Low Ozone in the Marine Boundary Layer of the Tropical Pacific Ocean

Aircraft measurements of ozone, its key precursors, and a variety of chemical tracers were made in the troposphere of the western and central Pacific in October 1991. These data are presented and analyzed to examine the occurrence of low ozone concentrations in the remote marine boundary layer of the tropical and equatorial Pacific Ocean. The data from these flights out of Guam, covering an area extending from the equator to 20 N and from south of the Philippines to Hawaii, show average O3 concentrations as low as 8-9 ppb (ppb=10(exp-9)v/v) at altitudes of 0.3-0.5 km in the boundary layer. Individual measurements as low as 2-5 ppb were recorded. Low O3 concentrations do not always persist in space and time. High O3, generally associated with the transport of upper tropospheric air, was also encountered in the boundary layer. In practically all cases, O3 increased to values as large as 25-30 ppb within 2 km above the boundary layer top. Steady state model computations are used to suggest that these low O3 concentrations are a result of net photochemical O3 destruction in a low NO environment, sea-surface deposition, and extremely low net entrainment rates (1-2 mm per second) from the free troposphere. Day/night measurements of ethane, propane, gaseous and aerosol Cl suggest that daytime (morning) Cl atom concentrations in the vicinity of 10(exp 5) molecules per cubic centimeter may be present in the marine boundary layer. This Cl atom abundance can be rationalized only if sea salt aerosols can release free chlorine (Cl2) to the gas phase in the presence of sun light (and possibly O3). These Cl atom concentrations, however, are still insufficient and Cl (or Br) chemistry is not likely to be an important cause of the observed low O3.