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Resonance-enhanced multiphoton ionisation time-of-flight mass spectrometry (REMPI-TOFMS) enables the fast and sensitive on-line monitoring of volatile organic compounds (VOC) formed during coffee roasting. On the one hand, REMPI-TOFMS was applied to monitor roasting gases of an industrial roaster (1500 kg/h capacity), with the aim of determining the roast degree in real-time from the transient chemical signature of VOCs. On the other hand, a previously developed μ-probe sampling device was used to analyse roasting gases from individual coffee beans. The aim was to explore fundamental processes at the individual bean level and link these to phenomena at the batch level. The pioneering single-bean experiments were conducted in two configurations: (1) VOCs formed inside a bean were sampled in situ, i.e. via a drilled μ-hole, from the interior, using a μ-probe (inside). (2) VOCs were sampled on-line in close vicinity of a single coffee bean's surface (outside). The focus was on VOCs originating from hydrolysis and pyrolytic degradation of chlorogenic acids, like feruloyl quinic acid and caffeoyl quinic acid. The single bean experiments revealed interesting phenomena. First, differences in time–intensity profiles between inside versus outside (time shift of maximum) were observed and tentatively linked to the permeability of the bean's cell walls material. Second, sharp bursts of some VOCs were observed, while others did exhibit smooth release curves. It is believed that these reflect a direct observation of bean popping during roasting. Finally, discrimination between Coffea arabica and Coffea canephora was demonstrated based on high-mass volatile markers, exclusively present in spectra of Coffea arabica. Copyright © 2013 John Wiley & Sons, Ltd.

Resonance-enhanced multiphoton ionization-time-of-flight mass spectrometry (REMPI TOFMS) is a selective as well as sensitive analytical technique, well suited for real-time on-line monitoring of organic compounds in complex pyrolysis gases. In the present work, the on-line REMPI-TOFMS technique was applied to investigate dynamic effects in ‘all day’ pyrolytic processes, namely the coffee roasting process and tobacco smoking.

A newly developed, mobile laser mass spectrometer (resonance-enhanced multiphoton ionization - time-of-flight mass spectrometer, REMPI-TOFMS) was applied to on-line measurements at a waste incineration pilot plant. REMPI-TOFMS combines the optical selectivity of resonance-enhanced multiphoton ionization with a time-of-flight mass analysis to give a two-dimensional analytical method. Special care was taken to build up a sampling and inlet system suitable for on-line measurements of large, semivolatile polycyclic aromatic hydrocarbons (PAHs). An effusive molecular beam inlet in combination with a fixed frequency UV laser (Nd:YAG at 266 nm or KrF excimer at 248 nm) was used. Under these conditions, many different PAHs can be ionized selectively from the complex flue gas matrix. For example, the achieved detection limit for naphthalene is in the 10 parts-per-trillion by volume (pptv) concentration range. Calibration was performed by using external concentration standards supplied in low ppbv concentrations. The instrumentation is sufficiently robust to be operated under industrial conditions at incineration plants, for instance. The REMPI mass spectra can be acquired at 5-50 Hz. Time profiles of the concentrations of different PAHs in the flue gas were monitored with a time resolution of 200 ms. Significant variations in the concentration profile of several PAHs up to mass 276 amu (e.g., benzo[ghi]perylene) and methylated PAHs have been observed while combustion parameters were changing. In summary, it was demonstrated that laser mass spectrometry (REMPI-TOFMS) enables a real-time on-line trace analysis of combustion flue gases or industrial process gases.

The combination of laser induced Resonance-Enhanced Multi-Photon Ionization and Time-Of-Flight Mass Spectrometry (REMPI-TOFMS) represents a highly selective and sensitive analytical technique ideal for real-time determination of organic trace components. For example, aromatic hydrocarbons can be continuously monitored in industrial off gases. We introduce a new mobile REMPI-TOFMS instrument, which is robust and easy to operate, even under industrial conditions. Instead of an on-line sampling system also a gas chromatograph can be coupled for ultratrace analytical work. The instrument can be equipped with different inlet techniques (effusive inlet, free and skimmed supersonic jet), different TOF mass spectrometric options (linear mode and reflectron mode for higher mass resolution) or different laser systems (robust fixed wavelength lasers or tunable lasers for more sophisticated applications). This flexibility allows the instrument to be readily adapted to a given analytical problem. New time-resolved dat...

