ABSTRACT
It has recently been reported that reactions can occur faster in microdroplets than in extended condensed matter. The electric charge of droplets has also been suggested as a possible cause of this phenomenon. Here, we investigate the influence of electric charges on the photodegradation of single, optically trapped oleic acid aerosol droplets in the absence of other reactive species. The temporal evolution of the chemical composition and the size of droplets with charge states ranging from 0 to 104 elementary charges were retrieved from Raman spectra and elastic light scattering, respectively. No influence of the droplet charge was observed, either on the chemical composition or on the kinetics. Based on a kinetic multilayer model, we propose a reaction mechanism with the photoexcitation of oleic acid into an excited state, subsequent decay into intermediates and further photoexcitation of intermediates and their decay into nonvolatile and volatile products.
ABSTRACT
Optical confinement (OC) structures the optical field and amplifies light intensity inside atmospheric aerosol particles, with major consequences for sunlight-driven aerosol chemistry. Although theorized, the OC-induced spatial structuring has so far defied experimental observation. Here, x-ray spectromicroscopic imaging complemented by modeling provides direct evidence for OC-induced patterning inside photoactive particles. Single iron(III)-citrate particles were probed using the iron oxidation state as a photochemical marker. Based on these results, we predict an overall acceleration of photochemical reactions by a factor of two to three for most classes of atmospheric aerosol particles. Rotation of free aerosol particles and intraparticle molecular transport generally accelerate the photochemistry. Given the prevalence of OC effects, their influence on aerosol particle photochemistry should be considered by atmospheric models.
ABSTRACT
The partitioning of components between droplets and the gas phase in e-cigarette aerosols has a significant impact on deposition within the respiratory tract. However, exclusive detection of droplet composition has, so far, been elusive. Consequently, the dynamics of partitioning between droplets and the gas phase remains unknown. Here, we combine optical trapping of single droplets with in situ Raman scattering for destruction-free monitoring of e-cigarette droplet composition with a time resolution of seconds. We find that the initial droplet composition is very close to the composition of the e-liquid. Upon dilution with air, the droplet composition changes exponentially on a time scale of seconds, mainly because of evaporation of propylene glycol. The nicotine content in the droplet is controlled by the pH. Nicotine evaporates from the droplets under basic conditions, but remains in the liquid under acidic conditions. These results are crucial for advancing e-liquid research and manufacturing.
ABSTRACT
Continuing efforts to quantify the influence of aerosol light absorption upon global heat budgets rely on high-quality measurements of aerosol optical properties. Of the available methods, photoacoustic spectroscopy stands out as a sensitive method for measurements of aerosol absorption with minimal sample modification. Theoretical treatments of photoacoustic aerosol detection have predicted size-dependent damping of the photoacoustic signal as a result of particle thermal inertia. We provide experimental confirmation of this prediction using a single-particle photoacoustic spectrometer, which allows us to measure photoacoustic signals with high sensitivity and size-specificity. Both the magnitude and phase of the photoacoustic response follow the linearized description of the heat flux. The quantification of this effect provides a basis for future, system-specific case studies.
