian Biomass Burning Emissions to North America During FIREX-AQ

Biomass burning from wildfires is a significant global source of aerosol and trace gases which impact air quality, tropospheric and stratospheric composition, and climate. During the summer of 2019, wildfire activity in central and eastern Siberia occurred during the Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) campaign conducted between July 24 and September 6, 2019. Ground-based lidar observations from the Autonomous Mobile Ozone Lidar for Tropospheric Experiments (AMOLITE) system in Alberta, Canada retrieved frequent anomalous ozone (O3) and aerosol lamina in the troposphere and lower stratosphere during this campaign. Data from NASA’s GEOS Composition Forecast (GEOS-CF) coupled chemistry meteorology model, TROPOspheric Monitoring Instrument (TROPOMI), Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO), and ground-based insitu data were used to define the trans-Pacific and trans-Arctic transport pathway of Siberian biomass burning emissions resulting in the enhanced O3 and aerosol lamina observed by AMOLITE in western Canada. Siberian wildfires impacted North American air quality resulting in enhancements of hourly-averaged surface carbon monoxide (CO) (total CO >150 ppb) and fine particulate matter (PM2.5) (>20 μg m-3) in western Canada, however, minimal increases in surface-level O3 were measured as well as modeled by GEOS-CF. The impact in western Canada due to Siberian wildfires was much larger in the free troposphere, demonstrated by GEOS-CF and AMOLITE O3 lamina 30–40 ppb above background values and model-predicted PM2.5 lamina >30 μg m-3. In addition to tropospheric composition effects, the large wildfire activity in Siberia may have influenced the stratosphere as data from AMOLITE, CALIPSO, and GEOS-CF all suggested aerosol layers from the fires were located 13–18 km above ground level (agl). This study shows that the Siberian biomass burning emissions in the summer of 2019 impacted tropospheric/stratospheric composition in western Canada, and potentially could have influenced areas in the vicinity of FIREX-AQ airborne measurements, and future studies of FIREX-AQ chemical composition should consider how this long-range transport could have influenced the background trace gas and aerosol concentrations being investigated.

Biomass↗

Interactions between molecular-scale processes and hyporheic exchange for understanding Fe-S-C cycling in riparian wetlands (Final Report)

Wetlands represent some of the most productive ecosystems on the planet and critically influence global environmental health. Specifically, wetlands promote water quality by transforming nutrients and organic compounds and sequestering metals and contaminants. Riparian wetland hyporheic zones, where toxic surface water and anoxic groundwater mix, exhibit dynamic conditions that drive steep redox gradients and promote hotspots of diverse and fluctuating microbial activity. Changes in climate, water quality, and water quantity can disturb hydrologic flow and biogeochemical processing in these environments. Understanding how sulfate loading, impacted by hydrologic flux and anthropogenic inputs, influences iron and carbon cycling in wetlands will be crucial for predicting water quality issues driven by iron mineral precipitation and sorption, such as the release of heavy metals and other toxic elements. We used a fully integrated multi-scale and multi-method approach to develop a mechanistic understanding of how hydrologic flow influences coupled iron and sulfur cycles in riparian wetlands. This entailed hydrological, geochemical, and microbial observations at two locations: an anthropogenic sulfate-impacted riparian wetland in northern Minnesota, and a low-sulfate Fe-rich riparian wetland in Tims Branch at the Savannah River Site (SRS). These sites were characterized by hydrologically dynamic conditions where the stream and wetland systems oscillated between gaining (upward flow) and losing (downward flow) conditions that recharged the system occasionally with oxidants that fueled a variety of biogeochemical reactions. Aqueous geochemical measurements of surface water, groundwater, and porewater samples were made alongside solid-phase geochemical analyses of sediment gravity cores. Bulk X-ray absorption spectroscopy at the Advanced Photon Source (APS; Argonne) interrogated the speciation and distribution of Fe and S mineral phases of the sediments. Interestingly, it was discovered that, despite strongly reducing conditions, Fe(III) compounds and a variety of intermediate valence S compounds were stable in the subsurface. Indeed, compounds like thiosulfate, S(0), and intermediate valence organosulfur compounds were more prevalent than FeS and pyrite. The composition of the sediments did change with changes in hydrologic flow, showing their reactivity in changing redox conditions. The abundance of these intermediate S compounds was likely formed as a result of anaerobic oxidation by aqueous and solid-phase Fe(III) compounds, fueling a cryptic S cycle that is driving the breakdown of organic matter in the hyporheic zone. Microbiome surveys showed a core community that seemed stable across the landscape, but changed with increasing depth into the sediment. The community composition did not seem to change dramatically with changes in season or hydrologic flow, except for some organisms that have the potential to contribute to S cycling. More work is needed to confirm their functional activity. These fine process-scale analyses were placed within a dynamic field context using physical flow parameters from surface water and groundwater level measurements. These data helped shed light on sulfur-driven biogeochemical processes in hydrologically dynamic riparian wetlands, addressing a gap in our understanding about the impacts of pollution and other anthropogenic changes on ecologically sensitive environments.

