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1.
G. Kockarts 《Planetary and Space Science》1976,24(6):589-604
The penetration in the terrestrial atmosphere of solar radiation corresponding to the spectral range of the Schumann-Runge bands of molecular oxygen is analyzed between 1750 and 2050 Å. The variation of the absorption cross section with temperature is taken into account and it is shown that average O2 absorption cross sections cannot lead to correct photodissociation coefficients. Reduction factors are defined in order to simplify the computation of the molecular oxygen photodissociation and to permit a simple determination of the photodissociation coefficients of any minor constituent with smoothly varying absorption cross section. Examples are given for O2, H2O, CO2, N2O, HNO3 and H2O2. Numerical approximations are developed for three types of spectral subdivisions: Schumann-Runge band intervals, 500 cm?1 and 10 Å intervals. The approximations are valid from the lower thermosphere down to the stratosphere and they can be applied for a wide range of atmospheric models and solar zenith distances. 相似文献
2.
Marcel Nicolet 《Planetary and Space Science》1981,29(9):951-974
A critical analysis has been made of solar irradiance in the spectral region covering wavelengths from 100 nm upwards; the absorption characteristics of molecules of oxygen and ozone have been taken into account with a view to the direct application of the results to atmospheric photochemistry. The absorption of radiation by these molecules results in the photodissociation of both of them in the homosphere, and it also makes possible the penetration of solar radiation from the thermosphere, through the mesosphere and the stratosphere, down to the troposphere.Special attention has been given to each of the following spectral regions: Lyman-alpha radiation at 121.6 nm, the O2 Schumann-Runge continuum at wavelengths less than 175 nm, the O2 Schumann-Runge band system from 200 to 175 nm, and the O2 Herzberg continuum at 242.4 nm. For absorption by ozone, the solar spectrum has been analysed in the following regions: the Hartley band at wavelengths less than 310 nm, the Huggins bands at wavelengths above 310 nm and the visible Chappuis bands. Finally, for the photodissociation of O3, particular attention has been given to the transition region (300–320 nm) in which there is a change-over from the production of the excited atom O(1D) to that of the atom in its ground state O(3p). 相似文献
3.
In the stratosphere of Venus, the available luminous flux which locally produces the photodissociation processes at a given altitude may be divided into three parts: direct incoming downward flux, flux resulting from the reflection on the surface of the clouds, and flux due to molecular scattering. A relatively simple computation method has been used to evaluate the relative importance of these three parts at altitudes between 65 and 100 km. It is shown that the extra contribution of the reflected and scattered fluxes to photodissociation processes cannot be neglected in the uv and visible regions. In the case of SO2, for instance, which presents an absorption band in the uv, the photodissociation coefficient is increased 30% due to these effects. Calculations of the photodissociation coefficients of CO2, O3, H2S, and SO2 are presented. As a result of the increase by 60% in the ozone photolysis rate, the calculated O2 infrared band at 1.27 μm is larger by a factor of nearly 2 than is expected from a calculation without taking albedo or scattering into account. 相似文献
4.
We have re-examined the prospects of HOCl as an inert reservoir for atmospheric chlorine in the light of new theoretical calculations and available experimental measurements of its photodissociation cross-sections. The theoretical calculations and most recent laboratory studies imply that the broad maxima 3200 Å observed in two other experimental spectra may not belong to HOCl. On the basis of this implication HOCl could have a long lifetime against photodissociation in the stratosphere, and could, thereby, become a reservoir for atmospheric chlorine comparable to ClONO2 or even HCl. In this capacity HOCl could reduce the predicted ozone destruction due to any given level of total chlorine burden. We have also examined the difficulties in laboratory measurements of the HOCl absorption spectrum with particular emphasis on identifying the impurities which may be present in the experimental system. It appears that specialized new experiments are needed to clearly establish the nature and strength of HOCl absorption in the neighbourhood of 3200 Å. Some refinements in the theoretical calculations also seem desirable. In view of the difficulties involved in the laboratory determination of HOCl photodissociation cross-sections, it is suggested that a search for possible stratospheric HOCl by atmospheric spectroscopists would be worthwhile. 相似文献
5.
《Physics and Chemistry of the Earth, Part C: Solar, Terrestrial & Planetary Science》2001,26(7):539-543
Absorption of solar radiation of wavelengths between 175 to 205 nm plays a fundamental role in the photochemistry of the middle atmosphere. Nitric oxide photodissociates in the δ(0-0) and δ(1-0) bands near 191 and 183 nm, respectively, initiating the primary mechanisms for NOx removal in the middle atmosphere. The spectrally rich Schumann-Runge (S-R) bands of O2 are the main source of atmospheric opacity at these wavelengths. A re-evaluation of O2 absorption has been made based on recent advances in understanding of S-R line shapes, leading to differences with conventional approaches assuming Voigt line profiles in line-by-line calculations of the O2 cross section. The new results are used to examine the impact of O2 transmission on the photodissociation of NO in the δ(0,0) and δ(1,0) bands. 相似文献
6.
