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NASA NTRS2018

Stable Isotope Fractionation in Titan Aerosol Formation

Stable isotope ratio measurements are a powerful tool used to understand both ancient and modern planetary processes. Instruments on the Cassini- Huygens spacecraft along with ground-based observations have measured several isotope pairs, including C-13/C-12 and N-15/N-14, in Titan's atmosphere. This includes isotopic measurements of the major atmospheric species, CH4 and N2, along with HCN, HC3N, C2H2. C2H6 and C4H2. However, the isotopic fractionation of Titan's organic aerosol has not conclusively been measured and therefore the effect of aerosol formation as an isotopic fractionation pathway in Titan's atmosphere has not been considered. Laboratory studies have measured the carbon and/or nitrogen isotopic fractionation of Titan aerosol analogs. [18] found that the carbon fractionation of photochemical organic aerosol analogs are more enriched in C-13. This enrichment in the aerosol analogs is opposite of what is predicted for photochemical products by the kinetic isotope effect. Additionally, both [16] and [18] found that the nitrogen fractionation in the organic aerosol analogs are opposite of what is observed in Titan's atmospheric N2 and HCN, with the aerosol analogs being a light nitrogen sink. Here we monitor the gas phase during photochemical aerosol analog production as a function of reaction time. In a recirculation experiment, the isotopic fractionation of carbon within the gas-phase products is measured as the CH4 reservoir is depleted. This allows us to monitor the isotopic fractionation pathway during photochemical aerosol analog formation.

Ugelow, M. S.↗
NASA NTRS2019

The K Dwarf Advantage for Biosignatures on Directly Imaged Exoplanets

Oxygen and methane are considered to be the canonical biosignatures of modern Earth, and the simultaneous detection of these gases in a planetary atmosphere is an especially strong biosignature. However, these gases may be challenging to detect together in the planetary atmospheres because photochemical oxygen radicals destroy methane. Previous work has shown that the photochemical lifetime of methane in oxygenated atmospheres is longer around M dwarfs, but M dwarf planet habitability may be hindered by extreme stellar activity and evolution. Here, we use a 1D photochemical-climate model to show that K dwarf stars also offer a longer photochemical lifetime of methane in the presence of oxygen compared to G dwarfs. For example, we show that a planet orbiting a K6V star can support about an order of magnitude more methane in its atmosphere compared to an equivalent planet orbiting a G2V star. In the reflected-light spectra of worlds orbiting K dwarf stars, strong oxygen and methane features could be observed at visible and near-infrared wavelengths. Because K dwarfs are dimmer than G dwarfs, they offer a better planet-star contrast ratio, enhancing the signal-to-noise ratio (S/N) possible in a given observation. For instance, a 50 hr observation of a planet at 7 pc with a 15 m telescope yields S/N = 9.2 near 1 m for a planet orbiting a solar-type G2V star, and S/N = 20 for the same planet orbiting a K6V star. In particular, nearby mid-late K dwarfs such as 61 Cyg A/B, Epsilon Indi, Groombridge 1618, and HD 156026 may be excellent targets for future biosignature searches.

Arney, Giada N.↗
NASA NTRS2019

The K Dwarf Advantage for Biosignatures on Directly Imaged Exoplanets

Oxygen and methane are considered to be the canonical biosignatures of modern Earth, and the simultaneous detection of these gases in a planetary atmosphere is an especially strong biosignature. However, these gases may be challenging to detect together in the planetary atmospheres because photochemical oxygen radicals destroy methane. Previous work has shown that the photochemical lifetime of methane in oxygenated atmospheres is longer around M dwarfs, but M dwarf planet habitability may be hindered by extreme stellar activity and evolution. Here, we use a 1-D photochemical-climate model to show that K dwarf stars also offer a longer photochemical lifetime of methane in the presence of oxygen compared to G dwarfs. For example, we show that a planet orbiting a K6V star can support about an order of magnitude more methane in its atmosphere compared to an equivalent planet orbiting a G2V star. In the reflected light spectra of worlds orbiting K dwarf stars, strong oxygen and methane features could be observed at visible and near-infrared wavelengths. Because K dwarfs are dimmer than G dwarfs, they offer a better planet-star contrast ratio, enhancing the signal-to-noise (SNR) possible in a given observation. For instance, a 50 hour observation of a planet at 7 pc with a 15-m telescope yields SNR = 9.2 near 1 µm for a planet orbiting a solar-type G2V star, and SNR = 20 for the same planet orbiting a K6V star. In particular, nearby mid-late K dwarfs such as 61 Cyg A/B, Epsilon Indi, Groombridge 1618, and HD 156026 may be excellent targets for future biosignature searches.

