Improved continuous measurement system for atmospheric total peroxy and total organic nitrate under the high NOx condition.

We improved the thermal dissociation cavity attenuated phase shift spectroscopy (TD-CAPS) instrument to measure atmospheric total peroxy nitrates (PNs) and organic nitrates (ONs) continuously under the condition of high NOx. In TD-CAPS, PNs and ONs are dissociated in heated quartz tubes to form NO2, and the NO2 concentration is measured by cavity attenuated phase shift spectroscopy (CAPS). The original TD-CAPS system overestimates PN and ON concentrations in the presence of high NO concentrations. Our laboratory experiments and numerical simulations showed that the main cause of the overestimation was NO oxidation to NO2 by peroxy radicals generated in the heated quartz tubes. In the improved system, NO was converted to NO2 by adding excess O3 after the quartz tubes so that CAPS detected NOx (NO and NO2) instead of NO2. The uncertainty of the improved system was less than 20% with ∼15 parts per billion by volume (ppbv) NO and ∼80 ppbv NO2. The estimated detection limit (3σ) was 0.018 ppbv with an integration time of 2 min in the presence of 64 ppbv NO2. The improved system was tested for measurement of PNs and ONs in an urban area, and the results indicated that interference from NO was successfully suppressed.

Potential Factors Contributing to Ozone Production in AQUAS-Kyoto Campaign in Summer 2020: Natural Source-Related Missing OH Reactivity and Heterogeneous HO2/RO2 Loss.

This study presents total OH reactivity, ancillary trace species, HO2 reactivity, and complex isoprene-derived RO2 reactivity due to ambient aerosols measured during the air quality study (AQUAS)-Kyoto campaign in September, 2020. Observations were conducted during the coronavirus disease (COVID-19) pandemic (associated with reduced anthropogenic emissions). The spatial distribution of missing OH reactivity highlights that the origin of volatile organic compounds (VOCs) may be from natural-emission areas. For the first time, the real-time loss rates of HO2 and RO2 onto ambient aerosols were measured continuously and alternately. Ozone production sensitivity was investigated considering unknown trace species and heterogeneous loss effects of XO2 (≡HO2 + RO2) radicals. Missing OH reactivity enhanced the ozone production potential by a factor of 2.5 on average. Heterogeneous loss of radicals could markedly suppress ozone production under low NO/NOx conditions with slow gas-phase reactions of radicals and change the ozone regime from VOC- to NOx-sensitive conditions. This study quantifies the relationship of missing OH reactivity and aerosol uptake of radicals with ozone production in Kyoto, a low-emission suburban area. The result has implications for future NOx-reduction policies. Further studies may benefit from the combination of chemical transport models and inverse modeling over a wide spatiotemporal range.

Decomposition of multifunctionalized α-alkoxyalkyl-hydroperoxides derived from the reactions of Criegee intermediates with diols in liquid phases.

The oxidation of volatile organic compounds in the atmosphere produces organic hydroperoxides (ROOHs) that typically possess not only -OOH but also other functionalities such as -OH and -C(O). Because of their high hydrophilicity and low volatility, such multifunctionalized ROOHs are expected to be taken up in atmospheric condensed phases such as aerosols and fog/cloud droplets. However, the characteristics of ROOHs that control their fates and lifetimes in liquid phases are poorly understood. Here, we report a study of the liquid-phase decomposition kinetics of multifunctionalized α-alkoxyalkyl-hydroperoxides (α-AHs) that possessed an ether, a carbonyl, a hydroperoxide, and two hydroxy groups. These ROOHs were synthesized by ozonolysis of α-terpineol in water in the presence of 1,3-propanediol, 1,4-butanediol, or 1,5-pentanediol. Their decomposition products were detected as chloride anion adducts by electrospray mass spectrometry as a function of reaction time. Experiments using H218O and D2O revealed that hemiacetal species were α-AH decomposition products that further transformed into other products. The result that the rate coefficients (k) of the decomposition of C15 α-AHs increased exponentially from pH 5.0 to 3.9 was consistent with an H+-catalyzed decomposition mechanism. The temperature dependence of k and an Arrhenius plot yielded activation energies (Ea) of 15.7 ± 0.8, 15.0 ± 2.4, and 15.9 ± 0.3 kcal mol-1 for the decomposition of α-AHs derived from the reaction of α-terpineol CIs with 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol, respectively. The determined Ea values were compared with those of related ROOHs. We found that alkyl chain length is not a critical factor for the decomposition mechanism, whereas the presence of additional -OH groups would modulate the reaction barriers to decomposition via the formation of hydrogen-bonding with surrounding water molecules. The derived Ea values for the decomposition of the multifunctionalized, terpenoid-derived α-AHs will facilitate atmospheric modeling by serving as representative values for ROOHs in atmospheric condensed phases.

