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Isoprene is the most relevant volatile organic compound emitted during the biosynthesis of metabolism processes. The oxidation of isoprene by a hydroxy radical (OH) is one of the main consumption schemes that generate six isomers of isoprene hydroxy hydroperoxide radicals (ISOPOOs). In this study, the rate constants of ISOPOOs + sulphur dioxide (SO2) reactions that eventually generate sulphur trioxide (SO3), the precursor of sulphate aerosol (SO42−(p)), are determined using microcanonical kinetic theories coupled with molecular structures and energies estimated by quantum chemical calculations. The results show that the reaction rates range from 10−27 to 10−20 cm3 molecule−1 s−1, depending on the atmospheric temperature and structure of the six ISOPOO isomers. The effect of SO3 formation from SO2 oxidation by ISOPOOs on the atmosphere is evaluated by a global chemical transport model, along with the rate constants obtained from microcanonical kinetic theories. The results show that SO3 formation is enhanced in regions with high SO2 or low nitrogen oxide (NO), such as China, the Middle East, and Amazon rainforests. However, the production rates of SO3 formation by ISOPOOs + SO2 reactions are eight orders of magnitude lower than that from the OH + SO2 reaction. This is indicative of SO42−(p) formation from the direct oxidation of SO2 by ISOPOOs, which is almost negligible in the atmosphere. The results of this study entail a detailed analysis of SO3 formation from gas-phase reactions of isoprene-derived products. [ABSTRACT FROM AUTHOR]

Jakarta Greater Area (JGA) has encountered recurrent challenges of air pollution, notably, high ozone levels. We investigate the trends of surface ozone (O3) changes from the air quality monitoring stations and resolve the contribution of meteorological drivers in urban Jakarta (2010–2019) and rural Bogor sites (2017–2019) using stepwise Multi Linear Regression. During 10 years of measurement, 41% of 1-h O3 concentrations exceeded Indonesia' s national threshold in Jakarta. In Bogor, 0.1% surpassed the threshold during 3 years of available data records. The monthly average of maximum daily 8-h average (MDA8) O3 anomalies exhibited a downward trend at Jakarta sites while increasing at the rural site of Bogor. Meteorological and anthropogenic drivers contribute 30% and 70%, respectively, to the interannual O3 anomalies in Jakarta. Ozone formation sensitivity with satellite demonstrates that a slight decrease in NO2 and an increase in HCHO contributed to declining O3 in Jakarta with 10 years average of HCHO to NO2 ratio (FNR) of 3.7. Conversely, O3 increases in rural areas with a higher FNR of 4.4, likely due to the contribution from the natural emission of O3 precursors and the influence of meteorological factors that magnify the concentration. [ABSTRACT FROM AUTHOR]

Ozone (O3) is a pollutant of concern in urban areas because of its effects on health, crops, ecosystems, and materials. Despite efforts to meet the Japanese air quality standard for O3 in the Kanto region, the attainment percentage is close to zero. Considering that O3 formation is sensitive to emissions of volatile organic compounds (VOC) and nitrogen oxides (NOx), this study evaluated a range of reductions in the emissions of both precursors using a regional air quality model (ADMER-PRO) and estimated their benefits measured as the economic change due to O3 concentration differences between scenarios. The simulation period was set during the 2016 O3 season. The results showed that O3 concentrations could be reduced using two approaches: significant reduction in VOC levels combined with minor NOx level changes or significant NOx emission reduction. Significant reduction in NOx levels was the most effective strategy for a generalized decrease in the O3 levels in the Kanto region, and the benefit analysis revealed that the most significant economic impacts could be achieved by adopting the latter approach. [ABSTRACT FROM AUTHOR]

