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At least 271 records · Page 15

Environmental and Polarization Characterizations of E-Beam Plasma-Based AlF 3 -Passivated Aluminum Mirrors for Astronomical Telescopes

Astronomical space telescopes to study astrophysical phenomena from the far ultraviolet (FUV) to the near infrared (NIR) will require mirror coatings with high reflectance over this entire spectral region. While coatings for the optical and NIR part of the spectrum are fairly well developed with proven performance, the FUV range has presented significant challenges, particularly below 120nm. Recent developments in electron-beam (e-Beam) generated plasma treatment in a SF 6 environments has enabled the effective passivation of aluminum (Al) coatings for applications in the FUV, by native oxide removal and the formation of a AlF 3 passivation layer which could be tuned to any desired AlF 3 thickness. These results have been produced through a collaboration between the Goddard Space Flight Center (GSFC) and the Naval Research Laboratory (NRL). The passivation experiments have been carried out using the Large Area Plasma Processing System (LAPPS) at NRL using bare aluminum samples and provided by the coating group at GSFC. This novel procedure has demonstrated improved Al mirrors with state-of-the-art FUV reflectivity (e.g. R=91% at 121.6nm). In this paper, we will be reporting on environmental testing, micro-roughness, as well as polarization studies of these E-beam treated samples. These characterizations are being done in order to advance the Technology Readiness Level (TRL) for these Al+AlF 3 mirror coatings produced at LAPPS. The ultimate goal is to demonstrate the promise of using this coating technology to deliver reflectance performance plus stability and uniformity over a large area for a future IR/O/UV space telescope observatory.

FUV reflectance↗

Volatile-rich Crater Interior Deposits in the Polar Regions of Mars: Evidence for Ice Cap Advance and Retreat

Many craters on Mars are partially filled by distinctive material emplaced by post-impact processes. This crater fill material is an interior mound which is generally separated from the walls of the crater by a trough that may be continuous along the crater circumference (i.e. a ring-shaped trough), or which may only partially contact the crater walls (i.e. a crescent-shaped trough). The fill deposit is frequently offset from the crater center and may be asymmetric in plan view. Populations of such craters include those in the circum-south polar cap region, in Arabia Terra, associated with the Medusae Fossae Formation, and in the northern lowlands proximal to the north polar cap. We focus on those craters in circumpolar regions and assess their relationship to polar cap advance and retreat, especially the possibility that fill material represents remnants of a formerly larger contiguous cap. Volatile-rich deposits have the property of being modifiable by the local stability of the solid volatile, which is governed by local energy balance. Here we test the hypothesis that asymmetries in volatile fill shape, profile, and center-location within a crater result from asymmetries in local energy balance within the crater, due mainly to variation of solar insolation and radiative effects of the crater walls over the crater interior. Model profiles of crater fill are compared with MOLA topographic profiles to assess this hypothesis. If asymmetry in morphology and location of crater fill are consistent with radiative-dominated asymmetries in energy budget within the crater, then 1) the volatile-rich composition of the fill is supported (this process should not be effective at shaping volcanic or sedimentary deposits), and 2) the dominant factor determining the observed shape of volatile-rich crater fill is the local radiative energy budget (and erosive processes such as eolian deflation are secondary or unnecessary). We also use a geographic and energy model approach to specifically test the idea that material in partially filled craters around the south pole may once have been contiguous to the cap and may have been sustained and modified by radiative processes specific to the crater environment (as opposed to the surrounding plains) as the cap retreated.

