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.

Laser-induced fluorescence of the trans-CHBrCHO radical.

A new laser-induced fluorescence spectrum was observed in the region of 350 nm-360 nm. The spectrum was observed in the reaction between the CHBrCHBr and OH radicals and in the reaction of CHBrCHBr and CH2CHBr with atomic oxygen O(3P). The spectrum was assigned to the B̃--X̃ transition of the trans-CHBrCHO (trans-2-bromovinoxy) radical. The B̃--X̃ electronic transition energy (T0) was 28 542 cm-1, which was 242 cm-1 lower than that of the unsubstituted vinoxy radical (CH2CHO). From an analysis of the laser-induced single vibronic level fluorescence aided by ab initio calculations, some of the vibrational frequencies were assigned to the ground electronic state ν3 (C-O str.) = 1581 cm-1, ν6 (C-C str.) = 1130 cm-1, and ν8 (C-C-O bend.) = 409 cm-1. The fluorescence lifetimes of the excited B̃ state were 35 ns-75 ns, depending on the excited vibrational modes, implying that predissociation had accelerated as the energy level (v') increased.

Rate Constants for Reactions of HCCO and HCCCO Radicals with O2 over the Temperature Range 243-423 K.

A pulsed laser photolysis-photoionization mass spectrometer system has been employed to measure the rate constants of HCCO + O2 and HCCCO + O2 over the temperature range 243-423 K in 1.2-8.4 Torr of He or N2. Radicals of HCCO and HCCCO were produced by 193 nm ArF laser photolysis of ethyl ethynyl ether and methyl propiolate, respectively. HCCO was photoionized by a Kr resonance lamp with a CaF2 window (10.03 eV), and HCCCO was ionized by a Xe lamp with a sapphire window (8.44 eV). Both ions were detected as parent ions in a quadrupole mass spectrometer. From analysis of the time profiles of the ion signals for various O2 concentrations, the overall rate constants at 298 K are represented by the values k2 = (6.3 ± 1.0) × 10-13 for HCCO + O2 and k5 = (5.7 ± 0.6) × 10-12 for HCCCO + O2 in the units cm3 molecule-1 s-1. The rate coefficients for the two reactions can be described by k2(T) = (1.5-0.7+1.5) × 10-12 exp[-(225 ± 220)/T] and k5(T) = (1.8-0.9+1.9) × 10-12 exp[(343 ± 228)/T] in the units cm3 molecule-1 s-1 over the temperature range 243-423 K.

Accurate identification of dimers from α-pinene oxidation using high-resolution collision-induced dissociation mass spectrometry.

Interest in mass spectrometry of highly oxidized dimers from α-pinene oxidation has increased in the atmospheric chemistry field. Here, we apply high-resolution collision-induced dissociation mass spectrometry (HR-CID-MS) with an atmospheric pressure ionization source to investigate in detail how α-pinene-derived dimers are detected and identified by MS. The resulting HR-CID spectra and specific fragmentation patterns suggest that a large fraction of dimer ions detected in full-scan mass spectra can be hydrogen-bonded artifact clusters and the residual small fraction includes covalently bonded actual dimers. We also show how individual fractions of the artifact clusters and actual dimers are calculated using the HR-CID spectra.

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.

Laser-induced fluorescence of the CHFCHO radical and reaction of OH radicals with halogenated ethylenes.

A new laser-induced fluorescence spectrum of the 2-fluorovinoxy (CHFCHO) radical was first observed around 335 nm. The radical was produced in the reaction of an OH radical with 1,2-difluoroethylene (CHF=CHF). A single weak band was observed, which was assigned to the 00 0 band of the B̃-X̃ transition of the trans-CHFCHO radical. The B̃←X̃ electronic transition energy (T0) for trans-CHFCHO was 29 871 cm-1, which was just 3 cm-1 lower than that of its isomer, the 1-fluorovinoxy (CH2CFO) radical. The fluorescence lifetime at 29 871 cm-1 was shorter than 20 ns. This means that strong predissociation is probable at v' = 0 in the excited B̃ state of trans-CHFCHO. From an analysis of the dispersed fluorescence spectrum, some of the vibrational frequencies can be assigned for the ground electronic state: ν3 = 1557 cm-1 (C-O stretch), ν7 = 1162 cm-1 (C-C stretch), and ν8 = 541 cm-1 (CCO bend). These vibrational assignments were supported by ab initio calculations. The structure of the C-C-O skeleton and the spectroscopic character of trans-CHFCHO were close to those of CHClCHO and CH2CHO than those of CH2CFO. For the reaction of CH2=CHF with O(3P), the formation of both the regioisomeric radicals, i.e., 1- and 2-fluorovinoxy radicals, was confirmed. The regioselectivity of the oxygen atom added to the double bond of monofluoroethylene is discussed.

