<p>Breakthrough emissions that dominate diurnal evaporative emissions from gasoline vehicles were observed in continuous 3-day diurnal breathing loss (DBL) tests. These measurements were conducted on nine vehicles for the Japanese market. Two of these vehicles, made by US and European manufacturers, also meet regulations in their countries of origin. Four vehicles exhibited marked emissions caused by breakthrough emissions during the experimental period, all made by Japanese manufacturers. Using our experimental results, we estimate the total diurnal evaporative emissions from gasoline vehicles in Japan to be 32,792 t y&minus;1. The compositions of the breakthrough and permeation emissions were analyzed in real time using proton transfer reaction plus switchable reagent ion mass spectrometry to estimate the ozone formation potential for the evaporative emissions. The real-time measurements showed that the adsorption of hydrocarbons in a sealed housing evaporative determination unit can result in underestimation, when concentrations are only monitored before and after a DBL test. The composition analysis gave an estimated maximum incremental reactivity (MIR) 20% higher for the breakthrough emissions than for the gasoline that was tested, while the MIR for the permeation emissions was almost the same as the MIR for the fuel. Evaporative emissions from gasoline vehicles in Japan were found to contribute 4.2% to emissions from stationary sources using a mass-based estimate, or 6.1% of emissions from stationary sources using a MIR-based estimate.</p>

<p>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 &plusmn; 1.5 and 2.7 &plusmn; 1.3 μmol/m(2)/day, respectively. These fluxes are in general in accordance with those reported by previous expeditions.</p>

<p>We carried out time-resolved experiments using a proton-transfer-reaction mass spectrometer and a chassis dynamometer to characterize nitromethane emission from automotive exhaust. We performed experiments under both cold-start and hot-start conditions, and determined the dependence of nitromethane emission on vehicle velocity and acceleration/deceleration as well as the effect of various types of exhaust-gas treatment system. We found that nitromethane emission was much lower from a gasoline car than from diesel trucks, probably due to the reduction function of the three-way catalyst of the gasoline car. Diesel trucks without a NOx reduction catalyst using hydrocarbons produced high emissions of nitromethane, with emission factors generally increasing with increasing acceleration at low vehicle velocities.</p>

<p>Nitro-organic compounds, some of which cause adverse health effects in humans, are emitted in diesel engine exhaust. Speciation and quantification of these nitro-organic compounds in diesel engine exhaust particles have been extensively conducted; however, investigations into the emissions of gaseous nitro-organic compounds in diesel engine exhaust have not. In the present study, the properties of gaseous nitro-organic compounds in diesel engine exhaust were investigated through time-resolved measurement with a proton-transfer-reaction mass spectrometer and a chassis dynamometer. Three diesel trucks were tested, each with a different type of exhaust-gas treatment system (i.e., aftertreatment). Among the nitro-organic compounds detected, the emission of nitromethane was commonly observed and found to be related to the emissions of carbon monoxide, benzene, and acetone. The emission of other nitro-organic compounds, such as nitrophenol, depended on the vehicle, possibly due to the type of aftertreatment installed.</p>

Emission of trace gases from the marine diatom Thalassiosira pseudonana (CCMP 1335) was continuously monitored with a proton transfer reaction-mass spectrometry (PTR-MS) in an axenic batch culture system under a 13:11-h light:dark cycle. Substantial increases in the signals at m/z 49, 63, and 69, attributable to methanethiol, dimethyl sulfide (DMS), and isoprene, respectively, were observed in response to increases in cell density. Signals at m/z 69 showed diurnal variations throughout the experiment whereas those at m/z 49 were more pronounced at the beginning of the incubation. Interestingly, the signals at m/z 49 and 69 changed immediately following the light-dark and dark-light transitions, suggesting that light plays a crucial role in the production of methanethiol and isoprene. However, in the latter half of the experiment, methanethiol showed negligible diurnal variations regardless of light conditions, suggesting the production of methanethiol from enzymatic cleavage of DMS. The trend ill signals at m/z 63 was similar to that of the abundance of senescent cells plus cell debris rather than vegetative cells. The results suggest that aging or death of phytoplankton cells could also substantially control DMS production in natural waters along with the other microbial processes related to bacteria and zooplankton.

