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This work evaluated the use of roasted coffee oil (RCO) and the effects of ultrasound (US)-assisted emulsification on RCO-in-water emulsion properties, the changes in the composition of volatile organic compounds (VOCs) of roasted coffee aroma during US and microencapsulation by spray drying, and VOCs release profile upon instant coffee reconstitution. VOCs were determined by gas chromatography-mass spectrometry, and the release profile was monitored in real-time by Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF–MS). US was found to be effective in producing stable submicron emulsions (≤ 2.0 µm) that resulted in high encapsulation efficiency (> 90%) of the microparticles. Significant changes were detected in VOC composition throughout the microencapsulation process. The addition of microparticles loaded with RCO in instant coffee did not change the VOCs release profile during the brew preparation but was effective in increasing coffee aroma.

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We report, on the successful addition of spray-dried microparticles containing roasted coffee oil, to soluble coffee (SC) and instant cappuccino (IC), to increase and tailor aroma release. Using PTR-ToF-MS (Proton Transfer Reaction Time-of-Flight Mass Spectrometry), five parameters were defined from time series intensity for each VOC, to compare the performance of different products: total area under the curve (AUC), area under the curve of burst (AUC-burst), maximum signal intensity, final intensity (5 min), and ratio AUC-burst/AUC. Microparticles with higher loads of roasted coffee oil were effective in increasing aroma intensity in SC while, for IC, all loads of microparticles improved aroma intensity. Volatility drove the VOC release in SC, and volatility and polarity for IC. Most compounds reached maximum headspace concentration in < 16 s upon start of reconstitution. These results open new perspectives for the development of instant coffee products and demonstrate their unique aroma release characteristics.

This study examined the influence of consumer behavior on furan, 2-methylfuran, 3-methylfuran, 2,5-dimethylfuran and 2,3-dimethylfuran exposure in coffee. Coffees brewed using a filter, fully automatic, capsule machine or reconstituted instant coffee were found to have a significant different cup concentrations of furan derivatives. Coffee brewed with the fully automatic machine contained the highest furan and furan derivative concentrations (99.05 µg/L furan, 263.91 µg/L 2-methylfuran, 13.15 µg/L 3-methylfuran and 8.44 µg/L 2,5-dimethylfuran) whereas soluble coffee did not contain detectable levels, thereby contributing least to a consumer’s dietary exposure. Furan and furan derivative concentrations were found to decrease significantly upon cooling, reducing consumer exposure by 8.0–17.2 % on average once the coffee reached drinking temperature 55–60 °C, in ceramic cups. Serving coffee in a ceramic or disposable cup were found to influence the cooling dynamics of the coffee but did not statistically influence the consumers exposure at a given temperature.

This article contains data related to the research article entitled “Quantitative assessment of specific defects in roasted ground coffee via infrared-photoacoustic spectroscopy” (Dias et al., 2018) [1] . A method potentially able for assessing the quality of roasted ground coffees is described in the origin paper. Infrared spectroscopy and photoacoustic detection (FTIR-PAS) associated with multivariate calibration were used. The samples were obtained blending whole and healthy coffee beans (C. arabica and C. canephora) with specific blends of defects, named selections, which contain broken, sour, and black beans, skin, woods and healthy beans still not collected. In addition to a reduction in commercial value, the presence of defects compromises the sensory attributes of coffee. On the other hand, selections are commonly found in coffee crops and can be added intentionally to the product. Twenty-five selections were used to obtain a panel of 154 blends. The FTIR-PAS spectra of each sample generated the prediction model of Partial Least Squares Regression parameters, which are also presented here.

Chemical analyses and sensory evaluation are the most applied methods for quality control of roasted and ground coffee (RG). However, faster alternatives would be highly valuable. Here, we applied infrared-photoacoustic spectroscopy (FTIR-PAS) on RG powder. Mixtures of specific defective beans were blended with healthy (defect-free) Coffea arabica and Coffea canephora bases in specific ratios, forming different classes of blends. Principal Component Analysis allowed predicting the amount/fraction and nature of the defects in blends while partial Least Squares Discriminant Analysis revealed similarities between blends (=samples). A successful predictive model was obtained using six classes of blends. The model could classify 100% of the samples into four classes. The specificities were higher than 0.9. Application of FTIR-PAS on RG coffee to characterize and classify blends has shown to be an accurate, easy, quick and “green” alternative to current methods.