Estimation of refueling emissions based on theoretical model and effects of E10 fuel on refueling and evaporative emissions from gasoline cars.

The effects of Reid vapor pressure (RVP) on refueling emissions and the effects of ethanol 10% (E10) fuel on refueling and evaporative emissions were observed using six cars and seven fuels. The results indicated that refueling emissions can be reproduced by a simple theoretical model in which fuel vapor in the empty space in the tank is pushed out by the refueling process. In this model, the vapor pressures of fuels can be estimated by the Clausius-Clapeyron equation as a function of temperature. We also evaluated E10 fuel in terms of refueling and evaporative emissions, excluding the effect of contamination of ethanol in the canister. E10 fuel had no effect on the refueling emissions in cases without onboard refueling vapor recovery. E10 showed increased permeation emissions in evaporative emissions because of the high permeability of ethanol. And with E10 fuel, breakthrough emissions appeared earlier but broke through slower than normal fuel. Finally, canisters could store more fuel vapor with E10 fuel.

Relative Reactivity Measurements of Stabilized CH2OO, Produced by Ethene Ozonolysis, Toward Acetic Acid and Water Vapor Using Chemical Ionization Mass Spectrometry.

We investigated the relative reactivity of stabilized CH2OO, produced by ethene ozonolysis, toward acetic acid and water vapor at a temperature of 298 ± 2 K and atmospheric pressure. Hydroperoxymethyl acetate produced through the reaction between stabilized CH2OO and acetic acid was monitored using a chemical ionization mass spectrometer as a function of the acetic acid concentration at different relative humidities. The rate of the reaction between CH2OO and water vapor depended quadratically on the water vapor concentration, suggesting that CH2OO reacted with water dimers in preference to water monomers. We obtained the bimolecular rate constant for the reaction between CH2OO and water dimer relative to the rate constant for the reaction between CH2OO and acetic acid, k3/k1, of (6.3 ± 0.4) × 10-2. The k3 value of (8.2 ± 0.8) × 10-12 cm3 molecule-1 s-1 was derived by combining with a k1 value of (1.3 ± 0.1) × 10-10 cm3 molecule-1 s-1, which has been previously reported by direct kinetic studies. The k3 value thus obtained is consistent with the absolute rate constants measured directly, suggesting that the reactivity of CH2OO is irrespective of the CH2OO generation method, namely, ethene ozonolysis or diiodomethane photolysis. We indirectly determined the yield of stabilized CH2OO from the ozonolysis of ethene of 0.59 ± 0.17 and 0.55 ± 0.16 under dry and humid (relative humidity 23-24%) conditions, respectively, suggesting that the yield is independent of the water vapor concentration. Our results suggest that hydroperoxymethyl acetate is the sole product of the reaction between stabilized CH2OO and acetic acid. The approach presented here can likely be extended to studies of the reactivities of more complicated and atmospherically relevant stabilized Criegee intermediates.

Mechanisms of Increased Particle and VOC Emissions during DPF Active Regeneration and Practical Emissions Considering Regeneration.

Mechanisms involved in increased particle and volatile organic compound (VOC) emissions during active and parked active regenerations of a diesel particulate filter (DPF) were investigated using heavy-duty trucks equipped with both a urea selective catalytic reduction system and a DPF (SCR + DPF) and a DPF-only. Particle emissions increased in the later part of the regeneration period but the mechanisms were different above and below 23 nm. Particles above 23 nm were emitted due to the lower filtering efficiency of the DPF because of the decreasing amount of soot trapped during regeneration. Small particles below 23 nm were thought to be mainly sulfuric acid particles produced from SO2 trapped by the catalyst, being released and oxidized during regeneration. Contrary to the particle emissions, VOCs increased in the earlier part of the regeneration period. The mean molecular weights of the VOCs increased gradually as the regeneration proceeded. To evaluate "practical emissions" in which increased emissions during the regeneration were considered, a Regeneration Correction Factor (RCF), which is the average emission during one cycle of regeneration/emission in normal operation, was adopted. The RCFs of PM and VOCs were 1.1-1.5, and those of PNs were as high as 3-140, although they were estimated from a limited number of observations.

