Grain sizes, surface areas, and porosities of vapor-deposited H2O ices used to simulate planetary icy surfaces.

Mean grain sizes and specific surface areas (SSAs) of ice substrates formed by vapor deposition at low temperatures are of importance in simulating external surfaces of icy satellites in the solar system. Environmental scanning electron microscopy (ESEM) was used to obtain granule sizes and to observe the phase of ice granules prepared on borosilicate, silicon, and metallic plates. Ices prepared at a temperature lower than 140 K appear to be amorphous, and their granule sizes are typically submicrometer. At slightly warmer temperatures, near 180-200 K, ice films are composed of either hexagonal or cubic granules with sizes up to a few micrometers. When briefly annealed to even warmer temperatures, ice granule sizes approach approximately 10 microm. SSAs of ice substrates were determined from BET (Brunauer, Emmett, and Teller) analysis of gas adsorption isotherms in the temperature range from 83.5 to 261 K. SSAs decrease drastically from 102 m2/g at 83.5 K to 0.87 m2/g at 150 K and further decrease slowly to 0.22 m2/g at 261 K, suggesting that the transition from amorphous to crystalline forms occurs at approximately 150 K. The overall decrease in SSAs is primarily due to metamorphism and sintering. These results are comparable to recent field and laboratory measurements. Possible implications for theoretical models of icy satellites of outer planets using remote sensing techniques are also discussed.

Acidity of frozen electrolyte solutions.

Ice is selectively intolerant to impurities. A preponderance of implanted anions or cations generates electrical imbalances in ice grown from electrolyte solutions. Since the excess charges are ultimately neutralized via interfacial (H(+)/HO(-)) transport, the acidity of the unfrozen portion can change significantly and permanently. This insufficiently recognized phenomenon should critically affect rates and equilibria in frozen media. Here we report the effective (19)F NMR chemical shift of 3-fluorobenzoic acid as in situ probe of the acidity of extensively frozen electrolyte solutions. The sign and magnitude of the acidity changes associated with freezing are largely determined by specific ion combinations, but depend also on solute concentration and/or the extent of supercooling. NaCl solutions become more basic, those of (NH(4))(2)SO(4) or Na(2)SO(4) become more acidic, while solutions of the 2-(N-morpholino)ethanesulfonic acid zwitterion barely change their acidity upon freezing. We discuss how acidity scales based on solid-state NMR measurements could be used to assess the degree of ionization of weak acids and bases in frozen media.

Kinetics of NO and NO2 evolution from illuminated frozen nitrate solutions.

The release of NO and NO2 from frozen aqueous NaNO3 irradiated at 313 nm was studied using time-resolved spectroscopic techniques. The kinetic behavior of NO and NO2 signals during on-and-off illumination cycles confirms that NO2 is a primary photoproduct evolving from the outermost ice layers and reveals that NO is a secondary species generated deeper in the ice, whence it eventually emerges due to its inertness and larger diffusivity. NO is shown to be more weakly held than NO2 by ice in thermal desorption experiments on preirradiated samples. The partial control of gaseous emissions by mass transfer, and hence by the morphology and metamorphisms of polycrystalline ice, is established by (1) the nonmonotonic temperature dependence of NO and NO2 signals upon stepwise warming under continuous illumination, (2) the fact that the NO, NO2 or NOx (NOx identical with NO + NO2) amounts released in bright thermograms performed under various heating ramps fail to scale with photon dose, due to irreversible losses in the adsorbed state. Because present NO/NO2 ratios are up to 10-fold smaller than those determined over sunlit snowpacks, we infer that the immediate precursors to NO mostly absorb at lambda > lambda(max) (NO3-) approximately 302 nm.

Photochemical production and release of gaseous NO2 from nitrate-doped water ice.

Temperature-programmed NO2 emissions from frozen aqueous NaNO3 solutions irradiated at 313 nm were monitored as function of nitrate concentration and heating rate, H, above -30 degrees C. Emissions increase nonmonotonically with temperature, displaying transitions suggestive of underlying metamorphic transformations. Thus, NO2 emissions surge at ca. -8 degrees C in frozen [NO3-] > 200 microM samples warmed at H = 0.70 degrees C min(-1) under continuous irradiation, and also in the dark from samples that had been photolyzed at -30 degrees C. The amounts of NO2 released in individual thermograms, SigmaN, increase less than linearly with [NO3-] or the duration of experiments, revealing the significant loss of photogenerated NO2. The actual SigmaN proportional, variant [NO3-]1/2 dependence (at constant H) is consistent with NO2 hydrolysis: 2NO2 + H2O --> NO3- + NO2- + 2H+, overtaking NO2 desorption, even below the eutectic point (-18 degrees C for aqueous NaNO3). The increasingly larger NO2 losses detected in longer experiments (at constant [NO3-]) are ascribed to secondary photolysis of trapped NO2. The relevance of present results to the interpretation of polar NO2 measurements is briefly analyzed.

Keeping Mars warm with new super greenhouse gases.

Our selection of new super greenhouse gases to fill a putative "window" in a future Martian atmosphere relies on quantum-mechanical calculations. Our study indicates that if Mars could somehow acquire an Earth-like atmospheric composition and surface pressure, then an Earth-like temperature could be sustained by a mixture of five to seven fluorine compounds. Martian mining requirements for replenishing the fluorine could be comparable to current terrestrial extraction.