Akihiro Yabushita

Direct Emission of I2 Molecule and IO Radical from the Heterogeneous Reactions of Gaseous Ozone with Aqueous Potassium Iodide Solution

Recent studies indicated that gaseous halogens mediate key tropospheric chemical processes. The inclusion of halogen-ozone chemistry in atmospheric box models actually closes the approximately 50% gap between estimated and measured ozone losses in the marine boundary layer. The additional source of gaseous halogens is deemed to involve previously unaccounted for reactions of O(3)(g) with sea surface water and marine aerosols. Here, we report that molecular iodine, I(2)(g), and iodine monoxide radical, IO(g), are released ([I(2)(g)] > 100[IO(g)]) during the heterogeneous reaction of gaseous ozone, O(3)(g), with aqueous potassium iodide, KI(aq). It was found that (1) the amounts of I(2)(g) and IO(g) produced are directly proportional to [KI(aq)] up to 5 mM and (2) IO(g) yields are independent of bulk pH between 2 and 11, whereas I(2)(g) production is markedly enhanced at pH < 4. We propose that O(3)(g) reacts with I(-) at the air/water interface to produce I(2)(g) and IO(g) via HOI and IOOO(-) intermediates, respectively.

Photodissociation of polycrystalline and amorphous water ice films at 157 and 193 nm

The photodissociation dynamics of amorphous solid water (ASW) films and polycrystalline ice (PCI) films at a substrate temperature of 100 K have been investigated by analyzing the time-of-flight (TOF) mass spectra of photofragment hydrogen atoms at 157 and 193 nm. For PCI films, the TOF spectrum recorded at 157 nm could be characterized by a combination of three different (fast, medium, and slow) Maxwell-Boltzmann energy distributions, while that measured at 193 nm can be fitted in terms of solely a fast component. For ASW films, the TOF spectra measured at 157 and 193 nm were both dominated by the slow component, indicating that the photofragment H atoms are accommodated to the substrate temperature by collisions. H atom formation at 193 nm is attributed to the photodissociation of water species on the ice surface, while at 157 nm it is ascribable to a mixture of surface and bulk photodissociations. Atmospheric implications in the high latitude mesopause region of the Earth are discussed.

Conversion of gaseous nitrogen dioxide to nitrate and nitrite on aqueous surfactants

The hydrolytic disproportionation of gaseous NO(2) on waters surface (2 NO(2) + H(2)O → HONO + NO(3)(-) + H(+)) (R1) has long been deemed to play a key, albeit unquantifiable role in tropospheric chemistry. We recently found that (R1) is dramatically accelerated by anions in experiments performed on aqueous microjets monitored by online electrospray mass spectrometry. This finding let us rationalize unresolved discrepancies among previous laboratory results and suggested that under realistic environmental conditions (R1) should be affected by everpresent surfactants. Herein, we report that NO(2)(g) uptake is significantly enhanced by cationic surfactants, weakly inhibited by fulvic acid (FA, a natural polycarboxylic acid) and anionic surfactants, and unaffected by 1-octanol. Surfactants appear to modulate interfacial anion coverage via electrostatic interactions with charged headgroups. We show that (R1) should be the dominant mechanism for the heterogeneous conversion of NO(2)(g) to HONO under typical atmospheric conditions throughout the day. The photoinduced reduction of NO(2) into HONO on airborne soot might play a limited role during daytime.

Hydrogen atom formation from the photodissociation of water ice at 193 nm

The TOF spectra of photofragment hydrogen atoms from the 193 nm photodissociation of amorphous ice at 90-140 K have been measured. The spectra consist of both a fast and a slow components that are characterized by average translational energies of 2k(B)T(trans)=0.39+/-0.04 eV (2300+/-200 K) and 0.02 eV (120+/-20 K), respectively. The incident laser power dependency of the hydrogen atom production suggests one-photon process. The electronic excitation energy of a branched cluster, (H(2)O)(6+1), has been theoretically calculated, where (H(2)O)(6+1) is a (H(2)O)(6) cyclic cluster attached by a water molecule with the hydrogen bond. The photoabsorption of this branched cluster is expected to appear at around 200 nm. The source of the hydrogen atoms is attributed to the photodissociation of the ice surface that is attached by water molecules with the hydrogen bond. Atmospheric implications are estimated for the photodissociation of the ice particles (Noctilucent clouds) at 190-230 nm in the region between 80 and 85 km altitude.

Translational and Rotational Energy Measurements of Photodesorbed Water Molecules in their Vibrational Ground State from Amorphous Solid Water

For interstellar grains coated with water ice, the most important desorption mechanism at the edge of molecular clouds is photodesorption of water. To reveal details of the photodesorption mechanism, we have measured the translational and rotational energies of H2 O( v = 0) molecules photodesorbed from amorphous solid water and polycrystalline ice following excitation within the first absorption band using a 157 nm laser. The measured translational and rotational temperatures are 1800 K and 300 K, respectively. These energies are in good accord with those predicted by classical molecular dynamics calculations for the “kick-out” of an H2O molecule in the ice by an energetic H atom. The statistical ortho:para ratio of gOPR = 3 is appropriate for the Boltzmann rotational distribution of the H2O molecules.

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.

A desorption mechanism of water following vacuum-ultraviolet irradiation on amorphous solid water at 90 K

Following 157 nm photoexcitation of amorphous solid water and polycrystalline water ice, photodesorbed water molecules (H(2)O and D(2)O), in the ground vibrational state, have been observed using resonance-enhanced multiphoton ionization detection methods. Time-of-flight and rotationally resolved spectra of the photodesorbed water molecules were measured, and the kinetic and internal energy distributions were obtained. The measured energy distributions are in good accord with those predicted by classical molecular dynamics calculations for the kick-out mechanism of a water molecule from the ice surface by a hot hydrogen (deuterium) atom formed by photodissociation of a neighboring water molecule. Desorption of D(2)O following 193 nm photoirradiation of a D(2)O/H(2)S mixed ice was also investigated to provide further direct evidence for the operation of a kick-out mechanism.

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 oceans topmost films should enhance I(2)(g) production in marine boundary layers.

Measurements of Energy Partitioning in H2 Formation by Photolysis of Amorphous Water Ice

We demonstrate experimentally that photodissociation of amorphous solid water at 100 K results in formation of H2 molecules with an ortho/para ratio of gOPR = 3. Two distinct mechanisms can be identified: endothermic abstraction of a hydrogen atom from H2O by a photolytically produced H atom yields vibrationally cold H2 products, whereas exothermic recombination of two H-atom photoproducts yields translationally and internally hot H2. These results are in accord with predictions by molecular dynamics calculations and their astrophysical implications are discussed.

Desorption of hydroxyl radicals in the vacuum ultraviolet photolysis of amorphous solid water at 90 K

We have studied the desorption dynamics of OH radicals from the 157 nm photodissociation of amorphous solid water (ASW) as well as H(2)O(2) deposited on an ASW surface at 90 K. The translational and internal energy distributions of OH were measured using resonance-enhanced multiphoton ionization methods. These distributions are compared to reported molecular dynamics calculations for the condensed phase photodissociation of water ice and also reported results for the gas phase photodissociation of H(2)O at 157 nm. We have confirmed that OH radicals are produced from two different mechanisms: one from primary photolysis of surface H(2)O of ASW, and the other being secondary photolysis of H(2)O(2) photoproducts on the ASW surface after prolonged irradiation at 157 nm.