Atmospheric Chemistry and Physics Discussions
www.atmos-chem-phys-discuss.net
1680-7367
1680-7375
8
1
2008
10.5194/acpd-8-3563-2008
http://www.atmos-chem-phys-discuss.net/8/3563/2008/
http://www.atmos-chem-phys-discuss.net/8/3563/2008/acpd-8-3563-2008.html
http://www.atmos-chem-phys-discuss.net/8/3563/2008/acpd-8-3563-2008.pdf
3563
3595
2008-02-20
Airborne measurements of HCl from the marine boundary layer to the lower stratosphere over the North Pacific Ocean during INTEX-B
S. Kim
L. G. Huey
R. E. Stickel
R. B. Pierce
G. Chen
M. A. Avery
J. E. Dibb
G. S. Diskin
G. W. Sachse
C. S. McNaughton
A. D. Clarke
B. E. Anderson
D. R. Blake
School of Earth and Atmospheric Sciences, Georgia Institute of Technology, USA
NASA Langley Research Center, USA
Institute for the Study of Earth, Oceans, and Space, University of New Hampshire, USA
Department of Oceanography, University of Hawaii, USA
Department of Chemistry, University of California, Irvine, USA
now at: Advanced Study Program, NCAR, Boulder CO, USA
now at: NOAA/NESDIS Advanced Satellite Products Branch, Madison Wiv
now at: National Institute of Aerospace, Hampton VA, USA
Gas phase HCl was measured from the marine boundary layer (MBL) to the lower
stratosphere from the NASA DC-8 during five science flights (41 h) of
the Intercontinental Chemical Transport Experiment-Phase B (INTEX-B) field
campaign. In the upper troposphere/lower stratosphere (UT/LS, 8–12 km) HCl
was observed to range from a few tens to 100 pptv due to stratospheric
influence with a background tropospheric level of less than 2 pptv. In the
8–12 km altitude range, a simple analysis of the O<sub>3</sub>/HCl correlation
shows that pure stratospheric and mixed tropospheric/stratospheric air
masses were encountered 30% and 15% of the time, respectively. In the
mid troposphere (4–8 km) HCl levels were usually below 2 pptv except for a
few cases of stratospheric influence and were much lower than reported in
previous work. These data indicate that background levels of HCl in the mid
and upper troposphere are very low and confirm its use in these regions as a
tracer of stratospheric ozone. However, a case study suggests that HCl may
be produced in the mid troposphere by the dechlorination of dust aerosols.
In the remote marine boundary layer HCl levels were consistently above 20 pptv (up to 140 pptv)
and strongly correlated with HNO<sub>3</sub>. Cl atom levels
were estimated from the background level of HCl in the MBL. This analysis
suggests a Cl concentration of ~3×10<sup>3</sup> atoms cm<sup>−3</sup>,
which corresponds to the lower range of previous studies. Finally, the
observed HCl levels are compared to predictions by the Real-time Air Quality
Modeling System (RAQMS) to assess its ability to characterize the impact of
stratospheric transport on the upper troposphere.
Arsene, C., Bougiatioti, A., Kanakidou, M., Bonsang, B., and Mihalopoulos, N.: Tropospheric OH and Cl levels deduced from non-methane hydrocarbon measurements in a marine site, Atmos. Chem. Phys., 7, 4661–4673, 2007.
Behnke, W., George, C., Scheer, V., and Zetzsch, C.: Production and decay of ClNO<sub>2</sub> from the reaction of gaseous N<sub>2</sub>O$_5$ with NaCl solution: Bulk and aerosol experiments, J. Geophys. Res., 102, 3795–3804, 1997.
Chang, S., McDonald-Buller, E. C., Kimura, Y., Yarwood, G., Neece, J. D., Russell, M., Tanaka, P., and Allen, D.: Sensitivity of urban ozone formation to chlorine emission estimates, Atmos. Environ., 36, 4991–5003, 2002.
Dibb, J. E., Talbot, R. W., Scheuer, E., Seid, G., and DeBell, L.: Stratospheric influence on the northern North American free troposphere during TOPSE: $^7$Be as a stratospheric tracer, J. Geophys. Res., 108, 8368, doi:8310.1029/2001JD001347, 2003.
Erickson, E.: The yearly circulation of chloride and sulfur in nature; meteorological, geochemical and pedological implications, Part I., Tellus, 11, 375–403, 1959.
Erickson, E.: The yearly circulation of chloride and sulfur in nature; meteorological, geochemical and pedological implications, Part II., Tellus, 12, 63–109, 1959.
Finley, B. and Saltzman, E.: Measurement of Cl<sub>2</sub> in coastal urban air, Geophys. Res. Lett., 33, L11809, doi:11810.11029/12006GL025799, 2006.