Water vapour effects on secondary organic aerosol formation in isoprene ozonolysis.

Secondary organic aerosol (SOA) formation from isoprene ozonolysis was investigated using a Teflon bag reactor under dry and humid conditions. Both the number and volume concentrations of SOA were found to be decreased by the addition of water vapour. Gas- and particle-phase product analyses with a negative ion chemical ionization mass spectrometer show that oligomers composed of stabilized Criegee intermediates as the chain units contribute to the SOA formation and that water vapour inhibits stabilized Criegee intermediates from forming the oligomers, resulting in the suppression of SOA formation. Additionally, it is suggested that a portion of stabilized Criegee intermediates other than CH2OO have low reactivity toward H2O, and thus can be involved in the oligomer and SOA formation even under humid conditions. Volatility estimation predicts that the oligomers containing even one or two stabilized Criegee intermediates can be partitioned into the aerosol phase.

Measurement of air-sea exchange of dimethyl sulfide and acetone by PTR-MS coupled with gradient flux technique.

We developed a new method for in situ measurement of air-sea fluxes of multiple volatile organic compounds (VOCs) by combining proton transfer reaction-mass spectrometry (PTR-MS) and gradient flux (GF) technique. The PTR-MS/GF system was first deployed to determine the air-sea flux of VOCs in the open ocean of the western Pacific, in addition to carbon dioxide and water vapor. Each profiling at seven heights from the ocean surface up to 14 m took 7 min. In total, 34 vertical profiles of VOCs in the marine atmosphere just above the ocean surface were obtained. The vertical gradient observed was significant for dimethyl sulfide (DMS) and acetone with the best-fit curves on quasi-logarithmic relationship. The mean fluxes of DMS and acetone were 5.5 ± 1.5 and 2.7 ± 1.3 µmol/m(2)/day, respectively. These fluxes are in general in accordance with those reported by previous expeditions.

Oligomerization reaction of the Criegee intermediate leads to secondary organic aerosol formation in ethylene ozonolysis.

Ethylene ozonolysis was investigated in laboratory experiments using a Teflon bag reactor. A negative ion chemical ionization mass spectrometer (NI-CIMS) using SO2Cl(-) and Cl(-) as reagent ions was used for product analysis. In addition to the expected gas-phase products, such as formic acid and hydroperoxymethyl formate, oligomeric hydroperoxides composed of the Criegee intermediate (CH2OO) as a chain unit were observed. Furthermore, we observed secondary organic aerosol (SOA) formation from the ethylene ozonolysis, and the particle-phase products were also analyzed by NI-CIMS. The CH2OO oligomers were also observed as particle-phase components, suggesting that the oligomeric hydroperoxides formed in the gas phase partition into the particle phase. By adding methanol as a stabilized Criegee intermediate scavenger, both the gas-phase oligomer formation and SOA formation were strongly suppressed. This indicates that CH2OO plays a critical role in the formation of oligomeric hydroperoxides followed by SOA formation in ethylene ozonolysis. A new formation mechanism for the oligomeric hydroperoxides, which includes sequential addition of CH2OO to hydroperoxides, is proposed.

Equilibrator inlet-proton transfer reaction-mass spectrometry (EI-PTR-MS) for sensitive, high-resolution measurement of dimethyl sulfide dissolved in seawater.

We developed an equilibrator inlet-proton transfer reaction-mass spectrometry (EI-PTR-MS) method for fast detection of dimethyl sulfide (DMS) dissolved in seawater. Dissolved DMS extracted by bubbling pure nitrogen through the sample was continuously directed to the PTR-MS instrument. The equilibration of DMS between seawater and the carrier gas, and the response time of the system, were evaluated in the laboratory. DMS reached equilibrium with an overall response time of 1 min. The detection limit (50 pmol L(-1) at 5 s integration) was sufficient for detection of DMS concentrations in the open ocean. The EI-PTR-MS instrument was deployed during a research cruise in the western North Pacific Ocean. Comparison of the EI-PTR-MS results with results obtained by means of membrane tube equilibrator-gas chromatography/mass spectrometry agreed reasonably well on average (R(2) = 0.99). EI-PTR-MS captured temporal variations of dissolved DMS concentrations, including elevated peaks associated with patches of high biogenic activity. These results demonstrate that the EI-PTR-MS technique was effective for highly time-resolved measurements of DMS in the open ocean. Further measurements will improve our understanding of the biogeochemical mechanisms of the production, consumption, and distribution of DMS on the ocean surface and, hence, the air-sea flux of DMS, which is a climatically important species.

