Peroxymonocarbonate (HCO4-) is a reactive oxygen species previously studied in chemical manufacturing and water detoxification. However, its role in atmospheric chemistry remains largely unexplored despite its high oxidative potential via oxygen-atom transfer reactions (E(HCO4-/HCO3-) = 1.8V) and the abundance of CO2, H2O and H2O2 in the atmosphere. This work explores the formation of HCO4- at the interface of an aqueous H2O2 jet and an intersection stream of CO2 gas in an online electrospray ionization mass spectrometry (o-ESI-MS) reacting for ~50 µs. The interfacial kinetics of HCO4- formation is measured to be &gt;104 times faster than the bulk phase kinetics, possibly due to the incomplete hydrogen bonding network at the gas-liquid interface. Peroxymonocarbonate may play an important yet previously unexplored role in the oxidation of atmospheric sulfides, (bi)sulfites and alkenes such as isoprene and pinene.

Fast peroxymonocarbonate formation on aqueous aerosols

ACS Fall 2021

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