Graedel, T. E. and Keene, W. C.: Tropospheric budget of reactive chlorine, Glob. Biogeochem. Cy., 9, 47–77, 1995.
Hanson, D. R. and Ravishankara, A. R.: The reaction probabilities of CONO$_2 $ and N<sub>2</sub>O$_5$ on 40 to 75% sulfuric acid solutions, J. Geophys. Res., 96, 17 307–17 314, 1991.
Hanson, D. R. and Ravishankara, A. R.: Reaction of CLONO$_2 $ with HCl on NAT, NAD, and frozen sulfuric acid and hydrolysis of N<sub>2</sub>O$_5$ and ClONO<sub>2</sub> on frozen sulfuric acid, J. Geophys. Res., 98, 22 931–22 936, 1993.
Hanson, D. R. and Ravishankara, A. R.: Reactive uptake of ClONO<sub>2</sub> onto sulfuric acid due to reaction with HCl and H<sub>2</sub>O, J. Phys. Chem., 98, 5728–5735, 1994.
Hanson, D. R., Ravishankara, A. R., and Solomon, S.: Heterogeneos reactions in sulfuric acid aerosols: A framework for model calculations, J. Geophys. Res., 99, 3615–3629, 1994.
Huey, L. G.: Measurement of trace atmospheric species by chemical ionization mass spectrometry: Speciation of reactive nitrogen and future directions, Mass Spectrom. Rev., 26, 166–184, 2007.
Huey, L. G., Hanson, D. R., and Howard, C. J.: Reactions of SF$_6^-$ and I$^-$ with atmospheric trace gases, J. Phys. Chem., 99, 5001–5008, 1995.
Jobson, B. T., Niki, H., Yokouchi, Y., Bottenheim, J., Hopper, F., and Leaitch, R.: Measurements of C2–C6 hydrocarbons during the Polar Sunrise 1992 Experiment: Evidence for Cl atom and Br atom chemistry, J. Geophy. Res., 99, D12, 25 355–25 368, 1994.
Jobson, B. T., Parrish, D., Goldan, P., Kuster, W., Feshenfeld, F. C., Blake, D. R., Blake, N. J., and Niki, H.: Spatial and temporal variability of nonmethane hydrocarbon mixing ratios and their relation to photochemical lifetime, J. Geophys. Res., 103, 13 557–13 567, 1998.
Keene, W. C., Aslam, M., Khalil, K., Erickson, D. J., McCulloch, A., Graedel, T. E., Lobert, J. M., Aucott, M. L., Gong, S. L., Harper, D. B., Kleiman, G., Midgley, P., Moore, R. M., Seuzaret, C., Sturges, W. T., Benkovitz, C. M., Koropalov, V., Barrie, L. A., and Li, Y. F.: Composite global emissions of reactive chlorine from anthropogenic and natural resorces; Reactive Chlorine Emissions Inventory, J. Geophys. Res., 104, 8429–8440, 1999.
Keene, W. C., Stutz, J., Pszenny, A. P., Maben, J. R., Fischer, E. V., Smith, A. M., von Glasow, R., Pechtl, S., Sive, B. C., and Varner, R. K.: Inorganic chlorine and bromine in coastal New England air during summer, J. Geophys. Res., 112, doi:10.1029/2006JD007689, 2004.
Kerminen, V.-M., Teinila, K., Hillamo, R., and Pakkanen, T.: Substitution of chloride in sea-salt paticles by inorganic and organic anions, J. Aerosol Sci., 29, 929–942, 1998.
Kim, S., Huey, L. G., Stickel, R. E., Tanner, D. J., Crawford, J. H., Olson, J. R., Chen, G., Brune, W. H., Ren, X., Lesher, R., Wooldridge, P. J., Bertram, T. H., Perring, A., Cohen, R. C., Lefer, B. L., Shetter, R. E., Avery, M., Diskin, G., and Sokolik, I.: Measurement of HO<sub>2</sub>NO<sub>2</sub> in the free troposphere during the Intercontinental Chemical Transport Experiment-North America 2004, J. Geophys. Res., 112, D12S01, doi:10.1029/2006JD007676, 2007.
Kerkweg, A., Buchholz J., Ganzeveld L., Pozzer, A., Tost H., and Jökel, P.: Technical Note: An implementation of the dry removal processes DRY DEPosition and SEDImentation in the Modular Earth Submodel System (MESSy), Atmos. Chem. Phys., 6, 4617–4632, 2006.
Lelieveld, J., Bregman, A., Scheeren, H. A., Strom, J., Carslaw, K. S., Fischer, H., Siegmund, P. C., and Arnold, F.: Chlorine activation and ozone destruction in the northern lowermost stratosphere, J. Geophys. Res., 104, 8201–8212, 1999.
