Calculation Of Photolysis Rates Research Articles

Heterogeneous Processes in the Atmosphere of Mars and Impact on H2O2 and O3 Abundances

AbstractCurrent models underestimate the highest observed ozone (O3) column densities on Mars. These estimates could be improved by including the uptake of odd hydrogen species (HOx) on water ice clouds, but the reported uptake coefficient of HO2 is likely overestimated for atmospheric conditions. This leaves a fundamental problem in Mars' atmospheric chemistry unsolved. Here, using the GEM‐Mars general circulation model, we explore a range of processes involving multiple phases (gas, adsorbed and solid) that may contribute to an alternative solution. First, we focus on hydrogen peroxide (H2O2) and discuss its physical states on Mars and its chemical impact. We also conjecture its photolytic destruction in ices with model simulations and Compact Reconnaissance Imaging Spectrometer for Mars observations. Then, we include in the model all relevant (for Mars) heterogeneous reactions, both on dust and water ice, recommended by the International Union of Pure and Applied Chemistry for terrestrial atmospheric studies. We find that only the uptake of HO2 and H2O2 on dust are efficient on Mars. Finally, we find that attenuation of sunlight by water ice clouds in the calculation of photolysis rates leads to increased O3 and H2O2 abundances below the ice clouds. The combination of the proposed processes leads to O3 increases without the need for strong uptake of HO2 on ice, but it remains difficult to find a good agreement with O3 and H2O2 observations on the global scale. We provide specific recommendations for future work in observations, laboratory experiments and modeling to advance our understanding of fundamental chemistry on Mars.

Development of aerosol optical properties for improving the MESSy photolysis module in the GEM-MACH v2.4 air quality model and application for calculating photolysis rates in a biomass burning plume

Abstract. The photolysis module in Environment and Climate Change Canada's online chemical transport model GEM-MACH (GEM: Global Environmental Multi-scale – MACH: Modelling Air quality and Chemistry) was improved to make use of the online size and composition-resolved representation of atmospheric aerosols and relative humidity in GEM-MACH, to account for aerosol attenuation of radiation in the photolysis calculation. We coupled both the GEM-MACH aerosol module and the MESSy-JVAL (Modular Earth Submodel System) photolysis module, through the use of the online aerosol modeled data and a new Mie lookup table for the model-generated extinction efficiency, absorption and scattering cross sections of each aerosol type. The new algorithm applies a lensing correction factor to the black carbon absorption efficiency (core-shell parameterization) and calculates the scattering and absorption optical depth and asymmetry factor of black carbon, sea salt, dust and other internally mixed components. We carried out a series of simulations with the improved version of MESSy-JVAL and wildfire emission inputs from the Canadian Forest Fire Emissions Prediction System (CFFEPS) for 2 months, compared the model aerosol optical depth (AOD) output to the previous version of MESSy-JVAL, satellite data, ground-based measurements and reanalysis products, and evaluated the effects of AOD calculations and the interactive aerosol feedback on the performance of the GEM-MACH model. The comparison of the improved version of MESSy-JVAL with the previous version showed significant improvements in the model performance with the implementation of the new photolysis module and with adopting the online interactive aerosol concentrations in GEM-MACH. Incorporating these changes to the model resulted in an increase in the correlation coefficient from 0.17 to 0.37 between the GEM-MACH model AOD 1-month hourly output and AERONET (Aerosol Robotic Network) measurements across all the North American sites. Comparisons of the updated model AOD with AERONET measurements for selected Canadian urban and industrial sites, specifically, showed better correlation coefficients for urban AERONET sites and for stations located further south in the domain for both simulation periods (June and January 2018). The predicted monthly averaged AOD using the improved photolysis module followed the spatial patterns of MERRA-2 reanalysis (Modern-Era Retrospective analysis for Research and Applications – version 2), with an overall underprediction of AOD over the common domain for both seasons. Our study also suggests that the domain-wide impacts of direct and indirect effect aerosol feedbacks on the photolysis rates from meteorological changes are considerably greater (3 to 4 times) than the direct aerosol optical effect on the photolysis rate calculations.

