Stefan Mitschke

Trace detection of organic compounds in complex sample matrixes by single photon ionization ion trap mass spectrometry: real-time detection of security-relevant compounds and online analysis of the coffee-roasting process.

An in-house-built ion trap mass spectrometer combined with a soft ionization source has been set up and tested. As ionization source, an electron beam pumped vacuum UV (VUV) excimer lamp (EBEL) was used for single-photon ionization. It was shown that soft ionization allows the reduction of fragmentation of the target analytes and the suppression of most matrix components. Therefore, the combination of photon ionization with the tandem mass spectrometry (MS/MS) capability of an ion trap yields a powerful tool for molecular ion peak detection and identification of organic trace compounds in complex matrixes. This setup was successfully tested for two different applications. The first one is the detection of security-relevant substances like explosives, narcotics, and chemical warfare agents. One test substance from each of these groups was chosen and detected successfully with single photon ionization ion trap mass spectrometry (SPI-ITMS) MS/MS measurements. Additionally, first tests were performed, demonstrating that this method is not influenced by matrix compounds. The second field of application is the detection of process gases. Here, exhaust gas from coffee roasting was analyzed in real time, and some of its compounds were identified using MS/MS studies.

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

In tobacco research, the comparison of different tobacco blends as well as the puff-dependent behaviour of cigarettes is a matter of particular interest. For the investigation of smoke characteristics, GC x GC offers different ways for data analysis, namely, compound target analysis, automated peak-based compound classification and comprehensive pixel-based data analysis. This study will show the application as well as the pros and cons of these types of data analysis for very complex matrices like cigarette particulate matter. In addition, new aspects about the recently discovered puff-dependent behaviour of compounds in cigarette smoke will be presented. Automated peak-based compound classification including mass spectrometric pattern recognition is used for the classification of tobacco particulate matter samples and the puff-dependent investigation of different compound classes. This compound group specific analysis is further reinforced by applying an even more comprehensive pixel-based analysis. This kind of analysis is used to generate fingerprints of different types of cigarettes. The combination of fast feature reduction methods like analysis of variance (ANOVA) and t-test with multivariate feature transformation methods like partial least squares discriminate analysis (PLSDA) for feature selection provides a powerful tool for a detailed inspection of different types of cigarettes.

Investigation of Tobacco Pyrolysis Gases and Puff-by-puff Resolved Cigarette Smoke by Single Photon Ionisation (SPI) - Time-of-flight Mass Spectrometry (TOFMS)

Abstract The work presented deals with the application of Single Photon Ionisation- Time-of-Flight Mass Spectrometry (SPI-TOFMS) for the investigation of tobacco smoke. SPI-TOFMS is a modern analytical technique, which enables the simultaneous analysis of a large number of organic species in complex gas mixtures in real time. The paper is a summary of a PhD thesis (1) and seven research articles, which were recently published in various scientific journals (2-8). Consequently, more detailed information on particular aspects can be found in there. The experimental part covers two different approaches, and therefore, it is divided into two sub-sections. In the first one, the SPI-TOFMS is coupled to a pyrolysis furnace. The objective is to examine the thermal behaviour of tobacco under various controlled conditions. In so doing, three tobacco types (Virginia, Oriental, and Burley) were pyrolysed in two reaction gas compositions (nitrogen and synthetic air) and seven different furnace temperatures (400 °C, 500 °C, 600 °C, 700 °C, 800 °C, 900 °C, and 1000 °C). Results can help to unravel the complex formation and decomposition reactions taking place when tobacco is heated. In the second part the SPI-TOFMS is connected to a cigarette smoking machine in order to investigate the behaviour of cigarette smoke constituents on a puff-by-puff basis. The work incorporates the comparison of whole smoke and gas phase of cigarette smoke, a puff-resolved quantification of several hazardous smoke constituents, and the overall chemical characterisation of the individual smoking puffs. In addition, a critical consideration of the prevailing smoking procedure is given when applied to single puff analysis. A further study examines the influence of five different cigarette lighting devices (gas lighter, electric lighter, candle, match, and burning zone of another cigarette) on the chemical composition of the first puff.

Time-resolved analysis of the emission of sidestream smoke (SSS) from cigarettes during smoking by photo ionisation/time-of-flight mass spectrometry (PI-TOFMS): towards a better description of environmental tobacco smoke

In this study, the chemical composition of sidestream smoke (SSS) emissions of cigarettes are characterised using a laser-based single-photon ionisation time-of-flight mass spectrometer. SSS is generated from various cigarette types (2R4F research cigarette; Burley, Oriental and Virginia single-tobacco-type cigarettes) smoked on a single-port smoking machine and collected using a so-called fishtail chimney device. Using this setup, a puff-resolved quantification of several SSS components was performed. Investigations of the dynamics of SSS emissions show that concentration profiles of various substances can be categorised into several groups, either depending on the occurrence of a puff or uninfluenced by the changes in the burning zone during puffing. The SSS emissions occurring directly after a puff strongly resemble the composition of mainstream smoke (MSS). In the smouldering phase, clear differences between MSS and SSS are observed. The changed chemical profiles of SSS and MSS might be also of importance on environmental tobacco smoke which is largely determined by SSS. Additionally, the chemical composition of the SSS is strongly affected by the tobacco type. Hence, the higher nitrogen content of Burley tobacco leads to the detection of increased amounts of nitrogen-containing substances in SSS.

Detection of security relevant substances within the cooperative project SAFE XUV

The objective of this project funded by the German BMBF was to show that security relevant substances can be detected in complex matrices at low concentrations using single photon ionization ion trap mass spectrometry (SPI-ITMS). The advantage of such a soft ionization technique is a reduction of unwanted fragment ions in mass spectra allowing identification of signals from complex matrices and enabling MS/MS capability. The MS/MS studies permit low false-positive and false-negative rates. Additionally, the accumulation of the ions in the ion trap decreases the detection limit. To obtain low detection limits the ionization potentials (IPs) of the relevant substances have to be below the IPs of the bulk matrix components. That enables the utilization of a photon energy unaffecting the matrix components resulting in increased sensitivity due to essentially non-existent background signals. As literature values for many ionization potentials are unavailable, IPs of several security relevant substances were determined using monochromatized synchrotron radiation from BESSY, Germany. All analyzed substances exhibited IPs significantly below the IPs of common matrix molecules such as water, nitrogen and oxygen. First measurements with a pre-demonstrator show that it is possible to shield matrix substances using a well chosen photon energy for soft ionization.

Photo-ionization mass spectrometry for on-line analysis of organic compounds in human breath and in tobacco smoke upon inhalation

Soft photo ionization mass spectrometry was applied successfully for on-line characterization of organic compounds in tobacco smoke during the smoking process (including mouth space measurements) and in the exhaled breath.