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At least 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
NASA NTRS2011

Testing and Results of Vacuum Swing Adsorption Units for Spacesuit Carbon Dioxide and Humidity Control

A principal concern for extravehicular activity (EVA) spacesuits is the capability to control carbon dioxide (CO2) and humidity (H2O) for the crewmember. The release of CO2 in a confined or unventilated area is dangerous for human health and leads to asphyxiation; therefore, CO2 and H2O control become leading factors in the design and development of the spacesuit. An amine-based CO2 and H2O vapor sorbent for use in pressure-swing regenerable beds has been developed by Hamilton Sundstrand. The application of solidamine materials with vacuum swing adsorption technology has shown the capacity to concurrently manage CO2 and H2O levels through a fully regenerative cycle eliminating mission constraints imposed with nonregenerative technologies. Two prototype solid amine-based systems, known as rapid cycle amine (RCA), were designed to continuously remove CO2 and H2O vapor from a flowing ventilation stream through the use of a two-bed amine based, vacuum-swing adsorption system. The Engineering and Science Contract Group (ESCG) RCA implements radial flow paths, whereas the Hamilton Sundstrand RCA was designed with linear flow paths. Testing was performed in a sea-level pressure environment and a reduced-pressure environment with simulated human metabolic loads in a closed-loop configuration. This paper presents the experimental results of laboratory testing for a full-size and a sub-scale test article. The testing described here characterized and evaluated the performance of each RCA unit at the required Portable Life Support Subsystem (PLSS) operating conditions. The test points simulated a range of crewmember metabolic rates. The experimental results demonstrated the ability of each RCA unit to sufficiently remove CO2 and H2O from a closed loop ambient or sub-ambient atmosphere.

McMillin, Summer D.↗
NASA NTRS2011

Visible and Near-IR Reflectance Spectra of Smectite Acquired Under Dry Conditions for Interpretation of Martian Surface Mineralogy

Visible and near-IR (VNIR) spectra from the MEx OMEGA and the MRO CRISM hyper-spectral imaging instruments have spectral features associated with the H2O molecule and M OH functional groups (M = Mg, Fe, Al, and Si). Mineralogical assignments of martian spectral features are made on the basis of laboratory VNIR spectra, which were often acquired under ambient (humid) conditions. Smectites like nontronite, saponite, and montmorillionite have interlayer H2O that is exchangeable with their environment, and we have acquired smectite reflectance spectra under dry environmental conditions for interpretation of martian surface mineralogy. We also obtained chemical, Moessbauer (MB), powder X-ray diffraction (XRD), and thermogravimetric (TG) data to understand variations in spectral properties. VNIR spectra were recorded in humid lab air at 25-35C, in a dynamic dry N2 atmosphere (50-150 ppmv H2O) after exposing the smectite samples (5 nontronites, 3 montmorillionites, and 1 saponite) to that atmosphere for up to approximately l000 hr each at 25-35C, approximately 105C, and approximately 215C, and after re-exposure to humid lab air. Heating at 105C and 215C for approximately 1000 hr is taken as a surrogate for geologic time scales at lower temperatures. Upon exposure to dry N2, the position and intensity of spectral features associated with M-OH were relatively insensitive to the dry environment, and the spectral features associated with H2O (e.g., approximately 1.90 micrometers) decreased in intensity and are sometimes not detectable by the end of the 215C heating step. The position and intensity of H2O spectral features recovered upon re-exposure to lab air. XRD data show interlayer collapse for the nontronites and Namontmorillionites, with the interlayer remaining collapsed for the latter after re-exposure to lab air. The interlayer did not collapse for the saponite and Ca-montmorillionite. TG data show that the concentration of H2O derived from structural OH was invariant to the dry N2 treatment for saponite and the montmorillionites, but the nontronites had additional structural OH after treatment. Upon exposure to dry N2, the VNIR spectra also acquired a red slope with decreasing albedo between approximately 0.4 and approximately 2.0 micrometers. The magnitude of the effects covaries with exposure time to dry N2 and heating temperature. Upon re-exposure to lab air, the slope and albedo do not completely recover to pre-exposure values. MB data show that these effects do not result from partial reduction of ferric to ferrous iron, and TG data show they do not result from loss of structural OH. Possible explanations include formation of small clusters of (superparamagnetic) ferric oxide and reduced smectite crystallinity. The difference in spectral properties between spectra acquired in humid lab air and under dry conditions are consequential for interpretation of CRISM and OMEGA spectra. For example, nontronite by itself and not nontronite plus ferrihydrite can account for the red spectral slope in martian spectra where nontronite is indicated by the Fe-OH spectral features.