Giada N Arney↗
NASA NTRS2021

Wintertime Formaldehyde: Airborne Observations and Source Apportionment Over the Eastern United States

Formaldehyde (HCHO) is generated from direct urban emission sources and secondary production from the photochemical reactions of urban smog. HCHO is linked to tropospheric ozone formation, and contributes to the photochemical reactions of other components of urban smog. In this study pollution plume intercepts during the Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) campaign were used to investigate and characterize the formation of HCHO in relation to several anthropogenic tracers. Analysis of aircraft intercepts combined with detailed chemical box modeling downwind of several cities suggest that the most important contribution to observed HCHO was primary emission. A box model analysis of a single plume suggested that secondary sources contribute 21±10% of observed HCHO. Ratios of HCHO/CO observed in the northeast U.S., from Ohio to New York, ranging from 0.2-0.6%, are consistent with direct emissions combined with at most modest photochemical production. Analysis of the nocturnal boundary layer and residual layer from repeated vertical profiling over urban influenced areas indicate a direct HCHO emission flux of 1.3 x 10 14 molecules cm -2 h -1 . In a case study in Atlanta, GA, nighttime HCHO exhibited a ratio to CO (0.6 – 1.8%) and was anti-correlated with O 3 . Observations were consistent with mixing between direct HCHO emissions in urban air masses with those influenced by more rapid HCHO photochemical production. The HCHO/CO emissions ratios determined from the measured data are 2.3 - 15 times greater than the NEI 2017 emissions database. The largest observed HCHO/CO was 1.7 – 1.8%, located near co-generating power stations.

Formaldehyde↗
NASA NTRS1978

Hydrogen from the solar photolysis of water

Developments related to the study of photosynthesis are examined and aspects of photosensitization by solids are considered. It is pointed out that solids photosensitization for solar photochemical fuel formation is now an extremely active research area as a consequence of the promising results obtained with semiconductor photoelectrodes. The investigation of water decomposition schemes involving heterogeneous reactions is likely to be a productive area. As is the case for photosynthesis, the known examples of water decomposition by solids photosensitization involve charge separation processes immediately following light absorption. Homogeneous photoredox reactions are also discussed, taking into account thermochemical and photochemical cycles leading to the formation of a photooxidized ion, hydrogen quantum yields in the photo-oxidation aqueous ions, and thermochemical and photochemical cycles leading to the formation of a photoreduced ion.

Ryason, P. R.↗
NASA NTRS1978

Status and summary of laser energy conversion

This paper presents a survey of the status of laser energy converters. Since the inception of these devices in the early 1970's, significant advances have been made in understanding the basic conversion processes. Numerous theoretical and experimental studies have indicated that laser energy can be converted at wavelengths from the ultraviolet to the far-infrared. These converters can be classified into five general categories: photovoltaics, heat engines, thermoelectronic, optical diode, and photochemical. The conversion can be directly into electricity (such as the photovoltaic, thermoelectronic, and optical diode) or it can go through an intermediate stage of conversion to mechanical energy, as in the heat engines. The photochemical converters result in storable energy such as hydrogen. Projected conversion efficiencies range from about 30% for the photochemical to nearly 75% for the heat engines.

Lee, G.↗
NASA NTRS1979

Numerical simulation of ozone production, transport and distribution with a global atmospheric general circulation model

The production, transport, and distribution of ozone are simulated for a January with a global atmospheric general circulation model. In this model, the ozone influences the radiational heating and the photochemical ozone production and destruction, the radiational heating influences the atmospheric circulation, and the circulation redistributes the ozone. The model has simulated the synoptic and time-averaged observed large-scale fields of temperature, mass, and velocity in the troposphere and stratosphere, although with deficiencies which are seen in the time-averaged O3 distribution. Transport of ozone in the summer and winter hemispheres, in different seasons, and in various latitudes is discussed, and it is concluded that the divergence of the ozone transport maintains it below its photochemical equilibrium concentration in the tropics and subtropics, and the convergence of the ozone transport maintains it above its photochemical equilibrium concentration in the middle and high latitudes of both hemispheres. Thus, both the atmospheric motions and the O3 photochemistry determine the O3 sources and sinks.

