Stability of Terpenoid-Derived Secondary Ozonides in Aqueous Organic Media.

1,2,4-Trioxolanes, known as secondary ozonides (SOZs), are key products of ozonolysis of biogenic terpenoids. Functionalized terpenoid-derived SOZs are readily taken up into atmospheric aerosols; however, their condensed-phase fates remain unknown. Here, we report the results of a time-dependent mass spectrometric investigation into the liquid-phase fates of C10 and C13 SOZs synthesized by ozonolysis of a C10 monoterpene alcohol (α-terpineol) in water:acetone (1:1 = vol:vol) mixtures. Isomerization of Criegee intermediates and bimolecular reaction of Criegee intermediates with acetone produced C10 and C13 SOZs, respectively, which were detected as their Na+-adducts by positive-ion electrospray mass spectrometry. Use of CD3COCD3, D2O, and H218O solvents enabled identification of three types of C13 SOZs (aldehyde, ketone, and lactol) and other products. These SOZs were surprisingly stable in water:acetone (1:1) mixtures at T = 298 K, with some persisting for at least a week. Theoretical calculations supported the high stability of the lactol-type C13 SOZ formed from the aldehyde-type C13 SOZ via intramolecular rearrangement. The present results suggest that terpenoid-derived SOZs can persist in atmospheric condensed phases, potentially until they are delivered to the epithelial lining fluid of the pulmonary alveoli via inhaled particulate matter, where they may exert hitherto unrecognized adverse health effects.

Effects of Metal Ions on Aqueous-Phase Decomposition of α-Hydroxyalkyl-Hydroperoxides Derived from Terpene Alcohols.

We report the results of a mass spectrometric study of the effects of atmospherically relevant metal ions on the decomposition of α-hydroxyalkyl-hydroperoxides (α-HHs) derived from ozonolysis of α-terpineol in aqueous solutions. By direct mass spectrometric detection of chloride adducts of α-HHs, we assessed the temporal profiles of α-HHs and other products in the presence of metal ions. In addition, reactions between α-HHs and FeCl2 in the presence of excess DMSO showed that the amount of hydroxyl radicals formed in a mixture of α-terpineol, O3, and FeCl2 was 5.7 ± 0.8% of the amount formed in a mixture of H2O2 and FeCl2. The first-order rate constants for the decay of α-HHs produced by ozonolysis of α-terpineol in the presence of 5 mM acetate buffer at a pH of 5.1 ± 0.1 were determined to be (4.5 ± 0.1) × 10-4 s-1 (no metal ions), (4.7 ± 0.2) × 10-4 s-1 (with 0.05 mM Fe2+), (4.7 ± 0.1) × 10-4 s-1 (with 0.05 mM Zn2+), and (4.8 ± 0.2) × 10-4 s-1 (with 0.05 mM Cu2+). We propose that in acidic aqueous media, the reaction of α-HHs with Fe2+ is outcompeted by H+-catalyzed decomposition of α-HHs, which produces the corresponding aldehydes and H2O2, which can in turn react with Fe2+ to form hydroxyl radicals.

Aqueous-phase fates of α-alkoxyalkyl-hydroperoxides derived from the reactions of Criegee intermediates with alcohols.

In the atmosphere, carbonyl oxides known as Criegee intermediates are produced mainly by ozonolysis of volatile organic compounds containing C[double bond, length as m-dash]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).

Proton-Catalyzed Decomposition of α-Hydroxyalkyl-Hydroperoxides in Water.

