Satoshi Inomata

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.

Emissions of nonmethane volatile organic compounds from open crop residue burning in the Yangtze River Delta region, China

Open crop residue burning is one of the major sources of air pollutants including the precursors of photooxidants like ozone and secondary organic aerosol. We made measurements of trace gases including nonmethane volatile organic compounds (NMVOCs) in a rural area in central East China in June 2010. During the campaign, we identified six biomass burning events in total through the simultaneous enhancement of carbon monoxide and acetonitrile. Four cases represented fresh plumes ( 3 h after emission), as determined by photochemical age. While we were not able to quantify formic acid, we identified an enhancement of major oxygenated volatile organic compounds (OVOCs) as well as low molecular alkanes and alkenes, and aromatic hydrocarbons in these plumes. The observed normalized excess mixing ratios (NEMRs) of OVOCs and alkenes showed dependence on air mass age, even in fresh smoke plumes, supporting the view that these species are rapidly produced and destructed, respectively, during plume evolution. Based on the NEMR data in the fresh plumes, we calculated the emission factors (EFs) of individual NMVOC. The comparison to previous reports suggests that the EFs of formaldehyde and acetic acid have been overestimated, while those of alkenes have been underestimated. Finally, we suggest that open burning of wheat residue in China releases about 0.34 Tg NMVOCs annually. If we applied the same EFs to all crops, the annual NMVOC emissions would be 2.33 Tg. The EFs of speciated NMVOCs can be used to improve the existing inventories.

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.

Laboratory measurements of emission factors of nonmethane volatile organic compounds from burning of Chinese crop residues

The emission factors (EFs) of nonmethane volatile organic compounds (NMVOCs) emitted during the burning of Chinese crop residue were investigated as a function of modified combustion efficiency in laboratory experiments. NMVOCs, including acetonitrile, aldehydes/ketones, furan, and aromatic hydrocarbons, were monitored by proton-transfer-reaction mass spectrometry. Rape plant was burned in dry conditions and wheat straw was burned in both wet and dry conditions to simulate the possible burning of damp crop residue in regions of high temperature and humidity. We compared the present data to field data reported by Kudo et al. (2014). Good agreement between field and laboratory data was obtained for aromatics under relatively more smoldering combustion of dry samples, but laboratory data were slightly overestimated compared to field data for oxygenated VOC (OVOC). When EFs from the burning of wet samples were investigated, the consistency between the field and laboratory data for OVOCs was stronger than for dry samples. This may be caused by residual moisture in crop residue that has been stockpiled in humid regions. Comparison of the wet laboratory data with field data suggests that Kudo et al. (2014) observed the biomass burning plumes under relatively more smoldering conditions in which approximately a few tens of percentages of burned fuel materials were wet.

Laser-induced fluorescence of the CH2CFO radical

A new laser-induced fluorescence spectrum has been observed in the region of 307–335 nm. Since this spectrum is observed when reacting oxygen atoms with CH2CHF, or CH2CF2, or CH2CFCl and also by photolysis of CH3CFO, the fluorescing molecule is the CH2CFO (fluoroformyl methyl) radical. From an analysis of the laser-induced single vibronic level fluorescence, some of the vibrational frequencies can be assigned for the ground electronic state ν3=1724 cm−1 (C–O stretch), ν5=1211 cm−1 (C–F stretch), ν6=906 cm−1 (CH2 rock), ν7=847 cm−1 (C–C stretch), ν8=584 cm−1 (FCO bend), and ν9=416 cm−1 (CCO bend), for the excited state ν3=1790, ν5=1253, ν6=911, ν7=874, ν8=537, and ν9=421 cm−1. Ab initio calculations on the CH2CFO radical give a planar geometry with vibrational frequencies that are consistent with the observed fundamental frequencies. The vibrational frequencies show that the structure of the ground state is closer to fluoroformyl methyl (⋅CH2CFO) rather than a vinoxy-type (CH2=CFO⋅) radical. The collision-...

