Characterizing the formation of process contaminants during coffee roasting by multivariate statistical analysis.

Coffee is a relevant source of dietary exposure for neoformed furan, alkyl furans and acrylamide. In this study, different statistical methods (hierarchical cluster analysis, correlation analysis, partial least squares regression analysis) were used for characterizing the formation of these process contaminants in green coffee beans roasted under the same standardized conditions. The results displayed a strong correlation between sucrose levels and furans in relation to the other sugars analyzed, while acrylamide formation was strongly related to the free asparagine. The data suggest that a sufficiently large amino acid pool in green coffee favors Maillard-induced acrylamide formation from asparagine, while reactions amongst the carbonyl-containing sugar fragmentation products leading to furan formation are suppressed. If the pool of free amino acids is small, it is depleted faster during roasting, thus favoring the formation of furans by caramelization, basically a sugar degradation process in which reactive carbonyl substances are generated and react together.

Hazard Ratio and Hazard Index as Preliminary Estimators Associated to the Presence of Furans and Alkylfurans in Belgian Foodstuffs.

This paper provides an estimation of the hazard related to the presence of furan and five alkyl furans (2- and 3-methylfuran, 2-ethylfuran, 2,5- and 2,3-dimethylfuran) in foodstuffs available in the Belgian market. To achieve this objective, a specific sampling plan was designed to ensure that the samples collected (n = 1003) represent the diversity of the Belgian food chain. Herein, the concepts of the Hazard Ratio of a sample (HRs) and the Hazard Index of a sample (HIs) were introduced to primarily characterize the hazard related to the co-occurrence of these compounds. The HRs was measured as the ratio of the potential daily exposure to a substance (expressed in mg/Kg of food) to both the 10% reference dose level for chronic effects (expressed in mg/(kg b.w*day)) and the human standard weight (expressed in kg). Whereas the HIs is the sum of the HRs of compounds that affect the same target organ/system, a hazard index greater than one indicates a highly contaminated matrix that could induce a hazard. It is an alarm indicating that additional attention should be given to this matrix. This may involve additional analyses to confirm the high level, to identify sources, etc. It is also an alarm for the risk assessor to be very careful with flagged matrices and to avoid combination with other matrices. The HIs highlight a relatively low concern for all foods analyzed (HI median < 1.0) with a relatively higher suspected hazard for coffee drinks (HI median = 0.068, HI max = 0.57). This preliminary estimation of the potential hazard suggests that coffee beverages should be examined in more detail in a full risk assessment and that coffee consumption should be taken with caution given the levels of furan and alkylfurans reported in this study.

Consumption Habits and Brand Loyalty of Belgian Coffee Consumers.

Coffee is usually subjected to a roasting process which is responsible for the formation of aroma and flavours but also of some undesirable compounds such as furan and alkyl furans. These compounds are known as process contaminants of the roasting process and exhibit some harmful effects. In order to evaluate the exposure to these compounds in coffee, it is necessary to know the levels of contamination as well as consumption habits. The degree of consumers' loyalty to specific coffee brands could also be an important driver affecting the level of exposure. This research aimed to evaluate the levels of consumption and the degree of loyalty to coffee brands available in Belgian markets, as well as the factors affecting the choice and the consumption of coffee products and coffee brands. Data were collected in Belgium through an online survey. The results show that for the 1930 participants, 87% reported daily coffee consumption and 13% never or occasionally consumed coffee. The global median coffee consumption was 3 cups per day, and the median for individual daily consumers only was 4 cups per day. The level of consumption of ground coffee was about twice higher than coffee beans, followed by instant coffee and relatively very low consumption of coffee substitutes. In total, 78% of participants reported brand loyalty but to different degrees. Two coffee brands sold in Belgian regions were listed together by more than 20% of the survey participants. The most frequent criteria for selecting a specific coffee brand were taste and price, followed by tradition and habit. The age of coffee consumers and several sociodemographic characteristics have significant effects on coffee consumption. The type of coffee product, the degree of loyalty, and also the type of packaging should be further considered (when available) in the exposure assessment to furan compounds.