Morris, Richard V.↗
NASA NTRS2013

Water Content of the Oceanic Lithosphere at Hawaii from FTIR Analysis of Peridotite Xenoliths

Although water in the mantle is mostly present as trace H dissolved in minerals, it has a large influence on its melting and rheological properties. The water content of the mantle lithosphere beneath continents is better constrained by abundant mantle xenolith data than beneath oceans where it is mainly inferred from MORB glass analysis. Using Fourier transform infrared (FTIR) spectrometry, we determined the water content of olivine (Ol), clinopyroxene (Cpx) and orthopyroxene (Opx) in spinel peridotite xenoliths from Salt Lake Crater, Oahu, Hawaii, which are thought to represent fragments of the Pacific oceanic lithosphere that was refertilized by alkalic Hawaiian melts. Only Ol exhibits H diffusion profiles, evidence of limited H loss during xenolith transport to the surface. Water concentrations (Ol: 9-28 ppm H2O, Cpx: 246-566 ppm H2O, Opx: 116-224 ppm H2O) are within the range of those from continental settings but higher than those from Gakkel ridge abyssal peridotites. The Opx H2O contents are similar to those of abyssal peridotites from Atlantic ridge Leg 153 (170-230 ppm) but higher than those from Leg 209 (10- 14 ppm). The calculated bulk peridotite water contents (94 to 144 ppm H2O) are in agreement with MORB mantle source water estimates and lower than estimates for the source of Hawaiian rejuvenated volcanism (approx 540 ppm H2O) . The water content of Cpx and most Opx correlates negatively with spinel Cr#, and positively with pyroxene Al and HREE contents. This is qualitatively consistent with the partitioning of H into the melt during partial melting, but the water contents are too high for the degree of melting these peridotites experienced. Melts in equilibrium with xenolith minerals have H2O/Ce ratios similar to those of OIB

Peslier, Anne H.↗
NASA NTRS2013

Pre- and Post-perihelion Observations of C/2009 P1 (Garradd): Evidence for an Oxygen-rich Heritage?

We conducted pre- and post-perihelion observations of Comet C/2009 P1 (Garradd) on UT 2011 October 13 and 2012 January 8, at heliocentric distances of 1.83 and 1.57 AU, respectively, using the high-resolution infrared spectrometer (NIRSPEC) at the Keck II 10-m telescope on Mauna Kea, HI. Pre-perihelion, we obtained production rates for nine primary volatiles (native ices): H2O, CO, CH3OH, CH4, C2H6, HCN, C2H2, H2CO, and NH3. Post-perihelion, we obtained production rates for three of these (H2O, CH4, and HCN) and sensitive upper limits for three others (C2H2, H2CO, and NH3). CO was enriched and C2H2 was depleted, yet C2H6 and CH3OH were close to their currentmean values asmeasured in a dominant group of Oort cloud comets. This may indicate processing of its pre-cometary ices in a relatively oxygen-rich environment. Our measurements indicate consistent pre- and post-perihelion abundance ratios relative to H2O, suggesting we were measuring compositional homogeneity among measured species to the depths in the nucleus sampled. However, the overall gas production was lower post-perihelion despite its smaller heliocentric distance on January 8. This is qualitatively consistent with other studies of C/2009 P1, perhaps due to seasonal differences in the heating of one or more active regions on the nucleus. On October 13, the water profile showed a pronounced excess towards the Sun-facing hemisphere that was not seen in other molecules, including H2O on January 8, nor in the dust continuum. Inter-comparison of profiles from October 13 permitted us to quantify contributions due to release of H2O from the nucleus, and fromits release in the coma. This resulted in the latter source contributing 25-30% of the total observed water within our slit, which covered roughly +/-300 km by +/-4500 km from the nucleus. We attribute this excess H2O, which peaked at a mean projected distance of 1300-1500 km from the nucleus, to release from water-rich, relatively pure icy grains