54 ENVIRONMENTAL SCIENCES↗

Ultrafast Neuromorphic Dynamics Using Hidden Phases in the Prototype of Relaxor Ferroelectrics

Materials possessing multiple states are promising to emulate synaptic and neuronic behaviors. Their operation frequency, typically in or below the GHz range, however, limits the speed of neuromorphic computing. Ultrafast THz electric field excitation has been employed to induce nonequilibrium states of matter, called hidden phases in oxides. One may wonder if there are systems for which THz pulses can generate neuronic and synaptic behavior, via the creation of hidden phases. Using atomistic simulations, we discover that relaxor ferroelectrics can emulate all the key neuronic and memristive synaptic features. Their occurrence originates from the activation of many hidden phases of polarization order, resulting from the response of nanoregions to THz pulses. We find such phases further possess different dielectric constants, which is also promising for memcapacitor devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Magnetosphere-ionosphere interactions: Near Earth manifestations of the plasma universe

As the universe consists almost entirely of plasma, the understanding of astrophysical phenomena must depend critically on the understanding of how matter behaves in the plasma state. In situ observations in the near Earth cosmical plasma offer an excellent opportunity of gaining such understanding. The near Earth cosmical plasma not only covers vast ranges of density and temperature, but is the site of a rich variety of complex plasma physical processes which are activated as a results of the interactions between the magnetosphere and the ionosphere. The geomagnetic field connects the ionosphere, tied by friction to the Earth, and the magnetosphere, dynamically coupled to the solar wind. This causes an exchange of energy an momentum between the two regions. The exchange is executed by magnetic-field-aligned electric currents, the so-called Birkeland currents. Both directly and indirectly (through instabilities and particle acceleration) these also lead to an exchange of plasma, which is selective and therefore causes chemical separation. Another essential aspect of the coupling is the role of electric fields, especially magnetic field aligned (parallel) electric fields, which have important consequences both for the dynamics of the coupling and, especially, for energization of charged particles.

Faelthammar, Carl-Gunne↗

Characterizing of a Mid-Latitude Ice-Rich Landing Site on Mars to Enable in Situ Habitability Studies

We suggest an ice-rich landing site at 188.5E 46.16N within Amazonis Planitia as a candidate location to support a Mars lander mission equipped to study past habitability and regions capable of preserving the physical and chemical signs of life and organic matter. Studies of the ice-rich subsurface on Mars are critical for several reasons. The subsurface environment provides protection from radiation to shield organic and biologic compounds from destruction. The ice-rich substrate is also ideal for preserving organic and biologic molecules and provides a source of H2O for biologic activity. Examination of martian ground ice can test several hypotheses such as: 1) whether ground ice supports habitable conditions, 2) that ground ice can preserve and accumulate organic compounds, and 3) that ice contains biomolecules evident of past or present biological activity on Mars. This Amazonis site, located near the successful Viking Lander 2, shows indirect evidence of subsurface ice (ubiquitous defined polygonal ground, gamma ray spectrometer hydrogen signature, and numerical modeling of ice stability) and direct evidence of exposed subsurface ice. This site also provides surface conditions favorable to a safe landing including no boulders, low rock density, minimal rough topography, and few craters.

Heldmann, J.↗

Lessons Learned from the Airborne Particulate Monitor ISS Payload

Particulate monitoring on spacecraft has not been undertaken for air quality purposes for the first twenty years of human habitation on the International Space Station (ISS). The Airborne Particulate Monitor (APM) is a reference-quality instrument technology demonstration that characterized the airborne particles in the ISS cabin in real-time. Onboard aerosols have been measured with this higher fidelity instrument, so future miniaturized low-power aerosol instruments can be reliably compared in future ISS experiments. Several issues were encountered during the payload operations that are a result of the unique environment on ISS, which could not have been anticipated or eliminated by ground testing. First, the ISS had very small amounts of particulate matter in the particle measurement size range of the APM, which was unexpected. Second, despite the measured ‘clean’ environment, larger debris such as lint accumulated regularly on the cleanable inlet screen, which required regular inspection and crew time. The third issue is that particle emissions measured on ISS depend only on the activities in the immediate vicinity of the particle instrument and total particle concentrations cannot be generalized for the entire module. Finally, the sampling efficiency of APM on ISS is unknown because aisle-deployed instruments attached to wall panels of ISS are in the boundary layer of the large-scale ventilation flow of the modules. These issues are discussed and potential solutions for future particulate monitors are presented.

