Observations of inorganic bromine (HOBr, BrO, and Br2) speciation at Barrow, Alaska, in spring 2009

J. Liao, L. G. Huey, D. J. Tanner, F. M. Flocke, J. J. Orlando, J. A. Neuman, J. B. Nowak, A. J. Weinheimer, S. R. Hall, J. N. Smith, A. Fried, R. M. Staebler, Y. Wang, J. H. Koo, C. A. Cantrell, P. Weibring, J. Walega, D. J. Knapp, P. B. Shepson, C. R. Stephens

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Abstract

Inorganic bromine plays a critical role in ozone and mercury depletions events (ODEs and MDEs) in the Arctic marine boundary layer. Direct observations of bromine species other than bromine oxide (BrO) during ODEs are very limited. Here we report the first direct measurements of hypobromous acid (HOBr) as well as observations of BrO and molecular bromine (Br2) by chemical ionization mass spectrometry at Barrow, Alaska in spring 2009 during the Ocean-Atmospheric-Sea Ice-Snowpack (OASIS) campaign. Diurnal profiles of HOBr with maximum concentrations near local noon and no significant concentrations at night were observed. The measured average daytime HOBr mixing ratio was 10 pptv with a maximum value of 26 pptv. The observed HOBr was reasonably well correlated (R2 = 0.57) with predictions from a simple steady state photochemical model constrained to observed BrO and HO2 at wind speeds <6m s-1. However, predicted HOBr levels were considerably higher than observations at higher wind speeds. This may be due to enhanced heterogeneous loss of HOBr on blowing snow coincident with higher wind speeds. BrO levels were also found to be higher at elevated wind speeds. Br2 was observed in significant mixing ratios (maximum = 46 pptv; average = 13 pptv) at night and was strongly anti-correlated with ozone. The diurnal speciation of observed gas phase inorganic bromine species can be predicted by a time-dependent box model that includes efficient heterogeneous recycling of HOBr, hydrogen bromide (HBr), and bromine nitrate (BrONO2) back to more reactive forms of bromine.

Original languageEnglish
Article numberD00R16
JournalJournal of Geophysical Research Atmospheres
Volume117
Issue number6
DOIs
Publication statusPublished - 2012 Jan 1

Fingerprint

bromine
Bromine
barrows
Oxides
oxides
oxide
acids
acid
wind speed
wind velocity
Ozone
mixing ratios
ozone
mixing ratio
night
Hydrobromic Acid
hypobromous acid
blowing snow
ozone depletion
Sea ice

All Science Journal Classification (ASJC) codes

  • Geophysics
  • Forestry
  • Oceanography
  • Aquatic Science
  • Ecology
  • Water Science and Technology
  • Soil Science
  • Geochemistry and Petrology
  • Earth-Surface Processes
  • Atmospheric Science
  • Earth and Planetary Sciences (miscellaneous)
  • Space and Planetary Science
  • Palaeontology

Cite this

Liao, J., Huey, L. G., Tanner, D. J., Flocke, F. M., Orlando, J. J., Neuman, J. A., ... Stephens, C. R. (2012). Observations of inorganic bromine (HOBr, BrO, and Br2) speciation at Barrow, Alaska, in spring 2009. Journal of Geophysical Research Atmospheres, 117(6), [D00R16]. https://doi.org/10.1029/2011JD016641
Liao, J. ; Huey, L. G. ; Tanner, D. J. ; Flocke, F. M. ; Orlando, J. J. ; Neuman, J. A. ; Nowak, J. B. ; Weinheimer, A. J. ; Hall, S. R. ; Smith, J. N. ; Fried, A. ; Staebler, R. M. ; Wang, Y. ; Koo, J. H. ; Cantrell, C. A. ; Weibring, P. ; Walega, J. ; Knapp, D. J. ; Shepson, P. B. ; Stephens, C. R. / Observations of inorganic bromine (HOBr, BrO, and Br2) speciation at Barrow, Alaska, in spring 2009. In: Journal of Geophysical Research Atmospheres. 2012 ; Vol. 117, No. 6.
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title = "Observations of inorganic bromine (HOBr, BrO, and Br2) speciation at Barrow, Alaska, in spring 2009",
abstract = "Inorganic bromine plays a critical role in ozone and mercury depletions events (ODEs and MDEs) in the Arctic marine boundary layer. Direct observations of bromine species other than bromine oxide (BrO) during ODEs are very limited. Here we report the first direct measurements of hypobromous acid (HOBr) as well as observations of BrO and molecular bromine (Br2) by chemical ionization mass spectrometry at Barrow, Alaska in spring 2009 during the Ocean-Atmospheric-Sea Ice-Snowpack (OASIS) campaign. Diurnal profiles of HOBr with maximum concentrations near local noon and no significant concentrations at night were observed. The measured average daytime HOBr mixing ratio was 10 pptv with a maximum value of 26 pptv. The observed HOBr was reasonably well correlated (R2 = 0.57) with predictions from a simple steady state photochemical model constrained to observed BrO and HO2 at wind speeds <6m s-1. However, predicted HOBr levels were considerably higher than observations at higher wind speeds. This may be due to enhanced heterogeneous loss of HOBr on blowing snow coincident with higher wind speeds. BrO levels were also found to be higher at elevated wind speeds. Br2 was observed in significant mixing ratios (maximum = 46 pptv; average = 13 pptv) at night and was strongly anti-correlated with ozone. The diurnal speciation of observed gas phase inorganic bromine species can be predicted by a time-dependent box model that includes efficient heterogeneous recycling of HOBr, hydrogen bromide (HBr), and bromine nitrate (BrONO2) back to more reactive forms of bromine.",
author = "J. Liao and Huey, {L. G.} and Tanner, {D. J.} and Flocke, {F. M.} and Orlando, {J. J.} and Neuman, {J. A.} and Nowak, {J. B.} and Weinheimer, {A. J.} and Hall, {S. R.} and Smith, {J. N.} and A. Fried and Staebler, {R. M.} and Y. Wang and Koo, {J. H.} and Cantrell, {C. A.} and P. Weibring and J. Walega and Knapp, {D. J.} and Shepson, {P. B.} and Stephens, {C. R.}",
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Liao, J, Huey, LG, Tanner, DJ, Flocke, FM, Orlando, JJ, Neuman, JA, Nowak, JB, Weinheimer, AJ, Hall, SR, Smith, JN, Fried, A, Staebler, RM, Wang, Y, Koo, JH, Cantrell, CA, Weibring, P, Walega, J, Knapp, DJ, Shepson, PB & Stephens, CR 2012, 'Observations of inorganic bromine (HOBr, BrO, and Br2) speciation at Barrow, Alaska, in spring 2009', Journal of Geophysical Research Atmospheres, vol. 117, no. 6, D00R16. https://doi.org/10.1029/2011JD016641