In the atmosphere, carbonyl oxides known as Criegee intermediates are produced mainly by ozonolysis of volatile organic compounds containing C＝C double bonds, such as biogenic terpenoids. Criegee intermediates can react with OH-containing species to produce labile organic hydroperoxides (ROOHs) that are taken up into atmospheric condensed phases. Besides water, alcohols are an important reaction partner of Criegee intermediates and can convert them into α-alkoxyalkyl-hydroperoxides (α-AHs), R1R2C(–OOH)(–OR′). Here, we report a study on the aqueous-phase fates of α-AHs derived from ozonolysis of α-terpineol in the presence of methanol, ethanol, 1-propanol, and 2-propanol. The α-terpineol α-AHs and the decomposition products were detected as their chloride adducts by electrospray mass spectrometry as a function of reaction time. Our discovery that the rate of decomposition of α-AHs increased as the pH decreased from 5.9 to 3.8 implied that the decomposition mechanism was catalyzed by H+. The use of isotope solvent experiments revealed that a primary decomposition product of α-AHs in an acidic aqueous solution was a hemiacetal R1R2C(–OH)(–OR′) species that was further transformed into other products such as lactols. The proposed H+-catalyzed decomposition of α-AHs, which provides H2O2 and multifunctional species in ambient aerosol particles, may be faster than other degradation processes (e.g., photolysis by solar radiation). [ABSTRACT FROM AUTHOR]

A kinetic study of the reaction of the 4‐methylphenyl radical (4‐C6H4CH3) with the oxygen molecule was conducted using experimental and theoretical approaches. The absorption spectrum for the λ = 266 nm photolysis of the 4‐C6H4CH3X (X = Cl, Br)/N2/O2 mixture was measured in the wavelength range of λ = 503‐512 nm using N2 as the buffer gas at a total pressure of 40 Torr using a cavity ring‐down spectroscopy apparatus coupled with a pulsed laser photolysis system. Based on the absorbance of the product of the 4‐C6H4CH3 + O2 reaction at λ = 504 nm, the reaction rate coefficient for the 4‐C6H4CH3 + O2 reaction was determined to be k = (1.21 ± 0.10) × 10−11 cm3 molecule−1 s−1 and k = (1.18 ± 0.21) × 10−11 cm3 molecule−1 s−1 using 4‐C6H4CH3Cl and 4‐C6H4CH3Br, respectively, as the radical precursor. And there was no pressure dependence in the total pressure range of 10‐90 Torr varying partial pressure of N2 buffer gas at T = 296 ± 5 K. The geometries, vibration frequencies, and potential energy surfaces of the reactants, major products, and transition states in the 4‐C6H4CH3 + O2 reaction were determined using the CBS‐QB3 method. The k value at the high‐pressure limit was calculated to be 1.26 × 10−11 cm3 molecule−1 s−1 using the variational transition‐state theory. The calculated value of k was consistent with the experimental value, which indicated that the 4‐C6H4CH3 + O2 reaction reaches the high‐pressure limit at 10 Torr. Therefore, the oxidation of the 4‐C6H4CH3 radical is almost 10 times faster than that of the benzyl radical, which has the same chemical formula, at the high‐pressure limit. [ABSTRACT FROM AUTHOR]

Despite ozone precursor emission reduction efforts in most polluted areas worldwide, photochemical ozone remains among the most concerning air pollutants in some regions, possibly because of spatial heterogeneity of ozone sensitivity to individual precursors. However, regional differences in ozone sensitivity to volatile organic compounds (VOCs), a major precursor, have not been quantitatively shown. Therefore, this study estimated the spatial variations in the efficacy of VOC emission reductions to mitigate photochemical ozone concentrations and population exposure (as related to ozone-related health problems) over Japan, and to inform policy makers pursuing effective ozone reduction strategies in polluted regions. Using air quality simulations, we found that the abovementioned efficacy differed substantially, up to 10-fold, among 20 × 20-km areas in which VOCs had been reduced. Using the above-calculated spatial distribution of the efficacy and data on emission source locations of several industries, upstream industries (e.g., petroleum and coal products) showed greater reduction efficacies than downstream industries (e.g., plastic products). By comparing the calculated ozone sensitivity to VOCs with the ozone–NOx–VOC sensitivity derived from space-based observations of the HCHO/NO2 column ratio from the Ozone Monitoring Instrument, the general spatial trends in ozone sensitivity to VOC emission reductions were verified qualitatively. Thus, regional countermeasures should be considered rather than the existing uniform nationwide measures in Japan. Moreover, to prioritize VOC emission reductions by industry, considering the reactivity or ozone formation potential of each emitted VOC exclusively, as is currently done, is insufficient, the emission locations of each industry should also be considered. [ABSTRACT FROM AUTHOR]