Schlesinger, M. E.↗
NASA NTRS1980

The influence of NO and ClO variations at twilight on the interpretation of solar occultation measurements

The influence of short lived photochemically produced species on solar occultation measurements of ClO and NO was examined. Time varying altitude profiles of ClO and NO were calculated with a time dependent photochemical model to simulate the distribution of these species during a solar occultation measurement. These distributions were subsequently used to calculate simulated radiances for various tangent paths from which mixing ratios were inferred with a conventional technique that assumes spherical symmetry. These results show that neglecting the variation of ClO in the retrieval process produces less than a 10 percent error between the true and inverted profile for both sunrise and sunset above 18 km. For NO, errors are less than 10 percent for tangent altitudes above about 35 km for sunrise and sunset; at lower altitudes, the error increases, approaching 100 percent at altitudes near 25 km. the results also show that average inhomogeneity factors, which measure the concentration variation along the tangent path and which can be calculated from a photochemical model, can indicate which species require more careful data analysis.

Boughner, R.↗
NASA NTRS1982

The photochemistry of the paleoatmosphere

Recent progress in the understanding of the chemistry and photochemistry of the paleoatmosphere is reviewed with emphasis on the application of photochemical models to the investigation of the evolution of the atmosphere. Photochemical calculations are presented which show that a primordial highly reducing atmosphere composed of methane and ammonia, if it formed at all, would be short-lived in the presence of solar ultraviolet radiation, giving way rapidly to a more mildly reducing atmosphere of carbon dioxide and nitrogen. Estimations of O2 produced from the photolysis of water vapor prior to the emergence of photosynthesis range from less than 10 to the -14th to 0.1 times the present atmospheric level, indicating the need for further research. A series of photochemical models of increasing complexity has been developed to study the evolution of atmospheric ozone taking into account reactions with O atoms, hydrogen oxides, nitrogen oxides, and chlorine as well as vertical transport, temperature and tropospheric chemistry so that the total content and vertical distribution of O3 may be determined for a specified level of paleoatmospheric O2.

Levine, J. S.↗
NASA NTRS1982

The prebiological paleoatmosphere - Stability and composition

In the past, it was generally assumed that the early atmosphere of the earth contained appreciable quantities of methane (CH4) and ammonia (NH3). This was the type of atmosphere believed to be the most suitable environment for chemical evolution, the nonbiological formation of complex organic molecules, the precursors of living systems. Photochemical considerations suggest that a CH4-NH3 dominated early atmosphere was probably very short-lived, if it ever existed at all. Instead, an early atmosphere of carbon dioxide (CO2) and nitrogen (N2) is favored by photochemical as well as geological and geochemical considerations. Photochemical calculations also indicate that the total oxygen column density of the prebiological paleoatmosphere did not exceed 10 to the -7th of the present atmospheric level.

Levine, J. S.↗
NASA NTRS1984

Review of solar fuel-producing quantum conversion processes

The status and potential of fuel-producing solar photochemical processes are discussed. Research focused on splitting water to produce dihydrogen and is at a relatively early stage of development. Current emphasis is primarily directed toward understanding the basic chemistry underlying such quantum conversion processes. Theoretical analyses by various investigators predict a limiting thermodynamic efficiency of 31% for devices with a single photosystem operating with unfocused sunlight at 300 K. When non-idealities are included, it appears unlikely that actual devices will have efficiencies greater than 12 to 15%. Observed efficiencies are well below theoretical limits. Cyclic homogeneous photochemical processes for splitting water have efficiencies considerably less than 1%. Efficiency can be significantly increased by addition of a sacrificial reagent; however, such systems are no longer cyclic and it is doubtful that they would be economical on a commercial scale. The observed efficiencies for photoelectrochemical processes are also low but such systems appear more promising than homogeneous photochemical systems. Operating and systems options, including operation at elevated temperature and hybrid and coupled quantum-thermal conversion processes, are also considered.

Peterson, D. B.↗
NASA NTRS1983

Photochemistry of methane in the earth's early atmosphere

The photochemical behavior of methane in the early terrestrial atmosphere is investigated with a detailed model in order to determine how much CH4 might have been present and what types of higher hydroocarbons could have been formed. It is found that any primordial methane accumulated during the course of earth accretion would have been dissipated by photochemical reactions in the atmosphere in a geologically short period of time after the segregation of the core. Abiotic sources of methane are not likely to have been large enough to sustain CH4 mixing ratios as high as 10 to the -6th, the threshold for a possible methane greenhouse, with a CO-rich atmosphere being a possible exception. After the origin of life an increasing biogenic source of methane may have driven CH4 mixing ratios well above 10 to the 6th. The rise of atmospheric oxygen in the early Proterozoic may have led to a more rapid photochemical destruction of methane, lowering the mixing ratio to its present value.

