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Spirocyclopropane formation and rearrangement in thermal and photochemical decomposition of 1-pyrazolines from 9-diazofluorene and bicyclic/2.2.1/olefins
Experimental laboratory techniques used in studying the photochemistry of stable and unstable molecules are discussed. The laboratory evidence for the photochemical formation of C2 from C2H, C3 from C3H2, and NH from NH2 is presented. Other recent results obtained in laboratory studies of H2O, H2S, NH3, and HCN are reported.
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An analysis procedure has been developed for derivation of information about the photochemical behavior of ozone near 1 mbar by explicitly accounting for the dynamical transport terms in the continuity equation for perturbations from the zonal mean. The procedure is shown to be valid using data from a numerical transport model and is then applied to LIMS ozone and temperature data, using geostrophic winds to estimate the transport terms. The data study is restricted to March at 2, 1, and 0.7 mbar. Because the temperature deviations are dynamically produced, large temperature deviations are associated with significant ozone transport terms. The anticorrelation between the deviations of ozone and temperature disappears when the transport terms are small. The derived photochemical information is compared to photochemical theory. Although there is overall agreement in the magnitude as well as the latitude, altitude, and time dependencies, discrepancies are suggested which may be related to the long-standing failure of photochemical models to calculate ozone accurately near 1 mbar. The theory suggests that the addition of Cl(x) to the stratosphere will affect the relationship of ozone and temperature at 2 and 1 mbar. Comparison of the photochemical information derived from future ozone and temperature measurements with the results of the present analysis should provide a critical test of the photochemical scheme thought to describe the behavior of odd chlorine in the stratosphere.
One-half of the total ozone column is predominantly under photochemical control under all conditions except polar winter. The other half is dynamically controlled. Since the photochemical forcing is phased with the solar declination and modulated by air temperature variation in the upper stratosphere and the dynamic forcing is tied to wave activity in the upper troposphere, the total ozone column is a mixture of the two drivers. If the total ozone is used to infer a property of the dynamic field, namely the tropopause height, it is necessary to correct for the photochemical variations. It should be possible to remove the photochemical component of the total ozone by using SBUV profile information along the orbital track as long as the spatial variations are low frequency. The column integral above the Umkehr levels in the lower stratosphere are examined to determine the level where the spatial variability decreases to the expected photochemical range to find an approximate dividing line between photochemical and dynamic control. Given this a spherical harmonic function will be fitted to the ozone field and subtracted from the TOMS total ozone field. This residual field will then be correlated with tropopause height to determine whether an improvement is obtained over the total ozone correlation.
The paper considers the 'ground rules' which govern the efficiency of photochemical solar energy conversion and then summarizes the most promising approaches in each of three categories: photochemically assisted thermal systems for the heating and/or cooling of structures; photogalvanic systems for the production of electrical power in applications, such as photorechargeable batteries or inexpensive 'solar cells'; and photochemical formation of fuels for combustion and for use as chemical feedstocks or foods. Three concepts for the photochemical utilization of solar energy in space are found to be particularly promising: (1) photochemical trans-cis isomerization of indigold dyes for photoassisted heating or cooling, (2) the redox stabilized photoelectrolysis cell for the production of hydrogen (and/or oxygen or other useful chemicals), and (3) the liquid-junction photovoltaic cell for the production of electrical power.
UV (ultraviolet) radiation can induce photochemical processes in the atmospheres of exoplanet and produce haze particles. Recent transmission spectra of super-Earths and mini-Neptunes have demonstrated the possibility that exoplanets have haze/cloud layers at high altitudes in their atmospheres. Haze particles play an important role in planetary atmospheres because they affect the chemistry, dynamics, and radiation flux in planetary atmospheres, and may provide a source of organic material to the surface which may impact the origin or evolution of life. However, very little information is known about photochemical processes in cool, high-metallicity exoplanetary atmospheres. We present here photochemical haze formation in laboratory simulation experiments with UV radiation; we explored temperatures ranging from 300 to 600 degrees Kelvin and a range of atmospheric metallicities (100 times, 1000 times, and 10000 times solar metallicity). We find that photochemical hazes are generated in all simulated atmospheres, but the haze production rates appear to be temperature dependent: the particles produced in each metallicity group decrease as the temperature increases. The images taken with an atomic force microscope (AFM) show that the particle size (15 nanometers to 190 nanometers) varies with temperature and metallicity. Our results provide useful laboratory data on the photochemical haze formation and particle properties, which can serve as critical inputs for exoplanet atmosphere modeling, and guide future observations of exoplanets with the Transiting Exoplanet Survey Satellite (TESS), the James Webb Space Telescope (JWST), and the Wide-Field Infrared Survey Telescope (WFIRST).
