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NASA NTRS2016

Isotopic Ordering in Atmospheric O2 as a Tracer of Ozone Photochemistry and the Tropical Atmosphere

The distribution of isotopes within O2 molecules can be rapidly altered when they react with atomic oxygen. This mechanism is globally important: while other contributions to the global budget of O2 impart isotopic signatures, the O(3P) + O2 reaction resets all such signatures in the atmosphere on subdecadal timescales. Consequently, the isotopic distribution within O2 is determined by O3 photochemistry and the circulation patterns that control where that photochemistry occurs. The variability of isotopic ordering in O2 has not been established, however. We present new measurements of 18O18O in air (reported as delta36 values) from the surface to 33 km altitude. They confirm the basic features of the clumped-isotope budget of O2: Stratospheric air has higher delta36 values than tropospheric air (i.e., more 18O18O), reflecting colder temperatures and fast photochemical cycling of O3. Lower delta36 values in the troposphere arise from photochemistry at warmer temperatures balanced by the influx of high-delta36 air from the stratosphere. These observations agree with predictions derived from the GEOS-Chem chemical transport model, which provides additional insight. We find a link between tropical circulation patterns and regions where delta36 values are reset in the troposphere. The dynamics of these regions influences lapse rates, vertical and horizontal patterns of O2 reordering, and thus the isotopic distribution toward which O2 is driven in the troposphere. Temporal variations in delta36 values at the surface should therefore reflect changes in tropospheric temperatures, photochemistry, and circulation. Our results suggest that the tropospheric O3 burden has remained within a +/-10 percent range since 1978.

oxygen↗

NASA NTRS2020

UV/Vis+ Photochemistry Database: Structure, Content and Applications

The “science-softCon UV/Vis+ Photochemistry Database” (www.photochemistry.org) is a large and comprehensive collection of EUV-VUV-UV–Vis-NIR spectral data and other photochemical information assembled from published peer-reviewed papers. The database contains photochemical data including absorption, fluorescence, photoelectron, and circular and linear dichroism spectra, as well as quantum yields and photolysis related data that are critically needed in many scientific disciplines. This manuscript gives an outline regarding the structure and content of the “science-softCon UV/Vis+ Photochemistry Database”. The accurate and reliable molecular level information provided in this database is fundamental in nature and helps in proceeding further to understand photon, electron and ion induced chemistry of molecules of interest not only in spectroscopy, astrochemistry, astrophysics, Earth and planetary sciences, environmental chemistry, plasma physics, combustion chemistry but also in applied fields such as medical diagnostics, pharmaceutical sciences, biochemistry, agriculture, and catalysis. In order to illustrate this, we illustrate the use of the UV/Vis+ Photochemistry Database in four different fields of scientific endeavor.

Photochemistry↗

NASA NTRS1980

Hydrocarbon photochemistry and Lyman alpha albedo of Jupiter

A combined study of hydrocarbon and atomic hydrogen photochemistry is made to calculate self-consistently the L alpha albedo of Jupiter. It is shown that the L alpha emissions observed by Voyagers I and II can be explained by resonance scattering of sunlight. Precipitation of energetic particles from the magnetosphere can provide the large required source of atomic hydrogen, although the contribution of direct particle excitation to the disk-averaged brightness is insignificant. The variability of the L alpha brightness inferred from many observations in recent years is examined. The large difference in the brightness of the He 584 A resonance line observed by Pioneer and Voyager is briefly discussed. Driving the photochemistry by solar ultraviolet radiation alone yields a maximum mixing ratio of C2H6 + C2H2 at 0.01 atm of about 4 x 10 to the -6th. The possibility of additional CH4 dissociation from precipitation of magnetospheric particles is discussed. The photochemistry of C2H2 and C2H3 is sufficiently uncertain not to permit accurate calculations of their densities and the ratio C2H6/C2H2.