Kasting, J. F.↗
NASA NTRS1985

A critical analysis of CLO and O3 in the mid-latitude stratosphere

The Caltech one-dimensional photochemical model is used to analyze important questions concerning the upper stratospheric O3 and the key HO(x), NO(x), and ClO(x) free radicals. The model is described and first order effects of the inclusion of diffuse radiation in a spherical rather than plane parallel atmosphere at solar zenith angles close to 90 deg are assessed. A comparison is made between photochemical theory and observations for upper stratospheric O3, where local photochemistry rather than dynamics should control the O3 abundance. The photochemical equilibrium relation for odd oxygen is studied, including the important radicals involves. It is concluded that a significant model ozone deficit exists in the upper stratosphere. Possible causes for such a discrepancy are investigated in light of current model and experimental uncertainties. In particular, the observational ratio of atomic oxygen to zone appears to disagree with the model results.

Froidevaux, L.↗
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.↗
NASA NTRS1987

Producing Hydrogen With Sunlight

Costs high but reduced by further research. Producing hydrogen fuel on large scale from water by solar energy practical if plant costs reduced, according to study. Sunlight attractive energy source because it is free and because photon energy converts directly to chemical energy when it breaks water molecules into diatomic hydrogen and oxygen. Conversion process low in efficiency and photochemical reactor must be spread over large area, requiring large investment in plant. Economic analysis pertains to generic photochemical processes. Does not delve into details of photochemical reactor design because detailed reactor designs do not exist at this early stage of development.

Biddle, J. R.↗
NASA NTRS1988

Modelling the Antarctic lower stratosphere

Results form modeling studies of the Antarctic lower stratosphere which have attempted to simulate the large springtime ozone losses and corresponding changes in other trace constituents are given. These studies were carried out in a photochemical box model, a one-dimensional model without transport and in a two-dimensional photochemical-dynamical-radiation model. The photochemical studies have investigated inter alia the sensitivity of ozone to inclusion in the model of heterogeneous chemistry, and to the inclusion of the ClO dimer. When both of these are incorporated in the model, ozone depletions resembling whose found in Halley Bay in 1987 (J.C. Farman, Nature, 329, 1987) can be reproduced. The temporal variations (both diurnal and during the August to October period) of a number of important tracers including HCl, ClONO2, OClO and BrO are discussed. The two-dimensional study concentrated on the difficulty of establishing in the model the dynamical preconditioning of the lower polar stratosphere - low temperatures, low N2O, etc., high ClOx. Calculations are presented to show: (1) the depletion of ozone during the springtime season, (2) the effect of large ozone losses on lower latitudes, and (3) the longer term (multi-year) variations of ozone in Antarctica, assuming realistic increases in the atmospheric halogen burden.

Chipperfield, M. P.↗
NASA NTRS1989

The mean ozone profile and its temperature sensitivity in the upper stratosphere and lower mesosphere - An analysis of LIMS observations

Multiple simultaneous LIMS (Limb Infrared Monitor of the Stratosphere) observations of both O3 and temperature T in the upper stratosphere and lower mesosphere are analyzed to derive O3-T correlations for comparisons with model calculations. The zonally averaged O3 profile is compared with results from a simplified photochemical model that assumes O3 to be in a photochemical steady state. The model profile is systematically lower than the observed profile. Key parameters are identified in which changes can systematically increase the O3 profile in both the stratosphere and the mesosphere. The LIMS-derived values for the sensitivity of O3 to changes in T are compared with equilibrium model calculations which include the T-driven opacity feedback effect on photodissociation rate constants. The theoretical O3 response to temperature perturbations is investigated. It is shown how the O3-T sensitivity coefficient is affected by zonal and vertical advection terms as well as by the photochemical coupling between O3 and T.

Froidevaux, Lucien↗
NASA NTRS1989

Ozone budgets from the Dynamics and Chemistry of Marine Stratocumulus experiment

Measurements from the Dynamics and Chemistry of marine Stratocumulus experiment have been used to study components of the regional ozone budget. The surface destruction rate is determined by eddy correlation of ozone and vertical velocity measured by a low-flying aircraft. Significant variability is found in the measured surface resistance; it is partially correlated with friction velocity but appears to have other controlling influences as well. The mean resistance is 4190 s/m which is higher (slower destruction) than most previous estimates for seawater. Flux and mean measurements throughout the marine boundary layer are used to estimate the net rate of in situ photochemical production/destruction of ozone. Averaged over the flights, ozone concentration is found to be near steady state, and a net of photochemical destruction of 0.02-0.07 ng/cu m per sec is diagnosed. This is an important confirmation of photochemical model results for the remote marine boundary layer. Ozone vertical distributions above the boundary layer show a strongly layered structure with very sharp gradients. These distributions are possibly related to the stratospheric ozone source.

Kawa, S. R.↗