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  HOME > GEISA-15-Description and Access > Cross description > UV-VIS > update 2011

Update details of the GEISA-2011 sub-database on absorption cross-sections : UV



Molecules list : NO2, CS2, O3, SO2, O2-O2, OCIO, H2CO, OBrO, BrO, CHOCHO, IO, OIO, Aromatic Hydrocarbons.



NO2 (Nitrogen dioxide)
For NO2, there is quite a variety of different laboratory measurements of ultraviolet-visible absorption cross-sections. For atmospheric applications, the currently recommended data set by Orphal [1] is the one of Vandaele et al. [2], but it is important to stress that also the data of Voigt et al. [3], Yoshino et al. [4], Harder et al. [5] and Frost et al. [6] are of high quality and show excellent agreement with each other. The cross-section of Harder et al. may contain a slight contamination by HONO, however. For applications where a very high signal-to-noise ratio is required or in spectral regions where the previously mentioned NO2 absorption cross-sections are limited, the data recorded with GOME by Burrows et al. [7] or with SCIAMACHY by Bogumil et al. [8] are recommended (again, it is important to note that these data are limited by the spectral resolution of the instruments). It has to be recalled that, in general, the cross-sections recorded by an FTS have a wavelength calibration of better than 0.01 nm [1] which is an important advantage for atmospheric applications, in particular when retrieving several absorbers simultaneously.

References :
[1] Orphal J. A critical review of the absorption cross-sections of O3 and NO2 in the ultraviolet and visible. J Photochem Photobiol 2003;157(A):185-209; Orphal J, Fellows CE, Flaud PM. The visible absorption spectrum of NO3 measured by high-resolution Fourier transform spectroscopy. J Geophys res 2003;108(D3):4077.
[2] Vandaele A-C, Hermans C, Fally S, Carleer M, Colin R, Mérienne M-F, et al. High-resolution Fourier transform measurement of the NO2 visible and near-infrared absorption cross sections: Temperature and pressure effects. J Geophys Res 2002;107(D), 43-8.
[3] Voigt S, Orphal J, Burrows JP. The temperature and pressure dependence of the absorption cross-sections of NO2 in the 250–800 nm region measured by Fourier-transform spectroscopy. J Photochem Photobiol 2002;149(A):1-7.
[4] Yoshino K, Esmond JR, Parkinson WH. High-resolution absorption cross section measurements of NO2 in the UV and visible region. Chem Phys 1997;221,169–74.
[5] Harder JW, Brault JW, Johnston PV, Mount GH. Temperature dependent NO2 cross sections at high spectral resolution Temperature dependent NO2 cross sections at high spectral resolution. J Geophys Res D 1997;102 :3861–79.
[6] Frost GJ, Goss LM, Vaida V. High Resolution UV-VIS Absorption Cross Sections of NO2 at Stratospheric Temperatures. J Geophys Res 1996;101:3869–77.
[7] Burrows JP, Richter A, Dehn A, B. Deters B, Himmelmann S, Voigt S, Orphal J. Atmospheric remote -sensing reference data from GOME-2. Temperature-dependent absorption cross sections of O3 in the 231–794 nm range. JQSRT 1999;509-17; Burrows JP, Dehn A, Deters B, Himmelmann S, Richter A, Voigt S, Orphal. J. Atmospheric remote-sensing reference data from GOME: Part1. Temperature-dependent absorption cross-sections of NO2 in the 231–794 nm range. JQSRT 1998;60:1025-31.
[8] Bogumil K, Orphal J, Homann T, Voigt S, Spietz P, Fleischmann OC, et al. Measurements of molecular absorption spectra with the SCIAMACHY pre-flight model: instrument characterization and reference data for atmospheric remote-sensing in the 230–2380 nm region. J Photochem Photobiol 2003;157(A):167-84.


CS2 (Carbon Disulfide)
Small amounts of carbon disulfide CS2 are released by volcanic eruptions and marshes. The absorption cross-sections, recorded with an FTS at 294 K covering the 290-350 nm spectral range are from Vandaele et al. [1].

References :
[1] Vandaele A-C, De Mazière M, Hermans C, Carleer M, Clerbaux C, Coheur P, et al. UV-visible and near-IR spectroscopy of atmospheric species. Recent Res Devel Chem Phys 2003;4:325-44.


