Water as a probe for pH measurement in individual particles using micro-Raman spectroscopy

Abstract

Atmospheric aerosol acidity impacts numerous physicochemical processes, but the determination of particle pH remains a significant challenge due to the nonconservative nature of the H+ concentration ([H+]). Traditional measurements have difficulty in describing the practical state of an aerosol because they comprise chemical components or hypotheses that change the nature of the particles. In this work, we present a direct pH measurement that uses water as a general probe to detect [H+] in individual particles by micro-Raman spectroscopy. Containing the vibrational bands of ions and water influenced by ions, the spectra of hydrated ion were decomposed from the solution spectra as standard spectra by multivariate curve resolution analysis. Meanwhile, ratios of hydrated ions were calculated between the Raman spectra and standard spectra to evaluate concentration profiles of each ion. It demonstrated that good quantitative models between the ratio and concentration for all ions including H+ can be built with correlation coefficients (R2) higher than 0.95 for the solutions. The method was further applied to individual particle pH measurement. The pH value of sulfate aerosol particles was calculated, and the standard error was 0.09 using pH values calculated from the [HSO4−]/[SO42−] as a reference. Furthermore, the applicability of the method was proven by detecting the pH value of chloride particles. Therefore, utilizing water, the most common substance, as the spectroscopic probe to measure [H+] without restriction of the ion system, this method has potential to measure the pH value of atmospheric particles with various compounds, although more work needs to be done to improve the sensitivity of the method.