Quantifying errors in surface ozone predictions associated with clouds over the CONUS: a WRF-Chem modeling study using satellite cloud retrievals

Abstract. Clouds play a key role in radiation and hence O3 photochemistry by modulating photolysis rates and light-dependent emissions of biogenic volatile organic compounds (BVOCs). It is not well known, however, how much error in O3 predictions can be directly attributed to error in cloud predictions. This study applies the Weather Research and Forecasting with Chemistry (WRF-Chem) model at 12 km horizontal resolution with the Morrison microphysics and Grell 3-D cumulus parameterization to quantify uncertainties in summertime surface O3 predictions associated with cloudiness over the contiguous United States (CONUS). All model simulations are driven by reanalysis of atmospheric data and reinitialized every 2 days. In sensitivity simulations, cloud fields used for photochemistry are corrected based on satellite cloud retrievals. The results show that WRF-Chem predicts about 55 % of clouds in the right locations and generally underpredicts cloud optical depths. These errors in cloud predictions can lead to up to 60 ppb of overestimation in hourly surface O3 concentrations on some days. The average difference in summertime surface O3 concentrations derived from the modeled clouds and satellite clouds ranges from 1 to 5 ppb for maximum daily 8 h average O3 (MDA8 O3) over the CONUS. This represents up to ∼ 40 % of the total MDA8 O3 bias under cloudy conditions in the tested model version. Surface O3 concentrations are sensitive to cloud errors mainly through the calculation of photolysis rates (for ∼ 80 %), and to a lesser extent to light-dependent BVOC emissions. The sensitivity of surface O3 concentrations to satellite-based cloud corrections is about 2 times larger in VOC-limited than NOx-limited regimes. Our results suggest that the benefits of accurate predictions of cloudiness would be significant in VOC-limited regions, which are typical of urban areas.

The very short-lived ozone depleting substance CHBr<sub>3</sub> (bromoform): revised UV absorption spectrum, atmospheric lifetime and ozone depletion potential

Abstract. CHBr3 (bromoform) is a short-lived atmospheric trace compound that is primarily of natural origin and is a source of reactive bromine in both the troposphere and stratosphere. Estimating the overall atmospheric impact of CHBr3 and its transport to the stratosphere requires a thorough understanding of its atmospheric loss processes, which are primarily UV photolysis and reaction with the OH radical. In this study, UV absorption cross sections, σ (λ ,T), for CHBr3 were measured at wavelengths between 300 and 345 nm at temperatures between 260 and 330 K using cavity ring-down spectroscopy. The present results are compared with currently recommended values for use in atmospheric models, and the discrepancies are discussed. A parameterization of the CHBr3 UV spectrum for use in atmospheric models is developed, and illustrative photolysis rate calculations are presented to highlight the impact of the revised σ (λ, T) values on its calculated local lifetimes. For example, the photolysis rate in the tropical region obtained with the present spectral data is 10–15% lower (longer lifetime) than obtained using currently recommended cross section values. Seasonally dependent ozone depletion potentials (ODPs) for CHBr3 emitted in the Indian sub-continent were calculated to be 0.10, 0.34, 0.72, and 0.23 (winter, spring, summer, fall) using the semi-empirical relationship of Brioude et al. (2010).

Incremental testing of the Community Multiscale Air Quality (CMAQ) modeling system version 4.7