O3 (Ozone)
As for NO2, there exist many laboratory measurements of UV-visible absorption cross-sections at atmospheric temperatures (see Orphal [1]). However, only a few of them cover the entire spectral range from the ultraviolet to the near-infrared. Therefore, it is difficult to recommend one single data set that would be best suited for all applications. For the Huggins bands (300-360 nm), the recommended reference data are those of Brion et al. [2] and those of Bass and Paur [3], since both data sets cover most relevant temperatures (note however that the data of Brion et al. are not available below 218 K) and have been recorded at high resolution. While the data of Bass and Paur were used as some kind of standard during the past 20 years, more recent studies tend to recommend the data of Brion et al. for atmospheric remote-sensing applications (since they show better wavelength calibration, wavelength sampling, less noise and less inconsistencies concerning the temperature dependence of the cross-sections). For applications where absorption cross-sections over a broader spectral range are needed (in particular in the visible and near-infrared, i.e. the Chappuis and Wulf bands, the O3 cross-sections recorded with GOME [4] or with SCIAMACHY [5] are recommended. These absorption cross-sections show also a very high signal-to-noise ratio, but are partly limited by the spectral resolution of the instruments. If O3 cross-sections at very high spectral resolution are needed, then the data of Voigt et al. [6] are recommended.

References :
[1] Orphal J. A critical review of the absorption cross-sections of O3 and NO2 in the ultraviolet and visible. J Photochem Photobiol 2003;157(A):185-209; Orphal J, Fellows CE, Flaud PM. The visible absorption spectrum of NO3 measured by high-resolution Fourier transform spectroscopy. J Geophys res 2003;108(D3):4077.
[2] Brion J, Daumont D, Malicet J. New measurements of the absolute absorption cross-sections of ozone at 294 and 223 K in the 310-350 nm spectral range. J Phys (Paris) Lett 1984;45:L57–L60. Brion J, Chakir A, Daumont D, Malicet J, Parisse C. High-resolution laboratory absorption cross section of O3. Temperature effect. Chem Phys Lett 1993;213:610–12. Daumont D, Brion J, Charbonnier J, Malicet J. Ozone UV spectroscopy I: absorption cross-sections at room temperature. J Atmos Chem 1992;15:145–55. Brion J, Chakir A, Charbonnier J, Daumont D, Parisse C, Malicet J. Absorption spectra measurements for the ozone molecule in the 350–830 nm region. J Atmos Chem 1998;30:291–99.
[3] Bass AM, Paur RJ. The ultraviolet cross-sections of ozone, Part I, The measurements, in: Zerefos CS, Ghazi A, Reidel D (Eds.), Atmospheric Ozone, Norwell, Mass.1985, pp. 606–10; Paur RJ, Bass AM. The ultraviolet cross-sections of ozone, Part II, Result and temperature dependence, in: C.S. Zerefos, A. Ghazi, D. Reidel (Eds.), Atmospheric Ozone, Norwell, Mass., 1985, pp. 611–16.
[4] Burrows JP, Richter A, Dehn A, B. Deters B, Himmelmann S, Voigt S, Orphal J. Atmospheric remote -sensing reference data from GOME-2. Temperature-dependent absorption cross sections of O3 in the 231–794 nm range. JQSRT 1999;509-17; Burrows JP, Dehn A, Deters B, Himmelmann S, Richter A, Voigt S, Orphal. J. Atmospheric remote-sensing reference data from GOME: Part1. Temperature-dependent absorption cross-sections of NO2 in the 231–794 nm range. JQSRT 1998;60:1025-31.
[5] Bogumil K, Orphal J, Homann T, Voigt S, Spietz P, Fleischmann OC, et al. Measurements of molecular absorption spectra with the SCIAMACHY pre-flight model: instrument characterization and reference data for atmospheric remote-sensing in the 230–2380 nm region. J Photochem Photobiol 2003;157(A):167-84.
[6] Voigt S, Orphal J, Bogumil K, Burrows JP. The temperature dependence (203–293 K) of the absorption cross sections of O3 in the 230–850 nm region measured by Fourier-transform spectroscopy. J Photochem Photobiol 2001;143(A):1-9.


