Water diffusion measurements of single charged aerosols using H2O/D2O isotope exchange and Raman spectroscopy in an electrodynamic balance.

Sea spray aerosols contain a large array of organic compounds that contribute to high viscosities at low relative humidity and temperature thereby slowing translational diffusion of water. The Stokes-Einstein equation describes how viscosity is inversely correlated with the translational diffusion coefficient of the diffusing species. However, recent studies indicate that the Stokes-Einstein equation breaks down at high viscosities achieved in the particle phase (>1012 Pa s), underestimating the predicted water diffusion coefficient by orders of magnitude and revealing the need for directly studying the diffusion of water in single aerosols. A new method is reported for measuring the water diffusion coefficient in single suspended charged sucrose-water and citric acid (CA)-water microdroplets in the 30-60 micron diameter range. The translational water diffusion coefficient is quantified using the H2O/D2O isotope exchange technique between 26 and 54% relative humidity (RH) for sucrose and 7 and 25% RH for CA using a recently developed mobile electrodynamic balance apparatus. The results are in good agreement with the literature, particularly the Vignes-type parameterization from experiments using isotope exchange and optical tweezers. Below 15% RH, CA droplets show incomplete H2O/D2O exchange. This mobile electrodynamic balance will allow future studies of atmospherically relevant chemical systems, including field studies.

Interfacial Nanostructure and Hydrogen Bond Networks of Choline Chloride and Glycerol Mixtures Probed with X-ray and Vibrational Spectroscopies.

The molecular distribution at the liquid-vapor interface and evolution of the hydrogen bond interactions in mixtures of glycerol and choline chloride are investigated using X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Nanoscale depth profiles of supersaturated deep eutectic solvent (DES) mixtures up to ∼2 nm measured by ambient-pressure XPS show the enhancement of choline cation (Ch+) concentration by a factor of 2 at the liquid-vapor interface compared to the bulk. In addition, Raman spectral analysis of a wide range of DES mixtures reveals the conversion of gauche-conformer Ch+ into the anti-conformer in relatively lower ChCl concentrations. Finally, the depletion of Ch+ from the interface (probing depth = 0.4 nm) is demonstrated by aerosol-based velocity map imaging XPS measurements of glyceline and water mixtures. The nanostructure of liquid-vapor interfaces and structural rearrangement by hydration can provide critical insight into the molecular origin of the deep eutectic behavior and gas-capturing application of DESs.

Photoinduced Reactions of Nitrate in Aqueous Microdroplets by Triplet Energy Transfer.

In-situ Raman spectroscopy of single levitated charged aqueous microdroplets irradiated by dual-beam (266 and 532 nm) lasers demonstrates that the nitrate anion (NO3-) can be depleted in the droplet through an energy transfer mechanism following excitation of sulfanilic acid (SA), a UV-absorbing aromatic organic compound. Upon 266 nm irradiation, a fast decrease of the NO3- concentration was observed when SA is present in the droplet. This photoinduced reaction occurs without the direct photolysis of NO3-. Instead, the rate of NO3- depletion was found to depend on the initial concentration of SA and the pH of the droplet. Based on absorption-emission spectral analysis and excited-state energy calculations, triplet-triplet energy transfer between SA and NO3- is proposed as the underlying mechanism for the depletion of NO3- in aqueous microdroplets. These results suggest that energy transfer mechanisms initiated by light-absorbing organic molecules may play a significant role in NO3- photochemistry.

Evolution of Hydrogen-Bond Interactions within Single Levitated Metastable Aerosols Studied by In Situ Raman Spectroscopy.

Atmospheric aerosols can exist as supersaturated (metastable) liquid or glassy states, with physical and chemical properties that are distinct from the solid or liquid phases. These unique properties of aerosols have substantial implications on climate and health effects. Direct investigations on metastable aerosols remain a challenge because any interfacial contact can cause heterogeneous nucleation. In this study, in situ Raman spectroscopic and Mie scattering imaging analysis is applied to metastable aerosols in the absence of physical contact using an environment-controlled electrodynamic balance (EDB). This has allowed a detailed study of the O-H stretching regions of the Raman spectrum, revealing evidence for the rearrangement of hydrogen-bonding structures of levitated aqueous citric acid (CA) and aqueous sucrose droplets at metastable liquid states. We found that carboxyl groups in a CA droplet yield distinctive dynamics of strong and weak hydrogen bonds, whereas hydroxyl groups in a sucrose droplet show correlated strong and weak interactions. Such effects are particularly important in a supersaturated solution. These results indicate that metastable liquid aerosols from different sources may exhibit distinct physical and chemical behavior.