Direct measurement of the pH of aerosol particles using carbon quantum dots

The pH of aerosol particles remains challenging to measure because of their small size, complex composition, and high acidity. Acidity in aqueous aerosol particles, which are found abundantly in the atmosphere, impacts many chemical processes from reaction rates to cloud formation. Only one technique - pH paper - currently exists for directly determining the pH of aerosol particles, and this is restricted to measuring average acidity for entire particle populations. Other methods for evaluating aerosol pH include filter samples, particle-into-liquid sampling, Raman spectroscopy, organic dyes, and thermodynamic models, but these either operate in a higher pH range or are unable to assess certain chemical species or complexity. Here, we present a new method for determining acidity of individual particles and particle phases using carbon quantum dots as a novel in situ fluorophore. Carbon quantum dots are easily synthesized, shelf stable, and sensitive to pH in the highly acidic regime from pH 0 to pH 3 relevant to ambient aerosol particles. To establish the method, a calibration curve was formed from the ratiometric fluorescence intensity of aerosolized standard solutions with a correlation coefficient (R-2) of 0.99. Additionally, the pH of aerosol particles containing a complex organic mixture (COM) representative of environmental aerosols was also determined, proving the efficacy of using carbon quantum dots as pH-sensitive fluorophores for complex systems. The ability to directly measure aerosol particle and phase acidity in the correct pH range can help parametrize atmospheric models and improve projections for other aerosol properties and their influence on health and climate.