Personal Exposure to Fine Particles (PM2.5) in Northwest Africa: Case of the Urban City of Bamako in Mali.

Personal exposure to particulate matter (PM) from anthropogenic activities is a major concern in African countries, including Mali. However, knowledge of particulates is scant. This study was undertaken to characterize personal exposure to PM2.5 microns or less in diameter (PM2.5) in the city of Bamako in Mali. The exposure to PM2.5, through daily activities was observed from September 2020 to February 2021. Participants wore palm-sized optical PM2.5 sensors on their chest during their daily activities. The exposure levels in four different groups of residents were investigated in relation to their daily activities. The variation in PM2.5 concentration was measured during different activities in different microenvironments, and the main sources of exposure were identified. The highest average 10 min concentrations were observed at home and in bedrooms, while the participants were using specific products typically used in Africa, Asia, and South America that included insecticides (IST; 999 µg/m3) and incense (ICS; 145 µg/m3), followed by traffic (216 µg/m3) and cooking (150 µg/m3). The lowest average 10 min concentrations were also observed in the same microenvironment lacking IST or ICS (≤14 µg/m3). With no use of specific products, office workers and students were the least exposed, and drivers and cooks were the most exposed. The concentrations are up to 7.5 and 3 times higher than the World Health Organization's yearly and daily recommended exposure levels, respectively, indicating the need to promptly elaborate and apply effective mitigation strategies to improve air quality and protect public health. This study highlights the importance of indoor air pollution sources related to culture and confirms previous studies on urban outdoor air pollution sources, especially in developing countries. The findings could be applied to cities other than Bamako, as similar practices and lifestyles are common in different cultures.

Total hydroxyl radical reactivity measurements in a suburban area during AQUAS-Tsukuba campaign in 2017.

Missing hydroxyl radical (OH) reactivity from unknown/unmeasured trace species empirically accounts for 10%-30% of total OH reactivity and may cause significant uncertainty regarding estimation of photochemical ozone production. Thus, it is essential to unveil the missing OH reactivity for developing an effective ozone mitigation strategy. In this study, we conducted simultaneous observations of total OH reactivity and 54 reactive trace species in a suburban area as part of the Air QUAlity Study (AQUAS)-Tsukuba campaign for the summer of 2017 to gain in-depth insight into total OH reactivity in an area that experienced relatively high contributions of secondary pollutants. The campaign identified on average 35.3% of missing OH reactivity among total OH reactivity (12.9 s-1). In general, ozone-production potential estimation categorized ozone formation in this area as volatile organic compound (VOC)-limited conditions, and missing OH reactivity may increase ozone production potential 40% on average if considered. Our results suggest the importance of photochemical processes of both AVOCs and BVOCs for the production of missing OH reactivity and that we may underestimate the importance of reducing precursors in approach to suppressing ozone production if we ignore the contribution of their photochemical products.

Characteristics of roadside volatile organic compounds in an urban area dominated by gasoline vehicles, a case study in Hanoi.

Volatile organic compounds (VOCs) are important air pollution issues because of their potential health effects, and the contribution to ground ozone and secondary particulate matter. In this study, 53 VOC species near nine roads in Hanoi were monitored by sampling and analyzed by GC-FID four times per day on weekdays and in the morning on the weekend, from December 2014 to January 2015. In parallel with VOC sampling, vehicle number was counted, and meteorological conditions were recorded. A large share of motorbikes was found, accounted for 82% of overall for all period, and 88% in rush hours. The average TVOC concentration was 305.1 ppb; while those of BTEX were 12.8/27.4/4.8/15.9/6.0 ppb for benzene/toluene/ethylbenzene/m,p-xylenes/o-xylene, respectively. Isopentane was the most abundant species of VOCs. A significant carcinogenic risk of benzene species was found. Ozone formation potential (OFP) of VOCs was of 1752.7 ppb. Levels of VOC species reflected well the transportation volume. Strong correlations between motorbike number related parameters and ethylbenzene were found. High correlations were also found among ethylbenzene and almost all other VOC species. It implied that the majority of VOCs near road emitted from the same source, which is motorbikes. The calculation using emission factors from COPERT 5 model with conditions of fleets in Hanoi showed that VOCs from motorbikes contributed to more than 90% of the VOC level.