Yung, Y. L.↗

NASA NTRS1984

Phosphine photochemistry in the atmosphere of Saturn

The photochemistry of PH3 in the atmosphere of Saturn is studied, including the effects of coupling with the photochemistries of NH3 and hydrocarbons. The vertical concentration of PH3 is found to be extremely sensitive to the eddy diffusion coefficient (K) profile used. If K is roughly 10,000 sq cm/sec in the upper troposphere, PH3 should be depleted there with a scale height of about 3.5 km. An upper limit of 100,000 sq cm/sec is estimated for K. If the gas phase concentration of P2H4 can be neglected, production of molecular phophorus is very unlikely unless the spin-forbidden recombination reaction PH+H2+M - PH3+M occurs with an exceptionally low rate. Coupling of PH3 and hydrocarbon photochemistries is very important. Possible observable amounts of the organophosphorus molecules CH3PH2 and HCP are tentatively predicted.

Kaye, J. A.↗

NASA NTRS2003

Spectra and Photochemistry of Relevance to Icy Outer Solar System Objects

The Astrochemistry Lab at NASA Ames (www.astrochem.org) has an interest in the organic photochemistry of extraterrestrial ices, having traditionally performed experiments under interstellar conditions. We have recently embarked on projects for PG\&G to measure spectra and elucidate the photochemistry of ices relevant to outer Solar System objects. 1) We will report on the determination of real and imaginary indicies of refraction of H2O and N2 dominated ices containing simple, common, extraterrestrial molecules such as NH3, HCN, formaldehyde, \& methanol. 2) We will compare and contrast the photochemistry of H2O ices containing organic molecules at 100 K with previously reported work at 15 K.

Bernstein, M. P.↗

NASA NTRS2007

An Overview of Snow Photochemistry: Evidence, Mechanisms and Impacts

It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3-4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively small boundary layer. Field and laboratory experiments have determined that the origin of the observed NOx flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future.

Grannas, A. M.↗

NASA NTRS1973

Photochemistry of interstellar molecules

The role of photochemistry in determining the lifetime of interstellar molecules is considered. The probability of photodecomposition depends on three factors, including the absorption cross section, the quantum yield or probability of dissociation following photon absorption, and the interstellar radiation field. A more detailed discussion of the photochemistry of five molecules is presented, giving attention to carbonyl sulfide, methyl acetylene, nitric oxide, acetylene, and benzene. Lifetimes of interstellar molecules in unobscured regions are in the range from 5 to 100 years. It is concluded that polyatomic molecules can exist only in dense clouds which protect them from the full interstellar radiation field.

Stief, L. J.↗

NASA NTRS1977

Tropospheric ozone - Coupling transport and photochemistry

The budget of tropospheric ozone is re-examined in the light of lower observed nitrogen oxide densities and revised reaction rates. To estimate the relative importance of transport and photochemistry, model calculations are presented which determine one-dimensional vertical ozone profiles at midlatitudes for equinoctial conditions. These calculations imply that both photochemistry and transport are important in controlling the abundance of tropospheric ozone. It is estimated that photochemical processes produce about 0.6 times 10 to the eleventh and destroy about 1.4 times 10 to the eleventh tropospheric ozone molecules per sq cm per sec, while mixing processes transport about 1.4 times 10 to the eleventh ozone molecules per sq cm per sec from the stratosphere into the troposphere and ground level fluxes destroy about 0.6 times 10 to the eleventh ozone molecules per sq cm per sec. The sensitivity of our model calculations to transport parameters, key rate coefficients, and nitrogen oxide densities are discussed.

Chameides, W. L.↗

NASA NTRS1978

Feasibility of an orbital simulator of stratospheric photochemistry

It is proposed that a stratospheric photochemistry simulator could be created in sun-synchronous orbit, so that diffusion and photochemistry could be decoupled and uncertainties in photochemical reaction rates could be substantially reduced. The proposed test chamber is described, and it is suggested that the technology of superpressure balloons seems to be the best short-term solution to the construction of the proposed facility. Both unreinforced polyester films and gelatin films are considered as candidate chamber coatings. It is noted that the experiments can be performed early in the space-manufacturing era and that at least three dedicated Shuttle launches will be required to establish the proposed facility.

