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NASA NTRS1987

Spatial characterization of acid rain stress in Canadian Shield Lakes

An analysis was performed to interpret the spatial aspects of lake acidification. Three types of relationships were investigated based upon the August to May seasonal scene pairing. In the first type of analysis ANOVA was used to examine the mean Thematic Mapper band one count by ecophysical strata. The primary difference in the two ecophysical strata is the soil type and depth over the underlying bedrock. Examination of the August to May difference values for TM band one produced similar results. Group A and B strata were the same as above. The third type of analysis examined the relationship between values of the August to May difference from polygons which have similar ecophysical properties with the exception of sulfate deposition. For this case lakes were selected from units with sandy soils over granitic rock types and the sulfate deposition was 1.5 or 2.5 g/sq m/yr.

Tanis, Fred J.↗
NASA NTRS1987

Spatial characterization of acid rain stress in Canadian Shield Lakes

The acidification of lake waters from airborne pollution is of continental proportions both in North America and Europe. A major concern of the acid rain problem is the cumulative ecosystem damage to lakes and forest. The number of lakes affected in northeastern U.S. and on the Canadian Shield is though to be enormous. How seasonal changes in lake transparency are related to annual acidic load was examined. The relationship between variations in lake acidification and ecophysical units was also examined. The utility of Thematic Mapper based observations to measure seasonal changes in the optical transparency in acid lakes was investigated. The potential for this optical response is related to a number of local ecophysical factors with bedrock geology being, perhaps, the most important. Other factors include sulfate deposition, vegetative cover, and terrain drainage/relief. The area of southern Ontario contains a wide variety of geologies from the most acid rain sensitive granite quartzite types to the least sensitive limestone dolomite sediments. Annual sulfate deposition ranges from 1.0 to 4.0 grams/sq m.

Tanis, Fred J.↗
NASA NTRS1987

On the role of convective motion during dendrite growth: Experiments under variable gravity, revised

Experiments show the effect of self induced convection on individual dendrite growth in uniformly supercooled samples and solidification of the resulting mush under conditions of high and low g. Convection is visualized by a Schlieren optical system or a Mach Zender interferometer. For ice crystals growing from the vapor in air, a slight reduction in linear growth rate occur under low g. For ice crystals growing from NaCl solution, dendrite tip velocities are unchanged, but subsequent mush solidification is enhanced through drainage channels under higher g. By contrast, sodium sulfate decahydrate dendrites growing from solution produce convective plumes which lead to higher tip growth rate only as the crystal growth direction approaches that of gravity. Convective plumes are laminar for small crystals under conditions of these experiments; the rise velocity of such plumes is greater than individual vortex rings under identical conditions. Convection effects are only present in solution under a critical supercooling less than about 5 C for sodium sulfate and 2 C for ice in NaCl since at higher supercooling the crystallization velocity, proportional to the square of the supercooling, exceeds the convective velocity, proportional to the square root of the supercooling. The role of convective velocity in bulk solidification is to give a large scale flow which under extreme cases may lead to extensive secondary crystal production, which alters the resulting crystal texture of the completely solidified melt.

Hallett, J.↗
NASA NTRS1987

Martian surface analogs: Laboratory spectral studies in the mid infrared

Ground-based telescopic reflectance spectra and analyses of Viking data have led to the conclusion that Martian surface fines are derived from a mafic to ultramafic source material, though the actual composition of these surface fines is still undetermined. A variety of possible compositions were proposed by several authors, however, with salts, particularly sulfates and carbonates, as important components in many of these models. Although salts are predicted components of the Martian surface, they are not identified in telescopic reflectance spectroscopic observations to date. One explanation for the absence of salts in these data is that they are not in quantities large enough to detect. This study was undertaken to determine the detectability of salts in various proposed Martian surface analog mixtures. This study concentrates on the carbonates and sulfate spectral features in the 2.5 to 25 micrometer spectral range because of recent work showing the usefulness of weak bands in the mid infrared for the remote sensing of particulate planetary surfaces. All measurements were made using a Nicolet 5SXC FTIR spectrometer with a bidirectional reflectance attachment, which uses an aluminum mirror as the background against which the sample is compared.

