A compilation of the absorption cross-sections of SO2 from 106 to 403 nm

Manatt, Stanley L.; Lane, A. L.

doi:10.1016/0022-4073(93)90077-u

Cited by 150 publications

(101 citation statements)

References 42 publications

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“…We used the same data and conditions as Sect. 4.3, using the cross sections of Manatt and Lane (1993 19 molecule cm −3 ) were used for termolecular reactions. Initial guesses were made for the concentration of species within the system.…”

Section: Constraining the Rate Of The So + O 2 + M Reaction Using A Kmentioning

confidence: 99%

“…Absorption cross sections of O 2 (Yoshino et al, 1988(Yoshino et al, , 1992, O 3 (Molina and Molina, 1986), and CO 2 (Shemansky, 1972) were used with concentration and column density data for the species to calculate the transmission of the atmosphere to radiation in the 180 to 220 nm absorption region at different altitudes. SO 2 photoly-1858 A. R. Whitehill et al: SO 2 photolysis as a source for sulfur mass-independent isotope signatures sis rates (J SO 2 ) were calculated as a function of altitude using the calculated spectral photon fluxes and the SO 2 absorption cross sections of Manatt and Lane (1993). The lifetime of SO with respect to oxidation by O 2 (i.e., Reactions (R5) and (R6)) is relatively short (on the order of seconds), so SO and SO 2 were assumed to be in photochemical steady state, i.e.,…”

Section: Contribution Of the So + O 2 + M Reaction To Sulfate Formatimentioning

confidence: 99%

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SO2 photolysis as a source for sulfur mass-independent isotope signatures in stratospehric aerosols

et al. 2015

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Abstract. Signatures of sulfur isotope mass-independent fractionation (S-MIF) have been observed in stratospheric sulfate aerosols deposited in polar ice. The S-MIF signatures are thought to be associated with stratospheric photochemistry following stratospheric volcanic eruptions, but the exact mechanism responsible for the production and preservation of these signatures is debated. In order to identify the origin and the mechanism of preservation for these signatures, a series of laboratory photochemical experiments were carried out to investigate the effect of temperature and added O 2 on the S-MIF produced by two absorption band systems of SO 2 : photolysis in the 190 to 220 nm region and photoexcitation in the 250 to 350 nm region. The SO 2 photolysis (SO 2 + hν → SO+O) experiments showed S-MIF signals with large 34 S/ 32 S fractionations, which increases with decreasing temperature. The overall S-MIF pattern observed for photolysis experiments, including high 34 S/ 32 S fractionations, positive mass-independent anomalies in 33 S, and negative anomalies in 36 S, is consistent with a major contribution from optical isotopologue screening effects and data for stratospheric sulfate aerosols. In contrast, SO 2 photoexcitation produced products with positive S-MIF anomalies in both 33 S and 36 S, which is different from stratospheric sulfate aerosols. SO 2 photolysis in the presence of O 2 produced SO 3 with S-MIF signals, suggesting the transfer of the S-MIF anomalies from SO to SO 3 by the SO + O 2 + M → SO 3 + M reaction. This is supported with energy calculations of stationary points on the SO 3 potential energy surfaces, which indicate that this reaction occurs slowly on a single adiabatic surface, but that it can occur more rapidly through intersystem crossing. Based on our experimental results, we estimate a termolecular rate constant on the order of 10 −37 cm 6 molecule −2 s −1 . This rate can explain the preservation of mass independent isotope signatures in stratospheric sulfate aerosols and provides a minor, but important, oxidation pathway for stratospheric SO 2 . The production and preservation of S-MIF signals requires a high SO 2 column density to allow for optical isotopologue screening effects to occur and to generate a large enough signature that it can be preserved. In addition, the SO 2 plume must reach an altitude of around 20 to 25 km, where SO 2 photolysis becomes a dominant process. These experiments are the first step towards understanding the origin of the sulfur isotope anomalies in stratospheric sulfate aerosols.

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Section: Constraining the Rate Of The So + O 2 + M Reaction Using A Kmentioning

confidence: 99%

Section: Contribution Of the So + O 2 + M Reaction To Sulfate Formatimentioning

confidence: 99%

SO2 photolysis as a source for sulfur mass-independent isotope signatures in stratospehric aerosols

et al. 2015

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“…Ammonia also has lines in the IR part of the spectrum, but in this region strong water bands may interfere with the ammonia lines. Chen et al, 1999), NO (T = 298 K; spectrum only partly available; Thompson et al, 1963), and SO2 (T = 293 K; Manatt and Lane, 1993). Lower graph: CO2…”