Abstract. This paper describes the scientific and structural updates to the latest release of the Community Multiscale Air Quality (CMAQ) modeling system version 4.7 (v4.7) and points the reader to additional resources for further details. The model updates were evaluated relative to observations and results from previous model versions in a series of simulations conducted to incrementally assess the effect of each change. The focus of this paper is on five major scientific upgrades: (a) updates to the heterogeneous N2O5 parameterization, (b) improvement in the treatment of secondary organic aerosol (SOA), (c) inclusion of dynamic mass transfer for coarse-mode aerosol, (d) revisions to the cloud model, and (e) new options for the calculation of photolysis rates. Incremental test simulations over the eastern United States during January and August 2006 are evaluated to assess the model response to each scientific improvement, providing explanations of differences in results between v4.7 and previously released CMAQ model versions. Particulate sulfate predictions are improved across all monitoring networks during both seasons due to cloud module updates. Numerous updates to the SOA module improve the simulation of seasonal variability and decrease the bias in organic carbon predictions at urban sites in the winter. Bias in the total mass of fine particulate matter (PM2.5) is dominated by overpredictions of unspeciated PM2.5 (PMother) in the winter and by underpredictions of carbon in the summer. The CMAQv4.7 model results show slightly worse performance for ozone predictions. However, changes to the meteorological inputs are found to have a much greater impact on ozone predictions compared to changes to the CMAQ modules described here. Model updates had little effect on existing biases in wet deposition predictions.

Temporal variations of atmospheric carbonyls in urban ambient air and street canyons of a Mountainous city in Southwest China

Carbonyl compounds in urban ambient air and street canyons were measured from December 2008 to August 2009 in a mountainous city in southwest China (Guiyang). The formaldehyde yield from the photo-oxidation of isoprene emitted by vegetation was estimated to be in the range of 0.63–3.62 μg m −3 from May to August, which accounted for 28.8–33.4% of ambient formaldehyde. Based on the calculation of photolysis rates and rates of reaction with the OH radical, it was found that photolysis was the predominant sink for formaldehyde and acetone in both summer and winter. For acetaldehyde, photo-oxidation by OH radicals and photolysis were the major sinks in summer while photo-oxidation by OH radicals was the dominant sink in winter. Wet precipitation was found to be an important removal process for the atmospheric carbonyls. In the urban ambient air, the average concentrations of formaldehyde, acetaldehyde, acetone and all carbonyls were 4.8 ± 2.1, 5.7 ± 3.3, 5.1 ± 2.5, and 25.1 ± 9.2 μg m −3 ( n = 139), respectively. The average concentrations of these species in street canyons were 18.8 ± 6.5, 9.4 ± 3.2, 10.9 ± 2.1, and 64.1 ± 16.3 μg m −3 ( n = 62), respectively. The significantly higher carbonyl levels on weekdays (compared to weekends) highlight the contribution of vehicle emissions to carbonyls in the street canyons.

Review of quantitative spectroscopy of polyynes

We propose a review of quantitative spectroscopy of polyynes in the infrared and ultraviolet domain focusing on essential spectroscopic parameters for the interpretation of observed spectra in the infrared and ultraviolet domain and for photochemical modeling. We point at the lacking data in both wavelength domains for C 2H 2, C 4H 2, C 6H 2, C 8H 2 and propose downloadable files of the ultraviolet absorption coefficient ready to use for photolysis rate calculations. For longer polyynes, we calculate extrapolated ultraviolet spectra and calculate their photolysis rate. Using a simplified photochemical model of the polyynes in Titan and CRL618, we predict their relative abundance and compare them with the observed ones. This also leads us to predict the abundances of the longer polyynes.

Effect of mineral dust aerosols on the photolysis rates in the clean and polluted marine environments