Volatile composition↗
NASA NTRS2019

Stellar Activity Effects on Moist Habitable Terrestrial Atmospheres Around M Dwarfs

Transit spectroscopy of terrestrial planets around nearby M dwarfs will be a primary goal of space missions in coming decades. Three-dimensional climate modeling has shown that slow-synchronous rotating terrestrial planets may develop thick clouds at the substellar point, increasing the albedo. For M dwarfs with T(eff)>3000 K, such planets at the inner habitable zone (IHZ) have been shown to retain moist greenhouse conditions, with enhanced stratospheric water vapor ( fH2O>10(exp −3)) and low Earth-like surface temperatures. However, M dwarfs also possess strong UV activity, which may effectively photolyze stratospheric H2O. Prior modeling efforts have not included the impact of high stellar UV activity on the H2O. Here, we employ a 1D photochemical model with varied stellar UV, to assess whether H2O destruction driven by high stellar UV would affect its detectability in transmission spectroscopy. Temperature and water vapor profiles are taken from published 3D climate model simulations for an IHZ Earth-sized planet around a 3300 K M dwarf with an N2–H2O atmosphere; they serve as self-consistent input profiles for the 1D model. We explore additional chemical complexity within the 1D model by introducing other species into the atmosphere. We find that as long as the atmosphere is well-mixed up to 1 mbar, UV activity appears to not impact detectability of H2O in the transmission spectrum. The strongest H2O features occur in the James Webb Space Telescope MIRI instrument wavelength range and are comparable to the estimated systematic noise floor of ∼50 ppm.

Badhan, Mahmuda Afrin↗
NASA NTRS2019

Stellar Activity Effects on Moist Habitable Terrestrial Atmospheres Around M Dwarfs

Transit spectroscopy of terrestrial planets around nearby M dwarfs is a primary goal of space missions in coming decades. 3-D climate modeling has shown that slow-synchronous rotating terrestrial planets may develop thick clouds at the substellar point, increasing the albedo. For M dwarfs with T(eff) > 3000 K, such planets at the inner habitable zone (IHZ) have been shown to retain moist greenhouse conditions, with enhanced stratospheric water vapor (fH2O > 10(exp -3)) and low Earth-like surface temperatures. However, M dwarfs also possess strong UV activity, which may effectively photolyze stratospheric H2O. Prior modeling efforts have not included the impact of high stellar UV activity on the H2O. Here, we employ a 1-D photochemical model with varied stellar UV, to assess whether H2O destruction driven by high stellar UV would affect its detectability in transmission spectroscopy. Temperature and water vapor profiles are taken from published 3-D climate model simulations for an IHZ Earth-sized planet around a 3300 K M dwarf with an N2-H2O atmosphere; they serve as self-consistent input profiles for the 1-D model. We explore additional chemical complexity within the 1-D model by introducing other species into the atmosphere. We find that as long as the atmosphere is well-mixed up to 1 mbar, UV activity appears to not impact detectability of H2O in the transmission spectrum. The strongest H2O features occur in the JWST MIRI instrument wavelength range and are comparable to the estimated systematic noise floor of ~50 ppm.