Russell, Patrick S.↗

The ozone hole - The role of polar stratospheric cloud particles

The role of polar stratospheric clouds in the formation of the Antarctic ozone hole is considered. Several researchers have suggested that the decrease in ozone over Antarctica is related to the polar stratospheric clouds (PSCs) which had been observed in the antarctic winter stratosphere. Some of the pertinent characteristics of polar stratospheric clouds are discussed, and it is shown how these clouds may participate in the ozone destruction process. The satellite data for PSCs is analyzed, and statistical information regarding the number and maximum extinctions of these clouds is presented. Evidence that the polar stratospheric clouds are composed of frozen nitric acid is considered. It is suggested that the evaporation of the clouds, in late August and September, will release HOCl and HNO3 to the environment. This could be followed by the photodissociation of HOCl to OH and Cl, which would very effectively destroy ozone. However, the ozone destruction mechanism could be halted when enough of the evaporated nitric acid is photolized.

Hamill, Patrick↗

A Mercury Lander Mission Concept Study for the Next Decadal Survey

Mariner 10 provided our first closeup reconnaissance of Mercury during its three flybys in 1974 and 1975. MESSENGER’s 2011–2015 orbital investigation enabled numerous discoveries, several of which led to substantial or complete changes in our fundamental understanding of the planet. Among these were the unanticipated, widespread presence of volatile elements (e.g., Na, K, S); a surface with extremely low Fe abundance whose darkening agent is likely C; a previously unknown landform—hollows— that may form by volatile sublimation from within rocks exposed to the harsh conditions on the surface; a history of expansive effusive and explosive volcanism; substantial radial contraction of the planet from interior cooling; offset of the dipole moment of the internal magnetic field northward from the geographic equator by ~20% of the planet’s radius; crustal magnetization, attributed at least in part to an ancient field; unexpected seasonal variability and relationships among exospheric species and processes; and the presence in permanently shadowed polar terrain of water ice and other volatile materials, likely to include complex organic compounds. Mercury’s highly chemically reduced and unexpectedly volatile-rich composition is unique among the terrestrial planets and was not predicted by earlier hypotheses for the planet’s origin. As an end-member of terrestrial planet formation, Mercury holds unique clues about the original distribution of elements in the earliest stages of the Solar System and how planets (and exoplanets) form and evolve in close proximity to their host stars. The BepiColombo mission promises to expand our knowledge of this planet and to shed light on some of the mysteries revealed by the MESSENGER mission. However, several fundamental science questions raised by MESSENGER’s pioneering exploration of Mercury can only be answered with in situ measurements from the planet’s surface.

Ernst, C. M.↗

Is Water a Universal Solvent for Life?

There are strong reasons to believe that the laws, principles and constraints of physics and chemistry are universal. It is much less clear how this universality translates into our understanding of the origins of life. Conventionally, discussions of this topic focus on chemistry that must be sufficiently rich to seed life. Although this is clearly a prerequisite for the emergence of living systems, I propose to focus instead on self-organization of matter into functional structures capable of reproduction, evolution and responding to environmental changes. In biology, most essential functions are largely mediated by noncovalent interactions (interactions that do not involve making or breaking chemical bonds). Forming chemical bonds is only a small part of what living systems do. There are specific implications of this point of view for universality. I will concentrate on one of these implications. Strength of non-covalent interactions must be properly tuned. If they were too weak, the system would exhibit undesired, uncontrolled response to natural fluctuations of physical and chemical parameters. If they were too strong kinetics of biological processes would be slow and energetics costly. This balance, however, is not a natural property of complex chemical systems. Instead, it has to be achieved with the aid of an appropriate solvent for life. In particular, potential solvents for life must be characterized by a high dielectric constant to ensure solubility of polar species and sufficient flexibility of biological structures stabilized by electrostatic interactions. Among these solvents, water exhibits a remarkable trait that it also promotes solvophobic (hydrophobic) interactions between non-polar species, typically manifested by a tendency of these species to aggregate and minimize their contacts with the aqueous solvent. Hydrophobic interactions are responsible, at least in part, for many self-organization phenomena in biological systems, such as the formation of cellular boundary structures or protein folding. Strengths of electrostatic and hydrophobic interactions are similar and can be balanced over a wide range of temperatures, which considerably increases the repertoire of interactions that can be used to modulate biological functions. Some properties of water, e.g. its chemical activity against polymerization reactions, are considered as unfavorable to life. In actuality, this might be a favorable trait because life requires a balance between constructive and destructive processes. For example, molecules synthesized in response to specific conditions must be degraded once these conditions change. Otherwise regulation of biological processes would be virtually impossible. Water might not be the only liquid with favorable properties for supporting life. It has been proposed that formamide, which might be present elsewhere in the universe in sufficient quantities to warrant interest, could be a potential alternative to water for the origin of life. However, this will remain highly hypothetical until it is demonstrated in further studies on its physical, chemical and biological properties it is capable of mediating self-organization of matter and providing proper balance between different types of non-covalent interactions.

