Direct Quantification Of The Effect Of Ammonium On Aerosol Droplet Ph

Ammonium is an important atmospheric constituent that dictates many environmental processes. The impact of the ammonium ion concentration on 10-50 mu m aerosol droplet pH was quantified using pH nanoprobes and surface-enhanced Raman spectroscopy (SERS). Sample solutions were prepared by mixing 1 M ammonium sulfate (AS), ammonium nitrate (AN), sodium sulfate (SS), or sodium nitrate (SN) solutions with 1 M phosphate buffer (PB) at different volume ratios. Stable pH values were measured for pure PB, AS, and AN droplets at different concentrations. The centroid pH of 1 M PB droplets was similar to 11, but when PB was systematically replaced with ammonium (AS- or AN-PB), the centroid pH within the droplets decreased from approximate to 11 to 5.5. Such a decrease was not observed in sodium (SS- or SN-PB) droplets, and no pH differences were observed between sulfate and nitrate salts. Ammonia partitioning to the gas phase in ammonium-containing droplets was evaluated to be negligible. Raman sulfate peak (similar to 980 cm(-1)) intensity measurements and surface tension measurements were conducted to investigate changes in ion distribution. The pH difference between ammonium-containing droplets and ammonium-free droplets is attributed to the alteration of the ion distribution in the presence of ammonium.