RESUMEN
Atmospheric aerosol particles are commonly complex, aqueous organic-inorganic mixtures, and accurately predicting the properties of these particles is essential for air quality and climate projections. The prevailing assumption is that aqueous organic-inorganic aerosols exist predominately with liquid properties and that the hygroscopic inorganic fraction lowers aerosol viscosity relative to the organic fraction alone. Here, in contrast to those assumptions, we demonstrate that increasing inorganic fraction can increase aerosol viscosity (relative to predictions) and enable a humidity-dependent gel phase transition through cooperative ion-molecule interactions that give rise to long-range networks of atmospherically relevant low-mass oxygenated organic molecules (180 to 310 Da) and divalent inorganic ions. This supramolecular, ion-molecule effect can drastically influence the phase and physical properties of organic-inorganic aerosol and suggests that aerosol may be (semi)solid under more conditions than currently predicted. These observations, thus, have implications for air quality and climate that are not fully represented in atmospheric models.
RESUMEN
The formation of gelatinous networks within an aerosol particle significantly alters the physicochemical properties of the aerosol material. Existing techniques for studying gel transitions rely on bulk rheometry, which is limited by contact with the sample, or microrheological techniques such as holographic optical tweezers, which rely on expensive equipment and high-powered lasers that can degrade light-absorbing aerosol. Here, we present a new technique to probe the microrheological characteristics of aerosol particles and explore gel formation under atmospheric conditions in a contactless environment without the need for high-power light sources. In a dual-balance quadrupole electrodynamic balance, levitated droplets of opposite polarity are trapped and equilibrated at fixed relative humidity (RH) and then subsequently merged, and the physical characteristics of the merged droplets are monitored as a function of time and RH using imaging techniques. By comparing the RH-dependent characteristics of MgSO4 (known to undergo a gel transition) to glucose and sucrose (known to remain as viscous Newtonian fluids) under fixed equilibration time scales, we demonstrate that gel phase transitions can be identified in aerosol particles, with MgSO4 abruptly transitioning to a rigid microgel at 30% RH. Further, we demonstrate this technique can be used to also measure aerosol viscosity and identify non-Newtonian fluid dynamics in model sea spray aerosol composed of NaCl, CaCl2, and sorbitol. Thus, using this experimental technique, it is possible to distinguish between aerosol compositions that form viscous Newtonian fluids and those that undergo a gel transition or form non-Newtonian fluids. This technique offers a simple and cost-effective analytical tool for probing gel transitions outside of bulk solubility limits, with relevant applications ranging from atmospheric science to microengineering of soft matter materials.