Pohorill, Andrew↗

Integrated process-structure–property–performance optimization of cold-sprayed zinc coatings on AZ91 magnesium alloy

High-pressure die cast (HPDC) AZ91 magnesium alloy is widely used in automotive components such as transmission housings and brackets for its excellent strength-to-weight ratio. Zinc-based cold spray coatings can be applied selectively to vulnerable areas to enhance corrosion resistance, minimize galvanic coupling with dissimilar metals, and eliminate the need for full-surface oxide coatings, making the process more efficient and targeted. A comprehensive evaluation of 16 combinations of nitrogen carrier gas temperatures and pressures led to the identification of an optimal range of process parameters, yielding Zn coatings with porosity <0.5 % by area, wear rates reduced by a factor of two compared to uncoated AZ91, and adhesion strengths up to 35 MPa. The enhanced mechanical performance of the coating is attributed to the low porosity and the formation of a metallurgical bond at the coating-substrate interface. Corrosion studies using macroscale potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) revealed a significant decrease in corrosion rate and a shift to more noble corrosion potentials (ZCP) for coated substrates. Furthermore, the Zn cold-sprayed samples exhibited significantly lower corrosion-induced evolved hydrogen content compared to the base AZ91 substrate and AZ91 coated with industrial coatings, demonstrating that the Zn layer effectively protects the substrate from the corrosive environment. Overall, cold spray Zn coatings significantly improve the mechanical and corrosion performance of AZ91 Mg alloys, addressing key material challenges and enabling their broader use in automotive applications.

Corrosion performance↗

Observations of Ozone-aerosol Correlated Behaviour in the Lower Stratosphere During the EASOE Campaign

The question of possible interactions between ozone and stratospheric aerosol has been open for a long time. Measurements carried out after the Mt. Agung and El Chicon eruptions showed evidence of negative correlations between the presence of volcanic stratospheric aerosols and ozone concentration. Evidence for negative correlations in the polar winter has been also found. It is only after the discovery of the Antarctic ozone hole that catalytic effects related to low temperature heterogeneous chemistry have become the object of much investigation, now extended to the role of volcanic aerosol in the ozone reduction. These phenomena can be the object of various interpretations, not mutually exclusive, including the effect of transport, diffuse radiation as well as heterogeneous chemistry. The present paper provides preliminary results of simultaneous measurements of ozone and aerosol, carried out at Thule, Greenland, during the winter 1991-92. The European Stratospheric Ozone Experiment (EASOE) was aimed at monitoring the winter Arctic stratosphere in order to obtain a deeper insight of the ozone destruction processes taking place in the polar regions. A large amount of aerosol was injected into the lower stratosphere by the recent eruption of Volcano Pinatubo. A lidar system, already operational in Thule since November 1990, has provided detailed measurements of the stratospheric aerosol concentration during EASOE. In the same period, a large number of ozonesondes were launched. Although no PSC formation was detected over Thule, the simultaneous measurement of the stratospheric aerosol and ozone profiles give the possibility to study interactions occurring in the stratosphere between these two constituents.