Section: Wavelength Selectionmentioning

confidence: 99%

Two instruments based on differential optical absorption spectroscopy (DOAS) to measure accurate ammonia concentrations in the atmosphere

et al. 2012

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Abstract. We present two Differential Optical Absorption Spectroscopy (DOAS) instruments built at RIVM: the RIVM DOAS and the miniDOAS. Both instruments provide virtually interference-free measurements of NH 3 concentrations in the atmosphere, since they measure over an open path, without suffering from inlet problems or interference problems by ammonium aerosols dissociating on tubes or filters. They measure concentrations up to at least 200 µg m −3 , have a fast response, low maintenance demands, and a high uptime. The RIVM DOAS has a high accuracy of typically 0.15 µg m −3 for ammonia for 5-min averages and over a total light path of 100 m. The miniDOAS has been developed for application in measurement networks such as the Dutch National Air Quality Monitoring Network (LML). Compared to the RIVM DOAS it has a similar accuracy, but is significantly reduced in size, costs, and handling complexity. The RIVM DOAS and miniDOAS results showed excellent agreement (R 2 = 0.996) during a field measurement campaign in Vredepeel, the Netherlands. This measurement site is located in an agricultural area and is characterized by highly variable, but on average high ammonia concentrations in the air. The RIVM-DOAS and miniDOAS results were compared to the results of the AMOR instrument, a continuous-flow wet denuder system, which is currently used in the LML. Averaged over longer time spans of typically a day, the (mini)DOAS and AMOR results agree reasonably well, although an offset of the AMOR values compared to the (mini)DOAS results exists. On short time scales, the (mini)DOAS shows a faster response and does not show the memory effects due to inlet tubing and transport of absorption fluids encountered by the AMOR. Due to its high accuracy, high uptime, low maintenance and its open path, the (mini)DOAS shows a good potential for flux measurements by using two (or more) systems in a gradient set-up and applying the aerodynamic gradient technique.

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“…The reason is in relatively small an absorption cross section (σ ) of these molecules for UV light near 254 nm (compare the respective σ in cm 2 : O 3 −1.5×10 −17 , HO 2 −2×10 −19 , H 2 O 2 −7×10 −20 , and SO 2 −1.5×10 −19 (Manatt and Lane, 1993;NIST, 2007). Moreover, the excited SO 2 ( 1 B) relaxes very rapidly in collisions with N 2 (with the rate of about 1×10 10 s −1 at atmospheric conditions) to ground electronic state and partially (no more than 10 %) to SO 2 ( 3 B) state and then to ground state with the rate of about 6×10 6 s −1 (Marvin and Reiss, 1978;Christensen et al, 1994).…”

Section: Electron-excited So 2 Formationmentioning

confidence: 99%

One conceivable mechanism of UV-light induced SO2 Oxidation to H2SO4

Sorokin

2010

Atmos. Chem. Phys.

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Abstract. The electron-excited chemistry of sulfur dioxide oxidation induced by UV irradiation of air with trace O 3 and SO 2 is considered. The importance of this mechanism is evaluated based on recent laboratory experiments on SO 2 oxidation in a laminar tube with air induced by UV irradiation. Results show that under respective conditions the route of SO 2 oxidation involving electron excited oxygen molecules may present an additional source of gaseous H 2 SO 4 production to known OH-radical mechanism.

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A compilation of the absorption cross-sections of SO2 from 106 to 403 nm

Cited by 150 publications

References 42 publications

SO<sub>2</sub> photolysis as a source for sulfur mass-independent isotope signatures in stratospehric aerosols

SO<sub>2</sub> photolysis as a source for sulfur mass-independent isotope signatures in stratospehric aerosols

Two instruments based on differential optical absorption spectroscopy (DOAS) to measure accurate ammonia concentrations in the atmosphere

One conceivable mechanism of UV-light induced SO<sub>2</sub> Oxidation to H<sub>2</sub>SO<sub>4</sub>

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A compilation of the absorption cross-sections of SO2 from 106 to 403 nm

Cited by 150 publications

References 42 publications

SO&lt;sub&gt;2&lt;/sub&gt; photolysis as a source for sulfur mass-independent isotope signatures in stratospehric aerosols

SO&lt;sub&gt;2&lt;/sub&gt; photolysis as a source for sulfur mass-independent isotope signatures in stratospehric aerosols

Two instruments based on differential optical absorption spectroscopy (DOAS) to measure accurate ammonia concentrations in the atmosphere

One conceivable mechanism of UV-light induced SO&lt;sub&gt;2&lt;/sub&gt; Oxidation to H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;

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SO<sub>2</sub> photolysis as a source for sulfur mass-independent isotope signatures in stratospehric aerosols

SO<sub>2</sub> photolysis as a source for sulfur mass-independent isotope signatures in stratospehric aerosols

One conceivable mechanism of UV-light induced SO<sub>2</sub> Oxidation to H<sub>2</sub>SO<sub>4</sub>