Application of Time-of-Flight Mass Spectrometry with Laser-Based Photoionization Methods for Time-Resolved On-Line Analysis of Mainstream Cigarette Smoke

Abstract

The application of soft photoionization mass spectrometry methods (PIMS) for cigarette mainstream smoke analysis is demonstrated. Resonance-enhanced multiphoton ionization (REMPI) at 260 nm and vacuum ultraviolet light single-photon ionization (SPI) at 118 nm were used in combination with time-of-flight mass spectrometry (TOFMS). An optimized smoking machine with reduced memory effects of smoke components was constructed, which in combination with the REMPI/SPI-TOFMS instrument allows PIMS smoke analysis with a time resolution of up to 10 Hz. The complementary character of both PIMS methods is demonstrated. SPI allows the detection of various aliphatic and aromatic compounds in smoke up to approximately 120 m/z while REMPI is well suited for aromatic compounds. The capability of the instrument coupled to the novel sampling system for puff-by-puff resolved measurements is demonstrated. The feasibility of using the experimental system for intrapuff smoke measurements is also shown. Two main patterns of puff-by-puff behaviors are observed for different smoke constituents. The first group exhibits a constant increase in smoke constituent yield from the first to the last puff. The second group shows a high yield of the constituent in the first puff, with lower and constant or slowly increasing yields in the following puffs. A third group cannot be clearly classified and is a combination of both observed profiles.

Application of comprehensive two‐dimensional gas chromatography mass spectrometry and different types of data analysis for the investigation of cigarette particulate matter

“…The puff profiles shown in Fig. 4 verify the puff behaviours for alkanes and alkenes/cycloalkanes already found in the gas phase [13,14] also for the particulate phase. In addition, this behaviour is now also obvious for carboxylic acids.…”

“…This is mainly possible due to the huge separation power and the picture-like 2-D chromatograms. In addition this part of the study adduced novel information that a puffdependent behaviour is not only valid for very volatile compounds, which was already reported by our group [13,14], but also for SVOCs. Besides this target analysis of a few compounds also more comprehensive types of data analysis are successfully applied.…”

“…Recently, it has been shown that there are also variances in the chemical composition of the volatile parts of different cigarette puffs, especially volatile unsaturated hydrocarbons, which show increased amounts during the first puff of a cigarette smoke cycle. Furthermore, concentrations and total amounts of several gas phase compounds may vary substantially during the smoking cycle [13,14]. These investigations are mainly done with online techniques based on soft photo ionisation coupled to mass spectroscopy.…”

Electron spin resonance study of puff-resolved free radical formation in mainstream cigarette smoke

“…1,2 Although the dynamic and reactive nature of cigarette smoke is recognized, it is only recently that studies based on fast mass spectrometers and laser-based techniques have begun to unravel the extent of formation of transient smoke species. [3][4][5][6][7][8][9][10][11][12][13][14] Routine smoke analysis methods used in the tobacco industry are usually developed to quantify the total yields of smoke constituents after the entire cigarette is machine-smoked under a standard puffing regime. To provide the accuracy and sensitivity required for puff-resolved analysis, fast analytical techniques are needed.…”

Rapid Sampling of Individual Organic Aerosol Species in Ambient Air with the Photoionization Aerosol Mass Spectrometer

“…The resonance enhanced multiphoton ionization technique, while highly sensitive to aromatic compounds, cannot be used for aliphatic compounds (Haefliger et al 2000). Other techniques such as photoelectron resonance capture ionization (LaFranchi and Petrucci 2004), filter-based infrared laser desorption-single photon ionization mass spectrometry (Ferge et al 2005) and hybrid-thermal desorption/photoionization mass spectrometry (Mitschke et al 2005;Streibel et al 2006), aerosol chemical ionization mass spectrometry (Hearn and Smith 2004), and the photoionization aerosol mass spectrometer (PIAMS) (Oktem et al 2004) use soft ionization methods that can be applied to both aliphatic and aromatic species. These instruments have the potential for highly time-resolved measurements, but they cannot distinguish isobaric compounds.…”