The objective of the project is to develop on-line, real-time, and noninvasive process control tools of coffee roasting that help deliver a consistent and high-quality coffee aroma. The coffee roasting process was analyzed by direct injection of the roaster gas into a time-of-flight mass spectrometer and ionized either by resonance enhanced multiphoton ionization (REMPI) at 266 and 248 nm or vacuum ultraviolet single-photon ionization (VUV-SPI) at 118 nm. The VUV ionization scheme allows detecting mainly the most volatile and abundant compounds of molecular mass below 100 m/z, while REMPI ionizes mainly aromatic compounds of molecular mass larger than 100 m/z. Combining the compounds ionized by resonant and single-photon ionization, approximately 30 volatile organic compounds are monitored in real time. Time-intensity profiles of 10 important volatile coffee compounds were discussed in connection with their formation chemistry during roasting. Applying multivariate statistics (principle component analysis) on time-intensity traces of nine volatile coffee compounds, the roasting degree could be traced as a consistent path in the score plot of the two most significant principle components (including 68% of the total variance), for a range of roasting temperatures (200-250 degrees C).

The formation of 4-vinylguaiacol, guaiacol, and phenol during coffee roasting was monitored in real-time, using resonance enhanced multiphoton ionization and time-of-flight mass spectrometry. A model is proposed, based on two connected reaction channels. One channel, termed the “low activation energy” channel, consists of ester hydrolysis of 5-FQA followed by decarboxylation of the ferulic acid to form 4-vinylguaiacol, and finally polymerization at the vinyl group to form partly insoluble polymers (coffee melanoidins). The second “high activation energy” channel opens up once the beans have reached higher temperatures. It leads to formation of guaiacol, via oxidation of 4-vinylguaiacol, and subsequently to phenol and other phenolic VOCs. This work aims at developing strategies to modify the composition of coffee flavor compounds based on the time−temperature history during roasting. Keywords: Coffee; aroma; roasting; real-time analysis; mass spectrometry; resonant laser ionization

REMPI@266nm-TOFMS is used for on-line analysis of the coffee roasting process. Volatile and flavor active compounds of coffee were ionized by REMPI@266nm and monitored on-line and in real-time by TOFMS during the coffee roasting process. The phenol and 4-vinylguaiacol time-intensity profiles, for example, show typical behavior for different roasting temperatures and provide an indicator to the achieved degree of roasting. The impact of the moisture level of the green coffee beans on the time shift of a typical (commercial) roasting time, correlates with REMPI-TOFMS measurements and literature data.

Using REMPI@266 nm or 248 nm several phenolic compounds, such as Phenol or the flavor-active 4-vinylguaiacol, can be detected in the roast off-gas.

Laser mass spectrometry is applied for on-line analysis of PAHs from a complex flue gas matrix in the combustion chamber of an incineration plant. Process monitoring of industrial processes can be performed. New insights into the formation of toxic combustion byproducts are possible.

Laser induced Resonance-Enhanced Multi-Photon Ionization Time-Of-Flight Mass Spectrometry (REMPI TOFMS) is a highly selective as well as sensitive analytical technique, well suited for species selective, on-line monitoring of trace-substances. In this contribution some analytical applications of a mobile REMPI-TOFMS are presented. This includes REMPI-TOMS on-line analysis of coffee roasting gas and waste incineration flue gas as well as headspace measurements of pulp processing lye or rapid analysis of polycyclic aromatic hydrocarbons from soil samples via thermal desorption.

We present first applications of resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (REMPI-TOFMS) for on-line monitoring of technical water incinerator flue gases and coffee roasting process off- gases. The results were obtained with a newly developed, mobile REMPI-TOFMS device. The combination of laser induced resonance-enhanced multiphoton ionization and time-of-flight mass spectrometry represents a highly selective as well as sensitive analytical technique, well suited for species selective real-time on-line monitoring of trace-products in of-gases from thermal processes or technical incinerators. The achievable sensitivities are in the ppb-range or better for aromatic compounds. The high selectivity is due to the combination of mass- and optical selectivity, the high sensitivity is caused by the high cross sections of resonance-enhanced two photon ionization with lasers. On- line monitoring of trace chemicals, formed during combustion- or pyrolysis-processes, is useful e.g. for feed back steering of combustion processes in order to minimize the formation of hazardous byproducts or for optimization of the economic efficiency of thermal production processes.© (1997) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.

Resonance-enhanced multiphoton ionization (REMPI) allows different degrees of optical ionization selectivity. The selectivity achievable with the REMPI-method is compared with that of other ionization methods for on-line mass spectrometry. “Semiselective” REMPI with effusive molecular beam inlet allows group selective ionization of mono- and polycyclic aromatic compounds and their methylated derivatives (REMPI at 266 nm). The patterns of the above mentioned aromatic compounds in flue gases can be used for characterization of industrial combustion processes. In this work, a novel approach of “semi-selective” REMPI for measure ment of the patterns of mono- and polycyclic aromatic compounds, with additional simultaneous target compound monitoring, is presented. By using REMPI at 269.8 nm monochloro benzene, which is an important indicator for the toxicity of the flue gas, can be monitored, together with the other aromatics. On-line recorded REMPI mass spectra from the flue gas of an industrial hazardous waste incineration plant are presented. The applications of REMPI on-line monitoring at incineration plants are discussed.