Photodissociation of iodine monochloride has been investigated at 235–248 nm by studying Doppler profiles of (2+1) resonance enhanced multiphoton ionization spectra of fragment chlorine atoms and two-photon laser induced fluorescence spectra of iodine atoms. At 235.3–237.8 nm, a measured branching ratio of [Cl*(2P1/2)]/[Cl(2P3/2)] is 0.68±0.10. At 248 nm, the [I*(2P1/2)]/[I(2P3/2)] ratio is 0.71±0.27. From the measured Doppler profiles and the ab initio calculation, the photoprepared states leading to Cl and Cl* production are assigned to the 3Π0+ (and possibly 3∑-0+) and the 1Π1 states, respectively. Nonadiabatic couplings between the potential curves have been discussed. [ABSTRACT FROM AUTHOR]

The reactions O(1D)+HCl→OH+Cl (1a) and OCl+H (1b), O(1D)+DCl→OD+Cl (2a) and OCl+D (2b), and O(1D)+Cl2→OCl+Cl (3) are studied at an average collision energy of 7.6, 7.7, and 8.8 kcal/mol for (1), (2), and (3), respectively. H, D, and Cl atoms are detected by the resonance-enhanced multiphoton ionization technique. The average kinetic energies released to the products are estimated from Doppler profile measurements of the product atoms. The relative yields [OCl+H]/[OH+Cl] and [OCl+D]/[OD+Cl] are directly measured, and a strong isotope effect (H/D) on the relative yields is found. The fine-structure branding ratios [Cl(2P1/2]/[Cl(2P3/2)] of the reaction products are also measured. The results suggest that nonadiabatic couplings take place at the exit channels of the reactions (1a) and (2a), while the reaction (3) is totally adiabatic. [ABSTRACT FROM AUTHOR]

The H, D, and Cl atoms from the photodissociation of HCl and DCl at 157 and 193 nm were detected by laser-induced fluorescence (LIF) in the vacuum ultraviolet region. The Doppler profiles of the H and D resonance lines at 121.6 nm in the LIF spectra indicate that the absorption of HCl and DCl at 157 nm is a mixture of perpendicular and parallel transition (A 1Π, a 3Π0+←X 1Σ+), while that at 193 nm results almost solely from the A 1Π←X 1Σ+ transition. The fine-structure branching ratios, are measured for the chlorine atom by LIF. Combined with the previous results, the branching ratios [Cl*(2P1/2)]/[Cl(2P3/2)] are 0.81±0.09 at 157 nm, 0.50±0.05 at 193 nm for HCl, and 0.23±0.05 at 193 nm for DCl. These results suggest that the nonadiabatic couplings during the breakup of HCl (DCl) in the excited states play an important role in determination of the fine-structure branching ratios. [ABSTRACT FROM AUTHOR]

Doppler profiles of chlorine and hydrogen atomic fragments produced in the photodissociation of mono- and dichloroethylenes at 193 nm have been measured in a pump-and-probe experiment using 2+1 resonance-enhanced multiphoton ionization. In a second experiment, the angular distributions of the Cl fragments produced from chloroethylenes at 235 and 238 nm were measured using a perfect-focusing mass spectrometer. In a third experiment, we measured the power dependence of the relative yields of H, Cl, HCl, and HCl+ produced from vinyl chloride at 193 nm. For Cl detachment, two primary processes have been confirmed. One produces an isotropic angular distribution of photofragments, while the other produces an anisotropic distribution. For H atom detachment, an isotropic angular distribution and a Boltzmann velocity distribution were found. The ratio of yields of the Cl and H fragments was found to be 4±1 for CH2CCl2 and higher than 10 for t-CHClCHCl and CCl2CClH. The H, Cl, and HCl yields were found to be first order in laser intensity, while the HCl+ yield was found to be third order. Saturation measurements of the ion yield indicate that the latter results from a 1+1+1 resonance-enhanced process involving a bound state of the parent molecule. This intermediate state may also be responsible for producing the statistical component of the Cl atom product. [ABSTRACT FROM AUTHOR]