SO2 (Sulphur dioxide)
SO2 presents three main regions of absorption in the near ultraviolet domain. The strongest band lies in the 45000 cm-1 (220 nm) region and corresponds to the Ĉ1B2-X1A1 electronic transition. A strong absorption structure extends between 29000 and 40000 cm-1, which can be ascribed to at least two electronic transitions. Underlying the structured bands of the A1A2-X1A1 [1], the ‘continuous’ absorption has been attributed to the B1B1-X1A1 transition, which has been predicted by theory [2] and measured by Brand et al. [3]. The A1A2-X1A1 transition is forbidden but is observed because of strong vibrational interactions through the ν3 vibration mode and is strongly perturbed by the 1B1 state. The allowed transition B1B1-X1A1 is so perturbed that no rotational or vibrational analysis is possible. It forms a continuum due to the density of weak absorptions. A weak absorption feature arises in the 25000-29000 cm-1 region (345-400 nm). It has been assigned to the a3B1-X1A1 electronic transition and is a spin-forbidden transition. In the previous edition of GEISA [6,7] the UV/VIS data set for SO2 consisted in cross-sections recorded with the SCIAMACHY spectrometer [4], covering five temperatures between 203 and 293 K and interesting for planetary science application. The 2011 update consists in recently obtained absorption cross-sections, at high resolution and at high temperatures, been obtained in support to planetary applications [5,6]. They were recorded in the 24000-44000 cm-1 spectral range (227-420 nm) with a Fourier Transform spectrometer at a resolution of 2 cm-1 (0.45 cm MOPD and boxcar apodisation). Pure SO2 samples were used and measurements were performed at room temperature (298 K) as well as at 318, 338 and 358 K. Temperature effects were investigated and were found in favorable agreement with existing studies in the literature. Comparison of the absorption cross-sections at room temperature [7,8] shows good agreement in intensity with most of the literature data, but shows that most of the latter suffer from inaccurate wavelength scale definition. Moreover, literature data are often given only on restricted spectral intervals, whereas this new data set offers the considerable advantage of covering the large spectral interval extending from 24000 to 44000 cm-1, at the four temperatures investigated. These data are also available in digital form from the website of the Belgian Institute for Space Aeronomy (http://www.aeronomie.be/spectrolab/).

References :
[1] Hamada Y, Merer AJ. Rotational Structure at the Long Wavelength End of the 2900 Å System of SO2. Can J Phys 1974;52:1443-57.
[2] Hillier IH, Saunders VR. A theoretical interpretation of the bonding, and the photoelectron and ultra-violet spectra of sulphur dioxide. Molecular Physics 1971;22:193-201.
[3] Brand JCD, Hardwick JL, Humphrey DR, Hamada Y, Merer AJ. Zeeman effects in the A1A2 <- X1A1 band System of sulfur dioxide. Can J Phys 1976;54:186-96.
[4] Bogumil K, Orphal J, Homann T, Voigt S, Spietz P, Fleischmann OC, et al. Measurements of molecular absorption spectra with the SCIAMACHY pre-flight model: instrument characterization and reference data for atmospheric remote-sensing in the 230–2380 nm region. J Photochem Photobiol 2003;157(A):167-84 .
[5] Vandaele AC, Hermans C, Fally S. Fourier Transform measurements of SO2 absorption cross sections: II. Temperature dependence in the 29 000-44 000 cm-1 (227-345 nm) region. JQSRT 2009;110:2115-26.
[6] Hermans C, Vandaele AC, Fally S. Fourier Transform measurements of SO2 absorption cross sections: I. Temperature dependence in the 24 000-29 000 cm-1 (345-420 nm) region. JQSRT 2009;110:756-65.
[7] Vandaele AC, Simon PC, Guilmot JM, Carleer M, Colin R. SO2 absorption cross section measurement in the UV using a Fourier transform spectrometer. J Geophys Res 1994;99(D12):25599-605.
[8] Rufus J, Stark G, Smith PL, Pickering JC, Thorne AP. High-resolution photoabsorption cross section measurements of SO2, 2: 220 to 325 nm at 295 K. J Geophys Res 2003;108:10.1029/2002JE001931.


O2-O2 (O4) (the so-called oxygen “dimer”)
These broad features are mainly used for air mass determination in atmospheric remote-sensing applications. It is rather difficult to recommend one particular set of data since the differences between the available cross-sections are still not well understood. At present, the data of Newnham and Ballard [1] are available in the archive; the ones of Greenblatt et al. [2] and of Vandaele et al. [3] will be added in a very near future.

