Drop size-dependent S(IV) oxidation in chemically heterogeneous radiation fogs

Abstract

Six radiation fog episodes were sampled in the Central Valley of California during winter 1998/1999. Drop size-resolved fog samples were sampled using a size-fractionating Caltech active strand cloudwater collector (sf-CASCC). The sf-CASCC collects a large fog drop sample, comprised mainly of drops larger than 17 μm diameter, and a small fog drop sample, comprised mainly of drops with diameters between 4 and 17 μm. The fog pH was found to vary between approximately pH 5.3 and 6.8, with the pH of the large fog drop sample typically several tenths of a pH unit higher than the simultaneously collected small fog drop sample. At these high pH values, dissolved sulfur dioxide can be rapidly oxidized by a variety of chemical pathways and also can react quickly with dissolved formaldehyde to form hydroxymethanesulfonate. The amount of sulfate produced by aqueous-phase oxidation during each fog episode was determined by application of a tracer technique. The ratio of large : small drop S(IV) oxidation was compared with theoretically predicted ratios of large : small drop S(IV) oxidation rates. Although the higher pH of the large fog drops should promote more rapid S(IV) oxidation by ozone, finite rates of mass transport into the large drops and an increasing rate of complexation of S(IV) by formaldehyde at high pH combine to depress theoretically predicted rates of aqueous sulfate production in large fog drops below rates expected for small fog drops. This prediction is supported by the tracer results that indicate the concentration of sulfate resulting from aqueous-phase S(IV) oxidation in small drops generally exceeded the concentration formed in large drops. These findings stand in sharp contrast to observations in acidic clouds at Whiteface Mountain, New York, where hydrogen peroxide was determined to be the dominant S(IV) oxidant and the rate of S(IV) oxidation was found to be independent of drop size.