Engineering topics

Pinto, J. P.

Publications and source records attributed to Pinto, J. P..

15 records

NASA NTRS1991

Kinetic conversion of CO to CH4 in the Solar System

Some of the most interesting chemistry in the Solar System involves changes in the oxidation state of the simple carbon species. The chemical pathways for the conversion of CH4 to CO and CO2 are for the most part known. The reverse process, the reduction of CO to CH4, is, however, poorly understood. This is surprising in view of the importance of the reduction process in the chemistry of the Solar System. Recently we investigated the chemical kinetics of a hitherto unsuspected reaction. It is argued that the formation of the methoxy radical (CH3O) from H+H2CO may play an essential role in the reduction of CO to CH4. The rate coefficient for this reaction has been estimated using the approximate theory of J. Troe and transition state theory. We will discuss the implications of this reaction for the chemistry of CO on Jupiter, in the solar nebula, for interpreting the laboratory experiments of A. Bar-Nun and A. Shaviv and A. Bar-Nun and S. Chang, and for organic synthesis in the prebiotic terrestrial atmosphere. The possible relation of CO reduction in the solar nebula and polyoxymethylene observed in comet Halley will be discussed.

Yung, Y. L.↗

NASA NTRS1989

Sulfur, ultraviolet radiation, and the early evolution of life

The present biosphere is shielded from harmful solar near ultraviolet (UV) radiation by atmospheric ozone. It is suggested that elemental sulfur vapor could have played a similar role in an anoxic, ozone-free, primitive atmosphere. Sulfur vapor would have been produced photochemically from volcanogenic SO2 and H2S. It is composed of ring molecules, primarily S8, that absorb strongly throughout the near UV, yet are expected to be relatively stable against photolysis and chemical attack. It is also insoluble in water and would thus have been immune to rainout or surface deposition over the oceans. Since the concentration of S8 in the primitive atmosphere would have been limited by its saturation vapor pressure, surface temperatures of 45 C or higher, corresponding to carbon dioxide partial pressures exceeding 2 bars, are required to sustain an effective UV screen. A warm, sulfur-rich, primitive atmosphere is consistent with inferences drawn from molecular phylogeny, which suggest that some of the earliest organisms were thermophilic bacteria that metabolized elemental sulfur.

Kasting, J. F.↗

NASA NTRS1986

The D to H ratio on Titan and the planets: Implications for origin and evolution of planetary atmospheres

Measurements of deuterated methane show that Titan's atmosphere is enriched by at least several times in deuterium compared to the major planets. Potential causative factors for this enrichment are condensation to form tropospheric methane clouds, fractionation occuring over a hypothetical CH4-C2H2 ocean and between the ocean and the clathrate crust beneath, fractionation which occurred during the formation of Titan and fractionation occuring as a result of the evolution of Titan's atmosphere. The greater part of the observed fractionation is probably derived from the formation of Titan and the subsequent evolution of Titan atmosphere driven by photochemistry. The latter process is developed here for the first time. The D/H ratio in a planetary atmosphere is one readily available measure of the origin and evolution of the hydrogen bearing volatiles on the planet. Comparison between D/H ratio in the inner solar system and the outer solar system may pose important constraints on current theories.

Pinto, J. P.↗

NASA NTRS1986

Paleosols and the chemical evolution of the atmosphere

The chemistry and mineralogy of soils reflects the chemistry of the atmosphere below which they develop. Today the presence of a cover of land plants can obscure the signature of a highly oxidizing atmosphere. Prior to the advent of higher land plants ca. 400 m.y. ago the obscuring effect of a biological interface should have been minor. It can be shown that under such conditions the behavior of ferrous iron during weathering depends on the relationship between the ratio of the net concentration of oxidants to the concentration of acids in rainwater, and on the ratio of the oxygen demand to the acid demand for complete weathering of the parent rock. An analysis of the behavior of iron in some 15 paleosols between 1.0 and 2.9 b.y. in age showed some time ago that iron was retained, or largely retained, in paleosols developed on rocks with a low ratio of oxidant demand to acid demand (R value) and was lost from paleosols with a high R value. The results indicate that between 1.1 and 2.9 b.y.b.p. the ratio of the net concentration of oxidants to CO2 in rainwater was less than ca. 1/600 of the present-day value. Work during the past year has sought to extend the data base for paleosols and to define more precisely the relationships between the composition of paleosols and the chemistry of the atmosphere below which they developed.

