Photochemical bromine production implicated in Arctic boundary-layer ozone depletion

McConnell, J. C.; Henderson, Grant S.; Barrie, L. A.; Bottenheim, J. W.; Niki, H.; Langford, Cooper H.; Templeton, E.M.J.

doi:10.1038/355150a0

Cited by 337 publications

(241 citation statements)

References 18 publications

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“…In contrast, Michalowski et al (2000) pointed out that the reaction of HCHO with BrO might lead to the formation of HOBr initiating subsequent heterogeneous reactions increasing halogen atom concentrations. H 2 O 2 could also contribute to the formation of gas-phase molecular bromine (Br 2 ) as a consequence of the reaction of H 2 O 2 with bromide (Br À ) in the aqueous phase (McConnell et al, 1992). Besides the involvement of both compounds in important photochemical processes, H 2 O 2 and HCHO are conserved in surface snow and ice cores providing valuable information about the oxidation capacity of the past troposphere (Staffelbach et al, 1991;Thompson et al, 1993;Neftel et al, 1995;Fuhrer et al, 1996;Hutterli et al, 1999Hutterli et al, , 2001.…”

Section: Introductionmentioning

confidence: 99%

“…Combined field and modeling studies have indicated, that current gas-phase chemistry models are unable to account for H 2 O 2 (Neftel et al, 1995;McConnell et al, 1997a;Hutterli et al, 2001) and HCHO concentrations (McConnell et al, 1992;De Serves, 1994;Sander et al, 1997;Rudolph et al, 1999;Hutterli et al, 1999) commonly observed at high latitudes. Model results also indicate that emissions from the snowpack can sustain measured gas-phase concentrations of H 2 O 2 and HCHO (Shepson et al, 1996;Michalowski et al, 2000;Hutterli et al, 1999Hutterli et al, , 2001.…”

Section: Introductionmentioning

confidence: 99%

“…It has been discussed that HCHO and H 2 O 2 can play critical roles in the atmospheric boundary layer (ABL) at high latitudes during the occurrence of ozone (O 3 ) depletion events that are commonly observed during polar sunrise in Arctic areas (McConnell et al, 1992). While the effective O 3 destruction is caused by reactions with chlorine (Cl) and bromine (Br) atoms (Barrie et al, , 1994Mickle et al, 1989;Bottenheim et al, 1990;Jobson et al, 1994;Solberg et al, 1996;Ariya et al, 1998;Ramacher et al, 1999), Cl and Br atoms also react quickly with HCHO and are transformed into nonreactive compounds like HCl and HBr that are subsequently removed from the gas phase Shepson et al, 1996).…”

Section: Introductionmentioning

confidence: 99%

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Measurements of hydrogen peroxide and formaldehyde exchange between the atmosphere and surface snow at Summit, Greenland

Jacobi

Frey

Hutterli

et al. 2002

Atmospheric Environment

115

123

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Tower-based measurements of hydrogen peroxide (H 2 O 2 ) and formaldehyde (HCHO) exchange were performed above the snowpack of the Greenland ice sheet. H 2 O 2 and HCHO fluxes were measured continuously between 16 June and 7 July 2000, at the Summit Environmental Observatory. The fluxes were determined using coil scrubber-aqueous phase fluorometry systems together with micrometeorological techniques. Both compounds exhibit strong diel cycles in the observed concentrations as well as in the fluxes with emission from the snow during the day and the evening and deposition during the night. The averaged diel variations of the observed fluxes were in the range of +1.3 Â 10 13 molecules m À2 s À1 (deposition) and À1.6 Â 10 13 molecules m À2 s À1 (emission) for H 2 O 2 and +1.1 Â 10 12 and À4.2 Â 10 12 molecules m À2 s À1 for HCHO, while the net exchange per day for both compounds were much smaller. During the study period of 22 days on average ð0:8 þ4:6 À4:3 Þ Â 10 17 molecules m À2 of H 2 O 2 were deposited and ð7:0 þ12:6 À12:2 Þ Â 10 16 molecules m À2 of HCHO were emitted from the snow per day. A comparison with the inventory in the gas phase demonstrates that the exchange influences the diel variations in the boundary layer above snow covered areas. Flux measurements during and after the precipitation of new snow shows that o16% of the H 2 O 2 and more than 25% of the HCHO originally present in the new snow were available for fast release to the atmospheric boundary layer within hours after precipitation. This release can effectively disturb the normally observed diel variations of the exchange between the surface snow and the atmosphere, thus perturbing also the diel variations of corresponding gas-phase concentrations. r

