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NASA NTRS1982

Seasonal carbon dioxide exchange between the regolith and atmosphere of Mars - Experimental and theoretical studies

CO2 penetration rate measurements have been made through basalt-clay soils under conditions simulating the penetration of the cap-induced seasonal CO2 pressure wave through the topmost regolith of Mars, and results suggest that existing theoretical models for the diffusion of a gas through a porous and highly adsorbing medium may be used to assess the importance of the Martian seasonal regolith-atmosphere CO2 exchange. The maximum effect of thermally driven exchange between the topmost seasonally (thermally) affected regolith and the atmosphere shows that, while this may be of greater importance than the isothermal exchange, the thermally driven exchange would be recognizable only if the pressure wave from CO2 exchanged at high latitudes did not propagate atmospherically faster than the rate at which the exchange itself occurred. This is an unreasonable assumption.

Fanale, F. P.↗

NASA NTRS1982

Sulfur-dioxide/water equilibria between 0 and 50 C - An examination of data at low concentrations

In order to resolve the discrepancy noted in values currently used for the first dissociation constant of SO2 in water, the pertinent literature was critically examined and a value of 0.0132 M at 25 C was recommended. An expression correlating this value as a function of temperature for zero-50 C has been developed. Attention is also given to the literature for the Henry's law constant, and a value of 1.242 M/atm at 25 C is recommended. Ionic activity corrections and speciation in more concentrated solutions are discussed, and recommendations are made for estimating the activity coefficients of the various ionic species in solutions of moderate ionic strength.

Maahs, H. G.↗

NASA NTRS1983

Variability of antarctic sea ice and changes in carbon dioxide

Available data for antarctic sea ice is examined for the presence of long terms trends which could signal a decrease in the total ice amount being brought on by atmospheric warming due to increased CO2 concentrations. The Nimbus 5 electrically scanning microwave radiometer derived ice concentrations from 1972-1976, after which the scanning multifrequency microwave radiometer on the Nimbus 7 spacecraft was used from 1978-1981. Additionally, ship reports, IR data from the NOAA 5 radiometer, and the Landsat visible light scanner were considered. The data were digitized for analyses, which covered seasonal, year-to-year, trends over several years, and interannual seasonal variations. The total ice amplitude varied by 30 pct annually, and decreases in one area corresponded to increases in ice in others. No particular long-term trends were observed, and it is suggested that the satellite ice coverage data be extended in time in order to uncover any trends that extend beyond 9 yr.

Zwally, H. J.↗

NASA NTRS1983

Spectrophone stabilization and offset tuning of a carbon dioxide waveguide laser

A sensitive spectrophone containing CO2 gas is incorporated into a feedback loop to stabilize the frequency of a CO2 waveguide laser. First or second harmonic detection combined with a zero offset feature and the relatively high operating pressure of the laser allows continuous tuning of the stabilized frequency over a 400 MHz range. Frequency stability of better than + or - 1 MHz is achieved.

Kavaya, M. J.↗

NASA NTRS1984

The plumes of IO: A detection of solid sulfur dioxide particles

Spectra of Io obtained during eclipse show a narrow deep absorption feature at 4.871 microns, the wavelength of the Nu sub 1 + Nu sub 3 band of solid SO2. The 4 micron radiation comes from volcanic hot spots at a temperature too high for the existence of solid SO2. It is concluded that the spectral feature results from SO2 particles suspended in plumes above the hot spots. The derived abundance of approximately 0.0003 gm/sq cm may imply an SO2 solid-to-gas ratio of roughly one for the Loki plume, which would in turn suggest that it is driven by the SO2 rather than by sulfur.

Howell, R. R.↗

NASA NTRS1984

Stabilized luminous arcs (rotating arcs) in nitrogen and carbon dioxide at pressures of one to forty atmospheres

The arcs were run in the axis of a rapidly rotating glass tube, at 1 to 20 atm. For pressures over 20 atm., a decrease of stability appeared and above 40 atm., the results were very unsatisfactory owing to turbulence. The voltage and longitudinal-field-strength curves for both gases had a descending character. The field strength was 1.5 to 2.0 times as high in CO2 as in N. Under 10 atm. of pressure approx. linear values obtained. In N the column diam. increased with pressure. C. d. increased with pressure in CO2. Good agreement with the Steenbeck minimum principle was in general obtained.

Foitzik, R.↗

NASA NTRS1983

Effects of nitric oxide and nitrogen dioxide on bacterial growth

While it is generally thought that the bactericidal effects of NO and NO2 derive from their reaction with water to form nitrous and nitric acids (Shank et al., 1962), this appears to be true only at high concentrations. The data presented here suggest that at low NO and NO2 concentrations, acids are not present in high enough concentrations to act as toxic agents. Reference is made to a study by Grant et al. (1979), which found that exposing acid forest soil to 1 ppm of NO2 did not cause the soil pH to drop. The results presented here show that at low concentrations of NO and NO2, the NO is bacteriostatic for some organisms and not for others, whereas NO2 may protect some bacteria from the inhibitory effects of NO. Since it has been shown that bacteria can divide while airborne (Dimmick et al., 1979), the present results suggest that NO at the low concentrations found in the atmosphere can select for resistant bacteria in the air and affect the viable airborne bacterial population.