A detailed study is made of the atmospheric attenuation of the dissociation of nitric oxide in the mesosphere and stratosphere. The nitric oxide dissociation profile depends on the absorption of the discrete Schumann-Runge bands of O2. The major contribution to the dissociation rate of NO is the predissociation of the δ(0-0) and δ(1-0) bands which can reach the stratosphere. 相似文献
7.
Guido Visconti 《Icarus》1981,45(3):638-652
We present computations of the photodissociation coefficients for NH3, N2H4, PH3, and H2S in the Jupiter atmosphere. The calculations take into account multiple scattering and absorption using the radiative-transfer method known as δ-Eddington approximation. The atmospheric models include two cloud layers of variable thickness and haze layers above the upper cloud and between the clouds. One of the results of the radiative computations deal with the reflectivity of the Jovian atmosphere as a function of wavelength. A comparison with available data on the albedo of the planet gives some important indications about mixing ratios and distributions of gases and aerosols. The results for the photolysis rates are compared with similar rates obtained by considering either the direct flux or the flux determined by the molecular gas absorption alone. The latter is usually the approximation used in aeronomic models. The results of this comparison show that a considerable difference exists with direct flux photodissociation but significant differences with molecular absorption flux exist only in atmospheric regions where photodissociation is relatively small. 相似文献
8.
《Physics and Chemistry of the Earth, Part C: Solar, Terrestrial & Planetary Science》2001,26(7):527-532
The nitrogen isotope ratio of middle atmosphere nitrogen oxide is predicted as a function of altitude. Nitrogen oxides originate photochemically either from stratospheric nitrous oxide reacting with O(1D) or in the mesosphere and thermosphere from direct dissociation of N2 and ionization-initiated reactions involving O2 and N2. During its formation process, N2O acquires a nitrogen isotopic composition of N isotopes different than N2. Photodissociation within the stratosphere also modifies the proportion of isotopes. Reaction of stratospheric NO with O3 produces NO2, which when photodissociated yields NO depleted in 15N relative to NO2 in laboratory air. The value of δ15NO in the stratosphere is −100‰. In the altitude region between 50 and 65 km, NO is transformed into NO2 and then returned to NO by reaction of NO2 with O and by NO2 photodissociation. These reactions determine the isotopic makeup of NO. Above 65 km, nitric oxide is produced by local ionization processes and gas phase photochemical reactions involving N2 and excited O2. These processes determine the isotopic composition of NO in the upper mesosphere and thermosphere. Here δ15NO is 0‰. Air transported into the mesosphere above 65 km will reflect the NO isotopic values of the region below, while mesospheric NO transported below 65 km will not be distinguishable from NO originating in the stratosphere. 相似文献
9.
Marcel Nicolet 《Planetary and Space Science》1985,33(1):69-80
An analysis is made of the photodissociation and photoionization processes in the mesosphere due to the solar H Lyman-alpha line. The irradiance of the line and its variation with solar activity are considered in the determination of the photodissociation of CH4, CO2, H2O and O2, and of the photoionization of NO. Lyman-alpha contributes directly to these processes in the mesosphere after its absorption, which depends on wavelength and temperature, by molecular oxygen. The H Lyman-alpha radiation considered for mesospheric processes is characterized by a profile of an emission line with a central reversal, and wings extending to about ± 1.75 A where the intensity reaches about 1% of that of the peak. Simple formulae are deduced for the photodissociation optical depths and frequencies and these take into account the various solar activity conditions and the different spectral characteristics of each molecule. 相似文献
10.
Absorption cross sections have been calculated for molecular oxygen as a function of wavelength over the domain for temperatures between 190 and 400°K. The spectrum has been divided into 19 wavelength intervals and opacity distribution functions have been constructed for each interval. Atmospheric photodissociation rates of O2, O3, CO2, H2O, H2O2, NO2 and HNO3 are presented. 相似文献
11.
