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The geochemical cycling of reactive chlorine through the marine troposphere
Author(s) -
Keene William C.,
Pszenny Alexander A. P.,
Jacob Daniel J.,
Duce Robert A.,
Galloway James N.,
SchultzTokos Joseph J.,
Sievering Herman,
Boatman Joe F.
Publication year - 1990
Publication title -
global biogeochemical cycles
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.512
H-Index - 187
eISSN - 1944-9224
pISSN - 0886-6236
DOI - 10.1029/gb004i004p00407
Subject(s) - aerosol , troposphere , sea salt , chlorine , dimethyl sulfide , environmental chemistry , chemistry , levoglucosan , scavenging , sink (geography) , particulates , atmospheric sciences , geology , organic chemistry , biomass burning , sulfur , antioxidant , cartography , geography
Heterogeneous reactions involving sea‐salt aerosol in the marine troposphere are the major global source for volatile inorganic chlorine. We measured reactant and product species hypothesized to be associated with these chemical transformations as a function of phase, particle size, and altitude over the North Atlantic Ocean during the summer of 1988. Concentrations of HCl were typically less than 1.0 ppbv near the sea surface and decreased with altitude and with distance from the U.S. east coast. Concentrations of Cl volatilized from aerosols were generally equivalent to the corresponding concentrations of HCl and ranged from less than detection limits to 125 nmol m −3 STP. Highest absolute and percentage losses of particulate Cl were typically associated with elevated concentrations of anthropogenic combustion products. Concentrations of product nss SO 4 2− and N0 3 − in coarse aerosol fractions indicate that on average only 38% of measured Cl − deficits could be accounted for by the combined effects of acid‐base desorption and reactions involving nonacidic N gases. We hypothesize a mechanism for the Cl loss initiated by reaction of O 3 at sea‐salt aerosol surfaces, generating Cl 2 followed by rapid photochemical conversion of Cl 2 to HCl via Cl atoms (Cl˙) and eventual recapture of HCl by the aerosol. Simulations with a zero‐dimension (0‐D) photochemical model suggest that oxidation by Cl˙ may be an important tropospheric sink for dimethyl sulfide and hydrocarbons. Under low‐NO x conditions, the rapid cycling of reactive Cl would provide a catalytic loss mechanism for O 3 , which would possibly explain the low O 3 concentrations often observed above the world's oceans.