Degradation of PAHs during long range transport based on simultaneous measurements at Tuoji Island, China, and at Fukue Island and Cape Hedo, Japan.

We investigated the degradation of polycyclic aromatic hydrocarbons (PAHs) during long-range transport. Aerosols were collected simultaneously at remote sites on Tuoji Island, China; Fukue Island, Japan; and the Cape Hedo Atmosphere and Aerosol Measurement Station (CHAAMS), Okinawa, Japan in April, October, and December from 2012 to 2013. These remote sites were convenient for investigating the degradation of PAHs during long-range transport. PAHs were analyzed via gas chromatography/mass spectrometry. We identified air masses that passed over all sites and combined our measurements with a chemical transport model. We estimated the relative contributions of the PAHs at the three sites by normalizing the PAH concentrations to elemental carbon. Benzo[a]pyrene persisted in 5-16% of samples. The results of this study are consistent with laboratory studies in which secondary organic aerosol (SOA) coatings protected PAHs from degradation by ozone. We detected an inhibition of the degradation PAHs by SOA coatings by collecting PAHs simultaneously at the three sites. To elucidate the major sources of the SOAs, we carried out a positive matrix factorization analysis to identify the major sources of SOA coating, which controls the lifetime of PAHs. In spring and winter, the contribution of vehicle emissions was higher (46%) at Tuoji Island than at CHAAMS (13%). In contrast, the contribution of coal combustion was higher at CHAAMS (59%) than at Tuoji Island (28%). This result implies that during long-range transport, PAHs derived from coal combustion are more slowly degraded than PAHs derived from vehicle emissions. We found that the viscosity of SOA coatings derived from vehicle emissions in China was low, and the corresponding PAHs were rapidly degraded. In contrast, the viscosity of SOA coatings derived from coal combustion was high, and degradation of the corresponding PAHs was relatively slow. These results imply that PAHs derived from coal combustion have long lifetime.

Aerosol Liquid Water Promotes the Formation of Water-Soluble Organic Nitrogen in Submicrometer Aerosols in a Suburban Forest.

Water-soluble organic nitrogen (WSON) affects the formation, chemical transformations, hygroscopicity, and acidity of organic aerosols as well as biogeochemical cycles of nitrogen. However, large uncertainties exist in the origins and formation processes of WSON. Submicrometer aerosol particles were collected at a suburban forest site in Tokyo in summer 2015 to investigate the relative impacts of anthropogenic and biogenic sources on WSON formations and their linkages with aerosol liquid water (ALW). The concentrations of WSON (ave. 225 ± 100 ngN m-3) and ALW exhibited peaks during nighttime, which showed a significant positive correlation, suggesting that ALW significantly contributed to WSON formation. Further, the thermodynamic predictions by ISORROPIA-II suggest that ALW was primarily driven by anthropogenic sulfate. Our analysis, including positive matrix factorization, suggests that aqueous-phase reactions of ammonium and reactive nitrogen with biogenic volatile organic compounds (VOCs) play a key role in WSON formation in submicrometer particles, which is particularly significant in nighttime, at the suburban forest site. The formation of WSON associated with biogenic VOCs and ALW was partly supported by the molecular characterization of WSON. The overall result suggests that ALW is an important driver for the formation of aerosol WSON through a combination of anthropogenic and biogenic sources.

Relative and Absolute Sensitivity Analysis on Ozone Production in Tsukuba, a City in Japan.

The change in the ozone production rate on reducing its precursors, namely, ozone production sensitivity, is important information for developing a strategy to reduce ozone. We expanded a conventional sensitivity analysis theory by including peroxy radical loss by uptake onto particle surfaces in the aim of examining their potential impact. We also propose a new concept of absolute sensitivity that enables us to evaluate the quantitative effectiveness of precursor reduction toward mitigating ozone production over a given period and area. This study applies the theory to observations in Tsukuba, a city in Japan. The relative sensitivity analysis shows that ozone production was more sensitive to volatile organic compounds (VOCs) in the morning and evening, and it became more sensitive to NOx in the afternoon. NO depletion was a main trigger in this sensitivity regime transition. The absolute sensitivity analysis indicates that the VOC-sensitive period in the morning determines the total ozone production sensitivity in a day. While particles did not have significant impact on regime classification in Tsukuba, they have a potential to decrease the mitigating effect of VOC reduction on ozone production and to moderate the enhancement effect of NOx reduction depending upon uptake coefficients. A further study will benefit from a combination with an observation-constrained box model simulation or chemical transport modeling system, which may provide sensitivity analysis over a large spatial and temporal range.