On-line analysis of coffee roasting was performed using ion mobility spectrometry–mass spectrometry (IMS–MS) with corona discharge ionization. This is the first time that formation of volatile organic compounds (VOCs) during coffee roasting was monitored not only in positive but also in negative ion mode, and not only with mass spectrometry, but also with ion mobility spectrometry. The temporal evolution of more than 150 VOCs was monitored during the roasting of Brazilian Coffea arabica. Mass-selective ion mobility spectrometry allowed a separation of isobaric and isomeric compounds. In positive ion mode, isomers of alkyl pyrazines were found to exhibit distinct time-intensity profiles during roasting, providing a unique insight into the complex chemistry of this important class of aroma active compounds. Negative ion mode gave access to species poorly detectable by other on-line methods, such as acids. In this study, the release of fatty acids during coffee roasting was investigated in detail. These increase early on in the roasting process followed by a decrease at the same time as other VOCs start to be formed.

This study presents an experimental approach to study the kinetics and fast release of volatile organic compounds (VOCs) upon reconstitution of instant coffee products. A sampling setup coupled to PTR-ToF-MS (Proton Transfer Reaction Time-of-Flight Mass Spectrometry) for the automated and reproducible reconstitution of instant coffee products was developed to monitor the dynamic release of VOCs. A rapid release of aroma compounds was observed in the first seconds upon hot water addition ("aroma burst"), followed by subsequent decrease in headspace (HS) intensities over the course of analysis. Differences in time-intensity release profiles of individual VOCs were correlated to their Henry's Law constant, vapor pressure and water solubility. The setup and approach proposed here have shown to be sensitive and to respond to fast dynamic changes in aroma release. It allows studying VOCs release upon reconstitution and supports the development of novel technologies and formulations for instant products with improved aroma release properties.

This article is part of the special issue of the Flavour and Fragrance Journal entitled “On‐line monitoring of odorants using direct‐injection mass spectrometry” edited by Jean‐Luc Le Quere., Changes in the headspace volatile profile of tea infusion during brewing were determined by analysing the aliquots taken every 30 s using proton transfer reaction time‐of‐flight mass spectrometry in conjunction with principal component analysis and hierarchical cluster analysis. The effect of three different brewing temperatures (60, 70 and 80°C), two leaf sizes (broken and full leaves) and two water mineralizations (soft and hard), on the concentration of volatile compounds in the headspace of tea, was studied as a function of infusion time. An increase in brewing temperature resulted in increased volatile content in the headspace, reflecting an increase in extraction efficiency. Such differences on extraction efficiency were more pronounced with increasing brewing times. Leaf size had also a big impact on the extraction of volatile compounds, but mainly during the early phase of brewing. Water mineralization had a low but noticeable impact on the volatile content. Furthermore, clusters of samples prepared with different combinations of brewing parameters but resulting in analogous volatile profiles could be identified using hierarchical clustering analysis.

The objective of this paper is to elucidate the variables that govern coffee extraction from single serve coffee capsules. The study was conducted on 43 Nespresso and Nespresso-compatible capsules of the same geometry, from all of which the coffee was extracted on the same machine. This allowed the link between a range of coffee and capsule (input) parameters with coffee brew (output) variables to be studied. It was demonstrated that the most efficient way to increase total dissolved solids in the brew is to use more coffee for extraction, and/or to grind the coffee more finely. However, grinding too finely can lead to excessive flow restriction. The most significant new insight from this study is the importance of the proportion of fines (particles smaller than 100 µm) regarding the capsule extraction dynamics. Capsules with a higher share of fines, for similar median particle size of the ground coffee, led to longer extraction times. General rules applicable for capsule coffee product development were established, although fine-tuning of parameters for successful capsule coffee extraction remains specific to production line and type of coffee.

Introduction Coffee is a widely consumed beverage containing antioxidant active compounds. During roasting the phytochemical composition of the coffee bean changes dramatically and highly polymeric substances are produced. Besides chlorogenic acids that are already present in green coffee beans, melanoidins show antioxidant capacity as well. Objective To employ post-column derivatisation by coupling high performance size exclusion chromatography (HPSEC) to an antioxidant assay to investigate the effect of roasting on the properties of antioxidant active compounds in coffee brews. Methodology We have investigated the antioxidant capacity of Coffea arabica (Arabica) and C. canephora (Robusta) beans that were roasted over the full spectrum of roast conditions (four roasting speeds to three roast degrees) by comparing the results from HPSEC coupled on-line to the ABTS assay with those from two batch assays, Folin Ciocalteu (FC) and oxygen radical absorbance capacity (ORAC) assay. Results The antioxidant capacity showed a general decrease towards slower and darker roasted coffee for all three assays, indicative of heat degradation of active compounds. Hence, low molecular weight (LMW) compounds such as chlorogenic acids (CGAs) decreased progressively already from relatively mild roasting conditions. In contrast, high molecular weight (HMW) compounds (e.g. melanoidins) increased from light to dark roast degrees with lowering magnitude towards slower roasting profiles. Conclusion By coupling HPSEC on-line to the ABTS assay we were able to separately quantify the contribution of HMW and LMW compounds to the total antioxidant capacity, increasing our understanding of the roast process. © 2016 The Authors. Phytochemical Analysis Published by John Wiley & Sons Ltd.

