Hygroscopicity of internally mixed particles composed of (NH₄)₂SO₄ and citric acid under pulsed RH change

In this research, we applied a pulsed RH controlling system and a rapid scan vacuum FTIR spectrometer (PRHCS-RSVFTIR) to investigate hygroscopicity of internally mixed (NH₄)₂SO₄(AS)/citric acid (CA) particles. The water content and efflorescence ratio of AS in the particles and ambient relative humidity (RH) as a function of time were obtained with a subsecond time resolution. The hygroscopic behavior of AS aerosols in two different RH control processes (equilibrium and RH pulsed processes) showed that AS droplets crystallize with RH ranging from 42% to 26.5%. It was found that the half-life time ratio between the water content in the CA particles and the gas phase under RH pulsed change was greater than one under low RH conditions (<40% RH), indicating the significant water transfer limitation due to the high viscosity of CA aerosols at low RH, especially at RH<20%. In addition, water diffusion constants between 10⁻¹² m² s⁻¹ and 10⁻¹³ m² s⁻¹ in micron size CA aerosols were obtained in a sub-second and second timescale. The addition of AS enhanced the water transfer limitation in the mixed aerosols. The efflorescence relative humidity (ERH) of the mixed particles with AS/CA by molar ratio 3:1 was found between 22.7% and 5.9%, which was much lower than AS particles. No efflorescence process was observed for the 1:1 mixed particles, indicating that CA greatly suppressed nucleation of AS. Our results have shown that the PRHCS-RSVFTIR is effective to simulate hygroscopicity and water transport of aerosols under fast variations in RH in atmosphere.