Looking into individual coffee beans during the roasting process: Direct micro-probe sampling on-line photo-ionisation mass spectrometric analysis of coffee roasting gases.

A micro-probe (μ-probe) gas sampling device for on-line analysis of gases evolving in confined, small objects by single-photon ionisation time-of-flight mass spectrometry (SPI-TOFMS) was developed. The technique is applied for the first time in a feasibility study to record the formation of volatile and flavour compounds during the roasting process within (inside) or in the direct vicinity (outside) of individual coffee beans. A real-time on-line analysis of evolving volatile and semi-volatile organic compounds (VOC and SVOC) as they are formed under the mild pyrolytic conditions of the roasting process was performed. The soft-ionisation mass spectra depict a molecular ion signature, which is well corresponding with the existing knowledge of coffee roasting and evolving compounds. Additionally, thereby it is possible to discriminate between Coffea arabica (Arabica) and Coffea canephora (Robusta). The recognized differences in the roasting gas profiles reflect the differences in the precursor composition of the coffee cultivars very well. Furthermore, a well-known set of marker compounds for Arabica and Robusta, namely the lipids kahweol and cafestol (detected in their dehydrated form at m/z 296 and m/z 298, respectively) were observed. If the variation in time of different compounds is observed, distinctly different evolution behaviours were detected. Here, phenol (m/z 94) and caffeine (m/z 194) are exemplary chosen, whereas phenol shows very sharp emission peaks, caffeine do not have this highly transient behaviour. Finally, the changes of the chemical signature as a function of the roasting time, the influence of sampling position (inside, outside) and cultivar (Arabica, Robusta) is investigated by multivariate statistics (PCA). In summary, this pilot study demonstrates the high potential of the measurement technique to enhance the fundamental knowledge of the formation processes of volatile and semi-volatile flavour compounds inside the individual coffee bean

Online measurement of volatile organic compounds released during roasting of cocoa beans.

The gaseous species evolving during the roasting of cocoa beans were analyzed by a newly developed technique, a micro-probe-photo-ionization-time-of-flight mass spectrometer system. A lot of volatile roasting products and typical aroma compounds, such as methylbutanal, phenylacetaldehyde and pyrazines, could be online detected. The differences between the roast gas composition inside and outside the bean were pointed out. Two additional signals at m/z 266 and 294 with resonance-enhanced multi-photon ionization (REMPI), which argues for an aromatic character, and a higher methanethiol signal with single photon ionization (SPI) could have been identified at first glance for the measurements inside the bean. Principal component analysis (PCA) and difference spectra revealed and confirmed these findings. Higher concentrations of theobromine and fatty acids are present outside and more caffeine inside the bean. With both ionization techniques, the changes in the PCA are more prominent at the beginning of the roast courses, which are mostly explained by caffeine and theobromine. Following the courses of these characteristic compounds showed the same results as obtained with the PCA and revealed that caffeine is always released before theobromine. The new analytical technique proved to be a fast, reliable and non-labor intensive method, which could therefore be a practical technique for the online analysis and monitoring of the cocoa roasting process

On-line process monitoring of coffee roasting by resonant laser ionisation time-of-flight mass spectrometry: Bridging the gap from industrial batch roasting to flavour formation inside an individual coffee bean.

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 -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 -hole, from the interior, using a -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

Highly time-resolved imaging of combustion and pyrolysis product concentrations in solid fuel combustion: NO formation in a burning cigarette.

The highly dynamic, heterogeneous combustion process within a burning cigarette was investigated by a miniaturized extractive sampling probe (microprobe) coupled to photoionization mass spectrometry using soft laser single photon ionization (SPI) for online real-time detection of molecular ions of combustion and pyrolysis products. Research cigarettes smoked by a smoking machine are used as a reproducible model system for solid-state biomass combustion, which up to now is not addressable by current combustion-diagnostic tools. By combining repetitively recorded online measurement sequences from different sampling locations in an imaging approach, highly time- and space-resolved quantitative distribution maps of, e.g.; nitrogen monoxide, benzene, and oxygen concentrations were obtained at a near microscopic level. The obtained quantitative distribution maps represent a time-resolved, movie-like imaging of the respective compounds formation and destruction zones in the various combustion and pyrolysis regions of a cigarette during puffing. Furthermore, spatially resolved kinetic data were ascertainable. The here demonstrated methodology can also be applied to various heterogenic combustion/pyrolysis or reaction model systems, such as fossil- or biomass-fuel pellet combustion or to a positional resolved analysis of heterogenic catalytic reactions

High-resolution time and spatial imaging of tobacco and its pyrolysis products during a cigarette puff by microprobe sampling photoionisation mass spectrometry.

The time- and space-resolved chemical signatures of gases and vapours formed in solid-state combustion processes are difficult to examine using recent analytical techniques. A machine-smoked cigarette represents a very reproducible model system for dynamic solid-state combustion. By using a special sampling system (microprobe unit) that extracts the formed gases from inside of the burning cigarette, which is coupled to a photoionisation mass spectrometer, it was possible to study the evolution of organic gases during a 2-s cigarette puff. The concentrations of various pyrolysis and combustion products such as 1,3-butadiene, toluene, acetaldehyde and phenol were monitored on-line at different sampling points within cigarettes. A near-microscopic-scale spatial resolution and a 200-ms time resolution were achieved. Finally, the recorded information was combined to generate time-resolved concentration maps, showing the formation and destruction zones of the investigated compounds in the burning cigarette. The combustion zone at the tip of cigarette, where e.g. 1,3-butadiene is predominately formed, was clearly separable from the pyrolysis zones. Depending on the stability of the precursor (e.g. lignin or cellulose), the position of pyrolytic formation varies. In conclusion, it was demonstrated that soft photoionisation mass spectrometry in conjunction with a microprobe sampling device can be used for time- and space-resolved analysis of combustion and pyrolysis reactions. In addition to studies on the model cigarette, further model systems may be studied with this approach. This may include further studies on the combustion of biomass or coal chunks, on heterogeneously catalysed reactions or on spray, dust and gas combustion processes