skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Active and widespread halogen chemistry in the tropical and subtropical free troposphere

Abstract

Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O 3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O 3 and methane (CH 4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10°N to 40°S), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O 3. The observed BrO concentrations increase strongly with altitude (~3.4 pptv at 13.5 km), and are 2–4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5–6.4 pptv total inorganic bromine (Br y), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination ofmore » sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. Lastly, the halogen-catalyzed loss of tropospheric O 3 needs to be considered when estimating past and future ozone radiative effects.« less

Authors:
 [1];  [2];  [3];  [3];  [3];  [3];  [4];  [5];  [4];  [6];  [5];  [7];  [8];  [9];  [4];  [4];  [4];  [10];  [4];  [11] more »;  [4];  [4];  [12];  [3] « less
  1. Univ. of Colorado, Boulder, CO (United States); The Hong Kong Univ. of Science and Technology, Hong Kong (China)
  2. Harvard Univ., Cambridge, MA (United States); Univ. of Copenhagen, Copenhagen (Denmark)
  3. Univ. of Colorado, Boulder, CO (United States)
  4. National Center for Atmospheric Research, Boulder, CO (United States)
  5. Univ. of York, York (United Kingdom)
  6. Univ. of Wisconsin, Madison, WI (United States)
  7. Princeton Univ., Princeton, NJ (United States); National Aeronautics and Space Administration, Hampton, VA (United States)
  8. Princeton Univ., Princeton, NJ (United States)
  9. National Oceanic and Atmospheric Administration, Boulder, CO (United States)
  10. Harvard Univ., Cambridge, MA (United States)
  11. National Oceanic and Atmospheric Administration, Madison, WI (United States)
  12. Electric Power Research Institute, Palo Alto, CA (United States)
Publication Date:
Research Org.:
Univ. of Colorado, Boulder, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1235122
Alternate Identifier(s):
OSTI ID: 1348399
Grant/Contract Number:  
SC0006080; EP-P27450/C13049; EP-P32238/C14974; 0602-02530B; 15121680
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 112; Journal Issue: 30; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES; atmospheric chemistry; oxidative capacity; halogens; heterogeneous chemistry; UTLS

