Direct Emission of I_2 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 ~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

コオリ ヒョウメンジョウ ニ キュウチャクシタ カンタンナ ブンシ ノ シガイコウ ブンカイ

京都大学0048新制・課程博士博士(工学)甲第10175号工博第2238号新制||工||1267(附属図書館)UT51-2003-H596京都大学大学院工学研究科分子工学専攻(主査)教授 川﨑 昌博, 教授 横尾 俊信, 教授 中辻 博学位規則第4条第1項該当Doctor of EngineeringKyoto UniversityDFA

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 ≥ 3 but unaffected by salicylic acid (pK_(a2) = 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 discusse

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

The hydrolytic disproportionation of gaseous NO2 on water's surface (2 NO_2 + H_2O → 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

Tropospheric aerosol as a reactive intermediate

In tropospheric chemistry, secondary organic aerosol (SOA) is deemed an end product. Here, on the basis of new evidence, we make the case that SOA is a key reactive intermediate. We present laboratory results on the catalysis by carboxylate anions of the disproportionation of NO_2 ‘on water’: 2NO_2 + H_2O = HONO + NO_3^− + H^+ (R1), and supporting quantum chemical calculations, which we apply to reinterpret recent reports on (i) HONO daytime source strengths vis-à-vis SOA anion loadings and (ii) the weak seasonal and latitudinal dependences of NO_x decay kinetics over several megacities. HONO daytime generation via R1 should track sunlight because it is generally catalyzed by the anions produced during the photochemical oxidation of pervasive gaseous pollutants. Furthermore, by proceeding on the everpresent substrate of aquated airborne particulates, R1 can eventually overtake the photolysis of NO_2: NO_2 + hν = NO + O(^3P) (R2), at large zenith angles. Thus, since R1 leads directly to ˙OH-radical generation via HONO photolysis: HONO + hν = NO + ˙OH, whereas the path initiated by R2 is more circuitous and actually controlled by the slower photolysis of O_3: O_3 + hν (+H_2O) = O_2 + 2˙OH, the competition between R1 and R2 provides a mechanistic switch that buffers ˙OH concentrations and NO_2 decay (via R1 and/or NO_2^+ ˙OH = HNO_3) from actinic flux variations

セッション 21セイキ ノ ニッチュウ カンケイ ニ ツイテ

日中台共同研究「現代中国と東アジアの新環境」 ②21世紀の日中関係 : 青年研究者の思索と対