Mahmuda Afrin Badhan↗
NASA NTRS2021

Testing Short-term Variability and Sampling of Primary Volatiles in Comet 46P/Wirtanen

The exceptionally favorable close approach of Jupiter-family comet 46P/Wirtanen in 2018 December enabled characterization of its primary volatile composition with exceptionally high spatial resolution and sensitivities using the iSHELL spectrograph at the NASA Infrared Telescope Facility on Maunakea, HI. We sampled emissions from H2O, HCN, C2H2, NH3,C2H6, and CH3OH on UT 2018 December 21 using two instrumental settings that spanned the 2.9–3.6μm spectral region. We also obtained a sensitive 3σupper limit for H2CO and for the rarely studied molecule HC3N. We report rotational temperatures, production rates, and mixing ratios(relative to H2O as well as to C2H6). We place our results in context by comparing them with other comets observed at near-IR wavelengths. We also compare our results with those obtained using the NIRSPEC-2 spectrograph on Keck II on UT December 17 and 18 and with results obtained from iSHELL on other dates during the same apparition. Within1–2σ uncertainty, production rates obtained for all molecules in this work were consistent with those obtained using NIRSPEC-2 except H2O, indicating low-level variability on a timescale of days. Mixing ratios with respect to H2O in 46P/Wirtanen were consistent with corresponding values from NIRSPEC-2 within the uncertainty with the exception of CH3OH, which yielded a higher ratio on December 21. Our measurements afforded a high temporal resolution that spanned∼2/3 of the rotational period of 46P/Wirtanen, enabling us to test short-term variability in the production rates of H2O and HCN due to rotational effects. Both H2O and HCN production rates showed similar temporal variability, resulting in nearly constant HCN/H2O

Younas Khan↗
NASA NTRS2020

Attribution of Chemistry-Climate Model Initiative (CCMI) Ozone Radiative Flux Bias from Satellites

The top-of-atmosphere (TOA) outgoing longwave flux over the 9.6-μm ozone band is a fundamental quantity for understanding chemistry-climate coupling. However, observed TOA fluxes are hard to estimate as they exhibit considerable variability in space and time that depend on the distributions of clouds, ozone (O3), water vapor (H2O), air temperature (Ta), and surface temperature (Ts). Benchmarking present day fluxes and quantifying the relative influence of their drivers is the first step for estimating climate feedbacks from ozone radiative forcing and predicting radiative forcing evolution. To that end, we constructed observational instantaneous radiative kernels (IRKs) under clear-sky conditions, representing the sensitivities of the TOA flux in the 9.6-μm ozone band to the vertical distribution of geophysical variables, including O3, H2O, Ta, and Ts based upon the Aura Tropospheric Emission Spectrometer (TES) measurements. Applying these kernels to present-day simulations from the Chemistry-Climate Model Initiative (CCMI) project as compared to a 2006 reanalysis assimilating satellite observations, we show that the models have large differences in TOA flux, attributable to different geophysical variables. In particular, model simulations continue to diverge from observations in the tropics, as reported in previous studies of the Atmospheric Chemistry Climate Model Inter-comparison Project (ACCMIP) simulations. The principal culprits are tropical mid and upper tropospheric ozone followed by tropical lower tropospheric H2O. Five models out of the eight studied here have TOA flux biases exceeding 100 mWm-2 attributable to tropospheric ozone bias. Another set of five models have flux biases over 50 mWm-2 due to H2O. On the other hand, Ta radiative bias is negligible in all models (no more than 30 mWm-2). We found that AM3 and CMAM have the lowest TOA flux biases globally but are a result of cancellation of opposite biases due to difference processes. Overall, the multi-model ensemble mean bias is –133±98 mWm-2, indicating that they are too atmospherically opaque due to trapping too much radiation in the atmosphere by overestimated tropical tropospheric O3 and H2O. Having too much O3 and H2O in the troposphere would have different impacts on the sensitivity of TOA flux to O3 and these competing effects add more uncertainties on the ozone radiative forcing. We find that the inter-model TOA outgoing longwave radiation (OLR) difference is well anti-correlated with their ozone band flux bias. This suggests that there is significant radiative compensation in the calculation of model outgoing longwave radiation.

