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 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 acid‐base desorption and reactions involving nonacidic N gases. We hypothesize a mechanism for the Cl loss initiated by reaction of O3 at sea‐salt aerosol surfaces, generating Cl2 followed by rapid photochemical conversion of Cl2 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‐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.

Abstract. Sulfate aerosol particles containing soot aggregates were observed in the marine troposphere in both hemispheres under conditions that ranged from extremely clean to heavily polluted. Even in clean air above the remote Southern Ocean during the First Aerosol Characterization Experiment (ACE 1), depending on the sample, between 10 and 45% of sulfate particles contained soot inclusions. We identified aircraft emissions and biomass burning as the most likely major sources of soot. Internally mixed soot and sulfate appear to comprise a globally significant fraction of aerosols in the troposphere. Anthropogenic combustion aerosols can thus potentially change the radiative climate effects of sulfate aerosols and may have an impact on cloud properties even in the remote troposphere.

A B S T R A C T Atmosphere-surface exchange represents one mechanism by which atmospheric particle mass and number size distributions are modified. Deposition velocities (v d ) exhibit a pronounced dependence on surface type, due in part to turbulence structure (as manifest in friction velocity), with minima of approximately 0.01 and 0.2 cm s −1 over grasslands and 0.1-1 cm s −1 over forests. However, as noted over 20 yr ago, observations over forests generally do not support the pronounced minimum of deposition velocity (v d ) for particle diameters of 0.1-2 μm as manifest in theoretical predictions. Closer agreement between models and observations is found over less-rough surfaces though those data also imply substantially higher surface collection efficiencies than were originally proposed and are manifest in current models. We review theorized dependencies for particle fluxes, describe and critique model approaches and innovations in experimental approaches, and synthesize common conclusions of experimental and modelling studies. We end by proposing a number of research avenues that should be pursued in to facilitate further insights and development of improved numerical models of atmospheric particles.

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