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Marine photosynthetic organisms emit organic gases, including the polyolefins isoprene (C 5 H 8 ) and monoterpenes (MTPs, C 10 H 16 ), into the boundary layer. Their atmospheric processing produces particles that influence cloud formation and growth and, as a result, the Earth's radiation balance. Here, we report that the heterogeneous ozonolysis of dissolved α-pinene by O 3 (g) on aqueous surfaces is dramatically accelerated by I - , an anion enriched in the ocean upper microlayer and sea spray aerosols (SSAs). In our experiments, liquid microjets of α-pinene solutions, with and without added I - , are dosed with O 3 (g) for τ &lt; 10 μs and analyzed online by pneumatic ionization mass spectrometry. In the absence of I - , α-pinene does not detectably react with O 3 (g) under present conditions. In the presence of ≥ 0.01 mM I - , in contrast, new signals appear at m / z = 169 (C 9 H 13 O 3  - ), m / z = 183 (C 10 H 15 O 3  - ), m / z = 199 (C 10 H 15 O 4  - ), m / z = 311 (C 10 H 16 IO 3  - ), and m / z = 461 (C 20 H 30 IO 4  - ), plus m / z = 175 (IO 3  - ), and m / z = 381 (I 3  - ). Collisional fragmentation splits CO 2 from C 9 H 13 O 3  - , C 10 H 15 O 3  - and C 10 H 15 O 4  - , and I - plus IO - from C 10 H 16 IO 3  - as expected from a trioxide IOOO • C 10 H 16  - structure. We infer that the oxidative processing of α-pinene on aqueous surfaces is significantly accelerated by I - via the formation of IOOO - intermediates that are more reactive than O 3 . A mechanism in which IOOO - reacts with α-pinene (and likely with other unsaturated species) in competition with its isomerization to IO 3  - accounts for present results and the fact that soluble iodine in SSA is mostly present as iodine-containing organic species rather than the thermodynamically more stable iodate. By this process, a significant fraction of biogenic MTPs and other unsaturated gases may be converted to water-soluble species rather than emitted to the atmosphere.

Iodide Accelerates the Processing of Biogenic Monoterpene Emissions on Marine Aerosols