Water Vapor Does Not Catalyze the Reaction between Methanol and OH Radicals.

Recent reports [Jara-Toro et al., Angew. Chem. Int. Ed. 2017, 56, 2166 and PCCP 2018, 20, 27885] suggest that the rate coefficient of OH reactions with alcohols would increase by up to two times in going from dry to high humidity. This finding would have an impact on the budget of alcohols in the atmosphere and it may explain differences in measured and modeled methanol concentrations. The results were based on a relative technique carried out in a small Teflon bag, which might suffer from wall reactions. The effect was reinvestigated using a direct fluorescence probe of OH radicals, and no catalytic effect of H2 O could be found. Experiments in a Teflon bag were also carried out, but the results of Jara-Toro et al. were not reproducible. Further theoretical calculations show that the water-mediated reactions have negligible rates compared to the bare reaction and that even though water molecules can lower the barriers of reactions, they cannot make up for the entropy cost.

Kinetics Study of OH Uptake onto Deliquesced NaCl Particles by Combining Laser Photolysis and Laser-Induced Fluorescence.

Despite the role of hydroxyl radical (OH) uptake onto sea-salt particles as a daytime chlorine source, affecting the chemical processes in the marine boundary layer, its uptake coefficient has not yet been confirmed by direct measurement methods. This study reports the application of a combination technique of laser flash photolysis generation and laser-induced fluorescence detection for the direct kinetic measurement of OH uptake onto deliquesced NaCl particles. The uptake coefficient was not constant and inversely depended on the initial OH concentration, indicating that the first uptake step is Langmuir-type adsorption. The resistance model, including surface processes, well reproduced the observed uptake coefficient. The model predicted an uptake coefficient for the atmospheric relevant OH concentration within the range from 0.77 to 0.95. Such values may lead to emissions of Cl2 higher than those predicted in previous studies based on other values. Hence, the proposed value may provide more reliable estimations of ozone formation, oxidation of volatile organic compounds, secondary organic aerosol formation, and lifetime of methane and elemental mercury in the marine boundary layer.

New System for Measuring the Photochemical Ozone Production Rate in the Atmosphere.

We have developed a new system for measuring photochemical ozone production rates in the atmosphere. Specifically, the system measures the net photochemical oxidant (Ox: the sum of ozone (O3) and nitrogen dioxide (NO2)) production rates (P-L(Ox)). Measuring Ox avoids issues from perturbations to the photostationary states between nitrogen oxides (NOx) and O3. This system has "reaction" and "reference" chambers. Ambient air is introduced into both chambers, and Ox is photochemically produced in the reaction chamber and not generated in the reference chamber. Air from the chambers is alternately introduced into an NO-reaction (NO: nitric oxide) tube to convert O3 to NO2, and then the Ox concentration is measured as NO2 using a laser-induced fluorescence technique. P-L(Ox) was obtained by dividing the difference in Ox concentrations between air samples from the two chambers by the mean residence time of the air in the reaction chamber. In this study, the P-L(Ox) measurement system was characterized, and the current detection limit of P-L(Ox) was determined to be 0.54 ppbv h-1 with an integration time of 60 s (S/N = 2), assuming an ambient Ox concentration of 100 ppbv. Field measurements of P-L(Ox) were conducted using the system at a remote forest location.

Reactive Uptake of Gaseous Sesquiterpenes on Aqueous Surfaces.

Sesquiterpenes emitted from biogenic sources play important roles in atmospheric HOx cycles and new particle formation. Current atmospheric models, however, fail to account for their fates, possibly due to missing heterogeneous sinks. Here we apply interface-specific mass spectrometry to detect carbocation products of the reactive uptake of gaseous sesquiterpenes C15H24 (ß-caryophyllene (ß-C), α-humulene (α-H), and alloaromadendrene (a-d)) on the surface of aqueous microjets as functions of water acidity and gas concentration. We find that these gases are effectively protonated to C15H25+ upon colliding with the surface of pH < 5 water microjets. We determine inflection points from plots of product yields vs bulk pH: pH1/2 = 4.17 ± 0.05, 4.28 ± 0.06, and 4.36 ± 0.19, and kinetic isotope effects (KIEs) from H2O/D2O (1:1 = vol/vol) experiments: KIE = 2.31 ± 0.08, 1.95 ± 0.05, and 2.71 ± 0.11, for ß-C, α-H, and a-d, respectively. These results are analyzed vis-a-vis previous reports on isoprene and monoterpenes experiments. We estimate 6.2 × 10-5 ≤ γ ≤ 3.1 × 10-4 for the reactive uptake of gaseous sesquiterpenes on acidic (1 < pH < 3) water surfaces. The atmospheric implications of present findings are discussed.