In the atmosphere, most biogenic terpenes undergo ozonolysis in the presence of water to form reactive α-hydroxyalkyl-hydroperoxides (α-HHs), and the lifetimes of these α-HHs are a key parameter for understanding the processes that occur during the aging of atmospheric particles. We previously reported that α-HHs generated by ozonolysis of terpenes decompose in water to give H2O2 and the corresponding aldehydes, which undergo hydration to form gem-diols. Herein, we report that this decomposition process was dramatically accelerated by acidification of the water with oxalic, acetic, hexanoic, cis-pinonic, or hydrochloric acid. In acidic solution, the temporal profiles of the α-HHs, detected as their chloride adducts by electrospray mass spectrometry, showed single-exponential decays in the pH range from 4.1 to 6.1, and the first-order rate coefficients (k) for the decays increased with decreasing pH. The lifetime of the α-HH derived from α-terpineol was 128 min (k = (1.3 ± 0.4) × 10-4 s-1) at pH 6.1 but only 8 min (k = (2.1 ± 0.1) × 10-3 s-1) at pH 4.1. Because the rate coefficients increased as the pH decreased and the increase depended on pH rather than on the properties of the acid, we propose that the decomposition of the α-HHs in water was specifically catalyzed by H+. Fast H+-catalyzed decomposition of α-HHs could be an important source of H2O2 and multifunctionalized compounds found in ambient atmospheric particles.

Stability of Monoterpene-Derived α-Hydroxyalkyl-Hydroperoxides in Aqueous Organic Media: Relevance to the Fate of Hydroperoxides in Aerosol Particle Phases.

The α-hydroxyalkyl-hydroperoxides [R-(H)C(-OH)(-OOH), α-HH] produced in the ozonolysis of unsaturated organic compounds may contribute to secondary organic aerosol (SOA) aging. α-HHs' inherent instability, however, hampers their detection and a positive assessment of their actual role. Here we report, for the first time, the rates and products of the decomposition of the α-HHs generated in the ozonolysis of atmospherically important monoterpenes α-pinene (α-P), d-limonene (d-L), γ-terpinene (γ-Tn), and α-terpineol (α-Tp) in water/acetonitrile (W/AN) mixtures. We detect α-HHs and multifunctional decomposition products as chloride adducts by online electrospray ionization mass spectrometry. Experiments involving D2O and H218O, instead of H216O, and an OH-radical scavenger show that α-HHs decompose into gem-diols + H2O2 rather than free radicals. α-HHs decay mono- or biexponentially depending on molecular structure and solvent composition. e-Fold times, τ1/e, in water-rich solvent mixtures range from τ1/e = 15-45 min for monoterpene-derived α-HHs to τ1/e > 103 min for the α-Tp-derived α-HH. All τ1/e's dramatically increase in <20% (v/v) water. Decay rates of the α-Tp-derived α-HH in pure water increase at lower pH (2.3 ≤ pH ≤ 3.3). The hydroperoxides detected in day-old SOA samples may reflect their increased stability in water-poor media and/or the slow decomposition of α-HHs from functionalized terpenes.

Detailed Inventory of the Evaporative Emissions from Parked Gasoline Vehicles and an Evaluation of Their Atmospheric Impact in Japan.

A detailed inventory was taken of evaporative emissions from parked gasoline vehicles in the Kanto region of Japan, 2015, based on the theoretical model to evaluate the amount of evaporative emissions. The inventory showed that evaporative emissions were high in metropolitan and urban areas because of the large populations in these areas and the high vehicle parking frequency. Using the new inventory, the sensitivity of evaporative emissions to the concentration of tropospheric ozone and secondary organic aerosol was evaluated using the chemical transport modeling solver, the community multiscale air quality modeling system (CMAQ), coupled with the weather research and forecasting (WRF) model. The calculation results showed that the evaporative emissions from permeation through fuel related parts were more significant in the generation of the tropospheric ozone than those from fuel tank venting. This was because the permeation emissions included a high proportion of high maximum incremental reactivity value components, such as aromatics. Neither of the evaporative emission types were significant secondary organic aerosol generators. Whole reduction of the evaporative emissions contributed an approximate 3 ppb decrease in tropospheric ozone in urban areas during the daytime. This information will contribute to the volatile organic compound (VOC) management strategy employed by governments worldwide.

Temperature Dependence of Aqueous-Phase Decomposition of α-Hydroxyalkyl-Hydroperoxides.

