Stability of Monoterpene-Derived α-Hydroxyalkyl-Hydroperoxides in Aqueous Organic Media: Relevance to the Fate of Hydroperoxides in Aerosol Particle Phases

摘要

The α-hydroxyalkyl-hydroperoxides [R-(H)C(-OH)(-OOH), α-HH] produced in the ozonolysis of unsaturated organic compounds may contribute to secondary organic aerosol (SOA) aging. α-HHs' inherent instability, however, hampers their detection and a positive assessment of their actual role. Here we report, for the first time, the rates and products of the decomposition of the α-HHs generated in the ozonolysis of atmospherically important monoterpenes α-pinene (α-P), d-limonene (d-L), γ-terpinene (γ-Tn), and a-terpineol (α-Tp) in water/acetonitrile (W/AN) mixtures. We detect a-HHs and multifunctional decomposition products as chloride adducts by online electrospray ionization mass spectrometry. Experiments involving D_2O and H_2_(18)O, instead of H_2_(16)O, and an OH-radical scavenger show that α-HHs decompose into gem-diols + H_2O_2 rather than free radicals. a-HHs decay mono- or biexponentially depending on molecular structure and solvent composition. e-Fold times, τ_(1/e), in water-rich solvent mixtures range from τ_(1/e) = 15-45 min for monoterpene-derived α-HHs to τ_(1/e) ＞ 10~3 min for the α-Tp-derived α-HH. All τ_(1/e)'s dramatically increase in ＜20% (v/v) water. Decay rates of the a-Tp-derived a-HH in pure water increase at lower pH (23 ＜ pH ＜ 3.3). The hydroperoxides detected in day-old SOA samples may reflect their increased stability in water-poor media and/or the slow decomposition of α-HHs from functionalized terpenes.