Global inorganic source of atmospheric bromine

被引:82
作者
Enami, S. [1 ]
Vecitis, C. D. [1 ]
Cheng, J. [1 ]
Hoffmann, M. R. [1 ]
Colussi, A. J. [1 ]
机构
[1] CALTECH, WM Keck Labs, Pasadena, CA 91125 USA
关键词
D O I
10.1021/jp074903r
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A few bromine molecules per trillion (ppt) causes the complete destruction of ozone in the lower troposphere during polar spring and about half of the losses associated with the "ozone hole" in the stratosphere. Recent field and aerial measurements of the proxy BrO in the free troposphere suggest an even more pervasive G global role for bromine. Models, which quantify ozone trends by assuming atmospheric inorganic bromine (Br-y) stems exclusively from long-lived bromoalkane gases, significantly underpredict BrO measurements. This discrepancy effectively implies a ubiquitous tropospheric background level of similar to 4 ppt Br-y of unknown origin. Here, we report that I- efficiently catalyzes the oxidation of Br- and Cl- in aqueous nanodroplets exposed to ozone, the everpresent atmospheric oxidizer, under conditions resembling those encountered in marine aerosols. Br- and Cl-, which are rather unreactive toward O-3 and were previously deemed unlikely direct precursors of atmospheric halogens, are readily converted into IBr2- and ICl2- en route to Br-2(g) and Cl-2(g) in the presence of I-. Fine sea salt aerosol particles, which are predictably and demonstrably enriched in I- and Br- are thus expected to globally release photoactive halogen compounds into the atmosphere, even in the absence of sunlight.
引用
收藏
页码:8749 / 8752
页数:4
相关论文
共 39 条
[1]   VERY LOW-PRESSURE REACTOR - NEW TECHNIQUE FOR MEASURING RATES AND EQUILIBRIA OF RADICAL MOLECULE REACTIONS AT LOW-TEMPERATURE - HEAT OF FORMATION OF METHYL RADICAL [J].
BAGHALVAYJOOEE, MH ;
COLUSSI, AJ ;
BENSON, SW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (10) :3214-3215
[2]   OZONE DESTRUCTION AND PHOTOCHEMICAL-REACTIONS AT POLAR SUNRISE IN THE LOWER ARCTIC ATMOSPHERE [J].
BARRIE, LA ;
BOTTENHEIM, JW ;
SCHNELL, RC ;
CRUTZEN, PJ ;
RASMUSSEN, RA .
NATURE, 1988, 334 (6178) :138-141
[3]   Oxidation of iodide and hypoiodous acid in the disinfection of natural waters [J].
Bichsel, Y ;
von Gunten, U .
ENVIRONMENTAL SCIENCE & TECHNOLOGY, 1999, 33 (22) :4040-4045
[4]   Gel electrophoresis coupled to inductively coupled plasma-mass spectrometry using species-specific isotope dilution for iodide and iodate determination in aerosols [J].
Bruechert, Wolfram ;
Helfrich, Andreas ;
Zinn, Nico ;
Klimach, Thomas ;
Breckheimer, Markus ;
Chen, Hongwei ;
Lai, Senchao ;
Hoffmann, Thorsten ;
Bettmer, Joerg .
ANALYTICAL CHEMISTRY, 2007, 79 (04) :1714-1719
[5]   Abiotic source of reactive organic halogens in the sub-arctic atmosphere? [J].
Carpenter, LJ ;
Hopkins, JR ;
Jones, CE ;
Lewis, AC ;
Parthipan, R ;
Wevill, DJ ;
Poissant, L ;
Pilote, M ;
Constant, P .
ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2005, 39 (22) :8812-8816
[6]   Experimental anion affinities for the air/water interface [J].
Cheng, Jie ;
Vecitis, Chad D. ;
Hoffmann, M. R. ;
Colussi, A. J. .
JOURNAL OF PHYSICAL CHEMISTRY B, 2006, 110 (51) :25598-25602
[7]   Mass accommodation and chemical reactions at gas-liquid interfaces [J].
Davidovits, P ;
Kolb, CE ;
Williams, LR ;
Jayne, JT ;
Worsnop, DR .
CHEMICAL REVIEWS, 2006, 106 (04) :1323-1354
[9]   Long-term observations of stratospheric bromine reveal slow down in growth [J].
Dorf, M. ;
Butler, J. H. ;
Butz, A. ;
Camy-Peyret, C. ;
Chipperfield, M. P. ;
Kritten, L. ;
Montzka, S. A. ;
Simmes, B. ;
Weidner, F. ;
Pfeilsticker, K. .
GEOPHYSICAL RESEARCH LETTERS, 2006, 33 (24)
[10]   KINETICS OF HALOGEN HYDROLYSIS [J].
EIGEN, M ;
KUSTIN, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1962, 84 (08) :1355-&