The possible detection of OBrO in the stratosphere

Renard, Jean‐Baptiste; Pirre, Michel; Robert, Claude; Huguenin, D.

doi:10.1029/98jd01805

Cited by 36 publications

(53 citation statements)

References 19 publications

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“…From balloon-borne UV/visible spectroscopic observations at both mid and high latitudes Renard et al [1997Renard et al [ , 1998] determined that significant quantities of OBrO are present at night. This study is motivated by the recent tentative observation of significant OBrO.…”

Section: Introductionmentioning

confidence: 80%

“…This study is motivated by the recent tentative observation of significant OBrO. Renard et al [1998] also observed OBrO at Arctic latitudes but with values a factor of 2 lower than at mid-latitudes. In fact, Renard et al [1998] argued that their observations at mid-latitude indicate an OBrO mixing ratio around 10-20 parts per 10 iS' by volume (pptv) throughout the lower and mid stratosphere, implying complete conversion of inorganic bromine (Bry) to OBrO.…”

Section: Introductionmentioning

confidence: 98%

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Model calculations of stratospheric OBrO indicating very small abundances

Chipperfield

Glassup

Pundt

et al. 1998

Geophysical Research Letters

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Section: Introductionmentioning

confidence: 80%

Section: Introductionmentioning

confidence: 98%

Model calculations of stratospheric OBrO indicating very small abundances

Chipperfield

Glassup

Pundt

et al. 1998

Geophysical Research Letters

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“…At present, this detection is not confirmed by other instruments, and is in contradiction with modeling results [ Chipperfield et al , 1998]. Analysis of nighttime UV‐visible measurements performed onboard a Transall airplane have allowed Erle et al [2000] to derive mixing ratios with upper limits at least three times smaller than those given by Renard et al [1998], and to conclude that OBrO does not exist at night. Consequently in order to resolve such opposite conclusions in the OBrO detection, further analysis of the various methods used, and the conditions under which observations are made, is required.…”

Section: Introductionmentioning

confidence: 99%

Analysis of OBrO, IO, and OIO absorption signature in UV‐visible spectra measured at night and at sunrise by stratospheric balloon‐borne instruments

et al. 2003

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[1] Absorption bands of OBrO, IO, and OIO in the visible region have been investigated in the data of the AMON (''Absorption par les Minoritaires Ozone et Nox'') and SALOMON (''Spectroscopie d'Absorption Lunaire pour l'Observation des Minoritaires Ozone et Nox'') balloon-borne spectrometers used to obtain measurements in the nighttime stratosphere, since 1992 and 1998 respectively. The absorption features initially detected in AMON residual spectra and attributed to OBrO are also observable in SALOMON data with better accuracy. New estimates of OBrO cross-section amplitudes taking into account recent laboratory measurements are used for the OBrO retrieval. A consequence is that previously published OBrO concentration and mixing ratio values are revised downwards of around 40%. Further tests are performed to assess the consistency of the OBrO detection. No correlation exists between OBrO and NO 2 vertical profiles which practically rules out the possibility for the structures ascribed to OBrO absorption to be due to remaining NO 2 contributions. It is shown that variability of OBrO quantities at high latitudes obtained from various AMON and SALOMON flights is possibly linked to the chemical processes involving the production of OClO. At midlatitudes, the exceptional and unexpected conditions of the April 28, 1999 SALOMON flight allow us to observe the drop in OBrO concentrations just after sunrise. As expected, if previous studies of stratospheric iodine species are considered, IO and OIO absorption lines are never detected in the residual spectra. The presence of unknown structures in the residual spectra in the IO and OIO absorption regions is obvious and tends to distort the retrievals. The possibility that these remaining features result from a temperature dependence effect or uncertainties of O 3 and/or NO 2 cross-sections is suggested. Thus, more accurate laboratory measurements and sets of cross-sections for low temperature are needed.INDEX TERMS: 0340 Atmospheric Composition and Structure: Middle atmospherecomposition and chemistry; 0343 Atmospheric Composition and Structure: Planetary atmospheres (5405, 5407, 5409, 5704, 5705, 5707); 0394 Atmospheric Composition and Structure: Instruments and techniques; 0399 Atmospheric Composition and Structure: General or miscellaneous; KEYWORDS: UV-visible spectroscopy, stratosphere, bromine and iodine species Citation: Berthet, G., J.-B. Renard, M. Chartier, M. Pirre, and C. Robert, Analysis of OBrO, IO, and OIO absorption signature in UVvisible spectra measured at night and at sunrise by stratospheric balloon-borne instruments,