Citation Formats

Wang, Siyuan, Schmidt, Johan A., Baidar, Sunil, Coburn, Sean, Dix, Barbara, Koenig, Theodore K., Apel, Eric, Bowdalo, Dene, Campos, Teresa L., Eloranta, Ed, Evans, Mathew J., DiGangi, Joshua P., Zondlo, Mark A., Gao, Ru -Shan, Haggerty, Julie A., Hall, Samuel R., Hornbrook, Rebecca S., Jacob, Daniel, Morley, Bruce, Pierce, Bradley, Reeves, Mike, Romashkin, Pavel, ter Schure, Arnout, and Volkamer, Rainer. Active and widespread halogen chemistry in the tropical and subtropical free troposphere. United States: N. p., 2015. Web. doi:10.1073/pnas.1505142112.
Wang, Siyuan, Schmidt, Johan A., Baidar, Sunil, Coburn, Sean, Dix, Barbara, Koenig, Theodore K., Apel, Eric, Bowdalo, Dene, Campos, Teresa L., Eloranta, Ed, Evans, Mathew J., DiGangi, Joshua P., Zondlo, Mark A., Gao, Ru -Shan, Haggerty, Julie A., Hall, Samuel R., Hornbrook, Rebecca S., Jacob, Daniel, Morley, Bruce, Pierce, Bradley, Reeves, Mike, Romashkin, Pavel, ter Schure, Arnout, & Volkamer, Rainer. Active and widespread halogen chemistry in the tropical and subtropical free troposphere. United States. doi:10.1073/pnas.1505142112.
Wang, Siyuan, Schmidt, Johan A., Baidar, Sunil, Coburn, Sean, Dix, Barbara, Koenig, Theodore K., Apel, Eric, Bowdalo, Dene, Campos, Teresa L., Eloranta, Ed, Evans, Mathew J., DiGangi, Joshua P., Zondlo, Mark A., Gao, Ru -Shan, Haggerty, Julie A., Hall, Samuel R., Hornbrook, Rebecca S., Jacob, Daniel, Morley, Bruce, Pierce, Bradley, Reeves, Mike, Romashkin, Pavel, ter Schure, Arnout, and Volkamer, Rainer. Mon . "Active and widespread halogen chemistry in the tropical and subtropical free troposphere". United States. doi:10.1073/pnas.1505142112.
@article{osti_1235122,
title = {Active and widespread halogen chemistry in the tropical and subtropical free troposphere},
author = {Wang, Siyuan and Schmidt, Johan A. and Baidar, Sunil and Coburn, Sean and Dix, Barbara and Koenig, Theodore K. and Apel, Eric and Bowdalo, Dene and Campos, Teresa L. and Eloranta, Ed and Evans, Mathew J. and DiGangi, Joshua P. and Zondlo, Mark A. and Gao, Ru -Shan and Haggerty, Julie A. and Hall, Samuel R. and Hornbrook, Rebecca S. and Jacob, Daniel and Morley, Bruce and Pierce, Bradley and Reeves, Mike and Romashkin, Pavel and ter Schure, Arnout and Volkamer, Rainer},
abstractNote = {Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O3 and methane (CH4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10°N to 40°S), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O3. The observed BrO concentrations increase strongly with altitude (~3.4 pptv at 13.5 km), and are 2–4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5–6.4 pptv total inorganic bromine (Bry), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. Lastly, the halogen-catalyzed loss of tropospheric O3 needs to be considered when estimating past and future ozone radiative effects.},
doi = {10.1073/pnas.1505142112},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 30,
volume = 112,
place = {United States},
year = {2015},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1505142112

Citation Metrics:
Cited by: 35 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Extensive halogen-mediated ozone destruction over the tropical Atlantic Ocean
journal, June 2008

  • Read, Katie A.; Mahajan, Anoop S.; Carpenter, Lucy J.
  • Nature, Vol. 453, Issue 7199
  • DOI: 10.1038/nature07035

Impact of reactive bromine chemistry in the troposphere
journal, January 2004

  • von Glasow, R.; von Kuhlmann, R.; Lawrence, M. G.
  • Atmospheric Chemistry and Physics, Vol. 4, Issue 11/12
  • DOI: 10.5194/acp-4-2481-2004

Estimating the climate significance of halogen-driven ozone loss in the tropical marine troposphere
journal, January 2012

  • Saiz-Lopez, A.; Lamarque, J. -F.; Kinnison, D. E.
  • Atmospheric Chemistry and Physics, Vol. 12, Issue 9
  • DOI: 10.5194/acp-12-3939-2012

Sources and deposition of reactive gaseous mercury in the marine atmosphere
journal, May 2009


Tropospheric bromine chemistry: implications for present and pre-industrial ozone and mercury
journal, January 2012

  • Parrella, J. P.; Jacob, D. J.; Liang, Q.
  • Atmospheric Chemistry and Physics, Vol. 12, Issue 15
  • DOI: 10.5194/acp-12-6723-2012

Changing concentration, lifetime and climate forcing of atmospheric methane
journal, April 1998


Analysis of BrO measurements from the Global Ozone Monitoring Experiment
journal, September 1998

  • Chance, Kelly
  • Geophysical Research Letters, Vol. 25, Issue 17
  • DOI: 10.1029/98GL52359

First profile measurements of tropospheric BrO
journal, September 2000

  • Fitzenberger, R.; Bösch, H.; Camy-Peyret, C.
  • Geophysical Research Letters, Vol. 27, Issue 18
  • DOI: 10.1029/2000GL011531

Spatial and temporal distribution of enhanced boundary layer BrO concentrations measured by the GOME instrument aboard ERS-2
journal, October 2001