We developed an equilibrator inlet–proton transfer reaction-mass spectrometry (EI–PTR-MS) system for high-resolution measurement of the concentrations of multiple volatile organic compounds (VOCs) dissolved in seawater. The equilibration of five VOCs (isoprene, propene, acetone, acetaldehyde, and methanol) between seawater samples and the carrier gas, and the response time of the system, were evaluated by means of a series of laboratory experiments. Although equilibrium between the seawater sample and the carrier gas in the equilibrator was not achieved for isoprene and propene (likely because of their low water solubility), the other species did reach equilibrium. The EI–PTR-MS system was deployed during a research cruise in the western North Pacific Ocean. Evaluation of several seawater sampling methods indicated that there was no significant contamination from the sampling apparatus for the target VOCs. For isoprene, comparison of EI–PTR-MS measurements with measurements obtained with a membrane equilibrator–gas chromatography/mass spectrometry system showed generally good agreement (R2 = 0.79). EI–PTR-MS captured the temporal variations of dissolved VOCs, including small-scale variability, which demonstrates that the performance of the EI–PTR-MS system was sufficient for simultaneous and continuous measurements of multiple VOCs of environmental importance in seawater.

The reactions of hydronium ions (H3O+) with ethanol (C2H5OH) and deuterium-labeled ethanols (CD3CH2OH and CH3CD2OH) were investigated by means of proton transfer reaction mass spectrometry (PTR-MS). Besides the protonation reaction of H3O+ with C2H5OH, three fragmentation processes yielding C2H5+, CH2OH+, and H3O+ ions were previously implied. In this paper, we report the branching ratios for those four channels at six different field strengths (E/N ratios) of the drift tube. The contribution of the channel that reproduces hydronium ions (H3O+) was determined by detecting H2DO+ ions at m/z 20 produced in reactions of H3O+ with deuterium-labeled ethanols (CD3CH2OH and CH3CD2OH). The reproduction of H3O+ ions was found to be significant between 108 and 162 Td of the E/N ratio, however, it did not quantitatively account for the low detection sensitivity of ethanol by PTR-MS, suggesting the presence of unidentified reaction channel(s). The unidentified reaction channel(s) might be the H3O+-reproducing channel itself, because the contribution from this channel would be underestimated in this experiment due to loss process(es) such as an H/D exchange between H2DO+ and H2O.

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.

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.

A proton transfer reaction-time-of-flight mass spectrometer (PTR-TOFMS) has been developed for real-time measurements of volatile organic compounds in air. The instrument is designed to be operated with a hollow cathode discharge ion source and an ion drift tube at relatively high pressures. Each component of the system, an ion source, a drift tube, an ion transfer region, and a time-of-flight mass spectrometer, are in detail characterized by a number of laboratory experiments. The optimized instrumental configuration enables us to gain high intensities of hydronium (H3O+) ions, typically ∼7 × 105 counts for 1-min integration at a drift tube pressure of ∼5 Torr. It also suppresses background signals, and interferences from sample air (NO+ and O2+), which undergo fast reactions with volatile organic compounds, to ∼0.5% of those of H3O+ ions. We find that the use of the custom-built discharge source show higher overall sensitivities than of a commercially available radioactive source. Potentials to detect oxygenated VOCs (aldehydes, ketones, and alcohols), halocarbons, and amines are also suggested. The detection limits for acetaldehyde, acetone, isoprene, benzene, toluene, and p-xylene were determined to be at the sub-ppbv levels for a 1-min integration time. A good linear response at trace levels is certified, but slight sensitivity dependency on water vapor contents is revealed. We finally demonstrate that the instrument can be used for on-line monitoring to detect large variations from emission sources in real-time.

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.