Determination of nitrous acid emission factors from a gasoline vehicle using a chassis dynamometer combined with incoherent broadband cavity-enhanced absorption spectroscopy.

Nitrous acid (HONO) is a well-known source of hydroxyl radicals in the troposphere. Vehicle exhaust is considered to be one of the primary emission sources of HONO. In this study, measurements of HONO in gasoline vehicle exhaust were carried out using a chassis dynamometer combined with incoherent broadband cavity-enhanced absorption spectroscopy. When catalysts were warm, concentrations of HONO were higher than those prior to catalysts warming. Other species, such as CO, and total hydrocarbons (THCs), showed the opposite pattern. There were no correlations evident between HONO and other trace species concentrations immediately after emission. The HONO/NOx ratio, a good proxy for the formation of HONO in atmosphere, ranged from 1.1 to 6.8×10-3, which was consistent with previous studies. HONO emission factors (EFs) were calculated to be 0.01-3.6mgkg-1 fuel, which was different from the vehicle's specifications and those reported under different driving cycles. Annual HONO emissions in Japan were estimated using the calculated EFs and other statistical data.

Carboxylate Ion Availability at the Air-Water Interface.

Amphiphilic organic compounds at the air-water interface play key roles in the nucleation, growth, and aging process of atmospheric aerosol. Surface-active species are expected to react preferentially with atmospheric oxidants, such as the OH radical, at the air-water interface via specific mechanisms. Establishing the relative availability of the different amphiphilic species to gas-phase oxidants at the air-water interface under atmospherically relevant conditions is, however, challenging. Here we report the interfacial availability of atmospherically relevant carboxylate ions Rn-COO- (n = 1-7) and n-, cyclo-, aromatic-R6-COO- at the air-water interface via a novel application of mass spectrometry of aqueous microjets. The breakup mechanism of microjets lets us determine the relative interfacial affinities of carboxylate ions in equimolar solutions of the corresponding carboxylic acids in the 1 µM to 1 mM range under ambient conditions. We find that the interfacial affinity of Rn-COO- increases exponentially with both chain-length and solvent-accessible surface area (SASA) except in the case of R1-COO-. The relative interfacial affinities for n-heptanoate (n-R6-COO-) > cyclohexanecarboxylate (c-R6-COO-) > benzoate (Ar-R6-COO-) are also determined. We attribute the smallest availability of Ar-R6-COO- at the air-water interface among the three carboxylate ions to a strong π-H bonding between the aromatic ring and water molecule. Molecular mechanisms on the availability of carboxylate ions at the air-water interface and the atmospheric implications are discussed.

Characterization of Chromophoric Water-Soluble Organic Matter in Urban, Forest, and Marine Aerosols by HR-ToF-AMS Analysis and Excitation-Emission Matrix Spectroscopy.

Chromophoric water-soluble organic matter in atmospheric aerosols potentially plays an important role in aqueous reactions and light absorption by organics. The fluorescence and chemical-structural characteristics of the chromophoric water-soluble organic matter in submicron aerosols collected in urban, forest, and marine environments (Nagoya, Kii Peninsula, and the tropical Eastern Pacific) were investigated using excitation-emission matrices (EEMs) and a high-resolution aerosol mass spectrometer. A total of three types of water-soluble chromophores, two with fluorescence characteristics similar to those of humiclike substances (HULIS-1 and HULIS-2) and one with fluorescence characteristics similar to those of protein compounds (PLOM), were identified in atmospheric aerosols by parallel factor analysis (PARAFAC) for EEMs. We found that the chromophore components of HULIS-1 and -2 were associated with highly and less-oxygenated structures, respectively, which may provide a clue to understanding the chemical formation or loss of organic chromophores in atmospheric aerosols. Whereas HULIS-1 was ubiquitous in water-soluble chromophores over different environments, HULIS-2 was abundant only in terrestrial aerosols, and PLOM was abundant in marine aerosols. These findings are useful for further studies regarding the classification and source identification of chromophores in atmospheric aerosols.