Matloff, G. L.↗

NASA NTRS1980

Iodine - Its possible role in tropospheric photochemistry

A detailed study of the photochemistry of iodine and its oxides indicates that iodine species may play an important role in the tropospheric photochemical system. Methyl iodide, often observed in the marine troposphere with an average concentration of 5-10 ppt, is photolyzed and thereby produces I atoms. Chemical interactions with O3, HxOy, and NOx cause I to be converted to other inorganic compounds such as IO, HOI, IONO2, and I2. The production of these species and their subsequent recycling back to I can lead to the catalytic removal of tropospheric O3, the enhancement of the NO2/NO ratio, the destruction of HxOy free radicals, and the conversion of HO2 to OH. Ultimately, tropospheric inorganic iodine is removed by heterogeneous processes. Calculations using a numerical model to simulate tropospheric photochemistry indicate that iodine may have a strong impact upon the atmospheric O3-NOx-HxOy system. The magnitude of these effects is dependent upon the value of several uncertain rate constants and the primary source distributions of CH3I and other organic and inorganic iodine compounds.

Chameides, W. L.↗

NASA NTRS1981

Effects of multiple scattering and surface albedo on the photochemistry of the troposphere

The effect of treatment of incoming solar radiation on the photochemistry of the troposphere is discussed. A one dimensional photochemical model of the troposphere containing the species of the nitrogen, oxygen, carbon, hydrogen, and sulfur families was developed. The vertical flux is simulated by use of the parameterized eddy diffusion coefficients. The photochemical model is coupled to a radiative transfer model that calculates the radiation field due to the incoming solar radiation which initiates much of the photochemistry of the troposphere. Vertical profiles of tropospheric species were compared with the Leighton approximation, radiative transfer, matrix inversion model. The radiative transfer code includes the effects of multiple scattering due to molecules and aerosols, pure absorption, and surface albedo on the transfer of incoming solar radiation. It is indicated that significant differences exist for several key photolysis frequencies and species number density profiles between the Leighton approximation and the profiles generated with, radiative transfer, matrix inversion technique. Most species show enhanced vertical profiles when the more realistic treatment of the incoming solar radiation field is included

Augustsson, T. R.↗

NASA NTRS1981

Comets and the photochemistry of the paleoatmosphere

Ozone (O3) is a key atmospheric gas in considerations of the photochemistry/chemistry of the paleoatmosphere, chemical evolution, and the origin and evolution of life. The photochemistry/chemistry of atmospheric O3 in the paleoatmosphere is investigated using a one-dimensional photochemical model that includes the chemistry of oxygen, nitrogen, hydrogen, carbon, and chlorine gases. The role of cometary influx of H2O on the photochemistry of the paleoatmosphere is also examined. Recently, it has been suggested that the planet received a significant portion of the volatiles presently in the atmospheric/oceanic/biospheric system from cometary volatile influx. Several consequences of a cometary H2O influx on the photochemistry and structure of the paleoatmosphere are presented.

Levine, J. S.↗

NASA NTRS1982

Photochemistry of the stratosphere of Venus - Implications for atmospheric evolution

The photochemistry of the Venus stratosphere is modeled using an updated and expanded chemical scheme along with the results of recent observations and laboratory studies. Three models, with H2 mixing ratio equal to 2 x 10 to the -5th, 5 x 10 to the -7th, and 1 x 10 to the -13th, respectively, are examined. All three models are found to satisfactorily account for the observations of CO, O2, O2(1Delta), and SO2 in the stratosphere, but only the last one may be able to account for the diurnal behavior of mesospheric CO and the UV albedo. Oxygen, derived from CO2 photolysis, is mainly consumed by CO2 recombination and oxidation of SO2 to H2SO4. The photolysis of HCl in the upper stratosphere provides a major source of odd hydrogen and free chlorine radicals, essential for the catalytic oxidation of CO. Oxidation of SO2 by O occurs in the lower stratosphere. The modeling reveals a number of interesting similarities, previously unsuspected between the chemistry of the stratosphere of Venus and that of the earth; photochemistry may have played a major role in the evolution of the atmosphere.