Laboratory measurements of reaction rate constants of magnesium ions and magnesium containing ions with O3, NO, HNO3, and H2O2 have been carried out in a flowing afterglow experiment. Mg+ ions react with O3 to produce MgO+ ions, which in turn react with O3 to produce Mg+ ions. Mg+ ions react with HNO3 and H2O2 to produce MgOH+ ions. MgOH+ ions react rapidly with HNO3 to produce NO+2 ions and Mg(HO)2. One can therefore conclude that Mg+, MgO+, or MgOH+ ions could not have significant concentrations in the stratosphere if gas phase magnesium compounds were present. The failure to observe these ions therefore cannot be used as evidence that the stratospheric magnesium, resulting from meteor ablation at higher altitudes, is in condensed phases. This is in contrast to the case for sodium where the ion chemistry is such that the failure to observe hydrated Na+ ions proves that gas phase sodium compounds are not present in the stratosphere. 相似文献
12.
《Planetary and Space Science》1987,35(6):769-784
Through a line by line calculation, the contributions of the Schumann-Runge bands of the ordinary and isotopic oxygen to the photodissociation of these molecules at different altitudes have been calculated. The photodissociation rates are expressed analytically. Contribution of the satellite lines has been taken into account. Due to the broadening of the SR lines, this contribution is insignificant. Similarly, it is shown that the first and higher vibrational states of the initial molecular states contribute insignificantly to the dissociation rates. It is also shown that the main contribution to the odd oxygen production in the important ozone producing altitudes is from the low vibrational and high rotational quantum numbers. The effect of the temperature on dissociation rates has similarly been studied.Due to its selective absorption, the isotopic oxygen 16O18O produces at 70 km 10 times as much odd oxygen as would be produced if the isotope did not have selective absorption. At this altitude 6% of the odd oxygen produced is due to this isotope. Also, 1.45% of the odd oxygen produced per second in an atmospheric column is due to 16O18O. However, the excess odd oxygen produced is not enough to explain the excess amount of ozone observed in the atmosphere which cannot be accounted for in the photochemical models.The calculated dissociation rates for the isotope are in moderate agreement with similar rates obtained by Blake et al. (1984, J. geophys. Res.89, 7277), but are by an order of magnitude smaller than similar rates given by Cicerone and McCrumb (1980, Geophys. Res. Lett.7, 251). 相似文献
13.
The photochemistry of the stratosphere of Venus was modeled using an updated and expanded chemical scheme, combined with the results of recent observations and laboratory studies. We examined three models, with H2 mixing ratio equal to 2 × 10?5, 5 × 10?7, and 1 × 10?13, respectively. All models satisfactorily account for the observations of CO, O2, O2(1Δ), 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 primarily consumed by CO2 recombination and oxidation of SO2 to H2SO4. 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. In the high-H2 model (model A) the OO bond is broken mainly by S + O2 and SO + HO2. In the low-H2 models additional reactions for breaking the OO bond must be invoked: NO + HO2 in model B and ClCO + O2 in model C. It is shown that lightning in the lower atmosphere could provide as much as 30 ppb of NOx in the stratosphere. Our modeling reveals a number of intriguing 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. The current atmosphere, as described by our preferred model, is characterized by an extreme deficiency of hydrogen species, having probably lost the equivalent of 102–103 times the present hydrogen content. 相似文献
14.
The near U.V. absorption cross-sections of CS2 and SO2 have been measured, at a 0.2 nm resolution, at different temperatures ranging from 200 to 300 K. These data will be used to interpret absorption measurements of the stratosphere of Venus. 相似文献
15.
Shashi K. Gupta 《Astrophysics and Space Science》1970,9(1):97-108
Rates of production of O(1
D) atoms in the upper atmosphere by photodissociation of O2, dissociative recombination of O2
+, NO+ and electron impact excitation of O(3
P) have been calculated for low, medium and high levels of solar activity. Variations with solar activity, of neutral and ionic composition, electron and neutral temperatures of the upper atmosphere and solar extreme ultraviolet fluxes incident on it have been taken into consideration.Emission rates ofOi red line (6300Å) have been computed taking into account the deactivation both by molecular oxygen and nitrogen. It has been shown that the integrated intensity from low to high activity period varies by approximately an order of magnitude in agreement with the results of experimental observations. 相似文献
16.
