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Improved methodologies for toxicant identification

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In addition to strengthening our routine analytical capabilities, we are working with leading academic institutions in developing advanced real-time smoke measurement techniques [1-5]. These are techniques based on laser or other soft ionisation, typically coupled with fast mass spectrometry which are capable of sampling different classes of smoke constituents in situ; either directly inside a bunring cigarette or through an sampling interface.

So far, real-time smoke formation studies have been carried out using Fourier-transform infrared spectroscopy [6], advanced laser spectroscopy [7], resonance-enhanced multiphoton ionisation-time of flight mass spectrometry (REMPI-TOFMS) as well as single-photon-ionisation time of flight-mass spectrometry (SPI-TOFMS [1-5]). These techniques have the potential to enhance our understanding on smoke toxicant formation processes.

In a recent study, we applied an in-house real-time system to investigate the formation of a number of volatile smoke constituents (nitric oxide, acetaldehyde, acetone, benzene, toluene, 1,3 butadiene, isoprene and carbon dioxide) in mainstream smoke on a puff-by-puff basis [8].

10117_Figure101v2

A schematic diagram of the real-time smoke analysis system used.

For a typical 35 mL puff, the system applied was able to delineate a smouldering source and a puffing source towards the measured mainstream smoke for some volatile species detected. For example, up to 30% benzene in the mainstream smoke could be in fact generated during the preceding smouldering period. It is trapped or absorbed by the tobacco rod and then eluted during the subsequent puff. This observation contributes to the fundamental knowledge of the cigarette smoke formation and may have implications on a wide range of smoke chemistry and associated effects.

10118_Figure-102

The graph above shows consecutive single-puff profiles of benzene at three durations at a 35ml puff for a 3R4F cigarette [8].

  1. Adam, T., Streibel, T., Mitschke, S., Muhlberger, F., Baker, R. R., Zimmermann, R. (2005). Application of time-of-flight mass spectrometry with laser-based photoionization methods for analytical pyrolysis of PVC and tobacco. Journal of Analytical and Applied Pyrolysis. 74 (1-2): 454-464. Abstract: Application of time-of-flight... Opens new window
  2. Adam, T., Ferge, T., Mitschkt, S., Streibel, T., Baker R.R., Zimmermann, R. (2005). Discrimination of three tobacco types (Burley, Virginia and Oriental) by pyrolysis single-photon ionisation (SPI)/time-of-flight mass spectrometry and advanced statistical methods. Anal. Bioanal. Chem. 381: 487-499. Abstract: Descrimination of thre tobacco types... Opens new window
  3. Adam, T., Mitschkt, S., Streibel, T., Baker, R.R., Zimmermann, R. (2006). Quantitative puff-by-puff resolved characterization of selected toxic compounds in cigarette mainstream smoke. Chem. Res. Toxicol. 19: 511–520. Abstract: Quantitative puff-by-puff... Opens new window
  4. Adam, T., Mitschkt, S., Streibel, T., Baker, R.R., Zimmermann, R. (2006). Puff-by-puff resolved characterisation of cigarette mainstream smoke by single photon ionisation (SPI) – time-of-flight mass spectrometery (TOFMS): comparison of 2R4F research cigarette and pure Burley, Virginia, Oriental and Maryland tobacco cigarettes. Anal. Chim. Acta. 572: 219 – 229. Abstract: Puff-by-puff... Opens new window
  5. Adam, T., McAughey, J., McGrath, C., Mocker, C., Zimmermann, R. (2009). Simultaneous on-line size and chemical analysis of gas phase and particulate phase of cigarette mainstream smoke. Anal. Bioanal. Luminescence /Trends in RNA Analysis. 394: 1193–1203. Abstract: Simultaneous on-line... Opens new window
  6. Thweatt, W,D,, Harward Sr, C.N., Parrish, M.E. (2007). Measurement of acrolein and 1,3-butadiene in a single puff of cigarette smoke using lead-salt tunable diode laser infrared spectroscopy. Spectrochimica Acta Part A. 67: 16-27.
  7. Baren, R.E., Parrish, M.E., Shafer, K.H., Harward, C.N., Shi, Q., Nelson, D.D., McManus, J.B., Zahniser, M.S. (2004). Quard quantum cascade lasyer spectrometer with dual gas cells for the simultaneous analysis of mainstream and sidestream cigarette smoke. Spectrochim. Acta Part A. 60: 3437–3447.
  8. Liu, C., Feng, S., van Heemst, J., McAdam, K.G. (2009). New insights into the formation of volatile compounds in mainstream cigarette smoke. Anal. Bioanal Volume 396, (5) 1817-1830. Full text: New insights... Opens new window
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