Yung, Y. L.↗

NASA NTRS1983

Photochemistry of acetylene at 1849 A

It is pointed out that the photochemistry of acetylene in the 1500-2000 A region at low pressure, particularly the quantum yield of C2H production and the reactions of C2H with H2 and hydrocarbons, is important in understanding the photochemistry of Jovian and Titan atmospheres. The present investigation was initiated to obtain information on these issues. The 1849 A light source used in the study was a sealed quartz tube containing a drop of Hg and 2 torr of Ar excited by a microwave generator. The lamp was attached to a Pyrex reaction cell. The amount of diacetylene produced was measured on the basis of absorption near 1650 A. Reaction mixtures of acetylene with N2, He, C2H6, or C3H8 were prepared. Attention is given to the absorption cross section, the photolysis of acetylene, and the photolysis of acetylene in the presence of other gases. It is found that the photochemical process of acetylene at 1849 A may represent that of acetylene in the Titan atmosphere.

Okabe, H.↗

NASA NTRS1983

Phosphine photochemistry in Saturn's atmosphere

The phosphine photochemistry on Saturn is studied with a 1D photochemical model. The PH3 concentration is rapidly depleted with height (scale height 3.5 km) in the upper troposphere. Formation of P, a probable precursor of P4, (a potential red chromophore in the atmosphere), is highly improbable unless the rate constant for the recombination reaction PH + H2 + M yields PH3 + M is less than 10 to the -41st cm exp 6/molecule-squared sec. Coupling of PH3 and hydrocarbon photochemistry, specifically the C2H2 catalyzed photodissociation of CH, is important. Column production rates of the organophosphorus compounds CH3PH2 and HCP of 3 x 10 to the 8th/sq cm sec are predicted, with potentially observable column densities of greater than 1 x 10 to the 17th/sq cm.

Kaye, J. A.↗

NASA NTRS1985

The photochemistry of biogenic gases in the early and present atmosphere

The distribution of gases in the prebiologial paleoatmosphere is investigated using photochemical models. A chart of the photochemical and chemical reactions and reaction rates for CH4, NH3, H2S, N2O, and CO atmospheric gases is given. Mixing ratios and surface mixing ratios for CH4, NH3, CO, and N2O are obtained using thermodynamic equilibrium calculations; an increase in CH4 and N2O is observed. The reactions, which explain the photochemistry of the gases studied, are presented. The sources of these gases and their concentration with regards to altitude are examined. Graphs of the vertical distribution of CH4, NH3, H2S, CO, O2, and N2O in prebiological paleoatmosphere are provided. The data reveals the presence of only N2, CO2, and N2O in the early atmosphere; with the evolution of life, sources of atmospheric gases increased and their influence on the photochemistry of the troposphere and stratosphere increased.

Levine, J. S.↗

NASA NTRS1985

The photochemistry of methane and carbon monoxide in the troposphere in 1950 and 1985

The roughly 1 percent/year increase in tropospheric methane and roughly 2 percent/year increase in tropospheric carbon monoxide deduced from recent analyses of ground-based solar infrared spectra recorded in 1950 and 1951 have very important implications for the photochemistry and chemistry of the troposphere. Photochemical calculations indicate that as a result of the increase of methane and carbon monoxide since 1950-51, levels of the hydroxyl radical, the key species in the photochemistry of the troposphere, may have decreased by about 25 percent.

Levine, J. S.↗

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.↗