Mancinelli, R. L.↗

NASA NTRS1984

Sulfur dioxide on Io - Spatial distribution and physical state

Observations of the 4-micron SO2 band on Jupiter's satellite Io and laboratory measurements of SO2 frost are presented. The observations confirm the existence of a large longitudinal variation in band strength, but show no evidence of temporal changes. Comparison of the band position and shape in Io's spectrum with those in the laboratory frost's suggests that the bulk of the absorption on Io is due to frost, not adsorbed gas. The derived SO2 coverage is large enough to require that SO2 be present in most terrain types on Io and not just in the white plains unit. To reconcile the infrared observations that indicate large amoutns of SO2 with the ultraviolet observations of Voyager and IUE that show little, the SO2 must be mixed intimately with the sulfur (or other material) so that at each wavelength the darker component dominates the spectrum.

Fanale, F. P.↗

NASA NTRS1984

Sulfur dioxide and particles in quiescent volcanic plumes from Poas, Arenal, and Colima volcanos, Costa Rica and Mexico

Measurements of SO2 emission rates and concentrations and of particle distribution, size, shape, and composition were made in quiescent volcanic plumes emitted into the troposphere from Poas and Arenal volcanos, Costa Rica, and Colima volcano, Mexico. SO2 emission rates were 700 + or - 180 metric tons per day (t/d) for Poas, 210 + or - 30 t/d for Arenal, and 320 + or - 50 t/d for Colima. The concentrations of SO2 calculated from the COSPEC/lidar data were 5-380 ppb. Concentrations of SO2 measured directly by flame photometry were 10-250 ppb. Particles collected in the plumes with a quartz crystal microbalance impactor were mostly less than 3 microns in diameter and consisted of droplets of dilute sulfur-bearing solutions and minor amounts of layer silicate particles coated with a sulfur-bearing film or crust. Total particle concentrations were 4.7 micrograms per cu.m for Poas and 18.8 micrograms per cu.m for Colima. Comparison of concentrations of SO2 in the plumes with gas samples collected at fumaroles on the ground suggests that the plumes are diluted by the atmosphere by factors of up to 100,000.

Casadevall, T. J.↗

NASA NTRS1984

Absolute intensities of spectral lines in carbon dioxide bands near 2050/cm

The absolute intensities of individual lines of eleven relatively weak bands of (C-12)(O-16)2, (C-13)(O-16)2, (O-16)(C-12)(O-18), and (O-16)(C-12)(O-17) near 2050/cm were measured and recorded at room temperature and 0.01/cm resolution with the Fourier transform spectrometer located in the McMath solar telescope complex located at the National Solar Observatory on Kitt Peak. Each spectrum was obtained with an integration time of one hour, the temperature and pressure were monitored during this time, and the signal-to-rms noise in the 5 micron region was approximately 4000 for all scans. The intensities were determined from analysis of 1-2/cm segments of spectra using nonlinear least-squares spectral curve fitting, and analyzed to determine the vibrational band intensity and F-factor coefficients for each of the bands. The results are pertinent to a wide variety of problems in atmospheric physics and for the analysis of remote-sensing data.

Rinsland, C. P.↗

NASA NTRS1985

Detection of volcanic eruptions from space by their sulfur dioxide clouds

The capabilities of the total ozone mapping spectrometer (TOMS) on the Nimbus 7 satellite for tracking volcano plumes are assessed. TOMS was installed on the sun-synchronous polar orbiting satellite to measure spatial variations in the global total ozone field. Radiance absorption coefficients of the atmosphere for four near-UV wavelengths from 312.5-380.0 are measured. Data from the El Chichon eruption in March-April 1982 revealed that SO2 was an absorbing species at 312.5 and 317.5 nm. The near-UV absorption level differences between SO2 and O3 permit discriminating the atmospheric densities of each species. An examination of the data base generated by TOMS since 1978 showed the perceptible tracks of all known major eruptions in the 1978-1982 time period. A constellation of three of the polar orbiting TOMS would be sufficient to provide near-real time alerts of plumes to warn aircraft of the hazards.

Krueger, A. J.↗

NASA NTRS1984

Mechanism of the atmospheric oxidation of sulfur dioxide - Catalysis by hydroxyl radicals

A flash photolysis/resonance fluorescence technique was used to investigate the decay of OH due to the reaction OH + SO2 (+M) to HOSO2 (+M). In the presence of small amounts of NO (10 to the 14th per cu cm), the decays deviated from the normal semilogarithmic linearity due to reformation of OH. On the basis of computer simulations of the decay curves, it is suggested that the reactions HOSO2 + O2 to HO2 + SO3 (k3), and HO2 + HO to OH + NO2 are the likely subsequent steps in SO2 oxidation. The upper limit for the binding energy of HOSO2 relative to OH + SO2 is estimated to be 32 kcal/mol. The atmospheric implications of a catalytic oxidation mechanism are briefly discussed.