Photofragment chlorine atoms in the 2Pj states from Cl2 at 266–500 nm are measured by a resonance-enhanced multiphoton ionization technique. The measured branching ratio of [Cl*(2P1/2)]/[Cl(2P3/2)] increases monotonically with dissociation wavelengths from (9.5±1.8)×10-3 at 308 nm to (4.7±0.5)×10-1 at 475 nm. At 375 nm≤λ≤475 nm, Doppler profiles of the chlorine atoms indicate adiabatic formation of two Cl(2P3/2) from the 1Π(1u) state of Cl2 and Cl(2P3/2)+Cl*(2P1/2) from the B 3Π(0+u) state. On the other hand, at a shorter wavelength (308 nm), Cl*(2P1/2) is generated from the 1Π(1u) state through nonadiabatic transitions during the dissociation. The relative contribution of the 1Π(1u)←X 1Σ(0+g) and B 3Π(0+u)←X 1Σ(0+g) transitions in the photoabsorption is estimated from the obtained branching ratios at 375 nm≤λ≤475 nm. [ABSTRACT FROM AUTHOR]

The O(2p 3Pj) (j=2, 1, and 0) fragments produced in the 157 nm photodissociation of CO2 were detected by resonance-enhanced multiphoton ionization in a molecular beam. The Doppler profiles and fine-structure branching ratios were measured for the oxygen-atom photofragment in the 3Pj states. The Doppler profiles were analyzed to give an anisotropy parameter of β=2.0±0.2 and an internal energy equivalent to 3.9±0.3 vibrational quanta of CO. The fine-structure populations were found to be 0.70±0.05, 0.16±0.03, and 0.14±0.03 (with error bars of ±σ) for j=2, 1, and 0, respectively. A mechanism is proposed in which complex on the 1B2 surface undergoes intersystem crossing to the 3B2 surface. A phase-space model with a constraint on the impact parameter is shown to be consistent with the observed energy release. The nonstatistical fine-structure population could be caused by long-range interactions on the triplet surface. In a bulb experiment, O(3P) was produced by quenching of O(1D). The fine-structure populations of the resulting O(3Pj) were 0.64±0.04, 0.25±0.04, and 0.11±0.04. This state distribution is consistent with a long-lived complex which decays to give statistical products. [ABSTRACT FROM AUTHOR]

The Doppler profiles of the O(1D) products from the photodissociation of O2 at 157.6 nm and NO2 and N2O at 205.47 nm are detected by a resonance enhanced multiphoton ionization technique. The translation energy and angular distributions are deduced for the O(1D) atoms. Present results indicate that (a) O2 (B 3Σ-u) has a short dissociative lifetime when irradiated at 157.6 nm, (b) NO(2Π) photofragment from NO2 at 205.47 nm is mostly vibrationally excited, and (c) most of the available energy is released as kinetic energy when N2O is photodissociated at 205.47 nm. [ABSTRACT FROM AUTHOR]

Hydrocarbons (CnH2n+2, n=3, 4, and 6) and methyl halides (CH3X, X=Cl, Br, I) are photodissociated at 157 nm. The hydrogen atom photofragments are detected by a resonance-enhanced multiphoton ionization technique. The Doppler profiles of the hydrogen atoms from hydrocarbons are well represented by a Gaussian profile, while those from methyl halides by a mixture of a Gaussian and a non-Gaussian profiles. These Doppler profiles are interpreted assuming that (a) hot ethyl photofragments from hydrocarbons result in the formation of hydrogen atoms and (b) methyl halides undergo both direct and indirect photolytic scissions of the C—H bonds at 157 nm. [ABSTRACT FROM AUTHOR]

