Direct measurement of aerosol pH in individual malonic acid and citric acid droplets under different relative humidity conditions via Raman spectroscopy.

Direct measurement of aerosol pH in individual malonic acid and citric acid droplets under different relative humidity conditions via Raman spectroscopy.

Chang, Pianpian;Chen, Zhe;Zhang, Yunhong;Liu, Yong;
Chemosphere 2019 Vol. 241 pp. 124960
259
chang2019directchemosphere

Abstract

Acidity of aerosol particles plays important roles in atmospheric chemistry, in turn, impacting climate system and public health. Current knowledge of acidity in atmosphere aerosols remains fairly scarce largely because of difficulty in direct measurement. On the other hand, indirect methods for estimating aerosol pH are often inconsistent with pH values predicted by thermodynamic models. Recently, a direct Raman spectroscopy method has been reported to determine pH values of acid-conjugate base equilibria systems based on Raman intensity of distinct characteristic peaks of conjugate acid-base pair. Nevertheless, for pure carboxylic acid aerosol particles, such as malonic acid (MA), characteristic peak of its conjugate base cannot be clearly observed in Raman spectra owing to small K value (weak acid dissociation constant), which leads to little dissociation of weak acid and low concentration of its conjugated base. As a result, pH of carboxylic acid particles cannot be directly determined by calibrating concentrations of acid and its conjugated base using the above-mentioned method. To address such an issue, we demonstrate a new approach for determining pH values of malonic acid (MA) and citric acid (CA) droplets under different relative humidity (RH) based on calibration curves. We measure Raman intensity ratios of acid solutions at different concentrations and their pH values to establish a calibration curve, and then using the intensity ratio of MA and CA droplets under different RH to determine aerosol particle pH based on calibration curves. Results have shown that aerosol pH of MA droplet decreases with a decreasing RH and pH values ranges from 1.03 to -0.12, when RH value is reduced from 90% to 26%, in good agreement with model prediction values. In addition, we also, for the first time, report pH values of CA droplets under different RH conditions and its pH values range from 1.13 to -0.74 when RH is reduced from 91% to 28%.

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