An oxygen scavenger based on a catalytic system with palladium (CSP) was recently developed to remove oxygen in food packagings. Although the CSP worked with various types of food, with some foods, an inhibition of the CSP was observed. Because such catalytic systems are susceptible to poisoning by sulfur-containing compounds, the aim of this study was to understand the inactivation of palladium-based catalysts in presence of foods containing volatile sulfur compounds (VSCs). To achieve this, the oxygen scavenging activity (OSA) of the CSP was evaluated in presence of selected food products. Afterwards, VSCs mainly present in these foods were exposed to the CSP, and the influence on the OSA was evaluated. Finally, headspace analysis was performed with the diluted VSCs and with the packaged food products using proton transfer reaction time-of-flight mass spectrometry. It was found that the catalytic activity of the CSP was inhibited when VSCs were present in the headspace in concentrations ranging between 10.8–36.0 ppbv (dimethyl sulfide, DMS), 1.2–7.2 ppbv (dimethyl disulfide), 0.7–0.9 ppbv (dimethyl trisulfide), 2.1–5.8 ppbv (methional) and 4.6–24.5 ppbv (furfuryl thiol). It was concluded that in packaged roast beef and cheese, DMS may be the compound mainly responsible for the inactivation of the CSP. In packagings containing ham, the key compounds were hydrogen sulfide and methanethiol; in peanuts, it was methanethiol; and in par-baked buns, an accumulation of methional, DMS, butanethiol and methionol. When potato chips were packaged, it was demonstrated that when VSCs are present in low concentrations, oxygen can still be scavenged at a reduced OSA.

The hot-water extraction process used to make an espresso coffee is affected by a large number of factors. A proper understanding of how these factors impact the profile of the final cup is important to the quality of an espresso coffee. This work examines the effect of water temperature and pressure on the extraction kinetics of volatile organic compounds (VOCs) in coffee. This was achieved by on-line monitoring of the volatiles directly from the coffee flow, using proton-transfer-reaction time-of-flight mass-spectrometry (PTR-ToF-MS). Using hierarchical cluster analysis (HCA), tentatively identified compounds were grouped into 5 families according to their time–intensity profiles. VOCs grouped into each family had similar physicochemical properties while polarity was found to be one of the main forces driving VOC extraction kinetics. The effect of pressure was studied by extracting espresso coffees at 7, 9 and 11 bar. A pressure of 11 bar resulted in an increased extraction of volatiles over the entire extraction time (25 s). To study the effect of temperature, espresso coffees were extracted at 82, 92 and 96 °C. An increase in temperature produced a significant increase in the extraction of VOCs, especially during the last part of the extraction. The effect of temperature on extractability was more pronounced for the less polar compounds.

Oxygen scavenging film based on a catalytic system with palladium (CSP) was used to prevent lipid oxidation in linseed oil. Linseed oil was packaged under normal (NA) or modified atmosphere with 2 vol% oxygen (MA) with or without the CSP and stored at 45 °C for 6 months in darkness. To evaluate the evolution of primary and secondary oxidation products, conjugated dienes/trienes, peroxide and para-anisidine values were measured. Additionally, volatile oxidation products in the headspace were analyzed. While a significantly higher level of oxidation products was measured in linseed oil stored under NA compared to MA without CSP, thresholds indicating good quality oil based on the peroxide value (15 milliequivalents O2/g oil) and the para-anisidine value (2 absorbance units/g oil) were exceeded under both packaging conditions. In packages with the CSP, however, removal of headspace oxygen kept oxidation parameters below these thresholds, indicating good quality oil over the whole storage period.

Coffee has been determined as the dominant source of furan within an adult’s diet. This study investigates the influence of coffee condiment use and stirring on the retention of furan. Three condiment lipid compositions were investigated, 0%, 3.5% and 35%, and kept at either 4 °C, 20 °C or 70 °C before addition to a freshly brewed cup of filter coffee which was subsequently mechanically stirred at three intensities, not stirred and moderately or heavily stirred. While five furans were monitored, furan, 2-methylfuran, 3-methylfuran, 2,5-dimethylfuran and 2,3-dimethylfuran, only two were quantifiable: furan and 2-methylfuran. Increasing condiment lipid concentration significantly increased retention of furan and 2-methylfuran, whereas stirring the coffee significantly increased furan release. A condiment temperature of 70 °C was found to significantly increase furan release.