A photochemical model for the atmosphere of Jupiter, including 1-D vertical eddy diffusive transport, was developed. It extends from the upper troposphere through the homopause. The hydrocarbon chemistry involves species containing up to four carbon atoms (and polyynes through C8H2). The calculations show that a large fraction of photochemical carbon may be contained in molecules with more than two carbon atoms. At the tropopause, C2H6 is the major photochemical species and C2H2, C3H8, and C4H10 are of comparable abundance and down from C2H6 by a factor of ten. These species may be detectable with the mass spectrometer of the Galileo Probe. The vertical distributions of the photochemical species are sensitive to the magnitude of eddy diffusive mixing in the troposphere and stratosphere and the details of the interface region.
We examine the effects of the loss of Mars atmospheric constituents by solar-wind-induced sputtering and by photochemical escape during the past 3.8 billion years. Sputtering is capable of efficiently removing species from the upper atmosphere, including the light noble gases; nitrogen and oxygen are removed by photochemical processes as well. Due to diffusive separation (by mass) above the homopause, removal from the top of the atmosphere will fractionate the isotopes of each species, with the lighter mass being preferentially lost. For carbon and oxygen, this allows us to determine the size of nonatmospheric reservoirs which mix with the atmosphere; these reservoirs can be CO2 adsorbed in the regolith and H2O in the polar ice caps. We have constructed both simple analytical models and time-dependent models of the loss of volatiles from and supply to the martian atmosphere. Both argon and neon require continued replenishment from outgassing over geologic time. For argon, sputtering loss explains the fractionation of (Ar-36)/(Ar-38) without requiring a distinct epoch of hydrodynamic escape (although fractionation of Xe isotopes still requires very early hydrodynamic loss). For neon, the current (Ne-22)/(Ne-20) ratio represents a balance between loss to space and continued resupply from the interior; the similarity of the ratio to the terrestrial value is coincidental. For nitrogen, the loss by both sputtering and photochemical escape would produce a fractionation of (N-15)/(N-14) larger than observed; an early, thicker carbon dioxide atmosphere could mitigate the nitrogen loss and produce the observed fractionation, as could continued outgassing of juvenile nitorgen. Based on the isotopic constraints, the total amount of carbon dioxide lost over geologic time is probably on the order of tens of millibars rather than a substantial fraction of a bar. The total loss from solar-wind-induced sputtering and photochemical escape, therefore, does not seem able to explain the loss of a putative thick, early atmosphere withput requiring formation of extensive surface carbonate deposits or other nonatmospheric reservoirs for CO2.
We have analyzed our 23-year merged ozone data set for variability and trends with a statistical time-series model. To assist in that analysis, we have analyzed the Goddard ED photochemical model for the same time period with the same time-series model. Multiple runs of the photochemical model allow us to separate the effects of various terms on ozone, such as solar cycle and volcanic eruptions. We use this to help us separate those signals from each other in the data. We also used a smoothed version of the photochemical model's prediction of global ozone change in place of a simple linear trend. We find a number of interesting results. This particular photochemical model is more sensitive to chlorine perturbations than the atmosphere appears to be. It is less sensitive to solar cycle. It predicts an effect from the Pinatubo eruption that is nearly symmetric in the two hemispheres, but the data appears to have not responded to Pinatubo in the southern mid-latitudes. These results and their uncertainties will be discussed.
We have analyzed our 23-year merged ozone data set for variability and trends with a statistical time-series model. To assist in that analysis, we have analyzed the Goddard 2D photochemical model for the same time period with the same time-series model. Multiple runs of the photochemical model allow us to separate the effects of various terms on ozone, such as solar cycle and volcanic eruptions. We use this to help us separate those signals from each other in the data. We also used a smoothed version of the photochemical model's prediction of global ozone change in place of a simple linear trend. We find a number of interesting results. This particular photochemical model is more sensitive to chlorine perturbations than the atmosphere appears to be. It is less sensitive to solar cycle. It predicts an effect from the Pinatubo eruption that is nearly symmetric in the two hemispheres, but the data appears to have not responded to Pinatubo in the southern mid-latitudes. These results and their uncertainties will be discussed.
We present a photochemical theory for tropospheric ozone in which the methane oxidation chain constitutes a large local source. This source produces about one trillion odd oxygen molecules per square centimeter per second and implies a photochemical lifetime for ozone of about 1 day, much shorter than characteristic mixing times. The photochemical model reproduces the altitude and seasonal dependence of ozone at 30 deg N. It also gives qualitative agreement with observed day-to-day variations of the ozone density.
