Drop size-dependent chemical composition in clouds and fogs. Part I. Observations

The first observations of size-dependent cloud and fog drop inorganic ion and trace metal concentrations obtained using the Colorado State University 5-Stage cloud water collector (CSU 5-Stage) during field studies of orographic clouds (Whiteface Mountain, NY, July 1998) and radiation fogs (Davis, CA, January 1999) are reported. Although some mixing between drop sizes occurs, the CSU 5-Stage effectively separates the largest drops (>≈30 μm in diameter) from the smallest ones (<≈10 μm in diameter) permitting the discernment of size-dependent drop composition not possible with previous two- or three-stage collectors. At Whiteface, pH and the concentrations of the “major” ions −NH₄⁺, NO₃⁻, and SO₄²⁻—appeared largely independent of drop size as measured by a two-stage collector. The same major ion concentrations differed in Davis fogs by up to a factor of approximately 10 in the two-stage collector with consistently higher small drop concentrations. In both locations, CSU 5-Stage data generally indicate a greater range of concentrations is present across the drop size spectrum. CSU 5-Stage data show “U”- shaped profiles of major ion concentration vs. drop size at Whiteface and “L”- shaped profiles at Davis and the maximum/minimum concentration differences between fractions increased up to a factor of 2 (Whiteface) and 30 (Davis). Lower concentration species at both locations showed multiple concentration vs. drop size profiles with CSU 5-Stage data again exhibiting more variability than observed with the two-stage collector. While rarely reported, significant nitrite concentrations—relatively higher in the larger drops—were observed, and copper concentrations merit further investigation in the Davis fogs. The findings presented here are consistent with other studies. The implications and benefits of the increased resolution of size-dependent drop composition provided by the CSU 5-Stage are explored for the Davis fogs in a companion paper (Moore et al., Atmos. Environ. (2004), this issue).