Walsh, P. A.↗
NASA NTRS1985

Ceramic oxide reactions with V2O5 and SO3

Ceramic oxides are not inert in combustion environments, but can react with, inter alia, SO3, and Na2SO4 to yield low melting mixed sulfate eutectics, and with vanadium compounds to produce vanadates. Assuming ceramic degradation to become severe only when molten phases are generated in the surface salt (as found for metallic hot corrosion), the reactivity of ceramic oxides can be quantified by determining the SO3 partial pressure necessary for molten mixed sulfate formation with Na2SO3. Vanadium pentoxide is an acidic oxide that reacts with Na2O, SO3, and the different ceramic oxides in a series of Lux-Flood type of acid-base displacement reactions. To elucidate the various possible vanadium compound-ceramic oxide interactions, a study was made of the reactions of a matrix involving, on the one axis, ceramix oxides of increasing acidity, and on the other axis, vanadium compounds of increasing acidity. Resistance to vanadium compound reaction increased as the oxide acidity increased. Oxides more acidic than ZrO2 displaced V2O5. Examination of Y2O3- and CeO2-stabilized ZrO2 sintered ceramics which were degraded in 700 C NaVO3 has shown good agreement with the reactions predicted above, except that the CeO2-ZrO2 ceramic appears to be inexplicably degraded by NaVO3.

Jones, R. L.↗
NASA NTRS1988

Sampling the oxidative weathering products and the potentially acidic permafrost on Mars

Large areas of Mars' surface are covered by oxidative weathering products containing ferric and sulfate ions having analogies to terrestrial gossans derived from sulfide mineralization associated with iron-rich basalts. Chemical weathering of such massive and disseminated pyrrhotite-pentlandite assemblages and host basaltic rocks in the Martian environment could have produced metastable gossaniferous phases (limonite containing poorly crystalline hydrated ferric sulfates and oxyhydroxides, clay silicates and opal). Underlying groundwater, now permafrost on Mars, may still be acidic due to incomplete buffering reactions by wall-rock alteration of unfractured host rock. Such acidic solutions stabilize temperature-sensitive complex ions and sols which flocculate to colloidal precipitates at elevated temperatures. Sampling procedures of Martian regolith will need to be designed bearing in mind that the frozen permafrost may be corrosive and be stabilizing unique complex ions and sols of Fe, Al, Mg, Ni and other minor elements.

Burns, Roger G.↗
NASA NTRS1987

Laboratory studies of binary salt CVD in combustion gas environments

A flash-evaporation technique is used to obtain vapor deposition characteristics for the binary alkali sulfates K2SO4 + Na2SO4 at 1 atm above 1100 K. The experimental equipment and techniques are described, and preliminary results are reported which indicate that this experimental technique meets most of the research requirements for studying multicomponent systems of current interest. The various deposition rate effects of introducing additives and the relevant inferences of condensate composition are presented, and the theoretical implications are discussed. It is concluded that alkali sulfate deposition and vaporization in combustion environments are inevitably influenced by chemical reactions such as hydroxide formation, and that solution nonideality is important even for homologous alkali-salt mixtures.

Liang, Baishen↗
NASA NTRS1989

Balloon-borne measurements of aerosol, condensation nuclei, and cloud particles in the stratosphere at McMurdo Station, Antarctica, during the spring of 1987

Measurements of the vertical profile of particles with condensation nuclei counters and eight channel aerosol detectors at McMurdo Station, Antarctica, in 1987 verified observations made in 1986 concerning the absence of upwelling in the polar vortex and the presence of a condensation nuclei layer in conjunction with the ozone hole region. New observations of a bimodal aerosol size distribution, consisting of a large-particle mode mixed in with the small-particle sulfate mode, at temperatures below -79 C are consistent with the presence of nitric acid-water particles at low concentrations. Higher concentrations of large particles were observed in association with nacreous clouds. An unusual particle layer which contained enhanced concentrations of both the small-particle (sulfate) mode and the large-particle (nitric acid) mode was detected at temperatures below -85 C, suggesting simultaneous nucleation and growth phenomena. The vortex condensation nuclei layer was observed to form at the same time as the ozone hole, indicating that formation of the layer is triggered by photochemical processes and may be important in controlling ozone depletion above 22 km.

Hofmann, D. J.↗
NASA NTRS1989

Filter measurement results from the Airborne Antarctic Ozone Experiment

Filter samples obtained as part of the AAOE to determine the total nitrate, sulfate, acidic chloride, and acidic fluoride content along the flight path of the NASA ER-2 are studied. These compounds were obtained in the aerosol and vapor phase. The ratio of particulate sulfate observed outside the chemically perturbed region (CPR) of the vortex to that inside the CPR was 2.6. The ratio of total acidic chloride to total acidic flouride within the CPR is near 1, indicating the removal of chloride from the air mass or the partitioning of chloride into an unmeasured species.