Differentiation of isomeric compounds by two-stage proton transfer reaction time-of-flight mass spectrometry.

We investigated a two-stage ion source for proton transfer reaction (PTR) ionization to achieve more selective mass spectrometric (MS) detection of selected volatile organic compounds (VOCs) than that achieved with commonly used PTR-MS instruments, which are based on single-step PTR ionization with H3O+. The two-stage PTR ion source generated reagent ions other than H3O+ by an initial PTR between H3O+ and a selected VOC, and then a second PTR ionization occurred only for VOCs with proton affinities larger than the affinity of the reagent VOC. Acetone and acetonitrile were useful as reagent VOCs because they provided dominant peaks as a protonated form. Using two-stage PTR-MS, we differentiated isomeric VOCs (for example, ethyl acetate and 1,4-dioxane) by means of differences in their proton affinities; protonated acetone formed the [M + H]+ ion from ethyl acetate but not from 1,4-dioxane. The PTR-MS-derived concentrations agreed quantitatively with those independently determined by Fourier transform infrared spectroscopy (FT-IR) at parts per million by volume (ppmv) levels. In addition, interfering fragment ions formed from alkyl benzenes at m/z 79 (C6H7+) could be distinguished from the m/z 79 ion arising from protonation of benzene, and therefore this method would prevent overestimation of benzene concentrations in air samples in which both benzene and alkyl benzenes are present. This two-stage PTR ionization may be useful for distinguishing various isomeric species, including aldehydes and ketones, if appropriate reagent ions are selected.

Multireference configuration interaction calculation of the B(2)a"-X(2)a" transition of halogen- and methyl-substituted vinoxy radicals.

Ground and second excited electronic states of halogen and monomethyl substituted vinoxy radicals were studied by multireference configuration interaction (MRCI) calculation. Optimized geometries, rotational constants and vibrational frequencies of vinoxy and 1-fluorovinoxy showed good agreement with experimental values. Differences in calculated and observed B-X electronic transition energies were less than 0.1 eV and observed trends of blue shift upon increasing the number of substituted halogen atoms were reproduced by MRCI calculation. Observed fluorescence lifetimes of the vibrationless level in B state were in good agreement with calculated values. Rotational profiles of the 0-0 vibronic bands were successfully simulated with calculated rotational constants and transition dipole moments. Energy differences between planar and nonplanar optimized geometries in B state showed good correlation with the onset of fast nonradiative decay in B state, supporting the proposed mechanism of nonradiative decay via avoided crossings from B to A state which is followed by the decay to the ground state via conical intersections.

A novel discharge source of hydronium ions for proton transfer reaction ionization: design, characterization, and performance.

A novel ion source based on direct current (d.c.) discharge has been developed for proton transfer reaction ionization operated at relatively high ion drift tube pressure. The shape and geometry of the ion source are designed to maximize overall ion intensity and to minimize interference from sample air. The initial performance of the technique, including speciation and intensity of reagent ions, their stability, and the impact of artifact signals, is evaluated by means of a proton transfer reaction time-of-flight mass spectrometer (PTR-TOFMS) newly built in our laboratory. Intensities of the hydronium (H(3)O(+)) ions are typically (5-7) x 10(5) counts for a 1-min integration time with a duty cycle of approximately 1%. The fluctuations of the ion signals over a period of hours are within 4%. Although the formation of artifact ions from sample air (NO(+) and O(2) (+)), which react with volatile organic compounds (VOCs) and subsequently cause fragmentation, is observed as background signals in addition to hydronium and mono- and di-hydrate H(3)O(+) ions, intensities of both NO(+) and O(2) (+) ions are only approximately 0.5% of those of H(3)O(+) ions. Using our PTR-TOFMS system at a drift tube pressure of approximately 5 Torr, the detection sensitivities are significantly improved and the detection limits for propene, acetaldehyde, acetone, isoprene, benzene, toluene, and p-xylene are estimated to be at the sub-ppbv level for 1-min integration.