References : [1] Newnham DA, Ballard J. Visible absorption cross sections and integrated absorption intensities of molecular oxygen (O2 and O4). J Geophys Res 1998;103D:28801-816.
[2] Greenblatt GD, Orlando JJ, Burkholder JB, Ravishankara AR. Absorption measurements of oxygen between 330 and 1140 nm. J Geophys Res 1990;95:18577–82.
[3] Vandaele A-C, De Mazière M, Hermans C, Carleer M, Clerbaux C, Coheur P, et al. UV-visible and near-IR spectroscopy of atmospheric species. Recent Res Devel Chem Phys 2003;4:325-44.


OClO (Chlorine dioxide)
OClO is involved in polar stratospheric chemistry, linking the catalytic cycles of ClO and BrO, and has been observed in ultraviolet-visible spectra from ground, air-borne platforms and satellites. It is important to monitor stratospheric OClO in order to validate the quantitative understanding of ozone destruction in polar winter. As in the previous edition of GEISA, the UV-visible absorption cross-sections of Kromminga et al. [1] that were recorded at different temperatures using high-resolution Fourier-transform spectroscopy are recommended.

References : [1] Kromminga H, Orphal J, Spietz P, Voigt S, Burrows JP. New measurements of OClO absorption cross-sections in the 325–435 nm region and their temperature dependence between 213 and 293 K. J Photochem Photobiol 2003;157(A):149-60.


H2CO (Formaldehyde, also called CH2O or HCHO)
Formaldehyde is another important source of OH radicals in the troposphere, and one of the smallest organic molecules in the atmosphere. Gratien et al. [1] have demonstrated that the high-resolution H2CO absorption cross-sections of Meller and Moortgat [2] are in excellent agreement with the available infrared cross-sections. For applications requiring a very high signal-to-noise ratio, the data recorded with SCIAMACHY [434] may also be of interest.

References :
[1] Gratien A, Picquet-Varrault B, Orphal J, Doussin J-F, Flaud J-M. Laboratory intercomparison of the formaldehyde absorption cross-sections in the infrared (1660–1820 cm-1) and ultraviolet (300–360 nm) spectral regions. J Geophys Res D 2007;112, D05305, doi:10.1029/2006JD007201.
[2] Meller R, Moortgat GK. Temperature dependence of the absorption cross- sections of formaldehyde between 223 and 323 K in the wavelength range 225–375 nm. J Geophys Res 2000;105:7089–101.


OBrO
Only cross-sections recorded by an FTS were selected. For OBrO (385-616 nm spectral range) cross-sections are available only at room temperature (Fleischmann et al. [1]).

Reference :
[1] Fleischmann OC, Meyer-Arnek J, Burrows JP, Orphal J. The visible absorption spectrum of OBrO, investigated by Fourier transform spectroscopy. J Phys Chem 2005;109:5093-103.


BrO (Bromine monoxide)
BrO is observed in the stratosphere but also in the marine troposphere and in volcanic plumes. There are two sets of data which have been recorded using high-resolution Fourier-transform spectroscopy and cover all relevant atmospheric temperatures: Wilmouth et al. [1] and Fleischmann et al. [2]; both show very good agreement. At present, the data of Fleischmann et al. [2] have been archived in GEISA 2011; the ones of Wilmouth et al. [1] will be added in a very near future As for OClO, for the sake of coherence with previous studies, GEISA 2011 also contains the BrO absorption cross-sections of Wahner et al. [3] that were used as reference spectra, before the new data became available.

References :
[1] Wilmouth DM, Hanisco TF, Donahue NM, Anderson JG. Fourier transform ultraviolet spectroscopy of the A 2Π3/2←X 2Π1/2 transition of BrO . J Phys Chem 1999;103:8935-45.
[2] Fleischmann OC, Burrows JP, Hartmann M, Orphal J. New ultraviolet absorption cross-sections of BrO at atmospheric temperatures measured by time-windowing Fourier transform spectroscopy. J Photochem Photobiol 2004;168(A):117-32.
[3] Wahner A, Ravishankara AR, Sander SP, Friedl RR. Absorption cross-section of BrO between 312 and 385 nm at 298 and 223 K. Chem Phys Lett 1988;152:507-12.


CHOCHO (Glyoxal)
Glyoxal is a small organic molecule involved in tropospheric chemistry and aerosol formation. It has only recently been measured for the first time in the Earth’s atmosphere using optical methods. Its sources are still not fully understood, especially since some CHOCHO is also observed over the Pacific Ocean. The recommended absorption cross-sections for CHOCHO are those of Volkamer et al. [1] recorded using high-resolution Fourier-transform spectroscopy.