Digirolamo, P.↗

Abstracts of the Annual Meeting of Planetary Geologic Mappers, Flagstaff, AZ, 2008

Topics discussed include: Merging of the USGS Atlas of Mercury 1:5,000,000 Geologic Series; Geologic Mapping of the V-36 Thetis Regio Quadrangle: 2008 Progress Report; Structural Maps of the V-17 Beta Regio Quadrangle, Venus; Geologic Mapping of Isabella Quadrangle (V-50) and Helen Planitia, Venus; Renewed Mapping of the Nepthys Mons Quadrangle (V-54), Venus; Mapping the Sedna-Lavinia Region of Venus; Geologic Mapping of the Guinevere Planitia Quadrangle of Venus; Geological Mapping of Fortuna Tessera (V-2): Venus and Earth's Archean Process Comparisons; Geological Mapping of the North Polar Region of Venus (V-1 Snegurochka Planitia): Significant Problems and Comparisons to the Earth's Archean; Venus Quadrangle Geological Mapping: Use of Geoscience Data Visualization Systems in Mapping and Training; Geologic Map of the V-1 Snegurochka Planitia Quadrangle: Progress Report; The Fredegonde (V-57) Quadrangle, Venus: Characterization of the Venus Midlands; Formation and Evolution of Lakshmi Planum (V-7), Venus: Assessment of Models using Observations from Geological Mapping; Geologic Map of the Meskhent Tessera Quadrangle (V-3), Venus: Evidence for Early Formation and Preservation of Regional Topography; Geological Mapping of the Lada Terra (V-56) Quadrangle, Venus: A Progress Report; Geology of the Lachesis Tessera Quadrangle (V-18), Venus; Geologic Mapping of the Juno Chasma Quadrangle, Venus: Establishing the Relation Between Rifting and Volcanism; Geologic Mapping of V-19, V-28, and V-53; Lunar Geologic Mapping Program: 2008 Update; Geologic Mapping of the Marius Quadrangle, the Moon; Geologic Mapping along the Arabia Terra Dichotomy Boundary: Mawrth Vallis and Nili Fossae, Mars: Introductory Report; New Geologic Map of the Argyre Region of Mars; Geologic Evolution of the Martian Highlands: MTMs -20002, -20007, -25002, and -25007; Mapping Hesperia Planum, Mars; Geologic Mapping of the Meridiani Region, Mars; Geology of Holden Crater and the Holden and Ladon Multi-Ring Impact Basins, Margaritifer Terra, Mars; Geologic Mapping of Athabasca Valles; Geologic Mapping of MTM -30247, -35247 and -40247 Quadrangles, Reull Vallis Region of Mars; Geologic Mapping of the Martian Impact Crater Tooting; Geology of the Southern Utopia Planitia Highland-Lowland Boundary Plain: First Year Results and Second Year Plan; Mars Global Geologic Mapping: Amazonian Results; Recent Geologic Mapping Results for the Polar Regions of Mars; Geologic Mapping of the Medusae Fossae Formation on Mars (MC-8 SE and MC-23 NW) and the Northern Lowlands of Venus (V-16 and V-15); Geologic Mapping of the Zal, Hi'iaka, and Shamshu Regions of Io; Global Geologic Map of Europa; Material Units, Structures/Landforms, and Stratigraphy for the Global Geologic Map of Ganymede (1:15M); and Global Geologic Mapping of Io: Preliminary Results.

Bleamaster, Leslie F., III↗

Humidity Effect on Nanoscale Electrochemistry in Solid Silver Ion Conductors and the Dual Nature of Its Locality

Scanning probe microscopy (SPM) is a powerful tool to investigate electrochemistry in nanoscale volumes. While most SPM-based studies have focused on reactions at the tip-surface junction, charge and mass conservation requires coupled and intrinsically non-local cathodic and anodic processes that can be significantly affected by ambient humidity. Here, we explore the role of water in both cathodic and anodic processes, associated charge transport, and topographic volume changes depending on the polarity of tip bias. The first-order reversal curve current-voltage technique combined with simultaneous detection of the sample topography, referred to as FORC-IVz, was applied to a silver solid ion conductor. We found that the protons generated from water affect silver ionic conduction, silver particle formation and dissolution, and mechanical integrity of the material. This work highlights the dual nature (simultaneously local and non-local) of electrochemical SPM studies, which should be considered for comprehensive understanding of nanoscale electrochemistry.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Visualization of large-scale charged domain Walls in hexagonal manganites