Gandrud, B. W.↗
NASA NTRS1989

Characterization and evaluation of acid rain in East Central Florida from 1978 to 1987: Ten year summary report

Rainfall was collected on the University of Central Florida (UCF) campus near Orlando since July 1977 and at the Kennedy Space Center (KSC), Florida since August 1977. Since November 1983, the KSC site has been affiliated with the National Atmospheric Deposition Network. Annual volume weighted pH was slightly above the 10 year mean of 4.58 during four of the past five years. Nitrate concentrations have risen somewhat during recent years while excess sulfate concentrations have remained below the 10 year mean during four of the past years. These observations hold for both the UCF and KSC data. The distribution of individual sample pH was nearly identical at UCF and KSC. Stepwise regression suggests that sulfate, nitrate, ammonium ion, and calcium play major roles in the description of rainwater acidity. Annual acid deposition and annual rainfall have varied from 30 to 50 meq/m2-yr and 100 to 180 cm/yr, respectively. Sea salt comprises about 25 percent (UCF) and greater than 50 percent (KSC) of total ionic composition.

Madsen, Brooks C.↗
NASA NTRS1989

Observations of condensation nuclei in the Airborne Antarctic Ozone Experiment - Implications for new particle formation and polar stratospheric cloud formation

This paper discusses the results of the ER-2 Condensation Nucleus Counter operated in the Airborne Ozone Experiment in August, September, and October 1987, providing data on the mixing ratio of aerosol condensation nuclei (CN) with diameters between about 0.02 and 1 micron. It is shown that the vertical profile of the CN mixing ratio is closely related to that of N2O, and that, between the -71 and -53 deg latitude, the location of the minima in the CN mixing ratio profile was near the 160 ppbv N2O isopleth, indicating that the processes of mixing and subsidence, which determine the inclination of that isopleth, also strongly affect the spatial distribution of the sulfate aerosol. Evidence for new sulfate particle formation is presented and related to the amount of subsidence experienced by air parcels in the formation of the polar vortex. Concentrations of CN are compared with those of larger particles (with diameters between 0.81 micron and 9.75 microns) to study polar stratospheric cloud formation mechanisms.

Wilson, J. C.↗
NASA NTRS1990

Wet chemical passivation of YBa2Cu3O(7-x)

Wet chemical techniques are described for treatment of YBa2Cu3O(7-x) surfaces, which result in the formation of native compounds known to have little or no reactivity to water. Suitable native compounds include CuI, BaSO4, CuS, Cu2S, YF3, and the oxalates. Formation of surface layers in which these nonreactive native compounds are major constituents is verified with X-ray photoelectron spectroscopy (XPS) measurements on YBa2Cu3O(7-x) films treated with dilute solutions of HI, H2SO4, Na2S, HF, or H2C2O4. No significant changes are observed in the XPS spectra when the sulfide, sulfate, or oxalate films are dipped in water, while the iodide and fluoride films show evidence of reaction with water. X-ray diffraction measurements show that the superconducting phase is absent in the sulfide film, but is unaffected by the oxalate and sulfate treatments.

Vasquez, R. P.↗
NASA NTRS1990

Precipitation chemistry in central Amazonia

Rain samples from three sites in central Amazonia were collected over a period of 6 weeks during the 1987 wet season and analyzed for ionic species and dissolved organic carbon. A continuous record of precipitation chemistry and amount was obtained at two of these sites, which were free from local or regional pollution, for a time period of over 1 month. The volume-weighted mean concentrations of most species were found to be about a factor of 5 lower during the wet season compared with previous results from the dry season. Only sodium, potassium, and chloride showed similar concentrations in both seasons. When the seasonal difference in rainfall amount is taken into consideration, the deposition fluxes are only slightly lower for most species during the wet season than during the dry season, again with the exception of chloride, potassium, and sodium. Sodium and chloride are present in the same ratio as in sea salt; rapid advection of air masses of marine origin to the central Amazon Basin during the wet season may be responsible for the observed higher deposition flux of these species. Statistical analysis suggests that sulfate is, to a large extent, of marine (sea salt and biogenic) origin, but that long-range transport of combustion-derived aerosols also makes a significant contribution to sulfate and nitrate levels in Amazonian rain. Organic acid concentrations in rain were responsible for a large fraction of the observed precipitation acidity; their concentration was strongly influenced by gas/liquid interactions.

