Iodine emission in the presence of humic substances at the water's surface.

Humic substances that preferentially adsorb at the air/water interfaces of water or aerosols consist of both fulvic and humic acid. To investigate the chemical reactivity for the heterogeneous reaction of gaseous ozone, O(3)(g), with aqueous iodide, I(-)(aq), in the presence of standard fulvic acid, humic acid, or alcohol, cavity ring-down spectroscopy was used to detect gaseous products, iodine, I(2)(g) and an iodine monoxide radical, IO(g). Fulvic acid enhanced the I(2)(g) production yield, but not the IO(g) yield. Humic acid, n-hexanol, n-heptanol, and n-octanol did not affect the yields of I(2)(g) or IO(g). We can infer that the carboxylic group contained in fulvic acid promotes the I(2)(g) emission by supplying the requisite interfacial protons more efficiently than water on its surface.

Weak acids enhance halogen activation on atmospheric water's surfaces.

We report that rates of I(2)(g) emissions, measured via cavity ring-down spectroscopy, during the heterogeneous ozonation of interfacial iodide: I(-)(surface, s) + O(3)(g) + H(+)(s) →→ I(2)(g), are enhanced several-fold, whereas those of IO·(g) are unaffected, by the presence of undissociated alkanoic acids on water. The amphiphilic weak carboxylic acids appear to promote I(2)(g) emissions by supplying the requisite interfacial protons H(+)(s) more efficiently than water itself, at pH values representative of submicrometer marine aerosol particles. We infer that the organic acids coating aerosol particles ejected from ocean's topmost films should enhance I(2)(g) production in marine boundary layers.

Heterogeneous reaction of gaseous ozone with aqueous iodide in the presence of aqueous organic species.

The fast reaction of gaseous ozone, O(3)(g), with aqueous iodide, I(-)(aq), was found to be affected by environmentally relevant cosolutes in experiments using cavity ring-down spectroscopy (CRDS) and electrospray ionization mass spectrometry (ESIMS) for the detection of gaseous and interfacial products, respectively. Iodine, I(2)(g), and iodine monoxide radical, IO(g), product yields were suppressed in the presence of a few millimolar phenol (pK(a) = 10.0), p-methoxyphenol (10.2), or p-cresol (10.3) at pH > or = 3 but unaffected by salicylic acid (pK(a(2)) = 13.6), tert-butanol, n-butanol, or malonic acid. We infer that reactive anionic phenolates inhibit I(2)(g) and IO(g) emissions by competing with I(-)(aq) for O(3)(g) at the air/water interface. ESIMS product analysis supports this mechanism. Atmospheric implications are discussed.