A ferroelectric charged domain wall (CDW) carries bound charges, originating from the variation of the normal components of polarization across the domain boundary, leading to a possible two-dimensional conductive interface in insulating materials. The ferroelectric CDW can be precisely created, erased, and manipulated, therefore offering an intriguing pathway toward the design of nano-devices. However, due to rather large energy costs, the size of the CDW is usually on the nanoscale. Here, taking flux-grown ferroelectric hexagonal manganites (h-RMnO 3 ) as an example, we creatively adopted an accessible inclined polishing process to reveal the domain evolution of stripe, loop, and vortex domain patterns by depth profiling. Interestingly, we observed an unexpected large-scale straight CDW in as-grown LuMnO 3 with length up to a millimeter size, which may result from the “polar catastrophe” during the flux growth. The large-scale CDW has a residual influence on the formation of the loop domain when the crystal anneals below the ferroelectric transition temperature, but completely disappears as the topological vortices emerge. The observed large-scale CDWs make h-RMnO 3 a potential candidate for advanced electronic devices, leading to a panoply of desired properties.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Microscopic Fuel Particles Produced by Self-Assembly of Actinide Nanoclusters on Carbon Nanomaterials

Many consider further development of nuclear power to be essential for sustained development of society; however, the fuel forms currently used are expensive to recycle. In this project, we sought to create the knowledge and knowhow that are needed to produce nanocomposite materials by directly depositing uranium nanoclusters on networks of carbon-­ based nanomaterials. The objectives of the proposed work were to (1) determine the control of uranium nanocluster surface chemistry on nanocomposite formation, (2) determine the control of carbon nanomaterial surface chemistry on nanocomposite formation, and (3) develop protocols for synthesizing uranium-­carbon nanomaterials. After examining a wide variety of synthetic methods, we show that synthesizing graphene-­supported UO 2 nanocrystals in polar ethylene glycol compounds by polyol reduction under boiling reflux can enable the use of an inexpensive graphene precursor graphene oxide in the production of uranium-carbon nanocomposites in a one-­pot process. We further show that triethylene glycol is the most suitable solvent for producing nanometer-­sized UO 2 crystals compared to monoethylene glycol, diethylene glycol, and polyethylene glycol. Graphene-­supported UO 2 nanocrystals synthesized with triethylene glycol show evidence of heteroepitaxy, which can be beneficial for facilitating heat transfer in nuclear fuel particles. Furthermore, we show that graphene-supported UO 2 nanocrystals synthesized by polyol reduction can be readily stored in alcohols, preventing oxidation from the prevalent oxygen in air. Together, these methods provide a facile approach for preparing and storing graphene-supported UO nanocrystals for further investigation and development under ambient conditions.

36 MATERIALS SCIENCE↗

Atomic scale study of polar Lomer–Cottrell and Hirth lock dislocation cores in CdTe

Dislocation cores have long dominated the electronic and optical behaviors of semiconductor devices and detailed atomic characterization is required to further explore their effects. Miniaturization of semiconductor devices to nanometre scale also puts emphasis on a material's mechanical properties to withstand failure due to processing or operational stresses. Sessile junctions of dislocations provide barriers to propagation of mobile dislocations and may lead to work-hardening. The sessile Lomer–Cottrell and Hirth lock dislocations, two stable lowest elastic energy stair-rods, are studied in this paper. More specifically, using atomic resolution high-angle annular dark-field imaging and atomic-column-resolved X-ray spectrum imaging in an aberration-corrected scanning transmission electron microscope, dislocation core structures are examined in zinc-blende CdTe. A procedure is outlined for atomic scale analysis of dislocation junctions which allows determination of their identity with specially tailored Burgers circuits and also formation mechanisms of the polar core structures based on Thompson's tetrahedron adapted to reactions of polar dislocations as they appear in CdTe and other zinc-blende solids. Strain fields associated with the dislocations calculated via geometric phase analysis are found to be diffuse and free of `hot spots' that reflect compact structures and low elastic energy of the pure-edge stair-rods.