O(2p3Pj) atoms produced from the reaction between H(1s2S) and O2(X3Σ-g) at collision energies (Ecoll) of 2.5 and 2.1 eV are detected by a resonance enhanced multiphoton ionization technique. From the Doppler profile measurements of O(3Pj), the average kinetic energy released to the products is estimated. The results suggest that the average fraction of the kinetic energy disposal at Ecoll =2.1 eV is larger than that at Ecoll =2.5 eV. The obtained branching ratios of O(3Pj) j=2, 1, and 0 at Ecoll =2.5 eV are (0.70±0.02), (0.21±0.02), and (0.09±0.02), and those at Ecoll =2.1 eV are (0.63±0.02), (0.25±0.04), and (0.12±0.02), respectively, with error bars of ±σ. The results suggest that the nonadiabatic couplings at the last stage of the reaction are important for the determination of the ratios. [ABSTRACT FROM AUTHOR]

Doppler profiles of O(2p 3Pj) (j=2,1,0) produced from the photodissociation of O2 in the Herzberg I system (A3Σ+u←X3Σ-g) at 226 nm are measured with a resonance-enhanced multiphoton ionization technique. The anisotropy parameter for the angular distribution of the photofragments is found to be 1.6±0.4, in quantitative agreement with theory and indicating that the Herzberg I system borrows most of its intensity from a parallel band. The branching ratios to the j levels of O(2p 3Pj) (j=2,1,0) are found to be (2.5±0.3):1:(0.26±0.03) and are compared with the values expected for the limits of adiabatic and diabatic dissociation. [ABSTRACT FROM AUTHOR]

Alkyl chlorides (R=CH3, C2H5, C3H7, and C4H9), chloromethanes (CHnCl4-n), and chlorofluoromethanes (CFnCl4–n) are photodissociated at 157 and 193 nm. The chlorine atom photofragments are detected by a resonance enhanced multiphoton ionization technique. The branching ratios of the Cl photofragments [Cl*(3p2P1/2)]/[Cl(3p2P3/2)] are almost identical (0.23±0.03) for alkyl monochlorides at 157 and 193 nm and for CH2Cl2 and CHCl3 at 157 nm, while the ratios are rather small (0.10±0.02) for CH2Cl2 and CHCl3 at 193 nm. No discernible isotope effects on the branching ratios were observed when D atoms were substituted for H atoms in chloromethanes. For CCl4, CF3Cl, CF2Cl2, CFCl3 at 157 and 193 nm, the ratios are small (<0.05) irrespective of the number of Cl atoms in the parent molecules. The Doppler profiles of the chlorine photofragments have been obtained and it is found that (a) CF3Cl undergoes a perpendicular optical transition at 157 nm and (b) for halomethanes containing more than two Cl atoms, the Cl photofragment has a Boltzmann distribution in translational energy and an isotropic angular distribution. [ABSTRACT FROM AUTHOR]

The Doppler profiles of the hydrogen atom photofragments from the photodissociation of HCl and HBr at 157 and 243 nm are observed to determine the symmetries of the photoexcited states by using a resonance enhanced multiphoton ionization technique. The phototransitions are perpendicular for HCl at 157 nm and 193 nm and for HBr at 157 nm and 243 nm. Isotope effects on the branching ratios of [Cl*(2P1/2)]/[Cl(2P3/2)] are observed for the photodissociation of HCl and DCl at 157 and 193 nm. Our results indicate that in the photodissociation processes of HCl (A 1Π) the dynamical curve crossings during the breakup of the molecule play important roles in the determination of the branching ratio. [ABSTRACT FROM AUTHOR]