Aura Tropospheric Emission Spectrometer (TES) meas↗
NASA NTRS2025

JWST Reveals Spectral Tracers of Recent Surface Modification on Europa

Europa has been modified by a variety of geologic processes, exposing internally-derived materials that are heavily irradiated by charged particles trapped in Jupiter’s magnetosphere. Prior spectral analysis of H2O ice on Europa relied on low signal-to-noise data at wavelengths >2.5 µm, limiting assessment of a 3.1 µm Fresnel peak that is diagnostic of exposed crystalline ice. We report new measurements of H2O ice spectral features using high signal-to-noise data collected by the NIRSpec spectrograph (1.48 – 5.35 µm) on the James Webb Space Telescope. These data reveal a narrow 3.1 µm crystalline H2O ice Fresnel peak, which is primarily located at southern latitudes in Tara and Powys Regiones. Our analysis indicates that crystalline ice exposed in these low-latitude regiones is likely sustained by ongoing thermal (re)crystallization outpacing charged particle amorphization of the top ∼10 µm of Europa’s regolith over short timescales (<15 days). We also measured H2O ice features centered near 1.5 µm, 1.65 µm, and 2.0 µm, and a broad 3.6 µm H2O continuum peak, which are all stronger at northern latitudes, in contrast to the 3.1 µm Fresnel peak identified at southern latitudes. These results support the hypothesis that H2O ice in Europa’s regolith is vertically stratified, with amorphous ice grains dominating its exposed surface, except in Tara and Powys Regiones. We also find that a previously detected 4.38 µm 13CO2 feature is present almost exclusively at southern latitudes in Tara and Powys Regiones, likely derived from an internal source of carbon-bearing material.

Surface processes (2116)↗
NASA NTRS2014

A Revised Calibration Function and Results for the Phoenix Mission TECP Relative Humidity Sensor

The original calibration function of the R(sub H) sensor on the Phoenix Thermal and Electrical Conductivity Sensor (TECP) has been revised in order to extend the range of the valid calibration, and to improve accuracy. The original function returned non-physical R(sub H) values at the lowest temperatures. To resolve this, and because the original calibration was performed against a pair of hygrometers that measured frost point (T(sub f)), the revised calibration equation is also cast in terms of frost point. Because of the complexity of maintaining very low temperatures and high R(sub H) in the laboratory, no calibration data exists at T is greater than 203K. However, sensor response during the mission was smooth and continuous down to 181 K. Therefore we have opted to include flight data in the calibration data set; selection was limited to data acquired during periods when the atmosphere is known to have been saturated. T(sub f) remained below 210 K throughout the mission(P is greater than 0.75 Pa). R(sub H), conversely, ranged from 1 to well under 0.01 diurnally, due to approximately 50 K temperature variations. To first order, both vapor pressure and its variance are greater during daylight hours. Variance in overnight humidity is almost entirely explained by temperature, while atmospheric turbulence contributes substantial variance to daytime humidity. Likewise, data gathered with the TECP aloft reflect higher H2O abundances than at the surface, as well as greater variance. There is evidence for saturation of the atmosphere overnight throughout much of the mission. In virtually every overnight observation, once the atmosphere cooled to T(sub f), water vapor begins to decrease, and tracks air temperature. There is no evidence for substantial decreases in water vapor prior to saturation, as expected for adsorptive exchange. Likewise, there is no evidence of local control of vapor by phases such as perchlorate hydrates hydrated minerals. The daytime average H2O pressure does not change substantially over the course of the mission, although the H2O column abundance varies by a factor of 2. Column abundances calculated from TECP data are lower than orbital measurements if one assumes that H2O is uniformly mixed through a single scale height. These results argue that the vertical distribution of H2O begins to change well in advance of surface concentrations as northern autumn approaches.

Phoenix Thermal and Electrical Conductivity Sensor↗
NASA NTRS1973

Reactions of HO2 with carbon monoxide and nitric oxide and of O/1 D/ with water.

