Indoor boundary layer chemistry modeling

Ozone (O₃ ) chemistry is thought to dominate the oxidation of indoor surfaces. We consider the hypothesis that reactions taking place within indoor boundary layers result in greater than anticipated hydroxyl radical (OH) deposition rates. We develop models that account for boundary layer mass-transfer phenomena, O₃ -terpene chemistry and OH formation, removal, and deposition; we solve these analytically and by applying numerical methods. For an O₃ -limonene system, we find that OH flux to a surface with an O₃ reaction probability of 10^-8 is 4.3 × 10^-5 molec/(cm² s) which is about 10 times greater than predicted by a traditional boundary layer theory. At very low air exchange rates the OH surface flux can be as much as 10% of that for O₃ . This effect becomes less pronounced for more O₃ -reactive surfaces. Turbulence intensity does not strongly influence the OH concentration gradient except for surfaces with an O₃ reaction probability >10^-4 . Although the O₃ flux dominates OH flux under most conditions, OH flux can be responsible for as much as 10% of total oxidant uptake to otherwise low-reactivity surfaces. Further, OH chemistry differs from that for ozone; therefore, its deposition is important in understanding the chemical evolution of some indoor surfaces and surface films.