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    Diol it up: The influence of NaCl on methylglyoxal surface adsorption and hydration state at the air-water interface

    Year: 2020

    Journal: J. Chem. Phys., Volume 153, OCT 28

    Authors: Gordon, Brittany P.; Lindquist, Grace A.; Crawford, Michael L.; Wren, Sumi N.; Moore, Frederick G.; Scatena, Lawrence F.; Richmond, Geraldine L.

    Organizations: National Science FoundationNational Science Foundation (NSF) [CHE 1505891, CHE 1051215]; ARCS Oregon Chapter

    Methylglyoxal (MG)-an atmospherically important alpha -dicarbonyl implicated in aqueous-phase secondary organic aerosol formation-is known to be surface-active. Due to the presence of carbonyl moieties, MG can hydrate to form geminal diols in solution. Recently, it has been shown that MG exists predominantly as a monohydrate at the neat air-water interface. However, inorganic aerosol constituents have the potential to "salt-out" MG to the interface, shift its hydration equilibria, and catalyze self- and cross-oligomerization reactions. Here, we study the influence of the non-reactive salt, sodium chloride (NaCl), on the MG's surface adsorption and hydration state using vibrational sum frequency spectroscopy. The presence of NaCl is found to enhance MG's surface activity but not to the extent that water is fully excluded from the interface. Perturbations in the interfacial water structure are attributed to shifts in MG's hydration equilibrium at higher ionic strengths. Evidence of surface-active MG oligomer species is presented, but such oligomers are not thought to contribute significantly to the interfacial population. This work builds on the published studies on MG in pure water and gives insight into the interface's perturbation by NaCl, which has important implications for understanding MG's atmospheric fate.
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