Direct Measurement of pH Evolution in Aerosol Microdroplets Undergoing Ammonium Depletion: A Surface-Enhanced Raman Spectroscopy Approach.

Accurately measuring the pH of atmospheric aerosols is a prerequisite for understanding the multiphase chemistry that profoundly affects the environment and climate systems. Despite the advancements of experimental techniques for in situ pH measurements in aerosols, current studies are limited to measuring the static pH of aerosol microdroplets with an unperturbed composition. This steady-state scenario, however, deviates from the real-world aerosols undergoing atmospheric aging reactions, specifically, those characterized with a spontaneous displacement of strong bases (or acids) with high volatility. Here, we introduce a continuous and in situ measurement of aerosol pH by using a 4-mercaptopyridine-functionalized silver nanoparticle probe and surface-enhanced Raman spectroscopy. We find that the ammonium depletion─a spontaneous displacement of ammonium by dicarboxylic acid salts─continuously acidifies aerosol water over time. The decaying trends of pH in the aerosols under various humidity conditions can be unified with a universal exponential function. Such an exponentially decaying function further indicates that the ammonium depletion reaction is a self-limiting process. Our technique can be applied to study the dynamic change of aerosol acidity during the complex atmospheric aging processes, toward elucidating their implications on atmospheric chloride, nitrate, and ammonium cycles.