Actinic flux and photolysis frequency comparison computations using the model PHOTOGT

The accurate radiative transfer model GOMETRAN, initially designed to yield radiances at TOA in the wavelength range 240–790 nm, has been extended to allow for the computation of actinic fluxes down to 175 nm and for the calculation of photolysis frequencies in the atmosphere. The capability of the extended model PHOTOGT (PHOTOGOMETRAN) is demonstrated in a number of successful comparison studies both with recent experiments (ground-based, balloonborne, airborne) and model calculations of radiances, actinic fluxes and photolysis frequencies in the stratosphere and troposphere. In an atmospheric case study, the impact of new quantum yield data for the O₃ » O₂+O(¹ d) photodissociation channel on the photolytic production of O(¹ d) atoms in the lower atmosphere has been quantified.     

Gas phase reactions of alkyl nitrates with hydroxyl radicals under tropospheric conditions in comparison with photolysis

Rate constants for the reaction of OH radicals with some branched alkyl nitrates have been measured applying a competitive technique. Methyl nitrite photolysis in synthetic air was used as OH radical source at 295±2 K and 1000 mbar total pressure. Using a rate constant of 2.53×10^-12 cm³ s^-1 for the reaction of OH radicals with n-butane as reference, the following rate constants were obtained (units: 10^-12 cm³ s^-1): isopropyl nitrate, 0.59±0.22; isobutyl nitrate, 1.63±0.20; 3-methyl-2-butyl nitrate, 1.95±0.15; 2-methyl-1-butyl nitrate, 2.50±0.15; 3-methyl-1-butyl nitrate, 2.55±0.35. These values have been combined with the literature data to recalculate the substituent factors F(X) for the different nitrate groups which can be used to predict OH rate constants for organic nitrates for which experimental data are not available.Preliminary measurements of the photolysis frequency of isopropyl nitrate have shown that for this nitrate as a model substance, OH reactions and direct photolysis are of equal importance under tropospheric conditions.     

太阳紫外光谱及NO2光解系数的观测

本文讨论了利用自动太阳光谱仪测量地面的紫外辐射光谱,并进一步计算了NO_2的光分解系数.光谱测量范围为310—375nm.测量结果表明,在北京地区秋季NO_2的光解系数变化在(1—4)×10~(-3)S~(-1),有明显的日变化.     

A photoelectric detector for the measurement of photolysis frequencies of ozone and other atmospheric molecules

Photoelectric detectors for the measurement of photolysis frequencies of different trace gases in the atmosphere are described. They exhibit uniform response characteristics over one hemisphere (2 sr) and wavelength characteristics closely matched to those of the photolysis frequencies J _O1D, J _NO2, and J _NO3, respectively. Absolute calibration of the J _O1D detector was performed by chemical actinometry with an accuracy of ±16 percent. Simultaneous measurements of J _NO2 and J _O1D are presented.     

Measurement of the photodissociation coefficient of NO2 in the atmosphere: II,stratospheric measurements

The photodissociation coefficient of NO₂, J _{NO 2}, has been measured from a balloon platform in the stratosphere. Results from two balloon flights are reported. High Sun values of J _{NO 2} measured were 10.5±0.3 and 10.3±0.3×10^-3 s^-1 at 24 and 32 km respectively. The decrease in J _{NO 2} at sunset was monitored in both flights. The measurements are found to be in good agreement with calculations of J _{NO 2} using a simplified isotropic multiple scattering computer routine.     

Calculations of the temperature dependence of the NO2 photodissociation coefficient in the atmosphere

The photodissociation coefficient, J _NO2 of NO₂ in the atmosphere was calculated at 235 and 298 K using the measured temperature dependences of the absorption cross-sections and quantum yields. These calculations gave a ratio J _NO2(298 K)/J _NO2(235 K)=1.155±0.010 which is only weakly dependent on altitude, surface albedo and solar zenith angle.     