This study examines the importance of spectral optical properties of mineral dust in calculations of photolysis rates in clean and polluted marine environments. A set of optical characteristics was computed with Mie theory using data on the size distribution and composition of mineral dust from recent experimental and modeling studies. These models were incorporated into the National Center for Atmospheric Research tropospheric ultraviolet‐visible radiation transfer code. The 13 analyzed photolysis reactions were classified into three groups according to their photolytic wavelengths and the vertical profile of J values in the aerosol‐free atmosphere. The photolysis reactions of O3(O1D), NO2, and NO3(NO) were selected as representative of groups I, II, and III, respectively. We find that depending on its properties, dust causes either a decrease or an increase in the spectral actinic fluxes relative to the aerosol‐free condition. The wavelength range in which the changes in actinic fluxes are negative becomes broader as the amount of dust load increases, a dust size distribution is shifted to coarse size mode, and the iron oxide content in dust aggregates increases. Changes in actinic fluxes also depend on the sun position (time of the day) and an altitude considered. As a result, dust exerts the differing impact on J values of the three photolytic groups. The diurnal cycle of dust‐affected J values of a given group is similar among the differing size distribution and dust compositions, but changes in J values vary by a factor of 1.5–2. For a given content of iron oxide, the largest changes are caused by the size distributions that are shifted to the fine size mode. A change in J values of groups I and II caused by the varying amount of iron oxide in dust aggregates (from 1% to 10%) is negative in and below the dust layer. In contrast, J values of group III increase in the presence of low absorbing dust (with 1% of iron oxide), but they decrease with increasing dust absorption. Our results indicate that the dust composition not only will be needed to accurately model a decrease in J values of groups I and II but also to determine a correct sign and value of changes of J values of group III. In the case of dust mixed with pollution, we find that the external mixing of dust and black carbon causes somewhat larger changes in J values compared to the internal mixing of these species. We conclude that regional differences in size and composition of mineral dust as well as related changes in the vertical profile and diurnal cycle of actinic fluxes and J values should be taken into account if more realistic assessments of the dust impact on photochemistry through photolysis are to be achieved.

A modified band approach for the accurate calculation of online photolysis rates in stratospheric-tropospheric Chemical Transport Models

Abstract. Here we present an efficient and accurate method for the online calculation of photolysis rates relevant to both the stratosphere and troposphere for use in global Chemistry Transport Models and General Circulation Models. The method is a modified version of the band model introduced by Landgraf and Crutzen (1998) which has been updated to improve the performance of the approach for solar zenith angles >72° without the use of any implicit parameterisations. For this purpose, additional sets of band parameters have been defined for instances where the incident angle of the light beam is between 72–93°, in conjunction with a scaling component for the far UV region of the spectrum (λ=178.6–202.0 nm). For incident angles between 85–93° we introduce a modification for pseudo-sphericity that improves the accuracy of the 2-stream approximation. We show that this modified version of the Practical Improved Flux Method (PIFM) is accurate for angles <93° by comparing the resulting height resolved actinic fluxes with a recently developed full spherical reference model. We also show that the modified band method is more accurate than the original, with errors generally being less than ±10% throughout the atmospheric column for a diverse range of chemical species. Moreover, we perform certain sensitivity studies that indicate it is robust and performs well over a wide range of conditions relevant to the atmosphere.

Actinic flux and photolysis in water droplets: Mie calculations and geometrical optics limit

Abstract. Photolysis of water-soluble components inside cloud droplets by ultraviolet/visible radiation may play an important role in atmospheric chemistry. Two earlier studies have suggested that the actinic flux and hence the photolysis frequency within spherical droplets is enhanced relative to that in the surrounding air, but have given different values for this enhancement. Here, we reconcile these discrepancies by noting slight errors in both studies that, when corrected, lead to consistent results. Madronich (1987) examined the geometric (large droplet) limit and concluded that refraction leads to an enhancement factor, averaged over all incident directions, of 1.56. However, the physically relevant quantity is the enhancement of the average actinic flux (rather than the average enhancement factor) which we show here to be 1.26 in the geometric limit. Ruggaber et al. (1997) used Mie theory to derive energy density enhancements slightly larger than 2 for typical droplet sizes, and applied these directly to the calculation of photolysis rates. However, the physically relevant quantity is the actinic flux (rather than the energy density) which is obtained by dividing the energy density by the refractive index of water, 1.33. Thus, the Mie-predicted enhancement for typical cloud droplet sizes is in the range 1.5, only coincidentally in agreement with the value originally given by Madronich. We also investigated the influence of resonances in the actinic flux enhancement. These narrow spikes which are resolved only by very high resolution calculations are orders of magnitude higher than the intermediate values but contribute only little to the actinic flux enhancement when averaged over droplet size distributions. Finally, a table is provided which may be used to obtain the actinic flux enhancement for the photolysis of any dissolved species.

