Real-Time Determination of Aromatics in Automobile Exhaust by Single-Photon Ionization Ion Trap Mass Spectrometry

Butcher, David J.; Goeringer, Douglas E.; Hurst, Gregory B.

doi:10.1021/ac9807971

Cited by 53 publications

(58 citation statements)

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“…4 with the associated vehicle speeds in the JC08 mode. We focused on the emission profiles of benzene and toluene since no other hydrocarbons with m/z = 78 and 92 were observed by GC/MS in this study and in previous exhaust measurements by Butcher et al 19 and Mühlberger et al 21 Two test runs in the JC08 mode were performed to confirm the reproducibility of the temporal emission profiles of benzene and toluene. In the gasoline vehicle exhaust, high concentrations of benzene and toluene were measured within the first few minutes, shown in Figs.…”

Section: Resultsmentioning

confidence: 92%

“…Hydrocarbons with low carbon number were measured with high ion signal intensities except for the m/z = 42 assigned to cyclopropane. Ion signals at m/z = 58, assigned to butanes and possibly acetone, 19 and 72, assigned to pentanes, in the diesel exhaust also displayed lower signal intensities than those of higher m/z alkanes. VOCs other than those mentioned above could not be assigned definitively to many peaks because these VOCs were not measured by the GC/MS analysis.…”

Section: Resultsmentioning

confidence: 95%

“…16,[19][20][21] Butcher et al measured oxygenated organics and aromatics in automobile exhaust using a SPI ion source and an ion-trap mass spectrometer. 19 Their ion source was 118 nm VUV generated by the frequency tripling of 355 nm third harmonic Nd:YAG laser pulses in a Xe gas cell. Zimmermann and coworkers developed a VUV-SPI-quadrupole MS (QMS) that used an electron beam pumped excimer lamp as the VUV source.…”

Section: Introductionmentioning

confidence: 99%

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Measurement of Volatile Organic Compounds in Vehicle Exhaust Using Single-Photon Ionization Time-of-Flight Mass Spectrometry

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Section: Resultsmentioning

confidence: 92%

Section: Resultsmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

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Measurement of Volatile Organic Compounds in Vehicle Exhaust Using Single-Photon Ionization Time-of-Flight Mass Spectrometry

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“…In contrast to standard CI and corona APCI sources, however, essentially equal concentrations for charged particles of both polarities are present in the reduced pressure atmospheric sampling glow discharge. Furthermore, the ion and electron number densities are sufficiently high (ϳ10 10 cm Ϫ3 ) that ion losses via drift and diffusion are negligible compared with ion-ion or ion-electron recombination. Therefore, analyte ion concentrations are not described by simple pseudo first-order kinetic expressions as employed for treating conventional CI or by similar expressions coupled with unipolar charge drift as used for modeling APCI.…”

Section: Discussionmentioning

confidence: 99%

“…Electron ionization (EI) has been employed for formation of positive ions in situations for which air is leaked directly into the mass spectrometer [5,6]. To enhance ionization selectivity over that exhibited by EI, single-and multi-photon ionization techniques have been used for determination of targeted aromatic compounds in automobile exhaust [7][8][9][10]. More widely used approaches for direct sampling are based on atmospheric pressure chemical ionization (APCI) [11] which is capable of making positive or negative ions.…”

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Factors influencing the analytical performance of an atmospheric sampling glow discharge ionization source as revealed via ionization dynamics modeling

Goeringer

2003

J. Am. Soc. Mass Spectrom.

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A kinetic model is developed for the dynamic events occurring within an atmospheric sampling glow discharge that affect its performance as an ion source for analytical mass spectrometry. The differential equations incorporate secondary electron generation and thermalization, reagent and analyte ion formation via electron capture and ion-molecule reactions, ion loss via recombination processes, diffusion, and ion-molecule reactions with matrix components, and the sampling and pumping parameters of the source. Because the ion source has a flow-through configuration, the number densities of selected species can be estimated by applying the steady-state assumption. However, understanding of its operation is aided by knowledge of the dynamic behavior, so numerical methods are applied to examine the time dependence of those species as well. As in other plasma ionization sources, the ionization efficiency is essentially determined by the ratio of the relevant ion formation and recombination rates. Although thermal electron and positive reagent ion number densities are comparable, the electron capture/ion-molecule reaction rate coefficient ratio is normally quite large and the ion-electron recombination rate coefficient is about an order of magnitude greater than that for ion-ion recombination. Consequently, the efficiency for negative analyte ion formation via electron capture is generally superior to that for positive analyte ion generation via ion-molecule reaction. However, the efficiency for positive analyte ion formation should be equal to or better than that for negative analyte ions when both ionization processes occur via ion-molecule reaction processes (with comparable rate coefficients), since the negative reagent ion density is considerably less than that for positive reagent ions. Furthermore, the particularly high number densities of thermal electrons and reagent ions leads to a large dynamic range of linear response for the source. Simulation results also suggest that analyte ion number densities might be enhanced by modification of the standard physical and operating parameters of the source. . In these and other applications, a number of methods have been utilized for generation of ions from compounds of interest. Electron ionization (EI) has been employed for formation of positive ions in situations for which air is leaked directly into the mass spectrometer [5,6]. To enhance ionization selectivity over that exhibited by EI, single-and multi-photon ionization techniques have been used for determination of targeted aromatic compounds in automobile exhaust [7][8][9][10]. More widely used approaches for direct sampling are based on atmospheric pressure chemical ionization (APCI) [11] which is capable of making positive or negative ions. APCI is effected by a sequence of electron-and ion-molecule reactions initiated by electrons that are generally produced via either a corona discharge [12] or a ␤-emitter such as 63 Ni [1,13]. Because the equilibrium distribution in such reactions under normal APCI operati...

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Spurenanalytik luftgetragener organischer Komponenten

Hoffmann

1999

Nachr. Chem. Tech. Lab.

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Organische Verbindungen spielen eine wesentliche Rolle für eine Vielzahl von atmosphärisch relevanten Prozessen. Dieser „Blickpunkt”︁ stellt die gängigen Methoden zur Bestimmung von organischen Komponenten in der Atmosphäre kurz vor und, weist, wo möglich, auf neuere Übersichtsarbeiten hin. Etwas mehr Raum wurde dabei der Beschreibung von Prinzipien und Anwendungen neuer, innovativer instrumenteller Verfahren zur Analytik luftgetragener organischer Spurenbestandteile gegeben.

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Real-Time Determination of Aromatics in Automobile Exhaust by Single-Photon Ionization Ion Trap Mass Spectrometry

Cited by 53 publications

References 35 publications

Measurement of Volatile Organic Compounds in Vehicle Exhaust Using Single-Photon Ionization Time-of-Flight Mass Spectrometry

Measurement of Volatile Organic Compounds in Vehicle Exhaust Using Single-Photon Ionization Time-of-Flight Mass Spectrometry

Factors influencing the analytical performance of an atmospheric sampling glow discharge ionization source as revealed via ionization dynamics modeling

Spurenanalytik luftgetragener organischer Komponenten

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