Laser-induced fluorescence of the CHXCFO (X=F,Cl) radicals

Laser-induced fluorescence spectra of the B←X transition for three new halogen substituted vinoxy radicals were observed in the 306–333 nm region. The spectra of the trans- and cis-CHFCFO radicals were observed in the reactions of CHFCHF and CHFCF2 with atomic oxygen, and the spectrum of the cis-CHClCFO radical was observed in the reactions of CHClCHF and CHClCF2 with atomic oxygen. From an analysis of the laser-induced single vibronic level fluorescence, some of the vibrational frequencies could be determined for the ground electronic states (X); these frequencies are listed in Tables III and V. Some of the vibrational frequencies for the excited state (B) were also determined. These vibrational assignments are supported by ab initio calculations. The experimental results show that the electronic B←X transition energy is increased by halogen atoms, especially by fluorine atoms at either the 1- or 2-positions. The C–C–O skeleton and the spectroscopic characteristics of trans-, cis-CHFCFO, and cis-CH...

Enhancement of dimethylsulfide production by anoxic stress in natural seawater

Dimethylsulfide (DMS) is produced by phytoplankton in the ocean and plays an important role in biogeochemical cycles and climate system of the Earth. Previous field studies reported a possible relationship between DMS enhancement and anoxic condition, although the governing processes are still to be identified. Here we show the first direct evidence for the enhancement of DMS production by natural planktonic assemblages caused by anoxic stress. Under the anoxic condition, DMS production was considerably enhanced and DMS bacterial consumption was inhibited, resulting in an eightfold higher rate of gross DMS production than that under the oxic condition. Our results demonstrated that anoxic stress is one of important “environmental factors” in the marine DMS dynamics, suggesting the possible global importance due to ubiquity of anoxic conditions in the coastal oceans. This process would become more important in the future due to expansion of coastal hypoxic and anoxic zones by global warming.

Laser-induced fluorescence of the CD2CFO radical

The laser-induced fluorescence spectrum of the B 2A″→X 2A″ transition of the CD2CFO radical has been observed in the region 316–335 nm. The radical was produced by 193 nm photolysis or by fluorine atom reaction with acetyl-d3 fluoride. The spectrum of CD2CFO was similar to that of CH2CFO reported previously except for small isotope shifts in the range 7–343 cm−1. The isotope shifts support the assignment of these spectra to fluorinated vinoxy radicals, and rule out the alternate assignment to FCO proposed by others. The X→B electronic transition energy (T0) for CD2CFO was measured to be 29 867 cm−1, which is only 7 cm−1 lower than that for CH2CFO. From an analysis of the laser-induced single vibronic level fluorescence, some of the vibrational frequencies can be assigned for the ground electronic state; ν3(CO str.)=1735; ν4(CD2 sciss.)=1043; ν5(CF str.)=1248; ν6(CD2 rock.)=774; ν7(CC str.)=863; ν8(CCF bend)=597; and ν9(CCO bend)=370 cm−1. For the B 2A″ state, ν3=1772; ν4=1073; ν5=1241; ν6=783; ν7=827...

Analysis of laser-induced fluorescence spectra of the B̃(2A″)–X̃(2A″) transition with calculated Franck–Condon factors of CH2CFO

Abstract Geometry optimization and vibrational analysis of the ground and lowest three excited states of the fluorovinoxy radical (CH2CFO) were performed by the CASSCF method. Franck–Condon factors of the B – X transition were calculated and then subjected to the assignment of vibronic bands in laser-induced fluorescence spectra. The calculated Franck–Condon factors satisfactorily reproduced the measured fluorescence excitation and dispersed fluorescence spectra after a small correction of the relative displacement between normal coordinate systems of two states. The effect of C–C torsion on predissociation in the B state was studied with calculated potential energy curves along the coordinate.