  • Wagner, T.; Leue, C.; Wenig, M.
  • Journal of Geophysical Research: Atmospheres, Vol. 106, Issue D20
  • DOI: 10.1029/2000JD000201

Gome measurements of stratospheric and tropospheric BrO
journal, June 2002


Sensitivity of ozone to bromine in the lower stratosphere
journal, January 2005


Retrieval of stratospheric and tropospheric BrO profiles and columns using ground-based zenith-sky DOAS observations at Harestua, 60° N
journal, January 2007

  • Hendrick, F.; Van Roozendael, M.; Chipperfield, M. P.
  • Atmospheric Chemistry and Physics, Vol. 7, Issue 18
  • DOI: 10.5194/acp-7-4869-2007

Retrieval of stratospheric and tropospheric BrO columns from multi-axis DOAS measurements at Reunion Island (21° S, 56° E)
journal, January 2007

  • Theys, N.; Van Roozendael, M.; Hendrick, F.
  • Atmospheric Chemistry and Physics, Vol. 7, Issue 18
  • DOI: 10.5194/acp-7-4733-2007

The CU ground MAX-DOAS instrument: characterization of RMS noise limitations and first measurements near Pensacola, FL of BrO, IO, and CHOCHO
journal, January 2011

  • Coburn, S.; Dix, B.; Sinreich, R.
  • Atmospheric Measurement Techniques, Vol. 4, Issue 11
  • DOI: 10.5194/amt-4-2421-2011

Global observations of tropospheric BrO columns using GOME-2 satellite data
journal, January 2011

  • Theys, N.; Van Roozendael, M.; Hendrick, F.
  • Atmospheric Chemistry and Physics, Vol. 11, Issue 4
  • DOI: 10.5194/acp-11-1791-2011

Detection of iodine monoxide in the tropical free troposphere
journal, January 2013

  • Dix, B.; Baidar, S.; Bresch, J. F.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 6
  • DOI: 10.1073/pnas.1212386110

Iodine monoxide in the north subtropical free troposphere
journal, January 2012

  • Puentedura, O.; Gil, M.; Saiz-Lopez, A.
  • Atmospheric Chemistry and Physics, Vol. 12, Issue 11
  • DOI: 10.5194/acp-12-4909-2012

Large contribution of natural aerosols to uncertainty in indirect forcing
journal, November 2013

  • Carslaw, K. S.; Lee, L. A.; Reddington, C. L.
  • Nature, Vol. 503, Issue 7474
  • DOI: 10.1038/nature12674

A large ozone-circulation feedback and its implications for global warming assessments
journal, December 2014

  • Nowack, Peer J.; Luke Abraham, N.; Maycock, Amanda C.
  • Nature Climate Change, Vol. 5, Issue 1
  • DOI: 10.1038/nclimate2451

Bromine in the tropical troposphere and stratosphere as derived from balloon-borne BrO observations
journal, January 2008

  • Dorf, M.; Butz, A.; Camy-Peyret, C.
  • Atmospheric Chemistry and Physics, Vol. 8, Issue 23
  • DOI: 10.5194/acp-8-7265-2008

Climatology of the stratospheric BrO vertical distribution by balloon-borne UV–visible spectrometry
journal, January 2002


Atmospheric iodine levels influenced by sea surface emissions of inorganic iodine
journal, January 2013

  • Carpenter, Lucy J.; MacDonald, Samantha M.; Shaw, Marvin D.
  • Nature Geoscience, Vol. 6, Issue 2
  • DOI: 10.1038/ngeo1687

Tropospheric bromine chemistry and its impacts on ozone: A model study
journal, January 2005

  • Yang, Xin; Cox, Richard A.; Warwick, Nicola J.
  • Journal of Geophysical Research, Vol. 110, Issue D23
  • DOI: 10.1029/2005JD006244

