An In Situ Method for Sizing Insoluble Residues in Precipitation and Other Aqueous Samples

Particles are frequently incorporated into clouds or precipitation, influencing climate by acting as cloud condensation or ice nuclei, taking up coatings during cloud processing, and removing species through wet deposition. Many of these particles, particularly ice nuclei, can remain suspended within cloud droplets/crystals as insoluble residues. While previous studies have measured the soluble or bulk mass of species within clouds and precipitation, no studies to date have determined the number concentration and size distribution of insoluble residues in precipitation or cloud water using in situ methods. Herein, for the first time we demonstrate that nanoparticle tracking analysis (NTA) is a powerful in situ method for determining the total number concentration, number size distribution, and surface area distribution of insoluble residues in precipitation, both of rain and melted snow. The method uses 500 mu L or less of liquid sample and does not require sample modification. Number concentrations for the insoluble residues in aqueous precipitation samples ranged from 2.0-3.0 (+/- 0.3)+/- 10(8) particles cm(-3), while surface area ranged from 1.8 (+/- 0.7)-3.2 (+/- 1.0) x 10(7) mu m(2) cm(-3). Number size distributions peaked between 133 and 150 nm, with both single and multi-modal character, while surface area distributions peaked between 173 and 270 nm. Comparison with electron microscopy of particles up to 10 mm show that, by number, >97% residues are <1 mu m in diameter, the upper limit of the NTA. The range of concentration and distribution properties indicates that insoluble residue properties vary with ambient aerosol concentrations, cloud microphysics, and meteorological dynamics. NTA has great potential for studying the role that insoluble residues play in critical atmospheric processes.