Ozonolysis of unsaturated organic species with water produces α-hydroxyalkyl-hydroperoxides (α-HHs), which are reactive intermediates that lead to the formation of H2O2 and multifunctionalized species in atmospheric condensed phases. Here, we report temperature-dependent rate coefficients (k) for the aqueous-phase decomposition of α-terpineol α-HHs at 283-318 K and terpinen-4-ol α-HHs at 313-328 K. The temporal profiles of α-HH signals, detected as chloride adducts by negative-ion electrospray mass spectrometry, showed single-exponential decay, and the derived first-order k for α-HH decomposition increased as temperature increased, e.g., k(288 K) = (4.7 ± 0.2) × 10-5, k(298 K) = (1.5 ± 0.4) × 10-4, k(308 K) = (3.4 ± 0.9) × 10-4, k(318 K) = (1.0 ± 0.2) × 10-3 s-1 for α-terpineol α-HHs at pH 6.1. Arrhenius plot analysis yielded activation energies of 17.9 ± 0.7 (pH 6.1) and 17.1 ± 0.2 kcal mol-1 (pH 6.2) for the decomposition of α-terpineol and terpinen-4-ol α-HHs, respectively. Activation energies of 18.6 ± 0.2 and 19.2 ± 0.5 kcal mol-1 were also obtained for the decomposition of α-terpineol α-HHs in acidified water at pH 5.3 and 4.5, respectively. Theoretical kinetic and thermodynamic calculations confirmed that both water-catalyzed and proton-catalyzed mechanisms play important roles in the decomposition of these α-HHs. The relatively strong temperature dependence of k suggests that the lifetime of these α-HHs in aqueous phases (e.g., aqueous aerosols, fog, cloud droplets, wet films) is controlled not only by the water content and pH but also by the temperature of these media.

Interfacial vs Bulk Ozonolysis of Nerolidol.

Ozone readily reacts with olefins with the formation of more reactive Criegee intermediates (CIs). The transient CIs impact HO x cycles, and they play a role in new particle formation in the troposphere. Oxidation by O3 occurs both in the gas-phase, in the liquid phase, and at air-water and air-aerosol interfaces. In light of the importance of O3 in environmental and engineered chemical transformations, we have investigated the ozonolysis mechanisms of a triolefin C15-alcohol, nerolidol (Nero, a biogenic sesquiterpene), at the air-water interface in the presence of acetonitrile. Surface-sensitive pneumatic ionization mass spectrometric detection of α-hydroxy-hydroperoxides and functionalized carboxylates, generated by the hydration and isomerization of CIs, respectively, enables us to evaluate the relative reactivity of each C=C toward O3. In addition, we compare bulk-phase ozonolysis chemistry to similar reactions taking place at the air-water interface. Our experimental results show that O3 reacts primarily with the (CH3)2C=CH- and -(CH3)C=CH- moieties (>∼98%), while the O3 attack on the terminal -HC=CH2 site (<∼2%) is a minor pathway during both interfacial and bulk ozonolysis. The presence of functionalized-carboxylates on interfaces but not in bulk-phase reactions with O3 indicates that the isomerization of the CIs is not hindered at the air-water interface due to the lower availability of water .

Effects of pH on Interfacial Ozonolysis of α-Terpineol.

Acidity changes the physical properties of atmospheric aerosol particles and the mechanisms of reactions that occur therein and on the surface. Here, we used surface-sensitive pneumatic ionization mass spectrometry to investigate the effects of pH on the heterogeneous reactions of aqueous α-terpineol (C10H17OH), a representative monoterpene alcohol, with gaseous ozone. Rapid (≤10 µs) ozonolysis of α-terpineol produced Criegee intermediates (CIs, zwitterionic/diradical carbonyl oxides) on the surface of water microjets. We studied the effects of microjet bulk pH (1-11) on the formation of functionalized carboxylate and α-hydroxy-hydroperoxide chloride adduct (HH-Cl-) products generated by isomerization and hydration of α-terpineol CIs, respectively. Compared with the signal at pH ≈ 6, the mass spectral signal of HH-Cl- was less intense under both basic and more acidic conditions, whereas the intensity of the functionalized carboxylate signal increased with increasing pH up to 4 and then remained constant. The decrease of HH-Cl- signals at bulk pH values of >6 is attributable to the accumulation of OH- at the air-water interface that suppresses the relative abundance of hydrophilic HH and Cl-. The present study suggests that α-terpineol in ambient aqueous organic aerosols will be converted into much lower volatile and potentially toxic organic hydroperoxides during the heterogeneous ozonolysis.