Impact of large solar zenith angles on lower stratospheric dynamical and chemical processes in a coupled chemistry-climate model

Abstract. Actinic fluxes at large solar zenith angles (SZAs) are important for atmospheric chemistry, especially under twilight conditions in polar winter and spring. The results of a sensitivity experiment employing the fully coupled 3D chemistry-climate model ECHAM4.L39(DLR)/CHEM have been analysed to quantify the impact of SZAs larger than 87.5º on dynamical and chemical processes in the lower stratosphere, in particular their influence on the ozone layer. Although the actinic fluxes at SZAs larger than 87.5º are small, ozone concentrations are significantly affected because daytime photolytic ozone destruction is switched on earlier, especially at the end of polar night the conversion of Cl2 and Cl2O2 into ClO in the lower stratosphere. Comparing climatological mean ozone column values of a simulation considering SZAs up to 93º with those of the sensitivity run with SZAs confined to 87.5º total ozone is reduced by about 20% in the polar Southern Hemisphere, i.e., the ozone hole is "deeper'' if twilight conditions are considered in the model because there is about 4 weeks more time for ozone destruction. This causes an additional cooling of the polar lower stratosphere (50 hPa) up to -4 K with obvious consequences for chemical processes. In the Northern Hemisphere the impact of large SZAs cannot be determined on the basis of climatological mean values due to the pronounced dynamic variability of the stratosphere in winter and spring. This study clearly shows the necessity of considering large SZAs for the calculation of photolysis rates in atmospheric models.

Effect of clouds on photolysis and oxidants in the troposphere

Cloud layers in the troposphere influence photolysis rates (J values) and hence concentrations of chemical species. In order to study the impact of clouds on photolysis rates and oxidants, we have developed a simplified version of the National Center for Atmospheric Research (NCAR) Tropospheric Ultraviolet‐Visible (TUV) model and have coupled the simplified TUV (otherwise known as the fast TUV (FTUV)) into the NCAR/Atmospheric Chemistry Division global transport chemical model (Model for Ozone and Related Chemical Tracers (MOZART‐2)). The FTUV model has the same physical processes as the TUV model, except that the wavelength bins between 121 and 750 nm are reduced from 140 to 17. As a result, FTUV is about 8 times faster than the original TUV. Differences in the calculated photolysis rates between TUV and FTUV are generally less than 5% in the troposphere. Subgrid vertical distributions of clouds are also considered in the calculation of photolysis rates in MOZART‐2. The method used in this study is a mixed maximum and random overlap scheme. The subgrid method increases the computation time for photolysis rates by a factor of 3 compared to a simple method in which clouds are uniformly distributed over the MOZART‐2 grids. Our calculation shows that the uniform cloud distribution method tends to significantly overestimate back scattering on the top of clouds and overestimates the impact on photochemistry in the troposphere. The results suggest that clouds have important impacts on tropospheric chemistry. Global mean OH concentration increases by about 20% due to the impact of clouds. As a result, the calculated CH4 lifetime changes to 11 years for clear sky and 9 years for cloudy sky. The latter value is closer to the methane lifetime estimated from previous studies. Calculated CO surface concentrations are compared with observed values, showing an improvement when the impact of clouds on the photolysis rates is taken into account. Clouds also have important impacts on tropospheric ozone budget. Our calculation suggest that because of clouds, the globally averaged photolysis rates of J[O3], J[CH2O], and J[NO2] are enhanced in the troposphere by about 12, 13, and 13%, respectively, leading to an 8% increase in the tropospheric O3 concentrations. Our study suggests that clouds strongly influence photolysis rates and hence play an important role in controlling the concentrations of the tropospheric oxidants. Such effects should be carefully considered and included in regional and global chemical transport models.