Holland, H. D.↗

NASA NTRS1986

D to H ratio and the origin and evolution of Titan's atmosphere

Potential causative factors for the unusually large ratio of CH3D to CH4 reported in the stratosphere of Titan (6 x 10 to the -4th) compared to that of Saturn (8.7 x 10 to the -5th) or Jupiter (6.7 x 10 to the -5th) are examined. With uncertainty in the observations and data reduction taken into account, an atmospheric enrichment factor of three or more is calculated for Titan relative to the planets. This enrichment factor is seen to be accounted for by condensation to form tropospheric methane clouds, fractionation occurring over a hypothetical CH4-C2H6 ocean and between the ocean and the clathrate crust beneath, fractionation which occurred during the formation of Titan, and fractionation as a result of the evolution of Titan's atmosphere. It is concluded that the greater part of the observed fractionation is probably derived from the last two of these mechanisms. The mechanisms studied do not account for the observed CH3D/CH4 value of 1.7 x 10 to the -3rd obtained by Kim and Caldwell (1982).

Pinto, J. P.↗

NASA NTRS1985

Oxidant abundances in rainwater and the evolution of atmospheric oxygen

H2O2 is probably the dominant oxidant in rainwater at O2 levels lower than 0.01-0.001 present atmospheric levels (PAL), and the magnitude of its dissolved flux is sensitive to the concentration of the trace gases NO, CO, and CH4 in the atmosphere, as well as to the partial pressure of atmospheric CO2. The earlier interpretation of the paleosol data in terms of the ratio of p-O2/p-CO2 in the atmosphere must be modified by taking into account the effects of photochemically produced oxidants and reactants at p-O2 of les than 0.01 PAL.

Kasting, J. F.↗

NASA NTRS1984

Photochemistry of the atmosphere of Titan - Comparison between model and observations

Updated chemical schemes and estimates of key rate coefficients are used in the present investigation of the photochemistry of Titan atmosphere C- H- and O-atom containing simple molecules, according to a model incorporating exospheric boundary conditions, vertical transport, and condensation processes at the tropopause. It is suggested that the composition, climatology, and evolution of the Titan atmosphere are controlled by five major processes: CH4 photolysis and photosensitized dissociation, H-to-H2 conversion and hydrogen escape, higher hydrocarbon synthesis, nitrogen and hydrocarbon coupling, and oxygen and hydrocarbon coupling. The model accounts for the minor species concentrations observed by Voyager instruments. Implications of abiotic organic synthesis on Titan for the origin of life on earth are briefly discussed.

Yung, Y. L.↗

NASA NTRS1983

A general circulation model study of atmospheric carbon monoxide

The carbon monoxide cycle is studied by incorporating the known and hypothetical sources and sinks in a tracer model that uses the winds generated by a general circulation model. Photochemical production and loss terms, which depend on OH radical concentrations, are calculated in an interactive fashion. The computed global distribution and seasonal variations of CO are compared with observations to obtain constraints on the distribution and magnitude of the sources and sinks of CO, and on the tropospheric abundance of OH. The simplest model that accounts for available observations requires a low latitude plant source of about 1.3 x 10 to the 15th g/yr, in addition to sources from incomplete combustion of fossil fuels and oxidation of methane. The globally averaged OH concentration calculated in the model is 750,000/cu cm. Models that calculate globally averaged OH concentrations much lower than this nominal value are not consistent with the observed variability of CO. Such models are also inconsistent with measurements of CO isotopic abundances, which imply the existence of plant sources.

Pinto, J. P.↗

NASA NTRS1980

Titan - Aerosol photochemistry and variations related to the sunspot cycle

A photochemical theory is proposed for producing complex polymers in a methane atmosphere. It is argued that the polyacetylenes (C2nH2) are the most likely precursor molecules for the formation of the stratospheric haze layer on Titan. The production of polyacetylenes involves a strong positive feedback, leading to more production of polyacetylenes. The thermosphere of Titan may undergo substantial expansion and contraction over a solar cycle, with important consequences for the chemistry of the upper atmosphere.

Allen, M.↗

NASA NTRS1980

Photochemical production of formaldehyde in earth's primitive atmosphere

Formaldehyde could have been produced by photochemical reactions in the earth's primitive atmosphere, at a time when it consisted mainly of molecular nitrogen, water vapor, carbon dioxide, and trace amounts of molecular hydrogen and carbon monoxide. Removal of formaldehyde from the atmosphere by precipitation can provide a source of organic carbon to the oceans at the rate of 100 billion moles per year. Subsequent reactions of formaldehyde in primeval aquatic environments would have implications for the abiotic synthesis of complex organic molecules and the origin of life.

