The formation and growth of calcium sulfate crystals through oxidation of SO2 by O3 on size-resolved calcium carbonate

Abstract

Calcium sulfate is a major constituent of atmospheric sulfate, with a typical rod-like morphology ranging from several hundred nanometers to approximately two micrometers observed in field studies. However, the chemical formation mechanism is still not well known. In this study, the kinetics and mechanism for the formation and growth of rod-like calcium sulfate crystals through oxidation of SO₂ by O₃ on size-resolved CaCO₃ at different relative humidity (RH) were investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and scanning electron microscopy (SEM). We found that the concentration and formation rate of sulfate decreased with the increasing diameter of CaCO₃ particles, and thus smaller particles could enhance the formation of sulfate due to more reactive sites on smaller particles. The rod-like calcium sulfate crystals were formed only at RH above 60% and in the presence of reactant gases through the heterogeneous pathway. The liquid-like water layer formed by promotion of high RH in the presence of reactant gases could facilitate the formation and aggregation of calcium sulfate hydrates and thus promote the formation and growth of rod-like calcium sulfate crystals. This study provides a possible mechanism for the formation and growth of rod-like calcium sulfate crystals existing in the atmosphere.