Sciatran - a new radiative transfer model for geophysical applications in the 240–2400 NM spectral region: the pseudo-spherical version

A radiative transfer model, SCIATRAN, has been developed mainly for the retrieval of atmospheric constituents from global nadir radiance measurements of the SCIAMACHY satellite spectrometer. This is a further development of the successful GOMETRAN. SCIATRAN solves the radiative transfer equation using the Finite Difference Method for a plane-parallel vertically inhomogeneous atmosphere taking into account multiple scattering. The present program version utilizes the pseudo-spherical approach, including refraction, appropriate for solar zenith angles up to about 92°. SCIATRAN comprises, amongst others, the following features: (i) quasi-analytical calculation of weighting functions of atmospheric and surface parameters, (ii) DOAS airmass factor calculations, (iii) height resolved radiation fluxes, including actinic fluxes for photolysis rate calculations, (iv) inelastic rotational Raman scattering by N 2 and O 2 molecules, (v) parameterization schemes for aerosols and clouds, (vi) a line-by-line and a correlated-k distribution mode for line absorption, and (vii) thermal emission. This paper presents an overview of the SCIATRAN model, focusing on the pseudo-spherical approach developed to consider the sphericity of the Earth. SCIATRAN will be made available via the world wide web for non-commercial scientific applications.

Stratospheric photolysis frequencies: Impact of an improved numerical solution of the radiative transfer equation

Numerical schemes for the calculation of photolysis rates are usually employed in simulations of stratospheric chemistry. Here, we present an improvement of the treatment of the diffuse actinic flux in a widely used stratospheric photolysis scheme (Lary and Pyle, 1991). We discuss both the consequences of this improvement and the correction of an error present in earlier applications of this scheme on the calculation of stratospheric photolysis frequencies. The strongest impact of both changes to the scheme is for small solar zenith angles. The effect of the improved treatment of the diffuse flux is most pronounced in the lower stratosphere and in the troposphere. Overall, the change in the calculated photolysis frequencies in the region of interest in the stratosphere is below about 20%, although larger deviations are found for H2O, O2, NO, N2O, and HCl.

UV absorption cross sections for SO3

Room temperature gas phase absorption cross sections for SO3 have been measured over the wavelength range 195 to 330 nm using a diode array spectrometer. The SO3 spectrum is continuous with weak diffuse vibrational band structure in the 225 to 295 nm region. Atmospheric photolysis rate calculations show that photolysis of SO3 in the 190 to 230 nm actinic window is important in determining the sulfur partitioning in the upper stratosphere.

Temperature dependent ultraviolet‐visible absorption cross sections of N2O and N2O4: Low‐temperature measurements of the equilibrium constant for 2NO2 ⇌ N2O4

A study of the temperature dependence of the ultraviolet‐visible absorption cross sections for NO2 has been made in the temperature range 213–298 K and between 310 and 570 nm using a diode array spectrometer. Analysis of the experimental data allowed the simultaneous measurement of the NO2 and N2O4 cross sections and the equilibrium constant for the dimerization of NO2. The absorption cross sections were measured at a spectral resolution of 0.54 nm full width at half maximum (FWHM) and are presented for use in the analysis of differential absorption spectra of atmospheric NO2. Averaged cross section data for NO2 are presented for use in photolysis rate calculations. Values of cross sections for N2O4 and equilibrium constant for the association of NO2 are presented in the range 213 to 263 K. No temperature effect was observed on the overall shape of the NO2 absorption spectrum or on the averaged cross section values used for calculating atmospheric photolysis rates. Changes in the fine structure of the NO2 spectrum with temperature are observed and this has important implications for measurements of atmospheric NO2 made by ultraviolet‐visible absorption techniques.

Photolytic rates for NO 2, O 3 and HCHO in the atmosphere of Mexico City

We report theoretical calculations of photolysis rates for NO 2, O 3 and HCHO in the atmosphere of Mexico City. To estimate the radiance needed in the calculations, the equation of transfer is solved by the delta-Eddington method. An atmosphere of air, NO 2, O 3 and dry aerosols is modeled.

ChemInform Abstract: Temperature‐Dependent Formaldehyde Cross Sections in the Near‐Ultraviolet Spectral Region.