Lin, C. L., Leu, M. T., and DeMore, W. B.: Rate constant for the reaction of atomic chlorine with methane, J. Phys. Chem., 82, 1772–1777, 1978.
Marcy, T. P., Fahey, D. W., Gao, R. S., Popp, P. J., Richard, E. C., Thompson, T. L., Rossenlof, K. H., Ray, E. A., Salawitch, R. J., Atherton, C. S., Bergmann, D. J., Ridley, B. A., Weinheimer, A. J., Loewenstein, M., Weinstock, E. M., and Mahoney, M. J.: Quantifying stratospheric ozone in the upper troposphere with in situ measurements of HCl, Science, 304, 261–265, 2004.
Molina, M. J. and Rowland, F. S.: Stratospheric sink for chlorofluoromethanes:Chlorine-atom catalysed destruction of ozone, Nature, 249, 810–812, 1974.
Ooki, A., and Uematsu, M.: Chemical interactions between mineral dust particles and acid gases during Asian dust events, J. Geophys. Res., 110, D03201, doi:10.1029/2004JD004737, 2005.
Pierce, R. B., Al-Saadi, J. A., Schaack, T., Lenzen, A., Zapotocny, T., Johnson, D. G., Kittaka, C., Buker, M., Hitchman, M. H., Tripoli, G., Fairlie, T. D., Olson, J. R., Natarajan, M., Crawford, J., Fishman, J., Avery, M., Browell, E., Creilson, J., Kondo, Y., and Sandholm, S. T.: Regional Air Quality Modeling System (RAQMS) predictions of the tropospheric ozone budget over east Asia, J. Geophys. Res., 108, 8825, doi:8810.1029/2002JD003176, 2003.
Pierce, R. B., Schaack, T., Al-Saadi, J. A., Fairlie, T. D., Kittaka, C., Lingenfelser, G., Natarajan, M., Olson, J., Soja, A., Zapotocny, T., Lenzen, A., Stobie, J., Johnson, D., Avery, M. A., Sachse, G. W., Thompson, A., Cohen, R., Dibb, J. E., Crawford, J., Rault, D., Martin, R., Szykman, J.,and Fishman, J.: Chemical data assimilation estimates of continental U.S. ozone and nitrogen budgets during the Intercontinental Chemical Transport Experiment-North America, J. Geophys. Res. 112, D12S21, doi:10.1029/2006JD007722, 2007.
Pszenny, A. A. P., Moldanova, J., Keene, W. C., Sander, R., Maben, J. R., Martinez, M., Crutzen, P. J., Perner, D., and Prinn, R. G.: Halogen cycling and aerosol pH in the Hawaiian marine boundary layer, Atmos. Chem. Phys., 4, 147–168, 2004.
Rossi, M. J.: Heterogeneous reactions on salts, Chemical Reviews, 103, 4823–4882, 2003.
Rotman, D. A., Atherton, C. S., Bergmann, D. J., Cameron-Smith, P. J., Chuang, C. C., Connell, P. S., Dignon, J. E., Franz, A., Grant, K. E., Kinnison, D. E., Molenkamp, C. R., Proctor, D. D., and Tannahill, J. R.: IMPACT, the LLNL 3-D global atmospheric chemical transport model for the combined troposphere and stratosphere: Model description and analysis of ozone and other trace gases, J. Geophys. Res. 109, D04303, doi:10.1029/2002JD003155, 2004.
Rudolph, J., Koppmann, R., and Plass-Dulmer, C.: The budget of ethane and tetrachloroethene: Is there evidence for an impact of reactions with chlorine atoms in the troposphere?, Atmos. Environ., 30, 1887–1894, 1996.
Rudolph, J., Ramacher, B., Plass-Dulmer, C., Muller, K.-P., and Koppmann, R.: The indirect determination of chlorine atom concentration in the troposhere from changes in the patterns of non-methane hydrocarbons, Tellus, 49B, 592–601, 1997.
Russell III, J. M., Deaver, L. E., Luo, M., Park, J. H., Gordley, L. L., Tuck, A. F., Toon, G. C., Gunson, M. R., Traub, W. A., Johnson, D. G., Jucks, K. W., Murcray, D. G., Zander, R., Nolt, I. G., and Webster, C. R.: Validation of hydrogen chloride measurements made by the Halogen Occultation Experiment from the UARS platform, J. Geophys. Res., 101, 10 151–10 162, 1996.
Sander, S. P., Friedl, R. R., Ravishankara, A. R., Golden, D. M., Kolb, C. E., Kurylo, M. J., Molina, M. J., Mootgat, G. K., Finlayson-Pitts, B. J., Wine, P. H., Huie, R. E., and Orkin, V. L.: Chemical kinetics and photochemical data for use in atmospheric studies, Evaluation Number 15, JPL Publication 06–2, 2006.