Reactions of Criegee Intermediates with Benzoic Acid at the Gas/Liquid Interface.

Secondary organic aerosol (SOA) found in polluted mega-cities contains benzoic acid (BA) as a major organic acid in addition to a variety of species including alkenes. In polluted air, ozone could be a major oxidizer for SOA and induces subsequent reactions involving Criegee intermediates (CIs, carbonyl oxide, RR'C•-O-O•/RR'C═O+-O-) formed by the -C═C- + O3 reaction at the gas/liquid interface. The possibility that abundant BA could be an effective scavenger of CIs at the interface remains to be investigated by direct experiments. Here, we showed that amphiphilic BA is able to compete with water molecules for the CIs produced in the prompt ozonolysis of ß-caryophyllene on the surface of a water/acetonitrile solvent microjet by generating hitherto uncharacterized C22 ester hydroperoxide products. Competition between BA vs octanoic acid vs cis-pinonic acid toward CIs reveals that BA is a much less-efficient scavenger of CIs on aqueous organic surfaces. We attribute it to the surface-specific orientation of BA at the gas/liquid interface, where the reactive -C(O)OH group is fully hydrated and not available for CIs generated at the topmost layers.

Reactivity of Monoterpene Criegee Intermediates at Gas-Liquid Interfaces.

Biogenic monoterpenes are major sources of Criegee intermediates (CIs) in the troposphere. Recent studies underscored the importance of their heterogeneous chemistry. The study of monoterpene CI reactions on liquid surfaces, however, is challenging due to the lack of suitable probes. Here, we report the first mass spectrometric detection of the intermediates and products, which include labile hydroperoxides, from reactions of CIs of representative monoterpenes (α-terpinene, γ-terpinene, terpinolene, d-limonene, α-pinene) with water, cis-pinonic acid (CPA) and octanoic acid (OA) on the surface of liquid microjets. Significantly, the relative yields of α-hydroxy-hydroperoxides production from CIs hydration at the gas-liquid interface-α-terpinene (1.00) ≫ d-limonene (0.18) > γ-terpinene (0.11) ∼ terpinolene (0.10) ≫ α-pinene (0.01)-do not track the rate constants of their gas-phase ozonolyses. Notably, in contrast with the inertness of the other CIs, the CIs derived from α-terpinene ozonolysis readily react with CPA and OA to produce C20 and C18 ester hydroperoxides, respectively. Present results reveal hitherto unknown structural effects on the reactivities of CIs at aqueous interfaces.

Spatial correlativity of atmospheric particulate components simultaneously collected in Japan.

The simultaneous sampling of total suspended particles was performed at 14 sites in Japan during July 2008-June 2009. The spatial correlativity of each particulate composition toward Osaka was obtained for nine selected sites to overview the chemical composition and geographical distribution of particulate components across a wide range of areas nationwide. The spatial correlatives of atmospheric particulate components were extended to an even wider range of areas up to 950 km distance (meso-alpha scale region, >200 km) for a far-reaching distance analysis unique in the literature. Overall, the spatial correlations of ionic species and both organic and elemental carbons were significant, suggesting their shared advections, including their long-range transport from East Asia. Although sulfate ions are widely dispersed across Japan, such is not necessarily correlated with organic and elemental carbon, possibly indicating that the sulfate emission source, including long-range transport, differs from that of carbonaceous particulates. By contrast, the characteristics of spatial correlatives of metallic constituents vary; for example, particulate Pb and Cd show a significantly wide range of spatial correlatives to Osaka, while Mn-though limited to cities neighboring Osaka-shows significant spatial correlations. Other metallic constituents showed no significant spatial correlatives, indicating the effects of local pollutants. Moreover, the extent of the spatial dispersion of the particulate components and the relationships among chemical components were analyzed via factor analysis to highlight the effects of long-range inflow and local original emissions. In this treatment, 13 particulate components among the 19 measured were implicated in long-range transport.