CdTe↗

Positron scattering by atomic hydrogen using optical potentials and with positronium formation

The scattering is considered of positrons by H(ls) in a two-state model which incorporates optical potentials. The model explicitly describes elastic scattering, i.e., positron + H(ls) yields positron + H(ls) and Ps(ls) yields Ps(ls) + p. The inelastic processes positron + H(ls) yields positron + H* Ps(ls) + p yields Ps* + p where * stands for a state other than ls, are implicitly taken into account through the optical potentials, which also allow for polarization of H(ls) and Ps(ls).

Walters, H. R. J.↗

On the role of the zirconia/ceria interface in the degradation of solid oxide electrolysis cells

Gd-doped Ceria (GDC) barrier layers are widely used in solid oxide electrolysis cells to prevent reactions between the Y-stabilized Zirconia (YSZ) electrolyte and oxygen electrode. In some cases, electrolysis operation causes fracture near the GDC/YSZ interface. Here, we explain this effect using a numerical calculation, showing that a peak oxygen pressure is observed near the GDC/YSZ interface during electrolysis operation. Moreover, GDC/YSZ interdiffusion and possible zirconate phase formation occurring during electrode firing yield a low oxygen ion conductivity region that introduces a much higher peak oxygen partial pressure at the interdiffusion layer/YSZ interface, thereby exacerbating degradation. The results indicate that the peak pressure can be reduced and, thereby, damage can be mitigated by altering processing in order to minimize interdiffusion, decreasing the GDC layer thickness, and reducing oxygen electrode polarization resistance or altering electrolyte transport properties, e.g., changing the Gd doping level of GDC to increase the oxygen vacancy diffusivity.

Physics↗

Propane clusters in Titan’s lower atmosphere: insights from a combined theory/laboratory study

ABSTRACT In spite of the considerable advances made by Cassini–Huygens in our understanding of Titan, many questions endure. In particular, the detailed processes that lead to the formation of haze aerosols in Titan’s atmosphere, found in high concentrations at low altitudes, are not well identified. Hydrocarbons, which are abundant constituents of Titan’s cold atmosphere originating from photochemical processes, may simultaneously condense on the surface of existing aerosols, nucleate and grow to generate new aerosol seeds. The relative importance of the various processes depends on several factors, including the saturation ratio. The dynamics of hydrocarbon condensation and nucleation in Titan’s atmosphere remains poorly known. Aiming to progress on these issues, we investigate here the kinetics of propane dimer formation at low temperature through state-of-the-art laboratory experiments combined with theoretical calculations. Our results provide an estimate of the rate coefficients, which are then employed to evaluate the abundance of propane dimers in the lower atmosphere of Titan. The mixing ratios of propane dimers inferred, with a maximum abundance of 10 cm−3 near 100 km, is found to be under the detection limit of the Composite Infrared Spectrometer of the Cassini spacecraft. Based on our results, homogeneous nucleation of the most abundant species appears not to be relevant for the growth of aerosols. Future studies should focus on homogeneous nucleation of polar molecules or alternatively on heterogeneous processes, which are usually more efficient.