Reference :
[1] Volkamer R, Spietz P, Burrows JH, Platt U. High-resolution absorption cross-section of glyoxal in the UV/VIS and IR spectral ranges. J Photochem Photobiol A: Chem 2005;175:35-46.


IO (Iodine monoxide)
IO has been observed only in the marine troposphere, and an upper limit of less than 1 pptV has been established for stratospheric IO. The reference data in GEISA are the cross-sections of Spietz et al. [1] which have an excellent signal-to-noise ratio, rather high resolution, and are in good agreement with other studies and with photochemical models of IO chemistry following flash photolysis of suitable precursors.

Reference :
[1] Spietz, P, Gómez Martín JC, Burrows JP. Spectroscopic studies of the I2/O3 photochemistry, Part 2: Improved Spectra of Iodine Oxides and Analysis of the IO Absorption Spectrum. J Photochem Photobiol A 2005;176:50-67.


OIO (Iodine dioxide)
As for IO, the OIO radical has been observed only in the marine troposphere. Its atmospheric relevance has been established only as late as 1996 when it was observed for the first time in flash-photolysis experiments by Himmelmann et al. [1]. The reference data in GEISA are the absorption cross-sections of Gomez-Martin et al. [2].

References
[1] Himmelmann S, Orphal J, Bovensmann H, Richter A, Ladstätter-Weissenmayer A, Burrows JP. First observation of the OIO molecule by time-resolved flash photolysis absorption spectroscopy. Chem Phys Lett 1996;251:330-4.
[2] Gómez-Martín JC, Spietz P, Burrows JP. Spectroscopic studies of the I2/O3 photochemistry: part 1: determination of the absolute absorption cross-sections of iodine oxides of atmospheric relevance. J Photochem Photobiol A 2005;176:15-38.


Aromatic Hydrocarbons
UV absorption cross-sections (cm2 molecule-1) of five gaseous aromatic hydrocarbons, i.e.: benzene (C6H6), toluene or methylbenzene (C7H8), and the three isomers of dimethyl-benzene (C6H4(CH3)2), also called meta-, ortho-, and para-xylene, ,have been measured with a FTS Bruker IFS120M at the resolution of 1 cm-1 (0.9 cm MOPD and boxcar apodisation) over the 30000 – 42000 cm-1 spectral range (238-333 nm). The recordings were carried out under different pressure and temperature conditions with pure samples. The complete dataset is composed of absorption cross-sections for: (i) benzene at 253, 263, 273, 283 and 293 K, (ii) toluene at 263, 273, 283 and 293 K, and (iii) the three isomers of xylene at 273, 283 and 293 K. Wavenumbers are given by increments of 0.2 cm-1. Systematic and non-systematic errors are given separately, a value of 8% being estimated for the former and individual values being reported in a separate column for the latter. The experimental set-up and the procedure of analysis are given in details in [1]. Comparisons with recent studies in the same UV region [1-4] show that large discrepancies are present in some cases which are largely attributed to the experimental difficulties and to a resolution effect. Compared to these studies, a better spectral resolution, an accurate wavelength scale, and several atmospheric temperatures are provided. A linear parameterization for the temperature effect is also proposed for benzene and toluene in support of remote sensing atmospheric studies both on Earth and on other planets. These data are also available in digital form from the website of the Belgian Institute for Space Aeronomy (http://www.aeronomie.be/spectrolab/)

References
[1] Fally S, Carleer M, Vandaele AC. UV Fourier transform absorption cross sections of benzene, toluene, meta-, ortho-, and para-xylene. JQSRT 2009;110:766,782.
[2] Etzkorn T, Klotz B, Sorensen S, Patroescu IV, Barnes I, Becker KH, et al. Gas-phase absorption cross sections of 24 monocyclic aromatic hydrocarbons in the UV and IR spectral ranges. Atmos Environ 1999;33:525-540.
[3] Suto M, Wang X, Shan J, Lee LC. Quantitative photoabsorption and fluorescence spectroscopy of benzene, naphtalene, and some derivatives at 106-295 nm. JQSRT 1992;48:79-89.
[4] Trost B, Stutz J, Platt U. UV-absorption cross sections of a series of monocyclic aromatic compounds. Atmos Environ 1997;31:3999-4008.