The aim of this project was to develop a general concept to assess the laboratory experiments in the instrumental analysis laboratory, at the Institute of Chemistry and Biological Chemistry (ICBC) at the Zurich University of Applied Sciences (ZHAW), in terms of their sustainability and, where possible, to improve the sustainability rating of the laboratory experiments. Hence, the primary objective was to implement an empirical assessment methodology, including the “Sustainability Code” that was composed of four parts and a “Sustainability Load Index”. During the spring semester 2015, 105 different experimental projects were performed in the ICBC’s analytical chemistry practical course. These were carried out on 18 different instrumental workspaces, encompassing 12 different analytical methodologies. For the development of the first and second parts of the Sustainability Code, information concerning the chemical substances (in any state- solid, liquid or gas) used and the energy consumption of the apparatus was recorded. The third and fourth parts contain (approximate) information on the use of consumables and the sustainability of the method with reference to the apparatus used. The Load Index (LI) consists of an aggregation (summary) of the direct causality indicators ‘substances’ and ‘energy’ into a single figure. The experiments were classified on a 3-level Load Index Scale into ‘ideal’ analysis methods (LI> 20), ‘sustainable’ methods of analysis (LI 20-200), and analysis methods ‘with potential for optimization’ (LI

Liquid–air partition coefficients (Henry's law constants, HLCs) of eight flavour compounds (volatile organic compounds, VOCs) were determined in water, over a temperature range of 4 °C to 85 °C. The HLCs were derived by using nitrogen to strip a dilute solution of a VOC and then determining the decrease in concentration of the VOC in real-time in the stripped gas using proton-transfer-reaction time-of-flight mass-spectrometry (PTR-ToF-MS). This approach provided HLCs of improved accuracy (small 95% standard deviation) over a large temperature range, especially for low volatility VOCs (HLC > 2 mol/(m 3 Pa)). The outstanding features of this approach are: (i) it is applicable for VOCs over a large range of volatility; (ii) it can be used over a wide temperature range (4 °C to 85 °C); (iii) it is automated (high-throughput); (iv) it does not require calibration or knowledge of the initial concentration of the analyte; and (v) the experimental temperature can be controlled very precisely (Δ T better than ±0.1 °C). The eight flavour compounds analysed in water were: (E)-β-damascenone, 2,3-butanedione, 2-ethyl-3,5-dimethylpyrazine, 2-methylfuran, 3-methylbutanal, acetaldehyde, ethyl-3-methyl butanoate and guaiacol. Based on the measured HLCs at five fixed temperatures (4 °C, 25 °C, 45 °C, 65 °C and 85 °C), accurate non-linear analytical expressions for the temperature dependence of HLCs were derived, which were then used to calculate thermodynamic constants.

During the roasting of coffee, thermally driven chemical reactions lead to the formation of gases, of which a large fraction is carbon dioxide (CO2). Part of these gases is released during roasting while part is retained inside the porous structure of the roasted beans and is steadily released during storage or more abruptly during grinding and extraction. The release of CO2 during the various phases from roasting to consumption is linked to many important properties and characteristics of coffee. It is an indicator for freshness, plays an important role in shelf life and in packaging, impacts the extraction process, is involved in crema formation, and may affect the sensory profile in the cup. Indeed, and in view of the multiple roles it plays, CO2 is a much underappreciated and little examined molecule in coffee. Here, we introduce an accurate, quantitative, and time-resolved method to measure the release kinetics of gases from whole beans and ground coffee using a gravimetric approach. Samples were placed in a container with a fitted capillary to allow gases to escape. The time-resolved release of gases was measured via the weight loss of the container filled with coffee. Long-term stability was achieved using a customized design of a semimicro balance, including periodic and automatic zero value measurements and calibration procedures. The novel gravimetric methodology was applied to a range of coffee samples: (i) whole Arabica beans and (ii) ground Arabica and Robusta, roasted to different roast degrees and at different speeds (roast air temperatures). Modeling the degassing rates allowed structural and mechanistic interpretation of the degassing process.

Coffees from different origins were roasted to different roast degrees and along varying time temperature roasting profiles. The formation of volatile organic compounds (VOCs) during roasting was analyzed on-line by proton-transfer-reaction time-of-flight mass-spectrometry (PTR-ToF-MS). Coffee samples were Coffea arabica from Colombia, Guatemala (Antigua La Ceiba), Ethiopia (Yirga Cheffe, Djimmah) and Coffea canephora var. robusta from Indonesia (Malangsari). The roasting profiles ranged from high temperature short time (HTST) to low temperature long time (LTLT) roasting, and from medium to dark roast degree. The release dynamics of the on-line monitored VOCs differed for the different coffees and showed a strong modulation with the time–temperature roasting profile. While for Guatemalan coffee the formation of VOCs started relatively early in the roasting process, the VOC formation started much later in the case of Yirga Cheffe and Malangsari. Off-line analysis of the coffee brew augmented the measurements. These included headspace solid phase micro extraction gas chromatography mass spectrometry (HS SPME GC/MS), content of total solids, chlorogenic acids, caffeine, total polyphenols (Folin Ciocalteu), organic acids (ion chromatography), titratable acidity and pH. Some general trends, irrespective of the coffee origin, were observed, such as an increase in pH when going from an HTST to an LTLT profile or from a medium to dark roast degree. Furthermore, a decrease of total headspace intensity was observed from an HTST to an LTLT roasting profile. In general, the changes of the time temperature roasting profiles and/or the roast degree influenced the intensity of the respective coffee constituents as well as their relative composition differently for different coffee origins.