Autoxidation of N(III), S(IV), and other Species in Frozen Solution – A Possible Pathway for Enhanced Chemical Transformation in Freezing Systems

The chemistry of glycolaldehyde (hydroxyacetaldehyde) relevant to the troposphere has been investigated using UV absorption spectrometry and FTIR absorption spectrometry in an environmental chamber. Quantitative UV absorption spectra have been obtained for the first time. The UV spectrum peaks at 277 nm with a maximum cross section of (5.5± 0.7)×10^–20 cm² molecule^–1. Studies of the ultraviolet photolysis of glycolaldehyde ( = 285 ± 25 nm) indicated that the overall quantum yield is > 0.5 in one bar of air, with the major products being CH₂OH and HCO radicals. Rate coefficients for the reactions of Cl atoms and OH radicals with glycolaldehyde have been determined to be (7.6± 1.5)×10^–11 and (1.1± 0.3)×10^–11 cm³ molecule^–1 s^–1, respectively, in good agreement with the only previous study. The lifetime of glycolaldehyde in the atmosphere is about 1.0 day for reaction with OH, and > 2.5 days for photolysis, although both wet and dry deposition should also be considered in future modeling studies.     

Parameterization of Ozone Photolysis Frequency in the Lower Troposphere Using Data from Photodiode Array Detector Spectrometers

Spectroradiometers using photodiode array detectors (PDAs) are increasingly applied for airborne and ground-based atmospheric measurements of spectral actinic flux densities due to their high time resolution (less than one second). However they have limited sensitivity of ultraviolet (UV) radiation for wavelengths less than about 305 nm. This results in uncertainties of ozone photolysis frequencies derived from spectral actinic flux density measurements using PDA spectrometers. To overcome this limitation a parameterization method is introduced which extrapolates the data towards the wavelength range of limited sensitivity of the PDA spectrometers (less than about 305 nm). The parameterization is based on radiative transfer simulations and is valid for measurements in the lower troposphere. The components of the suggested parameterization are the lower threshold wavelength of the PDA spectrometer, the slant ozone column (ratio of the total ozone column and the cosine of the solar zenith angle), and the ambient temperature. Tests of the parameterization with simulated actinic flux density spectra have revealed an uncertainty of the derived ozone photolysis frequency of ±5%. Field comparisons of the parameterization results with independent measurements of the ozone photolysis frequency were within ±10% for solar zenith angles less than 70^∘. Finally the parameterization was applied to airborne measurements to emphasize the advantage of high time resolution of PDA spectrometers to study ozone photolysis frequency fields in inhomogeneous cloud condtitions.     

Combined experimental and theoretical studies on methane photolysis at 121.6 and 248 nm—implications on a program of laboratory simulations of Titan’s atmosphere

Methane is, together with N₂, the main precursor of Titan’s atmospheric chemistry. In our laboratory, we are currently developing a program of laboratory simulations of Titan’s atmosphere, where methane is intended to be dissociated by multiphotonic photolysis at 248 nm. A preliminary study has shown that multiphotonic absorption of methane at 248 nm is efficient and leads to the production of hydrocarbons such as C₂H₂ (Romanzin et al., 2008). Yet, at this wavelength, little is known about the branching ratios of the hydrocarbon radicals (CH₃, CH₂ and CH) and their following photochemistry. This paper thus aims at investigating methane photochemistry at 248 nm by comparing the chemical evolution observed after irradiation of CH₄ at 248 and at 121.6 nm (Ly-α). It is indeed important to see if the chemistry is driven the same way at both wavelengths in particular because, on Titan, methane photolysis mainly involves Ly-α photons. An approach combining experiments and theoretical analysis by means of a specifically adapted 0-D model has thus been developed and is presented in this paper. The results obtained clearly indicate that the chemistry is different depending on the wavelength. They also suggest that at 248 nm, methane dissociation is in competition with ionisation, which could occur through a three-photon absorption process. As a consequence, 248 nm photolysis appears to be unsuitable to study methane neutral photochemistry alone. The implications of this result on our laboratory simulation program and new experimental developments are discussed. Additional information on methane photochemistry at 121.6 nm are also obtained.