Pinto, J. P.↗

NASA NTRS1980

Climatic effects due to halogenated compounds in the earth's atmosphere

Using a one-dimensional radiative-convective model, a sensitivity study is performed of the effect of ozone depletion in the stratosphere on the surface temperature. There could be a cooling of the surface temperature by approximately 0.2 K due to chlorofluoromethane-induced ozone depletion at steady state (assuming 1973 release rates). This cooling reduces significantly the greenhouse effect due to the presence of chlorofluoromethanes. Carbon tetrafluoride has a strong nu sub 3 band at 7.8 microns, and the atmospheric greenhouse effect is shown to be 0.07 and 0.12 K/ppbv with and without taking into account overlap with CH4 and N2O bands. At concentrations higher than 1 ppbv, absorption by the nu sub 3 band starts to saturate and the greenhouse effect becomes less efficient.

Wang, W.-C.↗

NASA NTRS1980

Atmospheric bromine and ozone perturbations in the lower stratosphere

The role of bromine compounds in the photochemistry of the natural and perturbed stratosphere has been reexamined using an expanded reaction scheme and the results of recent laboratory studies of several key reactions. The most important finding is that through the reaction BrO + ClO yielding Br + Cl + O2 there is a synergistic effect between bromine and chlorine which results in an efficient catalytic destruction of ozone in the lower stratosphere. One-dimensional photochemical model results indicate that BrO is the major bromine species throughout the stratosphere, followed by BrONO2, HBr, HOBr and Br. It is shown from the foregoing that bromine is more efficient than chlorine as a catalyst for destroying ozone, and the implications for stratospheric ozone of possible future growth in the industrial and agricultural use of bromine are discussed. Bromine concentrations of 20 pptv (2 x 10 to the -11th power), as suggested by recent observations, can decrease the present-day integrated ozone column density by 2.4%, and can enhance ozone depletion from steady-state chlorofluoromethane release at 1973 rates by a factor of 1.1-1.2.

Yung, Y. L.↗

NASA NTRS1979

Sensitivity of the predicted CO-OH-CH4 perturbation to tropospheric NOx concentrations

Measurements indicate that ambient NOx(NO + NO2) concentrations vary over at least an order of magnitude in the troposphere. Thus it is of interest to study atmospheric chemistry with NOx concentrations covering this range. In this paper we present steady state calculations which show that as NOx concentrations are increased from very low values, the hydroxyl radical concentration increases at first and then decreases. This change of behavior occurs at a concentration of NO2 of about 0.23 ppb in the model. Also, the response of the atmosphere to increased CO fluxes undergoes a qualitative change as a function of the concentration of NOx. At low levels of NOx concentration, an increase in CO fluxes into the atmosphere depletes the OH concentration and increases the concentrations of CH4 and H2, as reported in the literature. However, at high values of NOx concentration, increased CO fluxes give rise to an increase in the OH concentration and, consequently, a decrease in the concentrations of CH4 and H2.

Hameed, S.↗

NASA NTRS1978

Primitive atmosphere and implications for the formation of channels on Mars

It is suggested that, if primitive Mars had a reducing atmosphere composed mainly of methane, this atmosphere could be polymerized by solar ultraviolet radiation to produce higher hydrocarbons. These compounds, which would be low-viscosity liquids at present temperatures on Mars, could have contributed to the formation of channels. The Martian atmosphere model used in the analysis is similar to Sagan's (1977), except that ammonia is omitted. Major reactions in this early Martian atmosphere are examined, and the number densities of the lighter alkanes in the lower atmosphere of Mars are determined. Since the photochemical mechanism investigated here would provide only a modest amount of fluid for a comparatively brief period of time (10-100 million years), liquid alkanes would not be the major factor in the formation of the channels, although their derivatives could contribute to the greenhouse effect or depress the freezing point of water.

Yung, Y. L.↗

NASA NTRS1977

Photochemistry of tropospheric ozone

A photochemical equilibrium model of minor constituent chemistry in the troposphere was constructed to investigate the photochemistry of tropospheric ozone. We find that photochemical production must be supplemented by additional sources to account for observed ozone levels in clean air, while photochemical loss is more important than surface destruction as an ozone loss mechanism. Photochemically produced ozone is sensitive to the NO(x) background in the model, exhibiting a maximum of about 0.5 ppb of NO(x).

Stewart, R. W.↗