In a paper by Strobel (1977), opacity effects on the joint photochemical-radiative relaxation in the stratosphere were evaluated by a linear perturbation analysis. Significant reductions in the photochemical acceleration of the thermal relaxation rate and the ozone photochemical relaxation rate were obtained in the upper stratosphere as a result of opacity changes. For very large vertical scale height ozone density perturbations, amplifying solutions were generated by large opacity changes in the O3 dissociation and heating rates. Such solutions could indicate that the stratosphere does not possess an equilibrium ozone concentration. In the present paper, some illustrative numerical calculations are presented to demonstrate the properties of the amplifying solutions. The results indicate that ungeophysically large disturbances are required and that they cease growth before attainment of geophysically interesting amplitudes, and decay to the unperturbed state.
A computer study was performed with a photochemical box model, using a contemporary chemical mechanism and procedure, and a range of initial input pollutant concentrations thought to encompass those characteristic of the Southeastern Virginia region before a photochemical oxidant episode. The model predictions are consistent with the expectation of high summer afternoon ozone levels when initial nonmethane hydrocarbon (NMHC) levels are in the range 0.30-0.40 ppmC and NOx levels are in the range 0.02-0.05 ppm. Calculations made with a Lagrangian model, for one of the previously calculated cases, which had produced intermediate afternoon ozone levels, suggest that urban source additions of NMHC and NOx exacerbate the photochemical oxidant condition.
The effects of the relaxation to photochemical equilibrium are investigated for the electrons and NO(+) ions in the upper D-region and for the electrons and several species of positive and negative ions present in the lower D-region. In the upper D-region the photochemical model includes electrons, nitric oxide, and NO(+). A self-consisting model of the equilibrium concentrations is developed for the lower D-region, which includes electrons, nitric oxide, O2(-), heavy negative and positive ions, and the oxygen species O, O3, and O2(1 delta g). At altitudes of 75 and 80 km the time dependence of the oxygen species has a significant effect on the equilibration of the electron and O2(-) concentrations. The relaxation to photochemical equilibrium proceeds by five e-folding time scales in the lower D-region, where the time required for final equilibration due to recombination is very long.
Ozone variations expected in the uppermost stratosphere and mesosphere during a warming are estimated by a photochemical calculation based on temperatures measured at 40-80 km during the February 1966 warming at Fort Churchill, Canada. A simple linearized model of radiative-photochemical relaxation is then used to describe the coupled response of ozone and temperature to a specified heating due to dynamical forcing. By comparing the joint radiative-photochemical relaxation time with that for infrared emission alone shows that the ozone perturbation induced by the warming reduces the recovery time to approximately 65% of the pure radiative value near 70 km and to 90% near 50 km. Thus, the ozone changes induced by the dynamically forced temperature increases have a significant impact on the evolution of the warming.
It is found that the effect of energy addition due to photochemical processes in the cometary coma on the heating and accelerating of the expanding neutral gas is limited by the kinematic property of the energy transfer from the energetic fragments to the bulk flow. The effective scale length of the photochemical zone for an H2O comet is estimated to be only 10% of the dimension of the collision region due to the large mass ratio of H atom and H2O molecule. When this physical property is taken into consideration, the H2O gas is found to be expanding at a highly supersonic speed. In addition, it is shown that the addition of a mixture of CO and/or CO2 molecules in a medium-bright comet with total production rate of 10 to the 29th molecules/s would not change this conclusion since the photodissiation length scales of these molecules are a factor of 10-30 larger than that of the H2O molecules. Thus, most of the CO and CO2 molecules will be dissociated outside of the collision zone without depositing the excess kinetic energy to the neutral atmosphere. However, if the gas production rate is controlled by CO or CO2, the dimension of the collision zone of a CO comet at 1 AU will be increased by a factor of seven. The photochemical heating due to CO dissociation would thus be more effective, causing the atmospheric flow to be weakly supersonic. It is concluded that the neutral gas outflows from H2O comets and CO comets could be substantially different.
The role of photochemistry in the budget of tropospheric ozone is studied. Measurements of O3, NO, CO, H2O vapor, and temperature obtained during the fall of 1983 during the GTE/CITE project over the eastern and central North Pacific Ocean are analyzed. The effect of altitude on the measurements is discussed. The analysis reveals a correlation between ozone and NO levels; both increase in concentration and variability with altitude. It is observed that an additional source of secondary importance associated wih CO-rich air parcels exists. A photochemical model is utilized to calculate the net rate of ozone production by photochemical reactions. A net photochemical source of ozone in the free troposphere and a net sink in the boundary layer are detected. The relation between the ozone source in the free troposphere and NO is examined. It is estimated that photochemistry provides a net ozone source to the free troposphere overlying the eastern and central North Pacific Ocean of about 5 x 10 to the 10th molecules/sq cm sec and a net sink of ozone to the boundary layer overlying this region of about 3 x 10 to the 10th molecules/sq cm sec.