A sensor for the detection of ethylene (CH) in combustion exhaust based on a mid-infrared wavelength modulation spectroscopic technique was constructed using a distributed feedback interband cascade laser (DFB-ICL) with a wavelength of 3.3 μm. The direct absorption spectrum of CH in the range of 2978.8-2982.1 cm was recorded, where the spectrum was in good agreement with the spectrum simulated using parameters from the HITRAN 2012 database. The absorption line at 2979.581 cm [2.42 × 10 cm mol cm, ν P(5)] was selected for CH detection. This frequency was chosen to minimize spectral interference from other major combustion products in the emission frequency range of the DFB-ICL. A limit of detection for CH of 96 parts per billion by volume was achieved at a signal-to-noise ratio of two under 3 kPa of pressure using 2 f wavelength modulation spectroscopy. Using the developed sensor, the ethylene concentration in the exhaust from a portable power generator was also successfully determined. [ABSTRACT FROM AUTHOR]

Measurements of the local distribution of atmospheric nitrogen dioxide (NO2) by long-path pulsed differential optical absorption spectroscopy (LP-PDOAS) in Tokyo during August 2008 are presented. Two LP-PDOAS systems simultaneously measured average NO2 temporal mixing ratios along two different paths from a single observation point. Two flashing aviation obstruction lights, located 7.0 km north and 6.3 km east from the observation point, were used as light sources, allowing spatiotemporal variations of NO2 in Tokyo to be inferred. The LP-PDOAS data were compared with ground-based data measured using chemiluminescence. Surface wind data indicated that large inhomogeneities were present in the spatial NO2 distributions under southerly wind conditions, while northerly wind conditions displayed greater homogeneity between the two systems. The higher correlation in the NO2 mixing ratio between the two LP-PDOAS systems was observed under northerly wind conditions with a correlation factor R2 = 0.88. We demonstrated that the combined deployment of two LP-PDOAS systems oriented in different directions provides detailed information on the spatial distribution of NO2. [ABSTRACT FROM AUTHOR]

Particle mass spectrometers of two types-a time-of-flight aerosol mass spectrometer (AMS) of Aerodyne Research Inc. and a laser desorption/ionization single particle aerosol mass spectrometer (LISPA-MS) developed at Nagoya University-were deployed to characterize aerosol particles in the Tokyo metropolitan area during the summer of 2008. Based on the ensemble measurements by AMS, equivalent mass concentration of organic aerosol, traced by mass-to-charge ratio (m/z) 44, showed a closer correlation with particulate nitrate and gas-phase odd oxygen, [O3+NO2], whereas equivalent mass concentration of organic aerosol, traced by m/z 57, did not. On a particle-by-particle basis, the relative signal peak area of various target species in the LISPA-MS spectra, which was calculated as the ion-signal fraction of the species relative to the total signal peak area summed over all the ion peaks in each spectrum, was used as a measure of the relative amount of the species. A rough qualitative agreement was obtained between the temporal variation observed in the LISPA-MS RCOO- signal and that in the AMS m/z 44, but not the AMS m/z 57, in which the LISPA-MS RCOO- signal was defined as the sum of the relative signal peak areas of 17 different negative-ion mass peaks used as markers of oxygenated organics. Analysis of the LISPA-MS spectra also showed that approximately 95% of the oxygen-containing organic particles contained nitrate, which is expected to be responsible in part for the correlation between AMS m/z 44 and AMS nitrate. [ABSTRACT FROM AUTHOR]

We have investigated the pressure dependence of the detection sensitivity of CO2, N2O and CH4 using wavelength modulation spectroscopy (WMS) with distributed feed-back diode lasers in the near infrared region. The spectral line shapes and the background noise of the second harmonics (2f) detection of the WMS were analyzed theoretically. We determined the optimum pressure conditions in the detection of CO2, N2O and CH4, by taking into consideration the background noise in the WMS. At the optimum total pressure for the detection of CO2, N2O and CH4, the limits of detection in the present system were determined. [ABSTRACT FROM AUTHOR]

We have investigated the pressure dependence of the detection sensitivity of CO2, N2O and CH4 using wavelength modulation spectroscopy (WMS) with distributed feed-back diode lasers in the near infrared region. The spectral line shapes and the background noise of the second harmonics (2f) detection of the WMS were analyzed theoretically. We determined the optimum pressure conditions in the detection of CO2, N2O and CH4, by taking into consideration the background noise in the WMS. At the optimum total pressure for the detection of CO2, N2O and CH4, the limits of detection in the present system were determined. [ABSTRACT FROM AUTHOR]