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Measurements of hydrogen peroxide and formaldehyde exchange between the atmosphere and surface snow at Summit, Greenland

Jacobi

Frey

Hutterli

et al. 2002

Atmospheric Environment

115

123

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“…Among the findings of this program was a pronounced inverse correlation between ozone levels in the lower Arctic atmosphere and filterable bromine during the polar Spring [13]. Several mechanisms that involve heterogeneous processing on Arctic aerosols have been proposed to account for this observation [14][15][16][17].…”

Section: Background and Research Objectivesmentioning

confidence: 99%

Heterogeneous processing of bromine compounds by atmospheric aerosols: Relation to the ozone budget

Robinson¹,

Henson²,

Dubey³

et al. 1998

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“…[1][2][3][4] Bromine-containing species, of either biogenic or anthropogenic origin, released at the earth's surface have been linked to ozone destruction in various altitude regions of the earth's atmosphere. [5][6][7] Recent findings show 8, 9 that the effectively catalytic removal of ozone by bromine on a per atom basis in the polar stratosphere is higher one hundred times than that of chlorine. Consequently, thorough and extensive investigations of bromine-containing species from both experiments and theory are urgently needed.…”

Section: Introductionmentioning

confidence: 99%

Vacuum synthesis and determination of the ionization energies of different molecular orbitals for BrOBr and HOBr

Zhimin

Sun

et al. 2003

The Journal of Chemical Physics

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Rovibrationally selected and resolved pulsed field ionization-photoelectron study of propyne: Ionization energy and spin-orbit interaction in propyne cation J. Chem. Phys. 128, 094311 (2008) Pure BrOBr and HOBr were synthesized in vacuum by heterogeneous reactions of the dried bromine vapor and Br 2 /H 2 O mixture vapors ͑5:1͒ with HgO, respectively, and then characterized by He I photoelectron spectroscopy ͑PES͒ and augmented by ab initio GAUSSIAN 2 and the outer valence Green's functional calculations. The first PE band at 10.26 eV with vibrational spacing 550Ϯ60 cm Ϫ1 and the second PE band at 11.23 eV with vibrational spacing 240Ϯ60 cm Ϫ1 are, respectively, assigned as ionizations of the electrons of the highest occupied molecular orbital ͑HOMO͒ (6b 1 (39)) and the SHOMO(13b 2 (38)) orbitals of BrOBr. The first PE band at 10.73 eV with vibrational spacing 750Ϯ60 cm Ϫ1 and the second PE band at 11.56 eV with vibrational spacing 650Ϯ60 cm Ϫ1 are, respectively, assigned as ionizations of the electrons of the HOMO(6aЉ (22)) and the SHOMO(16aЈ(21)) orbitals of HOBr. The study does not only provide vacuum synthesis conditions for preparing pure BrOBr and HOBr, but also provide experimental PES results along with theoretical ionization energies of different molecular orbitals for BrOBr and HOBr.

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Photochemical bromine production implicated in Arctic boundary-layer ozone depletion

Cited by 337 publications

References 18 publications

Measurements of hydrogen peroxide and formaldehyde exchange between the atmosphere and surface snow at Summit, Greenland

Measurements of hydrogen peroxide and formaldehyde exchange between the atmosphere and surface snow at Summit, Greenland

Heterogeneous processing of bromine compounds by atmospheric aerosols: Relation to the ozone budget

Vacuum synthesis and determination of the ionization energies of different molecular orbitals for BrOBr and HOBr

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