ChemInformVolume 21, Issue 37 Physical Organic Chemistry ChemInform Abstract: Temperature-Dependent Formaldehyde Cross Sections in the Near-Ultraviolet Spectral Region. C. A. CANTRELL, C. A. CANTRELL Atmos. Chem. Div., Natl. Cent. Atmos. Res., Boulder, CO 80307-3000, USASearch for more papers by this authorJ. A. DAVIDSON, J. A. DAVIDSON Atmos. Chem. Div., Natl. Cent. Atmos. Res., Boulder, CO 80307-3000, USASearch for more papers by this authorA. H. MCDANIEL, A. H. MCDANIEL Atmos. Chem. Div., Natl. Cent. Atmos. Res., Boulder, CO 80307-3000, USASearch for more papers by this authorR. E. SHETTER, R. E. SHETTER Atmos. Chem. Div., Natl. Cent. Atmos. Res., Boulder, CO 80307-3000, USASearch for more papers by this authorJ. G. CALVERT, J. G. CALVERT Atmos. Chem. Div., Natl. Cent. Atmos. Res., Boulder, CO 80307-3000, USASearch for more papers by this author C. A. CANTRELL, C. A. CANTRELL Atmos. Chem. Div., Natl. Cent. Atmos. Res., Boulder, CO 80307-3000, USASearch for more papers by this authorJ. A. DAVIDSON, J. A. DAVIDSON Atmos. Chem. Div., Natl. Cent. Atmos. Res., Boulder, CO 80307-3000, USASearch for more papers by this authorA. H. MCDANIEL, A. H. MCDANIEL Atmos. Chem. Div., Natl. Cent. Atmos. Res., Boulder, CO 80307-3000, USASearch for more papers by this authorR. E. SHETTER, R. E. SHETTER Atmos. Chem. Div., Natl. Cent. Atmos. Res., Boulder, CO 80307-3000, USASearch for more papers by this authorJ. G. CALVERT, J. G. CALVERT Atmos. Chem. Div., Natl. Cent. Atmos. Res., Boulder, CO 80307-3000, USASearch for more papers by this author First published: September 11, 1990 https://doi.org/10.1002/chin.199037035AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume21, Issue37September 11, 1990 RelatedInformation

Visible‐ultraviolet absorption cross sections for NO2 as a function of temperature

A redetermination of the temperature dependence of the absorption cross section (σ) of NO2 in the visible‐ultraviolet region (264–649 nm) has been made in order to provide a more reliable data base for the calculation of NO2 photolysis rates in the atmosphere. Experiments over a wide range of temperatures (−40.6° to 124°C) and NO2 concentrations (3.4×1013–7.3×1014 molecules cm−3) were made at relatively low and high spectral resolutions, employing diode array and Fourier transform spectrometers, respectively. There are three aspects of the temperature dependence which were noted: (1) the integral of a plot of σ versus 1/λ (264–649 nm) was essentially independent of temperature; (2) increasing temperature produced a shift of the spectrum toward longer wavelengths, resulting in a small negative temperature dependence of σ over the 264‐ to 400‐nm range and a small positive dependence over the 450‐ to 649‐nm range; (3) increasing temperature produced broadening of individual spectral features, resulting in a systematic lowering of peaks and filling of valleys. Recommended cross sections, averaged over 5‐nm wavelength intervals, are presented for use in tropospheric NO2 photolysis rate calculations.

A two-dimensional photochemical model of the stratosphere with Rayleigh scattering

Computations of concentrations of minor stratospheric gases using a two-dimensional model of the stratosphere are reported. The model includes Rayleigh scattering. This results in an increase in the photodissociation rate computation time by a factor of 1.5. The effect of ground albedo is assessed by comparing our results with a calculation of photolysis rates for a constant albedo with latitude. Comparison of results with a reference model including only molecular absorption are also made. The largest differences (≲50%) occur in NO and OH. An approximate expression for including the effects of Rayleigh scattering and surface reflectance in multi-dimensional models is suggested.