Schweitzer, F., Mirabel, P., and George, C.: Multiphase chemistry of N<sub>2</sub>O$_5$, ClNO<sub>2</sub> and BrNO<sub>2</sub>, J. Phys. Chem. A, 102, 3942–3952, 1998.
Seinfeld J. H. and Pandis S. N.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, Wiley-Interscience, 2nd edition, New York, 2006.
Singh, H. B., Gregory, G. L., Anderson, B., Browell, E., Sachse, G. W., Davis, D. D., Crawford, J., Bradshaw, J. D., Talbot, R., Blake, D. R., Thornton, D., Newell, R., and Merrill, J.: Low ozone in the marine boundary layer of the tropical pacific ocean;Photochemical loss, chlorine atoms, and entrainment, J. Geophys. Res., 101, 1907–1914, 1996a.
Singh, H. B., Thakur, A. N., Chen, Y. E., and Kanakidou, M.: Tetrachloroethylene as an indicator of low Cl atom concentrations in the troposphere, Geophys. Res. Lett., 23, 1529–1532, 1996b.
Slusher, D. L., Huey, L. G., Tanner, D. J., Flocke, F., and Roberts, J. M.: A thermal dissociation-chemical ionization mass spectrometry (TD-CIMS) technique for the simultaneous measurement of peroxyacyl nitrates and dinitrogen pentaoxide, J. Geophys. Res., 109(D19), D19315, doi:10.1029/2004JD004670, 2004.
Slusher, D. L., Pitteri, S. J., Haman, B. J., Tanner, D. J., and Huey, L. G.: A chemical ionization technique for measurement of pernitric acid in the upper troposphere and the polar boundary layer, Geophys. Res. Lett., 28, 3875–3878, 2001.
Spicer, C. W., Chapman, E. G., Finlayson-Pitts, B. J., Plastridege, R. A., Hubbe, J. M., and Fast, J. D.: Unexpected high concentrations of molecular chlorine in coastal air, Nature, 394, 353–356, 1997.
Sullivan, R. C., Guazzotti, S. A., Sodeman, D. A., and Prather, K. A.: Direct observations of the atmospheric processing of Asian mineral dust, Atmos. Chem. Phys., 7, 1213–1236, 2007.
Tanaka, P. L., Riemer, D. D., Chang, S., Yarwood, G., McDonald-Buller, E. C., Apel, E. C., Orlando, J. J., Silva, P. J., Jimenez, J. L., Canagaratna, M. R., Neece, J. D., Mullins, C. B., and Allen, D. T.: Direct evidence for chlorine-enhanced urban ozone formation in Houston, Texas, Atmos. Environ., 37, 1393–1400, 2003.
Tolbert, M. A., Rossi, M. J., and Golden, D. M.: Heterogeneous interactions of chlorine nitrate hydrogen chloride and nitric acid with sulfuric acid surfaces at stratospheric temperatures, Geophys. Res. Lett., 15, 847–850, 1988.
Vierkorn-Rudolph, B., Bachmann, K., Schwarz, B., and Meixner, F. X.: Vertical profiles of hydrogen chloride in the troposphere, J. Atmos. Chem., 2, 47–63, 1984.
Webster, C. R., May, R. D., Jaegle, L., Hu, H., Sander, S. P., Gunson, M. R., Toon, G. C., Russell III, J. M., Stimpfle, R. M., Koplow, J. P., Salawitch, R. J., and Michelsen, H. A.: Hydrochloric acid and the chlorine budget of the lower stratosphere, Geophys. Res. Lett., 21, 2575–2578, 1994.
Wingenter, O. W., Sive, B. C., Blake, N. J., Blake, D. R., and Rowland, F. S.: Atomic chlorine concentration derived from ethane and hydroxyl measurements over the equatorial Pacific Ocean: Implication for dimethyl sulfide and bromine monoxide, J. Geophys. Res., 110, D20308, doi:10.1029/2005JD005875, 2005.
Wingenter, O. W., Blake, D. R., Blake, N. J., Sive, C., Rowland, F. S., Atlas, E., and Flocke, F.: Tropospheric hydroxyl and atomic chlorine concentrations, and mixing timescales determined from hydrocarbon and halocarbon measurements mad over the Southern Ocean, J. Geophys. Res., 104, 21 819–21 818, 1999.
Wingenter, O. W., Kubo, M. K., Blake, N. J., Smith, J., T. W., Blake, D. R., and Rowland, F. S.: Hydrocarbon and halocarbon measurements as photochemical and dynamical indicators of atmospheric hydroxyl, atomic chlorine, and vertical mixing obtained during Lagrangian flights, J. Geophys. Res., 101, 4331–4340, 1996.
Zhang, D., and Iwasaka, Y.: Chlorine deposition on dust particles in marine atmosphere, Geophys. Res. Lett., 28, 3613–3616, 2001.