Margitan, J. J.↗

NASA NTRS1984

Comments on the BLAG model - The carbonate-silicate geochemical cycle and its effect on atmospheric carbon dioxide over the past 100 million years

A self-consistent method of determining initial conditions for the model presented by Berner, Lasaga, and Garrels (1983) (henceforth, the BLAG model) is derived, based on the assumption that the CO2 geochemical cycle was in steady state at t = -100 m.y. (million years). This initialization procedure leads to a dissolved magnesium concentration higher than that calculated by Berner, Lasaga, and Garrels and to a low ratio of dissolved calcium to bicarbonate prior to 60 m.y. ago. The latter prediction conflicts with the geologic record of evaporite deposits, which requires that this ratio remain greater than 0.5. The contradiction is probably caused by oversimplifications in the BLAG model, such as the neglect of the cycles of organic carbon and sulfur.

Kasting, J. F.↗

NASA NTRS1985

Comparison of band model calculations of upper atmospheric cooling rates for the 15-micrometer carbon dioxide band

Within the atmosphere of the earth, absorption and emission of thermal radiation by the 15-micron CO2 bands are the largest contributors to infrared cooling rates in the stratosphere. Various techniques for calculating cooling rates due to these bands have been described. These techniques can be classified into one of two categories, including 'exact' or line-by-line calculations and other methods. The latter methods are based on broad band emissivity and band absorptance formulations. The present paper has the objective to present comparisons of the considered computational approaches. It was found that the best agreement with the exact line-by-line calculations of Fels and Schwarzkopf (1981) could be obtained by making use of a new Doppler band model which is described in the appendix of the paper.

Boughner, R. E.↗

NASA NTRS1985

The non-mass-dependent oxygen isotope effect in the electrodissociation of carbon dioxide - A step toward understanding NoMaD chemistry

A non-mass dependent (NoMaD) oxygen isotope effect is demonstrated in the dissociation of CO2 similar to that observed in the electrosynthesis of ozone. The molecular oxygen produced carries the signature of two separate isotopic fractionation processes; a mass-dependent fractionation probably due to CO2 + O isotopic exchange, and a secondary NoMaD fractionation (delta O-17 = 0.97 + or - 0.09 delta O-18, with the O2 depleted in O-17 and O-18). It is suggested that the effect is due to either the formation or relaxation of ozone in an excited electronic state. This represents the latest advance in the understanding of chemical NoMaD effects which may be essential to the explanation of non-mass-dependent fractionations observed in meteorites.

Heidenreich, J. E., III↗

NASA NTRS1985

Development of a carbon formation reactor for carbon dioxide reduction

Applied research, engineering development, and performance evaluation were conducted on a process for formation of dense carbon by pyrolysis of methane. Experimental research showed that dense (0.7 to 1.6 g/cc bulk density and 1.6 to 2.2 g/cc solid density) carbon can be produced by methane pyrolysis in quartzwool-packed quartz tubes at temperatrues of 1100 to 1300 C. This result supports the condensation theory of pyrolytic carbon formation from gaseous hydrocarbons. A full-scale Breadboard Carbon Formation Reactor (CFR) was designed, fabricated, and tested at 1100 to 1200 C with 380 to 2280 sccm input flows of methane. Single-pass conversion of methane to carbon ranged from 60 to 100 percent, with 89 percent average conversion. Performance was projected for an Advanced Carbon Reactor Subsystem (ACRS) which indicated that the ACRS is a viable option for management of metabolic carbon on long-duration space missions.

Noyes, G.↗

NASA NTRS1986

Carbon dioxide evolution rate as a method to monitor and control an aerobic biological waste treatment system

An experimental system was developed to study the microbial growth kinetic of an undefined mixed culture in an erobic biological waste treatment process. The experimental results were used to develop a mathematical model that can predict the performance of a bioreactor. The bioreactor will be used to regeneratively treat waste material which is expected to be generated during a long term manned space mission. Since the presence of insoluble particles in the chemically undefined complex media made estimating biomass very difficult in the real system, a clean system was devised to study the microbial growth from the soluble substrate.

Lee, S. S.↗

NASA NTRS1985

System study of the utilization of space for carbon dioxide research

The objectives included: compiling and selecting the Scientific Data Requirements (SDRs) pertinent to the CO2 Research Program that have the potential to be more successfully achieved by utilizing space-based sensor systems; assessment of potential space technology in monitoring those parameters which may be important first indicators of climate change due to increasing atmospheric CO2, including the behavior of the West Antarctic ice sheet; and determine the potential of space technology for monitoring those parameters to improve understanding of the coupling between CO2 and cloud cover.

Glaser, P. E.↗