Andreae, M. O.↗
NASA NTRS1991

Passivation Of High-Temperature Superconductors

Surfaces of high-temperature superconductors passivated with native iodides, sulfides, or sulfates formed by chemical treatments after superconductors grown. Passivating compounds nearly insoluble in and unreactive with water and protect underlying superconductors from effects of moisture. Layers of cuprous iodide and of barium sulfate grown. Other candidate passivating surface films: iodides and sulfides of bismuth, strontium, and thallium. Other proposed techniques for formation of passivating layers include deposition and gas-phase reaction.

Vasquez, Richard P.↗
NASA NTRS1990

Volatile compounds in shergottite and nakhlite meteorites

Since discovery of apparent carbonate carbon in Nakhla, significant evidence has accumulated for occurrence of volatile compounds in shergotties and nakhlites. Results are presented from a study of volatile compounds in three shergottites, one nakhlite, and three eucrite control samples. Shergotties ALHA77005, EETA79001, and Shergotty, and the nakhlite Nakhla, all contain oxidized sulfur (sulfate) of preterrestrial origin; sulfur oxidation is most complete in EETA79001/Lith-C. Significant bulk carbonate was confirmed in Nakhla and trace carbonate was substantiated for EETA79001, all of which appears to be preterrestrial in origin. Chlorine covaries with oxidized sulfur, whereas carbonate and sulfate are inversely related. These volatile compounds were probably formed in a highly oxidizing, aqueous environment sometime in the late stage histories of the rocks that are now represented as meteorites. They are consistent with the hypothesis that shergottite and nakhlite meteorites originated on Mars and that Mars has supported aqueous geochemistry during its history.

Gooding, James L.↗
NASA NTRS1990

Hot corrosion of silicon carbide and silicon nitride at 1000 C

The sodium sulfate hot corrosion of silicon-based ceramics at 1000 C has been extensively studied. Deposition of the sodium sulfate corrodant from combustion products is discussed in relation to sodium air impurity and sulfur fuel impurity content. Corrosion occurs by the combined processes of oxidation to form protective silica scales and dissolution of these scales to form nonprotective sodium silicates. The chemical corrosion mechanisms are presented in terms of acidic/basic dissolution of oxides in molten salts. The reactions are strongly influenced by the presence of free carbon in the ceramic. Strength reductions have been measured and are attributed to pitting in SiC and grain boundary attack in Si3N4. Initial results of burner corrosion of two ceramic matrix composites are consistent with the models developed for monolithic ceramics.

Fox, Dennis S.↗
NASA NTRS1991

Physical properties of cryovolcanic brines: Applications to the evolution of Ganymede

Carbonaceous chondrites contain abundant veins of water soluble salts, including carbonates and hydrated sulfates of Mg, Ca, Na, Ni, and Fe. These constitute over 1/4 of the mass of the meteorite Orgueil. Magnesium sulfate is the most abundant salt, constituting nearly half the mass of all salt components combined (anhydrous), and 73 pct. of the highly water soluble salts. The assumption that icy satellites and asteroids contain rock compositionally similar to carbonaceous chondrites suggests that salts may be important in the cryoigneous evolution of icy satellites and asteroids. Ordinary chondrites, an alternative rock component of icy satellites, lack abundant salts, although their anhydrous silicate assemblages are unstable with respect to water and would react to produce salts upon initial melting of ice. Some basic physiochemical properties are reviewed of likely cryovolcanic brines and how the existence of soluble salts in Ganymede might affect its structure and evolution is considered. Observations indicate late stage (post heavy bombardment and post tectonic) volcanism on Ganymede. The highly fluid character of Ganymedian volcanism is consistent with extrusions of either water or salt water brines.

Kargel, Jeffrey S.↗
NASA NTRS1991

Aqueous alteration on the parent bodies of carbonaceous chondrites: Computer simulations of late-stage oxidation

CI carbonaceous chondrites may be products of hydrous alteration of CV- or anhydrous CM-type materials. The CIs typically contain veins filled with carbonates and sulfates, probably indicating a period of late stage aqueous alteration under oxidizing conditions. To test this idea, computer simulations of aqueous alteration of CV- and CM-type carbonaceous were performed. Simulations were restricted to the oxidation of hydrous mineral assemblages produced in previous simulations in order to determine whether further reaction and oxidation results in the phyllosilicate, carbonate, sulfate and oxide vein assemblages typical of CI carbonaceous chondrites. Our simulations were performed at 1, 25, 100, and 150 C (the appropriate temperature range) for the CV and CM mineral assemblages and using the computer code EQ3/6.

Bourcier, W. L.↗