Kinetic study of isoprene hydroxy hydroperoxide radicals reacting with sulphur dioxide and their global-scale impact on sulphate formation.

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.

Ozone responses to reduced precursor emissions: A modeling analysis on how attainable goals can improve air quality in the Mexico City Metropolitan Area.

High tropospheric ozone (O3) concentrations prevent the improvement of the air quality in the Mexico City Metropolitan Area (MCMA). Although the problem has improved considerably since the 1990s, a rebound in O3 levels in recent years has raised concerns about the deteriorating air quality. The nonlinear relationship between O3 formation and the emissions of its main precursors, i.e., volatile organic compounds (VOCs) and nitrogen oxides (NOx), is a challenge when measures are enacted for effective mitigation of the O3 problem. This study evaluated the reduction in precursors, VOCs and NOx, using an up-to-date regional air quality model (HERMES-Mex-WRF-CMAQ). For evaluating realizable scenarios, the decline in VOC achieved in Japan after policy implementation was the targeted VOC reduction (40 % from area sources), and the NOx reduction observed in the MCMA during the COVID-19 pandemic was the targeted NOx reduction (40 % from mobile sources). The analysis evaluated the O3 responses to changes in a single precursor and a combination of both during a period of high O3 concentrations (April 2019). The results showed that 40 % reduction in VOC emissions would decrease the O3 8-h maximum concentrations by 16 %. However, 40 % reduction in NOx emissions would increase O3 by >15 %. The simultaneous reduction of both precursors did not significantly affect O3 levels. The diagnosis of ozone sensitivity using the H2O2/HNO3 ratios reinforced the simulation findings, indicating that VOC emissions limited ozone formation in most MCMA areas. As the simulated scenarios were based on factual case studies, our research offers insights into the realistic aims of MCMA policies to reduce O3 levels.

Comprehensive analysis of long-term trends, meteorological influences, and ozone formation sensitivity in the Jakarta Greater Area.

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.

Enhancement of gaseous iodine emission by aqueous ferrous ions during the heterogeneous reaction of gaseous ozone with aqueous iodide.

Gaseous I2 formation from the heterogeneous reaction of gaseous ozone with aqueous iodide in the presence of aqueous ferrous ion (Fe(2+)) was investigated by electron impact ionization mass spectrometry. Emission of gaseous I2 increased as a function of the aqueous FeCl2 concentration, and the maximum I2 formation with Fe(2+) was about 10 times more than without Fe(2+). This enhancement can be explained by the OH(-) scavenging by Fe(3+) formed from Fe(2+) ozonation to produce colloidal Fe(OH)3. This mechanism was confirmed by measurements of aqueous phase products using a UV-vis spectrometer and an electrospray ionization mass spectrometer. We infer that such a pH-buffering effect may play the key role in general halogen activations.

Measurements of the absorption line strength of hydroperoxyl radical in the ν3 band using a continuous wave quantum cascade laser.

Mid-infrared absorption spectroscopy has been applied to the detection of the hydroperoxyl (HO(2)) radical in pulsed laser photolysis combined with a laser absorption kinetics reactor. Transitions of the ν(3) vibrational band assigned to the O-O stretch mode were probed with a thermoelectrically cooled, continuous wave mid-infrared distributed feedback quantum cascade laser (QCL). The HO(2) radicals were generated with the photolysis of Cl(2)/CH(3)OH/O(2) mixtures at 355 nm. The absorption cross section at each pressure was determined by three methods at 1065.203 cm(-1) for the F(1), 13(1,13) ← 14(1,14) transition in the ν(3) band. From these values, the absolute absorption cross section at zero pressure was estimated. The relative line strengths of other absorptions in the feasible emitting frequency range of the QCL from 1061.17 to 1065.28 cm(-1) were also measured, and agreed with values reproduced from the HITRAN database. The ν(3) band absorption strength was estimated from the analytically obtained absolute absorption cross section and the calculated relative intensity by spectrum simulation, to be 21.4 ± 4.2 km mol(-1), which shows an agreement with results of quantum chemical calculations.