An amendment to this paper has been published and can be accessed via a link at the top of the paper. [ABSTRACT FROM AUTHOR]

This study evaluated gasoline evaporative emissions from fuel-cap removal during the refueling process (or "puff loss") for one gasoline vehicle in the Japanese market. Specifically, the puff loss emissions were measured after a real-world driving event in urban Tokyo, Japan for different seasons and gasoline types. The experimental results indicated higher puff loss emissions during summer than in winter and spring despite using low vapor pressure gasoline during summer. These higher puff loss emissions accounted maximally for more than 4 g of the emissions from the tested vehicle. The irregular emission trends could be attributed to the complex relationships between physical parameters such as fuel-tank filling, ambient temperature, ambient pressure, and gasoline vapor pressure. Furthermore, an estimation model was developed based on the theory of thermodynamics to determine puff loss emissions under arbitrary environmental conditions. The estimation model included no fitting parameter and was in good agreement with the measured puff loss emissions. Finally, a sensitivity analysis was conducted to elucidate the effects of three physical parameters, i.e., fuel tank-filling, ambient pressure, and gasoline type, on puff loss emissions. The results indicated that fuel tank-filling was the most important parameter affecting the quantity of puff loss emissions. Further, the proposed puff loss estimation model is likely to aid the evaluation of future volatile organic compound emission inventories. [ABSTRACT FROM AUTHOR]

The plans to introduce next-generation hybrid and zero-emission vehicles in the market are now enacted by governments in many countries to manage both global warming and air pollution problems. There are only a few studies evaluating the effects of the next-generation vehicles on the changes in concentrations of ozone generated by the photochemical reactions between volatile organic compounds and nitrogen oxides (NOx). To evaluate these changes, we performed chemical transport modeling in the Kanto region, Japan in the summer of 2013. The results show that if the vehicles are substituted by hybrid vehicles, average ozone concentrations increase in urban areas and decrease in suburban areas due to NOx titration. Substitution with zero-emission passenger vehicles decreases the concentrations in both urban and suburban areas. Substitution with both hybrid and zero-emission passenger and heavy-duty vehicles highly increases the concentrations in urban areas. Using the model results, we also discuss the effect of ozone concentration changes on premature mortality of humans in summer. The results suggest that, in some cases the introduction of next-generation vehicles might exasperate ozone concentrations, even leading to 5 to 10 times higher premature mortality during the summer compared to that of influenza and heat stroke in Japan. [ABSTRACT FROM AUTHOR]

Presents a correction on an article about photodissociation of hydrogen chloride and hydrogen bromide.

Presents a correction on an article about fine structure branching ratios and Doppler spectroscopy of chlorine atoms from the photodissociation of alkyl chlorides and chlorofluoromethanes.

We measured nitrous oxide (N2O) concentration by mid-infrared wavelength modulation spectroscopy at a wavelength of 3.87 µm. Mid-infrared laser light from difference frequency generation in a fiber-coupled direct-bonded quasi-phase-matched LiNbO3-ridge-waveguide module is obtained using a diode-pumped Nd-doped yttrium alminum garnet (Nd:YAG) laser at 1064 nm together with a distributed feedback diode laser at 1466 nm. The absorption line of N2O centered at 2583.39 cm-1 (3.871 µm), which originates from the first overtone band of the ν1 asymmetric stretching mode, is measured by second-harmonic wavelength modulation spectroscopy detection. The limits of N2O detection measured by wavelength modulation spectroscopy are found to be 150 ppbv using a 29.9 m Herriott multipass cell at a pressure of 12 kPa. We demonstrated the real-time monitoring of atmospheric N2O using our developed spectrometer with a difference-frequency-generation mid-infrared laser light source. [ABSTRACT FROM AUTHOR]