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“…BrO 2 has been detected in the stratosphere as a possible nighttime bromine reservoir. 22,23 The first observation of gasphase BrO 2 in the laboratory was reported by Butkovskaya et al, 24 which suggested that paramagnetic BrO 2 molecules with lifetime >10 s among the products of the O + Br 2 reaction were found with the discharge flow-mass spectrometry technique. The first spectroscopic study (visible absorption) of gas phase BrO 2 was reported by Rattigan et al 25 Since then, a numbers of studies have been devoted to investigate the properties of BrO 2 experimentally employing a variety of techniques, [23][24][25][26][27][28][29] including: rotational spectroscopy, 26 visible absorption in solid matrices, 27, 28 photoionization, 19,29 and high-resolution ultraviolet/visable (UV/Vis) absorption spectroscopy.…”

Section: Introductionmentioning

confidence: 98%

“…[6][7][8][9][10][11] Beyond chlorine species, the importance of bromine oxides and related species in ozone depletion also has been established. [14][15][16][17][18][19][20][21][22][23] It has been suggested that bromine species is roughly 45 times more effective than chlorine for global ozone destruction. 18 Despite the important roles they play in the stratospheric chemistry, bromine oxides are relatively less studied compared with their chlorine counterparts, particularly for higher bromine oxides.…”

Section: Introductionmentioning

confidence: 99%

Photoelectron spectroscopy of higher bromine and iodine oxide anions: Electron affinities and electronic structures of BrO2,3 and IO2–4 radicals

Wen

Hou

Huang

et al. 2011

The Journal of Chemical Physics

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This report details a photoelectron spectroscopy (PES) and theoretical investigation of electron affinities (EAs) and electronic structures of several atmospherically relevant higher bromine and iodine oxide molecules in the gas phase. PES spectra of BrO(2)(-) and IO(2)(-) were recorded at 12 K and four photon energies--355 nm/3.496 eV, 266 nm/4.661 eV, 193 nm/6.424 eV, and 157 nm/7.867 eV--while BrO(3)(-), IO(3)(-), and IO(4)(-) were only studied at 193 and 157 nm due to their expected high electron binding energies. Spectral features corresponding to transitions from the anionic ground state to the ground and excited states of the neutral are unraveled and resolved for each species. The EAs of these bromine and iodine oxides are experimentally determined for the first time (except for IO(2)) to be 2.515 ± 0.010 (BrO(2)), 2.575 ± 0.010 (IO(2)), 4.60 ± 0.05 (BrO(3)), 4.70 ± 0.05 (IO(3)), and 6.05 ± 0.05 eV (IO(4)). Three low-lying excited states along with their respective excitation energies are obtained for BrO(2) [1.69 (A (2)B(2)), 1.79 (B (2)A(1)), 1.99 eV (C (2)A(2))], BrO(3) [0.7 (A (2)A(2)), 1.6 (B (2)E), 3.1 eV (C (2)E)], and IO(3) [0.60 (A (2)A(2)), 1.20 (B (2)E), ∼3.0 eV (C (2)E)], whereas six excited states of IO(2) are determined along with their respective excitation energies of 1.63 (A (2)B(2)), 1.73 (B (2)A(1)), 1.83 (C (2)A(2)), 4.23 (D (2)A(1)), 4.63 (E (2)B(2)), and 5.23 eV (F (2)B(1)). Periodate (IO(4)(-)) possesses a very high electron binding energy. Only one excited state feature with 0.95 eV excitation energy is shown in the 157 nm spectrum. Accompanying theoretical calculations reveal structural changes from the anions to the neutrals, and the calculated EAs are in good agreement with experimentally determined values. Franck-Condon factors simulations nicely reproduce the observed vibrational progressions for BrO(2) and IO(2). The low-lying excited state information is compared with theoretical calculations and discussed with their atmospheric implications.

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The possible detection of OBrO in the stratosphere

Cited by 36 publications

References 19 publications

Model calculations of stratospheric OBrO indicating very small abundances

Model calculations of stratospheric OBrO indicating very small abundances

Analysis of OBrO, IO, and OIO absorption signature in UV‐visible spectra measured at night and at sunrise by stratospheric balloon‐borne instruments

Photoelectron spectroscopy of higher bromine and iodine oxide anions: Electron affinities and electronic structures of BrO2,3 and IO2–4 radicals

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