aerosol↗

Compositional changes of dissolved organic molecules along water flow and their influencing factors in the Three Gorges Reservoir

Molecular composition of dissolved organic matter (DOM) and its influencing factors in river reservoirs remains elusive. Here, molecular compositions of DOM, bacterial community structures, and water physiochemistry were investigated in the field and microcosm samples of the Three Gorges Reservoir (TGR). The results showed that DOM molecular compositions were significantly (R 2 = 0.245, p < 0.001) correlated with bacterial community structures in the studied field samples, suggesting that bacteria may actively interact with DOM molecules. In this study, the molecular compositions of DOM in the studied field samples were significantly (p < 0.05) affected by the distance between the sample sites and the Three Gorges Dam and by bacterial groups of Actinobacteria and Alphaproteobacteria, suggesting that both hydrological and bacterial processes may contribute to the variation in DOM molecular composition in the TGR water. Furthermore, microcosm experiments demonstrated that both microbial and abiotic processes may transform and/or produce DOM in the TGR, thereby affecting DOM molecular composition. Microbial process increased the average aromaticity index and decreased the carbon number of DOM molecules with increasing incubation duration; whereas average oxygen number, double bond equivalent, and oxidation state of carbon of DOM molecules increased during the first 14 days of incubation and began to decrease thereafter. Taken together, this study expands our understanding of the impact of microbial process on the DOM molecular composition in reservoir ecosystems, and has great implications for carbon cycling in major rivers.

58 GEOSCIENCES↗

Strain and ligand effects in Pt-Ni alloys studied by valence-to-core X-ray emission spectroscopy

Experimental detection of the Pt 5d densities of states in the valence band is conducted on a series of Pt-Ni alloys by high energy resolution valence-to-core X-ray emission spectroscopy (VTC-XES) at the Pt L 3 -edge. VTC-XES measurements reveal that the Pt d-band centroid shifts away from the Fermi level upon dilution, accompanied by concentration-dependent Pt d-band width. The competition between the strain effect and ligand effect is observed experimentally for the first time. It is found that the d-band widths in Pt 3 Ni and PtNi are broader than that of Pt metal due to compressive strain which overcompensates the effect of dilution, while it is narrower in PtNi 3 where the ligand effect dominates. VTC-XES is demonstrated to be a powerful tool to study the Pt d-band contribution to the valence band of Pt-based bimetallic. The implication for the enhanced activity of Pt-Ni catalysts in oxygen reduction reaction is discussed.

36 MATERIALS SCIENCE↗

Neutrons produced by known energies of ions abundant in space

Particle accelerator radiation measurements are applied to the problem of calculating biological dose from radiation produced in the walls of a spacecraft by various ions in space. Neutrons, one of the products of the interactions of energetic ions with matter, are usually quite penetrating and have large values of Q.F. or R.B.E. Ions of helium, boron, carbon, nitrogen, and oxygen were accelerated and directed onto target materials of copper or tantalum. The secondary neutron production was determined. Studies were made of the angular distribution and an inferred neutron spectrum was calculated from activities of threshold reaction detectors.

Wadman, W. W., III↗

Chemical, Mineralogical, and Physical Properties of Martian Dust and Soil

Global and regional dust storms on Mars have been observed from Earth-based telescopes, Mars orbiters, and surface rovers and landers. Dust storms can be global and regional. Dust is material that is suspended into the atmosphere by winds and has a particle size of 1-3 micrometer. Planetary scientist refer to loose unconsolidated materials at the surface as "soil." The term ''soil'' is used here to denote any loose, unconsolidated material that can be distinguished from rocks, bedrock, or strongly cohesive sediments. No implication for the presence or absence of organic materials or living matter is intended. Soil contains local and regional materials mixed with the globally distributed dust by aeolian processes. Loose, unconsolidated surface materials (dust and soil) may pose challenges for human exploration on Mars. Dust will no doubt adhere to spacesuits, vehicles, habitats, and other surface systems. What will be the impacts on human activity? The objective of this paper is to review the chemical, mineralogical, and physical properties of the martian dust and soil.