Optimization and Validation of HS-SPME-GC-MS for the Determination of Furan and Alkylfurans in Chocolate-Based Products: Impact of Tempering and Laser Printing.

BACKGROUND: Furan and its alkyl substituted (2-methylfuran, 3-methylfuran, 2,3-dimethylfuran, 2,5-dimethylfuran) are found in a range between ppm to sub-ppb levels in many foodstuffs undergoing heat treatments like coffee, chicory, or even chocolate. OBJECTIVES: Two major objectives are presented. First, we aim at optimizing and validating a HS-SPME-GC-MS method for the quantification of five alkylfurans in chocolate. Second, we focus our study on measuring the quantitative impact of engraving technique on the formation of furan and its derivatives in chocolate, from the raw callets to processed end-products. METHOD: HS-SPME-GC-MS method operating in SIM mode and using isotope dilution technique with deuterated homologue internal standards was used to quantify alkylfurans in chocolate. RESULTS: Good repeatability (RSD% = 0.1-8%, in duplicate) and intermediate precision (RSD% = 1.7-7%, n = 6) were obtained for these five process contaminants at 10, 25, and 50 µg/kg. Trueness was varying between 81 and 109%. LoQ ranged from 0.48 to 2.50 µg/kg. Relative expanded measurement uncertainties ranged from 6 to 30%. Finally, tempering is responsible for a 24% increase in furan contamination, while the laser engraving technique results in an additional 31% increase in furan. A similar trend was also observed for 2-methylfuran and 3-methylfuran, whereas no significant increases were observed for 2,3-dimethylfuran and 2,5-dimethylfuran. CONCLUSIONS AND HIGHLIGHTS: A reliable and sensitive method of HS-SPME-GC-MS was reported for the first time for the analysis of furan and four alkylfurans in chocolate. This paper demonstrated that engraving using laser-based techniques can increase the levels of these compounds by up to 30%.

Headspace Solid Phase Microextraction Coupled to GC/MS for the Analysis of Volatiles of Honeys from Arid and Mediterranean Areas of Algeria.

The volatile composition of seven honey samples collected from various regions of Algeria and feeding on different plants have been determined. The Headspace Solid-Phase MicroExtraction (HS-SPME) coupled with Gas Chromatography-Mass Spectrometry (GC/MS) was used to achieve the purpose. In this work, different parameters of the HS-SPME analytical method were investigated in order to reach maximal sensitivity, and thus to obtain maximum information about the volatile profile of Algerian honey. These parameters include saline medium, HS extraction temperature, and the nature of the fiber used. The results showed a great diversity in the chemical composition, in total 124 compounds from different chemical classes were identified, including compounds found for the first time in honey. The Ascending Hierarchical Classification (AHC) demonstrated the importance of choosing SPME extraction conditions to find volatile compounds, which could be as specific markers of the floral or geographical origin of honey, the latter was optimized in the parameter PDMS-55 °C.

Metabolomic analysis of the green microalga Chlamydomonas reinhardtii cultivated under day/night conditions.

Biomass composition of Chlamydomonas reinhardtii was studied during two consecutive cycles of 12h light/12h dark. As in our experimental conditions the two synchronized divisions were separated by 20h, it was possible to show that accumulation of dry weight, proteins, chlorophyll and fatty acids mainly depends on cell division, whereas starch accumulation depends on a circadian rhythm as reported previously. Our metabolomics analyses also revealed that accumulation of five (Ser, Val, Leu, Ile and Thr) of the nine free amino acids detected displayed rhythmicity, depending on cell division while Glu was 20-50 times more abundant than the other ones probably because this free amino acid serves not only for protein synthesis but also for biosynthesis of nitrogen compounds. In addition, we performed a thermodynamic-motivated theoretical approach known as 'surprisal analysis'. The results from this analysis showed that cells were close to a steady state all along the 48h of the experiment. In addition, calculation of free energy of cellular metabolites showed that the transition point, i.e. the state which immediately precedes cell division, corresponds to the most unstable stage of the cell cycle and that division is identified as the greatest drop in the free energy of metabolites.