Surface ozone and carbon monoxide levels observed at Oki, Japan: regional air pollution trends in East Asia.

Simultaneous ground-based measurements of ozone and carbon monoxide were performed at Oki, Japan, from January 2001 to September 2002 in order to investigate the O(3) and CO characteristics and their distributions. The observations revealed that O(3) and CO concentrations were maximum in springtime and minimum in the summer. The monthly averaged concentrations of O(3) and CO were 60 and 234 ppb in spring and 23 and 106 ppb in summer, respectively. Based on direction, 5-day isentropic backward trajectory analysis was carried out to determine the transport path of air masses, preceding their arrival at Oki. Comparison between classified results from present work and results from the year 1994-1996 was carried out. The O(3) and CO concentration results of classified air masses in our analysis show similar concentration trends to previous findings; highest in the WNW/W, lowest in N/NE and medium levels in NW. Moreover, O(3) levels are higher and CO levels are lower in the present study in all categories.

Atmospheric outflow of anthropogenic semivolatile organic compounds from East Asia in spring 2004.

To estimate the emissions of anthropogenic semivolatile organic compounds (SOCs) from East Asia and to identify unique SOC molecular markers in Asian air masses, high-volume air samples were collected on the island of Okinawa, Japan between 22 March and 2 May 2004. Contributions from different source regions (China, Japan, the Koreas, Russia, and ocean/local) were estimated by use of source region impact factors (SRIFs). Elevated concentrations of hexachlorobenzene (HCB), hexachlorcyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs), and particulate-phase polycyclic aromatic hydrocarbons (PAHs) were attributed to air masses from China. A large proportion of the variation in the current-use pesticides, gas-phase PAHs, and polychlorinated biphenyl (PCB) concentrations was explained by meteorology. Chlordanes showed a technical mixture profile and similar concentrations regardless of source region. alpha/gamma HCH and trans/cis chlordane ratios did not vary significantly with different source regions and had regional averages of 2.5 +/- 1.0 and 1.2 +/- 0.3, respectively. Particulate-phase PAH concentrations were significantly correlated (p value < 0.05) with other incomplete combustion byproduct concentrations, including elemental mercury (Hg0), CO, NOx, black carbon, submicrometer aerosols, and SO2. By use of measured PAH, CO, and black carbon concentrations and estimated CO and black carbon emission inventories, the emission of six carcinogenic particulate-phase PAHs was estimated to be 1518-4179 metric tons/year for Asia and 778-1728 metric tons/year for China, respectively. These results confirm that East Asian outflow contains significant emissions of carcinogenic particulate-phase PAHs.

Diurnal variations in H2O2, O3, PAN, HNO3 and aldehyde concentrations and NO/NO2 ratios at Rishiri Island, Japan: potential influence from iodine chemistry.

The presence of iodine chemistry, hypothesized due to the overprediction of HO(2) levels by a photochemical box model at Rishiri Island in June 2000, was quantitatively tested against the observed NO/NO(2) ratios and the net production rates of ozone. The observed NO/NO(2) ratios were reproduced reasonably well by considering the conversion of NO to NO(2) by IO, whose amount was calculated so as to reproduce the observed HO(2) levels. However, the net production rates of ozone were calculated to be negative when such high mixing ratios of IO were considered, which was inconsistent with the observed buildup of ozone during daytime. These results suggest that iodine chemistry may not be the sole mechanism for the reduced mixing ratios of HO(2), or that "hot spots" for iodine chemistry were present. Diurnal variations in the mixing ratios of HCHO, CH(3)CHO, peroxy acetyl nitrate (PAN) and HNO(3) observed during the study are presented along with the simulated ones. The box model simulations suggest that the effect of iodine chemistry on these concentrations is small and that important sources of CH(3)CHO and sinks of PAN are probably missing from our current understanding of the tropospheric chemistry mechanism.

Ultraviolet light-induced water-droplet formation from wet ambient air.

We report the formation of water droplets by irradiating wet ambient air with deep UV light. The light sources were either a continuous low-pressure mercury lamp or pulsed ArF laser, which both emit light shorter than 200 nm. Water droplets were produced in reaction vessels under different temperature, relative humidity, and moisture-supply conditions. The particles grew as large as about 0.2 mm. The suggested mechanism is discussed with the photo-dissociations of oxygen and successively formed ozone, and further dark reactions giving hydrogen peroxide as a seeding nucleus. Observed concentrations of intermediates were well explained by simulating the proposed chemical reactions. A possible application to artificial rain is briefly described.