Monitoring of atmospheric nitrogen dioxide by long-path pulsed differential optical absorption spectroscopy using two different light paths.

Measurements of the local distribution of atmospheric nitrogen dioxide (NO(2)) by long-path pulsed differential optical absorption spectroscopy (LP-PDOAS) in Tokyo during August 2008 are presented. Two LP-PDOAS systems simultaneously measured average NO(2) 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 NO(2) 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 NO(2) distributions under southerly wind conditions, while northerly wind conditions displayed greater homogeneity between the two systems. The higher correlation in the NO(2) mixing ratio between the two LP-PDOAS systems was observed under northerly wind conditions with a correlation factor R(2) = 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 NO(2).

Improvement of the Theoretical Model for Evaluating Evaporative Emissions in Parking and Refueling Events of Gasoline Fleets Based on Thermodynamics.

Evaporative emissions from gasoline vehicles are known as an emission source of volatile organic compounds that are the precursors of tropospheric ozone and secondary organic aerosols. We formulated new estimation models based on thermodynamics for two main evaporation processes, namely diurnal breathing loss (DBL) and refueling loss (RFL) from gasoline vehicles. The models enable us to evaluate real-world evaporative emissions using the fuel composition and environmental temperature as input parameters. The proposed models well replicated the experimental results of the canister breakthrough emission from DBL (DBLb) and RFL obtained in previous experimental studies. The evaporative DBLb and RFL emissions in Japan in 2015 were then estimated using the new models. The evaporative emission from DBLb was approximately 8800 t/y, and that from RFL was 73,300 t/y. In addition, we estimated the variation in fuel evaporative emissions due to the market penetration of zero-emission vehicles. Even if the sale of gasoline vehicles is banned from 2035, the evaporative emissions of DBLb and RFL from gasoline vehicles will only be halved after 2040. The two models proposed for estimating the DBLb and RFL in this study are expected to be applied in the evaluation of the emission inventories of volatile organic compounds in future work.

Decomposition mechanism of α-alkoxyalkyl-hydroperoxides in the liquid phase: temperature dependent kinetics and theoretical calculations.

Organic hydroperoxides (ROOHs) play key roles in the atmosphere as a reactive intermediate species. Due to the low volatility and high hydrophilicity, ROOHs are expected to reside in atmospheric condensed phases such as aerosols, fogs, and cloud droplets. The decomposition mechanisms of ROOHs in the liquid phase are, however, still poorly understood. Here we report a temperature-dependent kinetics and theoretical calculation study of the aqueous-phase decompositions of C12 or C13 α-alkoxyalkyl-hydroperoxides (α-AHs) derived from ozonolysis of α-terpineol in the presence of 1-propanol, 2-propanol, and ethanol. We found that the temporal profiles of α-AH signals, detected as chloride-adducts by negative ion electrospray mass spectrometry, showed single-exponential decay, and the derived first-order rate coefficient k for α-AH decomposition increased as temperature increased, e.g., k(288 K) = (5.3 ± 0.2) × 10-4 s-1, k(298 K) = (1.2 ± 0.3) × 10-3 s-1, k(308 K) = (2.1 ± 1.4) × 10-3 s-1 for C13 α-AHs derived from the reaction of α-terpineol Criegee intermediates with 1-propanol in the solution at pH 4.5. Arrhenius plot analysis yielded an activation energy (E a) of 12.3 ± 0.6 kcal mol-1. E a of 18.7 ± 0.3 and 13.8 ± 0.9 kcal mol-1 were also obtained for the decomposition of α-AHs (at pH 4.5) derived from the reaction of α-terpineol Criegee intermediates with 2-propanol and with ethanol, respectively. Based on the theoretical kinetic and thermodynamic calculations, we propose that a proton-catalyzed mechanism plays a central role in the decomposition of these α-AHs in acidic aqueous organic media, while water molecules may also participate in the decomposition pathways and affect the kinetics. The decomposition of α-AHs could act as a source of H2O2 and multifunctionalized species in atmospheric condensed phases.