Inorganic bromine in the marine boundary layer: a critical review
journal, January 2003

  • Sander, R.; Keene, W. C.; Pszenny, A. A. P.
  • Atmospheric Chemistry and Physics, Vol. 3, Issue 5
  • DOI: 10.5194/acp-3-1301-2003

Bromine partitioning in the tropical tropopause layer: implications for stratospheric injection
journal, January 2014

  • Fernandez, R. P.; Salawitch, R. J.; Kinnison, D. E.
  • Atmospheric Chemistry and Physics, Vol. 14, Issue 24
  • DOI: 10.5194/acp-14-13391-2014

Convective transport of very short lived bromocarbons to the stratosphere
journal, January 2014


Climatology of intrusions into the tropical upper troposphere
journal, December 2000

  • Waugh, Darryn W.; Polvani, Lorenzo M.
  • Geophysical Research Letters, Vol. 27, Issue 23
  • DOI: 10.1029/2000GL012250

Separation of the lapse rate and the cold point tropopauses in the tropics and the resulting impact on cloud top-tropopause relationships
journal, July 2014

  • Munchak, Leigh A.; Pan, Laura L.
  • Journal of Geophysical Research: Atmospheres, Vol. 119, Issue 13
  • DOI: 10.1002/2013JD021189

Impact of deep convection and dehydration on bromine loading in the upper troposphere and lower stratosphere
journal, January 2011

  • Aschmann, J.; Sinnhuber, B. -M.; Chipperfield, M. P.
  • Atmospheric Chemistry and Physics, Vol. 11, Issue 6
  • DOI: 10.5194/acp-11-2671-2011

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VI – heterogeneous reactions with liquid substrates
journal, January 2013

  • Ammann, M.; Cox, R. A.; Crowley, J. N.
  • Atmospheric Chemistry and Physics, Vol. 13, Issue 16
  • DOI: 10.5194/acp-13-8045-2013

Re-evaluating the reactive uptake of HOBr in the troposphere with implications for the marine boundary layer and volcanic plumes
journal, January 2014

  • Roberts, T. J.; Jourdain, L.; Griffiths, P. T.
  • Atmospheric Chemistry and Physics, Vol. 14, Issue 20
  • DOI: 10.5194/acp-14-11185-2014

Cirrus clouds and deep convection in the tropics: Insights from CALIPSO and CloudSat
journal, January 2009

  • Sassen, Kenneth; Wang, Zhien; Liu, Dong
  • Journal of Geophysical Research, Vol. 114
  • DOI: 10.1029/2009JD011916

Aerosols that form subvisible cirrus at the tropical tropopause
journal, January 2010

  • Froyd, K. D.; Murphy, D. M.; Lawson, P.
  • Atmospheric Chemistry and Physics, Vol. 10, Issue 1
  • DOI: 10.5194/acp-10-209-2010

Clarifying the Dominant Sources and Mechanisms of Cirrus Cloud Formation
journal, May 2013


Transport analysis and source attribution of seasonal and interannual variability of CO in the tropical upper troposphere and lower stratosphere
journal, January 2012

  • Liu, Junhua; Logan, J. A.; Murray, L. T.
  • Atmospheric Chemistry and Physics Discussions, Vol. 12, Issue 7
  • DOI: 10.5194/acpd-12-17397-2012

Distribution of halon-1211 in the upper troposphere and lower stratosphere and the 1994 total bromine budget
journal, January 1998

  • Wamsley, P. R.; Elkins, J. W.; Fahey, D. W.
  • Journal of Geophysical Research: Atmospheres, Vol. 103, Issue D1
  • DOI: 10.1029/97JD02466

Global lifetime of elemental mercury against oxidation by atomic bromine in the free troposphere
journal, January 2006

  • Holmes, Christopher D.; Jacob, Daniel J.; Yang, Xin
  • Geophysical Research Letters, Vol. 33, Issue 20
  • DOI: 10.1029/2006GL027176