Observations of inorganic bromine (HOBr, BrO, and Br2) speciation at Barrow, Alaska, in spring 2009. / Liao, J.; Huey, L. G.; Tanner, D. J.; Flocke, F. M.; Orlando, J. J.; Neuman, J. A.; Nowak, J. B.; Weinheimer, A. J.; Hall, S. R.; Smith, J. N.; Fried, A.; Staebler, R. M.; Wang, Y.; Koo, J. H.; Cantrell, C. A.; Weibring, P.; Walega, J.; Knapp, D. J.; Shepson, P. B.; Stephens, C. R.

In: Journal of Geophysical Research Atmospheres, Vol. 117, No. 6, D00R16, 01.01.2012.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Observations of inorganic bromine (HOBr, BrO, and Br2) speciation at Barrow, Alaska, in spring 2009

AU - Liao, J.

AU - Huey, L. G.

AU - Tanner, D. J.

AU - Flocke, F. M.

AU - Orlando, J. J.

AU - Neuman, J. A.

AU - Nowak, J. B.

AU - Weinheimer, A. J.

AU - Hall, S. R.

AU - Smith, J. N.

AU - Fried, A.

AU - Staebler, R. M.

AU - Wang, Y.

AU - Koo, J. H.

AU - Cantrell, C. A.

AU - Weibring, P.

AU - Walega, J.

AU - Knapp, D. J.

AU - Shepson, P. B.

AU - Stephens, C. R.

PY - 2012/1/1

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N2 - Inorganic bromine plays a critical role in ozone and mercury depletions events (ODEs and MDEs) in the Arctic marine boundary layer. Direct observations of bromine species other than bromine oxide (BrO) during ODEs are very limited. Here we report the first direct measurements of hypobromous acid (HOBr) as well as observations of BrO and molecular bromine (Br2) by chemical ionization mass spectrometry at Barrow, Alaska in spring 2009 during the Ocean-Atmospheric-Sea Ice-Snowpack (OASIS) campaign. Diurnal profiles of HOBr with maximum concentrations near local noon and no significant concentrations at night were observed. The measured average daytime HOBr mixing ratio was 10 pptv with a maximum value of 26 pptv. The observed HOBr was reasonably well correlated (R2 = 0.57) with predictions from a simple steady state photochemical model constrained to observed BrO and HO2 at wind speeds <6m s-1. However, predicted HOBr levels were considerably higher than observations at higher wind speeds. This may be due to enhanced heterogeneous loss of HOBr on blowing snow coincident with higher wind speeds. BrO levels were also found to be higher at elevated wind speeds. Br2 was observed in significant mixing ratios (maximum = 46 pptv; average = 13 pptv) at night and was strongly anti-correlated with ozone. The diurnal speciation of observed gas phase inorganic bromine species can be predicted by a time-dependent box model that includes efficient heterogeneous recycling of HOBr, hydrogen bromide (HBr), and bromine nitrate (BrONO2) back to more reactive forms of bromine.

AB - Inorganic bromine plays a critical role in ozone and mercury depletions events (ODEs and MDEs) in the Arctic marine boundary layer. Direct observations of bromine species other than bromine oxide (BrO) during ODEs are very limited. Here we report the first direct measurements of hypobromous acid (HOBr) as well as observations of BrO and molecular bromine (Br2) by chemical ionization mass spectrometry at Barrow, Alaska in spring 2009 during the Ocean-Atmospheric-Sea Ice-Snowpack (OASIS) campaign. Diurnal profiles of HOBr with maximum concentrations near local noon and no significant concentrations at night were observed. The measured average daytime HOBr mixing ratio was 10 pptv with a maximum value of 26 pptv. The observed HOBr was reasonably well correlated (R2 = 0.57) with predictions from a simple steady state photochemical model constrained to observed BrO and HO2 at wind speeds <6m s-1. However, predicted HOBr levels were considerably higher than observations at higher wind speeds. This may be due to enhanced heterogeneous loss of HOBr on blowing snow coincident with higher wind speeds. BrO levels were also found to be higher at elevated wind speeds. Br2 was observed in significant mixing ratios (maximum = 46 pptv; average = 13 pptv) at night and was strongly anti-correlated with ozone. The diurnal speciation of observed gas phase inorganic bromine species can be predicted by a time-dependent box model that includes efficient heterogeneous recycling of HOBr, hydrogen bromide (HBr), and bromine nitrate (BrONO2) back to more reactive forms of bromine.

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