Investigation of the reactions of the hydroperoxyl radical with carbon monoxide and nitric oxide in a static system, and reexamination of the reaction of O(1 D) with water. The HO2 radicals were generated by the photolysis of N2O at 2139 A in the presence of excess H2O or H2 and smaller amounts of CO and O2. The O(1 D) atoms produced from the photolysis of N2O react with H2O or with H2 to give OH radicals in the case of H2O or OH radicals and H atoms in the case of H2. With H2O, two OH radicals are produced for each O(1 D) removed at low pressures, but the OH yield drops as the pressure is raised. This drop is attributed to an insertion reaction which removes from 10 to 30% of the O(1 D) atoms at about 650 torr of H2O at 200 F. The OH radicals generated can react with either CO or H2 to produce H atoms, which then add to O2 to produce HO2. In the absence of NO, the HO2 radicals could react by two routes, while with NO present NO2 is produced in a long chain process.

Simonaitis, R.↗
NASA NTRS1980

Water-deuterium oxide exchange in polymers used in spacecraft applications

The replacement of water (H2O) by deuterium oxide (D2O) and the exchange between atmospheric water and adsorbed or absorbed D2O were investigated for the polymeric materials Kapton and Mylar using thermal gravimetric analysis and infrared spectroscopy. Replacement of H2O by D2O is easily accomplished. However, exposure of D2O samples to the ambient atmosphere or gases containing H2O results in rapid proton and deuteron exchange between H2O vapor and adsorbed D2O. Replacement of H2O by D2O would not be a practical solution to alleviate spectral interferences that would result from water outgassing in spacecraft orbital environments. Maintaining the materials of interest in a dehydrated state is a more reasonable approach.

Carre, D. J.↗
NASA NTRS1982

Water absorption lines, 931-961 nm - Selected intensities, N2-collision-broadening coefficients, self-broadening coefficients, and pressure shifts in air

Intensities were measured for 97 lines of H2O vapor between 932 and 961 nm. The lines were selected for their potential usefulness for remote laser measurements of H2O vapor in the earth's atmosphere. The spectra were obtained with several different H2O vapor abundances and N2 broadening gas pressures; the spectral resolution was 0.046/cm FWHM. Measured H2O line intensities range from 7 x 10 to the -25th to 7 x 10 to the -22nd/cm per (molecules/sq cm). H2O self-broadening coefficients were measured for 13 of these strongest lines; the mean value was 0.5/cm per atm. N2-collision-broadening coefficients were measured for 73 lines, and the average was 0.11 cm per atm HWHM. Pressure shifts in air were determined for a sample of six lines between 948 and 950 nm; these lines shift to lower frequency by an amount comparable to 0.1 of the collision-broadened widths measured in air or N2. The measured intensities of many lines of 300-000 band are much larger than expected from prior computations, in some cases by over an order of magnitude. Coriolis interactions with the stronger 201-000 band appear to be the primary cause of the enhancement of these line intensities.

Giver, L. P.↗
NASA NTRS1982

Experimental studies of the ion-induced binary nucleation

The aerosol nucleation phenomenon is studied in a binary mixture of H2O and H2SO4 vapors in a carrier stream of N2 gas in the presence of ions produced by a low energy beta source. Cluster spectra of the form (H2SO4)n.(H2O)m.H(+) are identified from the measurements of the cluster masses using a quadrupole mass spectrometer. Results show that the number of H2SO4 molecules in the clusters ranged from 0 to 6 whereas the number of H2O molecules ranged from 1 to 20 depending on the concentration of H2SO4 and H2O vapors in the reaction chamber. Among other conclusions, it is noted that a large number of clusters of the type investigated are formed in the presence of an ionization source even when the partial pressures of H2SO4 and H2O are very low. The cluster composition is found to be strongly dependent on the r.h. and r.a. values in the reaction cell. The cluster spectrum (n, m, l) contains a large number of low n- and low m-value clusters when the reaction cell pressure is high.