Marcel Nicolet 《Planetary and Space Science》1984,32(7):871-880
The photodissociation of water vapour in the mesosphere depends on the absorption of solar radiation in the region (175–200 nm) of the O2 Schumann-Runge band system and also at H-Lyman alpha. The photodissociation products are OH + H, OH + H, O + 2H and H2 + O at Lyman alpha; the percentages for these four channels are 70, 8, 12 and 10%, respectively, but OH + H is the only channel between 175 and 200 nm. Such proportions lead to a production of H atoms corresponding to practically the total photodissociation of H2O, while the production of H2 molecules is only 10% of the H2O photodissociation by Lyman alpha.The photodissociation frequency (s?1) at Lyman alpha can be expressed by a simple formula where F10.7 cm is the solar radioflux at 10.7 cm and N the total number of O2 molecules (cm?2), and when the following conventional value is accepted for the Lyman alpha solar irradiance at the top of the Earth's atmosphere () qLyα,∞ = 3 × 1011 photons cm?2 s1?.The photodissociation frequency for the Schumann-Runge band region is also given for mesospheric conditions by a simple formula where JSRB,∞(H2O) = 1.2 × 10?6 and 1.4 × 10?6 s?1 for quiet and active sun conditions, respectively.The precision of both formulae is good, with an uncertainty less than 10%, but their accuracy depends on the accuracy of observational and experimental parameters such as the absolute solar irradiances, the variable transmittance of O2 and the H2O effective absorption cross sections. The various uncertainties are discussed. As an example, the absolute values deduced from the above formulae could be decreased by about 25-20% if the possible minimum values of the solar irradiances were used. 相似文献
17.
A variety of models are explored to study the photochemistry of CO2 in the Martian atmosphere with emphasis on reactions involving compounds of carbon, hydrogen, and oxygen. Acceptable models are constrained to account for measured concentrations of CO and O above 90 km, with an additional requirement that they should be in accord with observations of CO, O2, and O3 in the lower atmosphere. Dynamical mixing must be exceedingly rapid at altitudes above 90 km, with effective eddy diffusion coefficients in excess of 107 cm2 sec?1. If recombination of CO2 is to occur mainly by gas phase chemistry, catalyzed by trace quantities of H, OH, and HO2, mixing must be rapid over the altitude interval 30 to 40 km. The value implied for the diffusion coefficient in this region is a function of assumptions made regarding the rates for reaction of OH with HO2 to form H2O and of the rate for reaction of HO2 with itself to form H2O2. If rates for these reactions are taken to have values similar to rates used in current models for the Earth's stratosphere, the eddy diffusion coefficient at 40 km on Mars should be about 5 × 107 cm2 sec?1, consistent with Zurek's (1976) estimate for this parameter inferred from tidal theory. Surface chemistry could have an influence on the abundances of atmospheric CO and O2, but a major effect would imply sluggish mixing at all altitudes below 50 km and in addition would carry implications for the magnitude of the rates for reaction of OH with HO2 and HO2 with itself. 相似文献
18.
John Lee Grenfell Joachim W. Stock Stefanie Gebauer 《Planetary and Space Science》2010,58(10):1252-1257
We propose a mechanism for the oxidation of gaseous CO into CO2 occurring on the surface mineral hematite (Fe2O3(s)) in hot, CO2-rich planetary atmospheres, such as Venus. This mechanism is likely to constitute an important source of tropospheric CO2 on Venus and could at least partly address the CO2 stability problem in Venus’ stratosphere, since our results suggest that atmospheric CO2 is produced from CO oxidation via surface hematite at a rate of 0.4 petagrammes (Pg) CO2 per (Earth) year on Venus which is about 45% of the mass loss of CO2 via photolysis in the Venusian stratosphere. We also investigated CO oxidation via the hematite mechanism for a range of planetary scenarios and found that modern Earth and Mars are probably too cold for the mechanism to be important because the rate-limiting step, involving CO(g) reacting onto the hematite surface, proceeds much slower at lower temperatures. The mechanism may feature on extrasolar planets such as Gliese 581c or CoRoT-7b assuming they can maintain solid surface hematite which, e.g. starts to melt above about 1200 K. The mechanism may also be important for hot Hadean-type environments and for the emerging class of hot Super-Earths with planetary surface temperatures between about 600 and 900 K. 相似文献
19.
Measurements of the [OI] 6300 Å twilight airglow during 1973 near Boulder, Colorado, show a strong dependence upon geomagnetic activity for the morning enhancement at solar depression angles where production of O1D) is due primarily to photodissociation of O2 and local photoelectron excitation. Analysis indicates that photodissociation is the dominant source; hence we infer a well defined magnetic dependence for the O2/N2 concentration ratio in the thermosphere. A seasonal variation in the twilight enhancement intensity is barely evident, in contrast with earlier observations made near solar maximum; the smaller variation is associated with a corresponding reduction in the seasonal variation of geomagnetic activity. 相似文献
20.
The results of calculations of the multiply-scattered solar-induced radiation field in the troposphere and stratosphere are presented for direct application to photochemical models. The enhancement factors due to multiple scattering are given for the heights, solar zenith angles and wavelengths (between 800 and 300 nm) which play a role in the photodissociation of various atmospheric constituents. 相似文献