Water is an essential ingredient for coffee extraction, typically making up more than 90% of the final beverage. This chapter introduces the basic characteristics of water and the most common dissolved contents. The concepts of water hardness and alkalinity are explained while discerning between technical and sensory aspects with regards to coffee extraction. The existing recommendations on the optimum water composition are discussed as well as the potential off-flavors that can arise from nonideal composition. As a link between a given water composition and a targeted recommendation the most common water treatment methods are systematically characterized. The chapter concludes with practical examples on the impact of different water compositions in a cupping experiment and espresso extraction.

Coffee is a relatively young beverage that has only been known about since the 17th century. Initially consumed by the aristocracy, coffee has developed since the early 20th century into one of the world’s most popular beverages and is now part of our daily routine and lifestyle. It also represents a major source of income for many coffee-producing countries and is a significant business sector in consumer countries. The triumph of this beverage may have been driven by various factors, but there is no doubt that its unique flavor is the prime reason for its amazing success. Here we will review current knowledge on the aroma of coffee from a chemical and analytical perspective and outline future trends. It is believed that most coffee aroma compounds have already been identified and quantified. Yet little is understood about how these aroma compounds are generated from green coffee precursors during roasting. A true definition of the aroma of freshly roasted and/or brewed coffee is very elusive and some aroma compounds start to degrade the moment they form. Furthermore, research on interindividual differences in the sensation and perception of coffee aromas is still in its infancy. After reviewing our current knowledge on coffee aroma compounds, we will outline recent developments in time-resolved analysis in three fields: 1. Aroma formation during roasting 2. Aroma extraction during espresso preparation and 3. In-mouth release during consumption. Finally, we will address predictive models for sensory profiles derived from instrumental measurements – possibly the holy grail of aroma sciences.

Since the early days of the specialty coffee movement, freshness has been one of its central pillars. Freshness is best defined as having original unimpaired qualities. In coffee, it is most often seen as freshly roasted, ground within a few days, immediately extracted, and consumed. But despite this pivotal role of freshness for high quality coffee, the objective and scientific measurement of freshness have often been vague and elusive. How can one measure the level of freshness of coffee? In this chapter we will outline two approaches. One is based on the degassing of the freshly roasted coffee and the other on the evolution of its aroma profile during storage. In terms of the evolution of the aroma profile, we will introduce one particular freshness index: the ratio of dimethyl disulfide to methanethiol, suited to assess the evolution of freshness of roasted coffee during storage. Although this ratio has been shown to increase during storage, the speed at which this freshness index increases depends on the packaging and storage temperature. This has opened the possibility to use this index to assess the freshness of roasted coffee and compare the quality of different packaging materials for preserving the freshness of the coffee inside.

Coffees and teas are beverages that are both exceptionally rich in antioxidant molecules, and are also both associated with beneficial health effects. Thus although the quality characteristics of these beverages are conventionally assessed on the basis of their sensory properties, their antioxidant contents represent an additional and increasingly valued attribute of quality based on their contributions to healthy diets. Both beverages are prepared by hot water extraction of a pure plant-derived product, and thus their compositions can potentially change quite rapidly as a result of oxidation in contact with air. Oxidative processes often proceed via free radical intermediates, and sometimes also result in the formation of stable radical end-products; thus EPR spectroscopy is a convenient technique for investigating some of the various free radical reactions that occur in these beverages. This paper reviews progress that has been made in elucidating free radical processes that occur during the preparation and storage of coffees and teas, and the results are discussed in terms of quality criteria of the beverages.