Singh, J. J.↗
NASA NTRS1983

A laboratory study of the infrared spectra of interstellar ices

The 3 micron 'ice' band observed in absorption and polarization and other absorption features in interstellar infrared spectra are studied in the laboratory in low temperature (10-130 K) solid mixtures of H2O and other molecules. General empirical rules are derived which relate the shape and relative intensity of the H2O infrared absorptions to thermal history, degree of H2O dilution and hydrogen bonding capacity of the dilutant. Observations of specific features anticipated in low noise medium resolution spectra will yield potentially valuable information on the degree of H2O dilution, the nature of the dilutant and the thermal history of the absorbing solid mixture. Under well defined conditions the peak of the hitherto unobserved librational '12 micron' H2O absorption is shifted to outside the current infrared observation window beyond 13.5 microns.

Hagen, W.↗
NASA NTRS1983

Interstellar ice

The 3250/cm 'ice' band observed in absorption and polarization in interstellar spectra is studied in the laboratory in low-temperature solid mixtures of H2O and other molecules. General empirical rules are derived which relate the shape and relative intensity of the H2O infrared absorptions to the degree of H2O dilution and hydrogen-bonding capacity of the dilutant. The chemical composition of mantles accreting on interstellar grains inside dense (1000-100,000/cu cm) molecular clouds has been calculated numerically. The reaction scheme comprises gas-phase as well as grain surface reactions. The results show that in most circumstances grain mantles consist of the molecules H2O, H2CO, NH3, N2, O2, CO, and CO2. The expected infrared characteristics of the calculated grain mantles are discussed with an emphasis on the observed 3250/cm 'ice' band. Grain mantles accreted at a density of about 10,000/cu cm contain large concentrations of H2O (about 60 percent) and produce a broad 3250/cm 'ice' band.

Tielens, A. G. G. M.↗
NASA NTRS1985

Magmas as Selective Filters of Volatiles Between Planetary Mantles and Surfaces

The composition of early planetary atmospheres and biospheres which is a knowledge of the relationship between mantle volatiles and volcanic gases was analyzed. In the case of Earth it appears that volcanic rocks and gases are relatively oxidized compared to the upper mantle. In the case of the C-O-H volatiles, (H2O, CO2, CO, CH4, H2) the volcanic gases are enriched in H2O and CO2 while the volatiles in the mantle may be dominated by H2O, H2 and possibly CH4. An experimental technique was perfected for phase equilibrium studies in the 5-30 kbar range which allows accurate control of volatile species activities in the fluid phase. The system was used to measure the relative solubilities of H2O, CO2, CO, CH4 and H2 in magmas at 10 kbar pressure. It is found that mantle magmas will selectively screen volatiles from planetary surfaces, forcing volcanic gases towards the neutral QFM oxidation state where H2O is the dominant species.

Holloway, J. R.↗
NASA NTRS1985

The photochemistry of the early atmosphere

The composition of the earth's present atmosphere is described. The formation of the earth from the coalescence and accretion of the refractory elements of the solar nebula is examined. Two possible compositions of the prebiological paleoatmosphere, which are a reducing atmosphere of CH4, NH3, and H2 or a mildly reducing atmosphere of H2O, CO2, and N2, and their photochemistry are analyzed. General photochemical and chemical processes are reviewed. The use of the coupled continuity-transport equation to calculate the vertical distribution of each species is discussed. A study of the photochemical process of CH4 and NH3 reveals that the reducing atmosphere could not possibly exist. An analysis of the photochemistry and chemistry of the H2O, CO2, and N2 atmosphere reveals that the photodissociation of H2O and CO2 results in a prebiotic source of O2, H2CO, and HCN, which are the components for the evolution of photosynthetic organisms and a strongly oxidizing atmosphere. The reactions which produce O2 and H2CO from H2O and CO2, and the relation between H2O and CO2 concentrations and O2 levels are investigated. The formation of O3 photochemically from O2 is explained.

Levine, J. S.↗