Ming, D. W.↗

Seasonal Impact of Regional Outdoor Biomass Burning on Air Pollution in Three Indian Cities: Delhi, Bengaluru, and Pune

Air pollution in many of India's cities exceeds national and international standards, and effective pollution control strategies require knowledge of the sources that contribute to air pollution and their spatiotemporal variability. In this study, we examine the influence of a single pollution source, outdoor biomass burning, on particulate matter (PM) concentrations, surface visibility, and aerosol optical depth (AOD) from 2007 to 2013 in three of the most populous Indian cities. We define the upwind regions, or "airsheds," for the cities by using atmospheric back trajectories from the HYSPLIT model. Using satellite fire radiative power (FRP) observations as a measure of fire activity, we target pre-monsoon and post-monsoon fires upwind of the Delhi National Capital Region and pre-monsoon fires surrounding Bengaluru and Pune. We find varying contributions of outdoor fires to different air quality metrics. For the post-monsoon burning season, we find that a subset of local meteorological variables (air temperature, humidity, sea level pressure, wind speed and direction) and FRP as the only pollution source explained 39% of variance in Delhi station PM(sub 10) anomalies, 77% in visibility, and 30% in satellite AOD; additionally, per unit increase in FRP within the daily airshed (1000 MW), PM(sub 10) increases by 16.34 micrograms per cubic meter, visibility decreases by 0.097 km, and satellite AOD increases by 0.07. In contrast, for the pre-monsoon burning season, we find less significant contributions from FRP to air quality in all three cities. Further, we attribute 99% of FRP from post-monsoon outdoor fires within Delhi's average airshed to agricultural burning. Our work suggests that although outdoor fires are not the dominant air pollution source in India throughout the year, post-monsoon fires contribute substantially to regional air pollution and high levels of population exposure around Delhi. During 3-day blocks of extreme PM(sub 2.5) in the 2013 post-monsoon burning season, which coincided with statistically significant high fire activity, concentrations in Delhi averaged 304 micrograms per cubic meter, or more than 1000% above the 24-h PM(sub 2.5) guideline (25 micrograms per cubic meter) of the World Health Organization. These results suggest that providing viable alternatives to agricultural residue burning could help improve post-monsoon air quality for a growing population of 63 million (39% in urban areas) within Delhi's airshed.

Air quality; Outdoor fires; Crop residue burning; ↗

Are Compton-thin AGNs Globally Compton Thin?

We select eight nearby active galactic nuclei (AGNs) which, based on previous work, appear to be Compton-thin in the line of sight. We model with MYTORUS their broadband X-ray spectra from 20 individual observations with Suzaku, accounting self-consistently for Fe Kα line emission, as well as direct and scattered continuum from matter with finite column density and solar Fe abundance. Our model configuration allows us to measure the global, out of the line of sight, equivalent hydrogen column density separately from that in the line of sight. For 5 out of 20 observations (in 3 AGNs) we find that the global column density is in fact ≳1.5 × 1024 per sq.cm, consistent with the distant scattering matter being Compton-thick. For a fourth AGN, two out of five observations are also consistent with being Compton-thick, although with large errors. Some of these AGNs have been reported to host relativistically broadened Fe Kα emission. Based on our modeling, the Fe Kα emission line is not resolved in all but two Suzaku observations, and the data can be fitted well with models that only include a narrow Fe Kα emission line.

P. Tzanavaris↗

Models, In situ, and Remote sensing of Aerosols (MIRA)

There is a natural partitioning of scientific interest amongst three specialties of aerosol research: modeling, in situ measurements, and remote sensing. The community sees enhanced measurement capabilities when these groups interact, and this strengthens the overall scientific impact on climate and air quality. The Models, In situ, and Remote sensing of Aerosols (MIRA) working group connects members of the different aerosol communities through collaborative projects. What is MIRA? MIRA is a forum that fosters international collaborations amongst the aerosol specialties. MIRA is also a collection of interdisciplinary projects with clear goals that are pursued by small working groups. Finally, MIRA projects are generally characterized by requests for additional scientific data (both observational and modeled). Why? The purpose of MIRA is to contextualize both observations and model results through the encouragement of holistic projects and collaborations. How does MIRA differ from other projects? MIRA focuses on interdisciplinarity to improve measurements and their utility, so MIRA complements the activities of other groups. For example, ensemble model runs of AeroCom could be used in a MIRA project with greater robustness than a similar effort that uses single-model analyses. We present a description of MIRA and brief descriptions of some of the current MIRA topics, which include Satellite-Assisted Particulate Matter (SAPM), Mapping of Aerosol lidar ratios for CALIPSO (MAC), Tables of Aerosol Optics (TAO), and the Harmonization of aerosol Assimilation Models and Retrievals (HAMR). Finally, we discuss the immediate science goals and organization of MIRA. See https://science.larc.nasa.gov/mira-wg/ for more information.

Travis Toth↗