79 ASTRONOMY AND ASTROPHYSICS↗

A wet-geology and cold-climate Mars model: Punctuation of a slow dynamic approach to equilibrium

It was suggested that Mars may have possessed a relatively warm humid climate and a vigorous hydrological cycle involving meteoric precipitation, oceans, and continental ice sheets. Baker hypothesized that these geologically active conditions may have been repeated several times; each of these dynamic epochs was followed by a collapse of the climate and hydrologic cycle of Mars into essentially current conditions, completing what is termed a 'Baker cycle'. The purpose is to present an endmember possibility that Martian glacial landscapes, including some that were previously considered to have formed under warm climatic conditions, might be explained by processes compatible with an extremely cold surface. Two aspects of hypothesized Martian glacial terrains were cited as favoring a warm climate during Baker cycles: (1) the formation of some landscapes, including possible eskers, tunnel channels, drumlins, and outwash plains, appears to have required liquid water, and (2) a liquid-surfaced ocean was probably necessary to feed the glaciers. The requirement for liquid water, if these features were correctly interpreted, is difficult to avoid; it is entirely possible that a comparatively warm climate was involved, but it is not clear that formation of landforms by wet-based glaciers actually requires a warm climate. Even less certain is the supposed requirement for liquid oceans. Formation of glaciers only requires a source of water or ice to supply an amount of precipitation that exceeds losses due to melting and sublimation. At Martian temperatures precipitation is very low, but so are melting and sublimation, so a large body of ice that is unstable with respect to sublimation may take the role of Earth's oceans in feeding the glaciers. Recent models suggest that even current Martian polar caps, long thought to be static bodies of ice and dust, might actually be slow-moving, cryogenic continental glaciers. Is it possible that subglacial processes beneath cryogenic (but wetbased) ice sheets formed the hypothesized Martian glacial landscapes?

Kargel, J. S.↗

Water as a matrix for life

"Follow the water" is the canonical strategy in searching for life in the universe. Conventionally, discussion of this topic is focused on how solvent supports organic chemistry sufficiently rich to seed life. Perhaps more importantly, solvent must promote self-organization of organic matter into functional structures capable of responding to environmental changes. This process is based on non-covalent interactions. They are constantly formed and broken in response to internal and external stimuli. This requires that their strength must be properly tuned. If they were too weak, the system would exhibit undesired, uncontrolled response to natural fluctuations of physical and chemical parameters. If they were too strong kinetics of biological processes would be slow and energetics costly. Non-covalent interactions are strongly mediated by the solvent. Specifically, high dielectric solvents for life are needed for solubility of polar species and flexibility of biological structures stabilized by electrostatic interactions. Water exhibits a remarkable trait that it promotes solvophobic interactions between non-polar species, which are responsible for self-organization phenomena such as the formation of cellular boundary structures, and protein folding and aggregation. Unusual temperature dependence of hydrophobic interactions - they often become stronger as temperature increases - is a consequence of the temperature insensitivity of properties of the liquid water. This contributes to the existence of robust life over a wide temperature range. Water is not the only liquid with favorable properties for supporting life. Other pure liquids or their mixtures that have high dielectric constants and simultaneously support some level of self-organization will be discussed.

Pohorille, Andrew↗

Concentration Effects and Ion Properties Controlling the Fractionation of Halides during Aerosol Formation

During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air−water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO2, NaNO3, NaClO4, and NaIO4. The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of anions (f (Isub x-)) and their correlation with ion properties. Although no correlation exists between f (sub x-) and the limiting equivalent ionic conductivity, the correlation coefficient of the linear fit with the size of the anions R(sub x-), dehydration free-energy ΔGdehyd, and polarizability alpha, follows the order: (R(sub x-)(exp −2)) > (R(sub x-)(exp −1)) >(R(sub x-) > delta G(sub dehyd) > alpha. The same pure physical process is observed in H2O and D2O. The factor f (sub x-) does not change with pH (6.8−8.6), counterion (Li+, Na+, K+, and Cs+) substitution effects, or solvent polarity changes in methanol − and ethanol−water mixtures (0 <= xH2O <= 1). Sodium polysorbate 20 surfactant is used to modify the structure of the interface. Despite the observed enrichment of I− on the air−water interface of equimolar solutions, our results of seawater mimic samples agree with a model in which the interfacial composition is increasingly enriched in I− < Br− < Cl− over the oceanic boundary layer due to concentration effects in sea spray aerosol formation.

iodine↗