Technical note: Comparison and interconversion of pH based on different standard states for aerosol acidity characterization

Abstract

Aerosol pH is often calculated based on different standard states thus making it inappropriate to compare aerosol acidity parameters derived thereby. However, such comparisons are routinely performed in the atmospheric science community. This study attempts to address this issue by comparing PM2.5 aerosol pH based on different scales (molarity, molality and mole fraction) on the basis of theoretical considerations followed with a set of field data from Guangzhou, China as an example. The three most widely used thermodynamic models (E-AIM-IV, ISORROPIA-II, and AIOMFAC) are employed for the comparison. Established theory dictates that the difference between pHx (mole fraction based) and pHm (molality based) is always a constant (1.74, when the solvent is water) within a thermodynamic model regardless of aerosol property. In contrast, pHm and pHc (molarity based) are almost identical with a minor effect from temperature and pressure. However, when the activity coefficient is simplified as unity by thermodynamic models, the difference between pHm and pHc ranges from 0.11 to 0.25 pH units, depending on the chemical composition and the density of hygroscopic aerosol. Therefore, while evaluating aerosol acidity (especially, trend analysis) when the activity coefficient is simplified as 1, considering the pH scale is important. The application of this pH standardization protocol might influence some conclusions on aerosol acidity reported by past studies, and thus a clear definition of pH and a precise statement of thermodynamic model parameters are recommended to avoid bias when pH comparisons are made across studies.