Global atmospheric model for mercury including oxidation by bromine atoms
journal, January 2010

  • Holmes, C. D.; Jacob, D. J.; Corbitt, E. S.
  • Atmospheric Chemistry and Physics, Vol. 10, Issue 24
  • DOI: 10.5194/acp-10-12037-2010

Thermodynamics of reactions of ClHg and BrHg radicals with atmospherically abundant free radicals
journal, January 2012


Formation and fate of oxidized mercury in the upper troposphere and lower stratosphere
journal, December 2011

  • Lyman, Seth N.; Jaffe, Daniel A.
  • Nature Geoscience, Vol. 5, Issue 2
  • DOI: 10.1038/ngeo1353

Observations of Mercury-Containing Aerosols
journal, May 2006

  • Murphy, D. M.; Hudson, P. K.; Thomson, D. S.
  • Environmental Science & Technology, Vol. 40, Issue 10
  • DOI: 10.1021/es052385x

Total depletion of Hg° in the upper troposphere-lower stratosphere: HG° DEPLETION IN UPPER TROPOSPHERE
journal, December 2007

  • Talbot, R.; Mao, H.; Scheuer, E.
  • Geophysical Research Letters, Vol. 34, Issue 23
  • DOI: 10.1029/2007GL031366

Observations of speciated atmospheric mercury at three sites in Nevada: Evidence for a free tropospheric source of reactive gaseous mercury
journal, January 2009

  • Weiss-Penzias, Peter; Gustin, Mae Sexauer; Lyman, Seth N.
  • Journal of Geophysical Research, Vol. 114, Issue D14
  • DOI: 10.1029/2008JD011607

Cloud-resolving simulations of mercury scavenging and deposition in thunderstorms
journal, January 2013


Global Biogeochemical Cycling of Mercury: A Review
journal, November 2009


The CU Airborne MAX-DOAS instrument: vertical profiling of aerosol extinction and trace gases
journal, January 2013

  • Baidar, S.; Oetjen, H.; Coburn, S.
  • Atmospheric Measurement Techniques, Vol. 6, Issue 3
  • DOI: 10.5194/amt-6-719-2013

Chemical evolution of volatile organic compounds in the outflow of the Mexico City Metropolitan area
journal, January 2010

  • Apel, E. C.; Emmons, L. K.; Karl, T.
  • Atmospheric Chemistry and Physics, Vol. 10, Issue 5
  • DOI: 10.5194/acp-10-2353-2010

Vertical cavity laser hygrometer for the National Science Foundation Gulfstream-V aircraft
journal, January 2010

  • Zondlo, Mark A.; Paige, Mark E.; Massick, Steven M.
  • Journal of Geophysical Research, Vol. 115, Issue D20
  • DOI: 10.1029/2010JD014445

The Monte Carlo atmospheric radiative transfer model McArtim: Introduction and validation of Jacobians and 3D features
journal, April 2011

  • Deutschmann, Tim; Beirle, Steffen; Frieß, Udo
  • Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 112, Issue 6
  • DOI: 10.1016/j.jqsrt.2010.12.009

Chemical data assimilation estimates of continental U.S. ozone and nitrogen budgets during the Intercontinental Chemical Transport Experiment–North America
journal, January 2007

  • Pierce, Robert B.; Schaack, Todd; Al-Saadi, Jassim A.
  • Journal of Geophysical Research, Vol. 112, Issue D12
  • DOI: 10.1029/2006JD007722

    Works referencing / citing this record:

    Modeling the observed tropospheric BrO background: Importance of multiphase chemistry and implications for ozone, OH, and mercury: MODELING THE TROPOSPHERIC BrO BACKGROUND
    journal, October 2016

    • Schmidt, J. A.; Jacob, D. J.; Horowitz, H. M.
    • Journal of Geophysical Research: Atmospheres, Vol. 121, Issue 19
    • DOI: 10.1002/2015jd024229