The geochemical cycling of reactive chlorine through the marine troposphere

• Published in: Global Biogeochemical Cycles
• Main Authors: Keene, William C., Pszenny, Alexander A. P., Jacob, Daniel J., Duce, Robert A., Galloway, James N., Schultz-Tokos, Joseph J., Sievering, Herman, Boatman, Joe F.
• Format: Text
• Language: unknown
• Published: DigitalCommons@URI 1990
• Subjects: North Atlantic
• Online Access: https://digitalcommons.uri.edu/gsofacpubs/208; https://doi.org/10.1029/GB004i004p00407; https://digitalcommons.uri.edu/context/gsofacpubs/article/1198/viewcontent/Duce_GeochemicalCycling_1990.pdf

Heterogeneous reactions involving seaâ€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 SO42− and N03− in coarse aerosol fractions indicate that on average only 38% of measured Cl− deficits could be accounted for by the combined effects of acidâ€base desorption and reactions involving nonacidic N gases. We hypothesize a mechanism for the Cl loss initiated by reaction of O3 at seaâ€salt aerosol surfaces, generating Cl2 followed by rapid photochemical conversion of Cl2 to HCl via Cl atoms (ClË™) and eventual recapture of HCl by the aerosol. Simulations with a zeroâ€dimension (0â€D) photochemical model suggest that oxidation by ClË™ may be an important tropospheric sink for dimethyl sulfide and hydrocarbons. Under lowâ€NOx conditions, the rapid cycling of reactive Cl would provide a catalytic loss mechanism for O3, which would possibly explain the low O3 concentrations often observed above the world's oceans.