Introduction Coffee is a widely consumed beverage containing antioxidant active compounds. During roasting the phytochemical composition of the coffee bean changes dramatically and highly polymeric substances are produced. Besides chlorogenic acids that are already present in green coffee beans, melanoidins show antioxidant capacity as well. Objective To employ post‐column derivatisation by coupling high performance size exclusion chromatography (HPSEC) to an antioxidant assay to investigate the effect of roasting on the properties of antioxidant active compounds in coffee brews. Methodology We have investigated the antioxidant capacity of Coffea arabica (Arabica) and C. canephora (Robusta) beans that were roasted over the full spectrum of roast conditions (four roasting speeds to three roast degrees) by comparing the results from HPSEC coupled on‐line to the ABTS assay with those from two batch assays, Folin Ciocalteu (FC) and oxygen radical absorbance capacity (ORAC) assay. Results The antioxidant capacity showed a general decrease towards slower and darker roasted coffee for all three assays, indicative of heat degradation of active compounds. Hence, low molecular weight (LMW) compounds such as chlorogenic acids (CGAs) decreased progressively already from relatively mild roasting conditions. In contrast, high molecular weight (HMW) compounds (e.g. melanoidins) increased from light to dark roast degrees with lowering magnitude towards slower roasting profiles. Conclusion By coupling HPSEC on‐line to the ABTS assay we were able to separately quantify the contribution of HMW and LMW compounds to the total antioxidant capacity, increasing our understanding of the roast process. © 2016 The Authors. Phytochemical Analysis Published by John Wiley & Sons Ltd., The composition of green coffee beans is complex, yet roasting adds to this complexity by producing highly polymeric melanoidins. Next to chlorogenic acids melanoidins also show antioxidant capacity, which was measured with batch assays as well as by on‐line coupling to size exclusion chromatography to investigate the roasting effect on the formation and/or degradation of high and low molecular weight compounds. Adding chromatography enabled us to separately quantify antioxidant activity of high and low molecular weight compounds to increase our understanding of the roasting process.

A real-time automated process control tool for coffee roasting is presented to consistently and accurately achieve a targeted roast degree. It is based on the online monitoring of volatile organic compounds (VOC) in the off-gas of a drum roaster by proton transfer reaction time-of-flight mass spectrometry at a high time (1Hz) and mass resolution (5,500m/Δm at full width at half-maximum) and high sensitivity (better than parts per billion by volume). Forty-two roasting experiments were performed with the drum roaster being operated either on a low, medium or high hot-air inlet temperature (= energy input) and the coffee (Arabica from Antigua, Guatemala) being roasted to low, medium or dark roast degrees. A principal component analysis (PCA) discriminated, for each one of the three hot-air inlet temperatures, the roast degree with a resolution of better than ±1 Colorette. The 3D space of the three first principal components was defined based on 23 mass spectral profiles of VOCs and their roast degree at the end point of roasting. This provided a very detailed picture of the evolution of the roasting process and allowed establishment of a predictive model that projects the online-monitored VOC profile of the roaster off-gas in real time onto the PCA space defined by the calibration process and, ultimately, to control the coffee roasting process so as to achieve a target roast degree and a consistent roasting. Figure Online monitoring of coffee roasting by real-time analysis of the roaster off-gas using PTR-ToF-MS. In a first phase, 42 calibration experiments were conducted at three different roasting temperatures and to three final roast degrees, to generate the 3D space defined by the three first principle components PC1, PC2 and PC3. Inverted triangles mark the dark roast degree, square medium and circle light, respectively. The hot-air inlet temperature is marked as follows: high (black), medium (grey), low (white). The different hot-air inlet temperatures and roast degrees are clearly separated. In a second phase, an online monitored PTR-ToF-MS spectrum of a roasting process was projected onto the 3D space, allowing following in real-time the roasting process and halting the roasting with a precision better that ± 1 Colorette roast degree

In the past decade, we have witnessed rapid development of direct-injection mass spectrometric (DIMS) technologies that combine ever-improving mass and time resolution with high sensitivity and robustness. Here, we review some of the most significant DIMS technologies, which have been applied to rapid monitoring and quantification of volatile organic compounds (VOCs) and biogenic VOCS (BVOCs). They include MS-e-noses, atmospheric-pressure chemical ionization (APCI), proton-transfer-reaction mass spectrometry (PTR-MS), and selected ion-flow-tube mass spectrometry (SIFT-MS). DIMS-based MS-e-noses provide the possibility to screen large sample sets and may yield rich analytical information. APCI is a widespread ionization method and pioneered DIMS in environmental and flavor-release applications. SIFT-MS and PTR-MS allow better control of precursor-ion generation and hence of the ionization process. SIFT-MS puts the focus on control of the ionization process, while PTR-MS does so on sensitivity. Most (B)VOCs of interest can be efficiently detected and often identified by DIMS, thanks also to the possibility of switching between different precursor ions and the recent realization of time-of-flight-based equipments. Finally, we give selected examples of applications for each of the key technologies, including research in food-quality control (MS-e-nose), flavor release (APCI), environmental sciences (PTR-MS) and health sciences (SIFT-MS).

