When Does Multiphase Chemistry Influence Indoor Chemical Fate?

Human chemical exposure often occurs indoors, where large variability in contaminant concentrations and indoor chemical dynamics make assessments of these exposures challenging. A major source of uncertainty lies in the rates of chemical transformations which, due to high surface-to-volume ratios and rapid air change rates relative to rates of gas-phase reactions indoors, are largely gas-surface multiphase processes. It remains unclear how important such chemistry is in controlling indoor chemical lifetimes and, therefore, human exposure to both parent compounds and transformation products. We present a multimedia steady-state fugacity-based model to assess the importance of multiphase chemistry relative to cleaning and mass transfer losses, examine how the physicochemical properties of compounds and features of the indoor environment affect these processes, and investigate uncertainties pertaining to indoor multiphase chemistry and chemical lifetimes. We find that multiphase reactions can play an important role in chemical fate indoors for reactive compounds with low volatility, i.e., octanol-air equilibrium partitioning ratios (Koa) above 108, with the impact of this chemistry dependent on chemical identity, oxidant type and concentration, and other parameters. This work highlights the need for further research into indoor chemical dynamics and multiphase chemistry to constrain human exposure to chemicals in the built environment.

Volcanic ash ice nucleation activity is variably reduced by aging in water and sulfuric acid: the effects of leaching, dissolution, and precipitation.

Volcanic ash nucleates ice when immersed in supercooled water droplets, giving it the potential to influence weather and climate from local to global scales. This ice nucleation activity (INA) is likely derived from a subset of the crystalline mineral phases in the ash. The INA of other mineral-based dusts can change when exposed to various gaseous and aqueous chemical species, many of which also interact with volcanic ash in the eruption plume and atmosphere. However, the effects of aqueous chemical aging on the INA of volcanic ash have not been explored. We show that the INA of two mineralogically distinct ash samples from Fuego and Astroni volcanoes is variably reduced following immersion in water or aqueous sulfuric acid for minutes to days. Aging in water decreases the INA of both ash samples by up to two orders of magnitude, possibly due to a reduction in surface crystallinity and cation availability accompanying leaching. Aging in sulfuric acid leads to minimal loss of INA for Fuego ash, which is proposed to reflect a quasi-equilibrium between leaching that removes ice-active sites and dissolution that reveals or creates new sites on the pyroxene phases present. Conversely, exposure to sulfuric acid reduces the INA of Astroni ash by one to two orders of magnitude, potentially through selective dissolution of ice-active sites associated with surface microtextures on some K-feldspar phases. Analysis of dissolved element concentrations in the aged ash leachates shows supersaturation of certain mineral species which could have precipitated and altered the INA of the ash. These results highlight the key role that leaching, dissolution, and precipitation likely play in the aqueous aging of volcanic ash with respect to its INA. Finally, we discuss the implications for understanding the nature and reactivity of ice-active sites on volcanic ash and its role in influencing cloud properties in the atmosphere.

Atmospheric aging enhances the ice nucleation ability of biomass-burning aerosol.

Ice-nucleating particles (INPs) in biomass-burning aerosol (BBA) that affect cloud glaciation, microphysics, precipitation, and radiative forcing were recently found to be driven by the production of mineral phases. BBA experiences extensive chemical aging as the smoke plume dilutes, and we explored how this alters the ice activity of the smoke using simulated atmospheric aging of authentic BBA in a chamber reactor. Unexpectedly, atmospheric aging enhanced the ice activity for most types of fuels and aging schemes. The removal of organic carbon particle coatings that conceal the mineral-based ice-active sites by evaporation or oxidation then dissolution can increase the ice activity by greater than an order of magnitude. This represents a different framework for the evolution of INPs from biomass burning where BBA becomes more ice active as it dilutes and ages, making a larger contribution to the INP budget, resulting cloud microphysics, and climate forcing than is currently considered.