Volatile profiles of 63 black and 38 green teas from different countries were analysed with Proton Transfer Reaction-Time of Flight-Mass Spectrometry (PTR-ToF-MS) both for tea leaves and tea infusion. The headspace volatile fingerprints were collected and the tea classes and geographical origins were tracked with pattern recognition techniques. The high mass resolution achieved by ToF mass analyser provided determination of sum formula and tentative identifications of the mass peaks. The results provided successful separation of the black and green teas based on their headspace volatile emissions both from the dry tea leaves and their infusions. The volatile fingerprints were then used to build different classification models for discrimination of black and green teas according to their geographical origins. Two different cross validation methods were applied and their effectiveness for origin discrimination was discussed. The classification models showed a separation of black and green teas according to geographical origins the errors being mostly between neighbouring countries. Fil: Yener, Sine. Instituto Agrario San Michele all'Adige Fondazione Edmund Mach; Italia. Universidad de Innsbruck; Austria Fil: Sánchez-López, José A.. Universitat Zurich; Suiza. Universität Rostock; Alemania Fil: Granitto, Pablo Miguel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Centro Internacional Franco Argentino de Ciencias de la Información y de Sistemas. Universidad Nacional de Rosario. Centro Internacional Franco Argentino de Ciencias de la Información y de Sistemas; Argentina Fil: Cappellin, Luca. Instituto Agrario San Michele all'Adige Fondazione Edmund Mach; Italia Fil: Märk, Tilmann D.. Universidad de Innsbruck; Austria Fil: Zimmermann, Ralf. Universität Rostock; Alemania. Technische Universitat Munchen; Alemania Fil: Bonn, Günther K.. Universidad de Innsbruck; Austria. Austrian Drug Screening Institute; Austria Fil: Yeretzian, Chahan. Universitat Zurich; Suiza Fil: Biasioli, Franco. Instituto Agrario San Michele all'Adige Fondazione Edmund Mach; Italia

We introduce a real-time method to monitor the evolution of oak aromas during the oak toasting process. French and American oak wood boards were toasted in an oven at three different temperatures, while the process-gas was continuously transferred to the inlet of a proton-transfer-reaction time-of-flight mass spectrometer for online monitoring. Oak wood aroma compounds important for their sensory contribution to oak-aged wine were tentatively identified based on soft ionization and molecular mass. The time-intensity profiles revealed toasting process dynamics illustrating in real-time how different compounds evolve from the oak wood during toasting. Sufficient sensitivity was achieved to observe spikes in volatile concentrations related to cracking phenomena on the oak wood surface. The polysaccharide-derived compounds exhibited similar profiles; whilst for lignin-derived compounds eugenol formation differed from that of vanillin and guaiacol at lower toasting temperatures. Significant generation of oak lactone from precursors was evident at 225 oC. Statistical processing of the real-time aroma data showed similarities and differences between individual oak boards and oak wood sourced from the different origins. This study enriches our understanding of the oak toasting process and demonstrates a new analytical approach for research on wood volatiles.

The formation of acrylamide was measured in real time during thermal treatment (120-170 degrees C) of potato as well as in Maillard model systems composed of asparagine and reducing sugars, such as fructose and glucose. This was achieved by on-line monitoring of acrylamide released into the headspace of the samples using proton transfer reaction mass spectrometry (PTR-MS). Unambiguous identification of acrylamide by PTR-MS was accomplished by gas chromatography coupled simultaneously to electron-impact MS and PTR-MS. The PTR-MS ion signal at m/z 72 was shown to be exclusively due to protonated acrylamide obtained without fragmentation. In model Maillard systems, the formation of acrylamide from asparagine was favored with increasing temperature and preferably in the presence of fructose. Maximum signal intensities in the headspace were obtained after approximately 2 min at 170 degrees C, whereas 6-7 min was required at 150 degrees C. Similarly, the level of acrylamide released into the headspace during thermal treatment of potato was positively correlated to temperature.

The goal of this study was to better understand the correspondence between sensory perception and in-nose compound concentration. Five aroma compounds at three different concentrations increasing by factors of 4 were added to four matrixes (water, skim milk, 2.7% fat milk, and 3.8% fat milk). These were evaluated by nosespace analysis with detection by proton transfer reaction mass spectrometry (PTR-MS), using five panellists. These same panellists evaluated the perceived intensity of each compound in the matrixes at the three concentrations. PTR-MS quantification found that the percent released from an aqueous solution swallowed immediately was between 0.1 and 0.6%, depending on the compound. The nosespace and sensory results showed the expected effect of fat on release, where lipophilic compounds showed reductions in release as fat content increases. The effect is less than that observed in headspace studies. A general correlation between nosespace concentration and sensory intensity ratings was found. However, examples of perceptual masking were found where higher fat milks showed reductions in aroma compound intensity ratings, even if the nosespace concentrations were the same.

We report on the in vivo breath-by-breath analysis of volatiles released in the mouth during eating of ripe and unripe banana. The air exhaled through the nose, nosespace (NS), is directly introduced into a proton transfer reaction mass spectrometer and the time-intensity profiles of a series of volatiles are monitored on-line. These include isopentyl and isobutyl acetate, two characteristic odour compounds of ripe banana, and 2E-hexenal and hexanal, compounds typical of unripe banana. Comparing the NS with the headspace (HS) profile, two differences are outlined. First, NS concentrations of some compounds are increased, compared to the HS, while others are decreased. This indicates that the in-mouth situation has characteristics of its own—mastication, mixing/dilution with saliva, temperature and pH—which modify the aroma relative to an HS aroma. Second, we discuss the temporal evolution of the NS. While 2E-hexenal and hexanal steadily increase in the NS during mastication of unripe banana, no such evolution is observed in volatile organic compounds (VOCs) while eating ripe banana. Furthermore, ripe banana shows high VOC concentrations in the swallow breath in contrast to unripe banana.

The quality of green coffee is influenced by the degree of ripeness of the fruit at harvest. The aim of this study was to identify chemical markers differentiating between degrees of ripeness. Two coffee varieties, Catuai and Tipica, from the same farm were analysed using the following parameters and methods: caffeine and chlorogenic acid content using high-performance liquid chromatography (HPLC), sucrose content using hydrophilic interaction chromatography, high-molecular weight fraction (HMW) using high-performance size-exclusion chromatography (HPSEC) and volatile compounds using headspace solid phase micro extraction gas chromatography/mass spectrometry. The best method for differentiating between degrees of ripeness was found to be principal component analysis (PCA) based on HPLC data. HPSEC showed differences in the HMW fraction for different degrees of ripeness and both coffee varieties. Volatile profiles allowed separation of both varieties; yet, except for ripe Catuai, no separation was achieved for the degree of ripeness.

This chapter describes the measurement of free radical processes in liquid coffee samples, and their impact on the quality and stability of the beverage. Free radicals generated during the roasting process are relatively stable and located in the polymeric melanoidins, but their concentrations change in coffee solutions via O2-independent decay and O2-dependent formation processes. In addition, the chemistry of coffee solutions is strongly influenced by highly unstable free radicals, presumably hydroxyl radicals generated via Fenton reaction chemistry. These radicals react virtually indiscriminately with organic molecules by hydrogen atom extraction, and can thus initiate progressive degradation of coffee brews. Identification of stable markers of such reactions are discussed along with possible strategies for slowing the rate of alteration of liquid coffee products during storage.

This chapter briefly reviews the roles played by free radical processes during the roasting and storage of coffee beans and solid coffee products. During roasting, free radical production occurs in distinct phases, possibly related to the Maillard and caramelization reactions. At the same time there is also generation of large quantities of molecules with antioxidant properties, thus demonstrating that antioxidant production does not necessarily equate to free radical scavenging, insofar as it is measured by current assays. Furthermore, with respect to chemical components that are associated with desirable sensory properties of coffee, free radical processes may have both beneficial and detrimental effects.

With the growing demand for high-quality coffee, it is becoming increasingly important to establish quantitative measures of the freshness of coffee, or the loss thereof, over time. Indeed, freshness has become a critical quality criterion in the specialty coffee scene, where the aim is to deliver the most pleasant flavor in the cup, from highest quality beans. A series of intensity ratios of selected volatile organic compounds (VOC) in the headspace of coffee (by gas chromatography–mass spectrometry) were revisited, with the aim to establish robust indicators of freshness of coffee – called freshness indices. Roasted whole beans in four different packaging materials and four commercial capsule systems from the Swiss market were investigated over a period of up to one year of storage time. These measurements revealed three types of insight. First, a clear link between barrier properties of the packaging material and the evolution of selected freshness indices was observed. Packaging materials that contain an aluminum layer offer better protection. Second, processing steps prior to packaging are reflected in the absolute values of freshness indices. Third, differences in the standard deviations of freshness-indices for single serve coffee capsule systems are indicative of differences in the consistency among systems, consistency being an important quality attribute of capsules.

Using proton-transfer-reaction time-of-flight mass-spectrometry (PTR-ToF-MS), we investigated the extraction dynamic of 95 ion traces in real time (time resolution: 1 second) during espresso coffee preparation. Fifty-two of these ions were tentatively identified. This was achieved by on-line sampling of the volatile organic compounds (VOCs) in close vicinity to the coffee flow, at the exit of the extraction hose of the espresso machine (single serve capsules). Ten replicates of six different single serve coffee types were extracted to a final volume of between 30 - 110 mL, according to the recommended cup size of the respective coffee capsule (Ristretto, Espresso and Lungo), and analyzed. The results revealed considerable differences in the extraction kinetics between compounds, which led to a fast evolution of the volatile profiles in the extract flow and consequently to an evolution of the final aroma balance in the cup. Besides exploring the time-resolved extraction dynamics of VOCs, the dynamic data also allowed the coffees types (capsules) to be distinguished from one another. Both Hierarchical Cluster Analysis (HCA) and Principal Component Analysis (PCA) showed full separation between the coffees types. The methodology developed provides a fast and simple means of studying the extraction dynamics of VOCs and differentiating between different coffee types.