Monitoring of cocoa volatiles produced during roasting by selected ion flow tube-mass spectrometry (SIFT-MS)

Selected ion flow tube-mass spectrometry (SIFT-MS) was used to measure the real-time concentrations of cocoa volatiles in the headspace during roasting. Alkalized and unalkalized Don Homero and Arriba cocoa beans were roasted at 120, 150, and 170 °C in a rotary roaster. The concentrations of total alcohols, acids, aldehydes, esters, ketones, and alkylpyrazines increased, peaked, and decreased within the timeframe used for typical roasting. The concentrations of alkylpyrazines and Strecker aldehydes increased as the roasting temperature increased from 120 to 170 °C. For most of the volatile compounds, there was no significant difference between Arriba and Don Homero beans, but Arriba beans showed higher concentrations of 2-heptanone, acetone, ethyl acetate, methylbutanal, phenylacetaldehyde, and trimethylpyrazine. For unalkalized Don Homero beans (pH 5.7), the time to peak concentration decreased from 13.5 to 7.4 min for pyrazines, and from 12.7 to 7.4 min for aldehydes as the roasting temperature increased from 120 to 170 °C. Also, at 150 °C roasting, the time to peak concentration was shortened from 9 to 5.1 min for pyrazines, and from 9.1 to 5 min for aldehydes as the pH increased from 5.7 to 8.7. PRACTICAL APPLICATION: SIFT-MS allows for real-time monitoring of the key volatile compounds contributing to chocolate flavor, with minimal sample preparation, thus can be used to facilitate adjusting the roasting conditions, such as temperature and time, to optimize chocolate flavor during roasting. Real-time monitoring during roasting can also be used to evaluate the flavor quality of different types of beans by comparing the concentrations of key flavor compounds.     

Analysis of factors affecting volatile compound formation in roasted pumpkin seeds with selected ion flow tube-mass spectrometry (SIFT-MS) and sensory analysis

Pumpkin (Cucurbita pepo and maxima) seeds are uniquely flavored and commonly consumed as a healthy roasted snack. The objective was to determine dominant volatiles in raw and roasted pumpkin seeds, and the effect of seed coat, moisture content, fatty acid ratio, total lipids, reducing sugars, and harvest year on volatile formation. Sensory was conducted to evaluate overall liking of seed variety and texture. Seed processing included extraction from the fruit, dehydration, and roasting (150 °C). Oil extraction was done using soxhlet, fatty acid profile using Gas Chromatography Flame Ionization Detector, and reducing sugars using 3,5-dinitrosalicylic acid and UV-spectroscopy. Headspace analysis of seeds was performed by selected ion flow tube-mass spectrometry (SIFT-MS). Volatiles dominating in raw pumpkin seeds were lipid aldehydes, ethyl acetate, 2,3-butandione, and dimethylsulfide. Compounds contributing to roasted aroma include alkylpyrazines and Strecker and lipid aldehydes. Overall, hull-less seeds had higher volatile lipid aldehydes and Strecker aldehydes. Seeds dehydrated to a moisture content of 6.5% before roasting had higher initial and final volatile concentrations than seeds starting at 50% moisture. Higher oil content resulted in higher lipid aldehyde formation during roasting with a moderate correlation between free fatty acid ratio and corresponding lipid aldehyde. Harvest year (2009 compared with 2010) had a significant impact on volatile formation in hull-less seeds, but not as much as variety differences. No significant correlation was found between reducing sugars and volatile formation. Sensory showed that hull-less seeds were liked significantly more than hulled seeds. PRACTICAL APPLICATION: Elucidation of aromatic flavor development during roasting with SIFT-MS provides information on flavor release and offers better control during processing. Knowledge of volatiles in raw and roasted pumpkin seeds and effects of seed coat, moisture content, seed composition, and harvest date will allow for better control over the production/storage/transportation process and a more educated decision during selection of a variety for production of pumpkin seeds in the snack food industry.     

Factors influencing quality variation in cocoa (Theobroma cacao) bean flavour profile — A review

This review examined the factors that influence flavour volatiles of cocoa beans and the volume of work that needs to be done on these factors and their impact on the flavour volatiles of commercial cocoa beans. Cocoa bean flavour is one of the most important quality attributes as flavour is central to acceptability of cocoa beans and cocoa products such as chocolate. The complex composition of cocoa bean flavour depends on bean genotype, postharvest treatments such as pulp pre-conditioning, fermentation and drying, industrial processes such as roasting as well as the type of soil and age of cocoa tree. The bean genotype determines the chemical composition of the bean, specifically the contents of bean storage proteins, polysaccharides, and polyphenols. This determines the quantities and type of precursors formed during fermentation and drying processes leading to flavour formation, hence, influencing both flavour type and intensity. Cocoa bean fermentation and drying result in the breakdown of the storage proteins by endogenous proteases into amino acids and short chain oligopeptides while the polysaccharides are also degraded by invertase to glucose and fructose. The amino acids, oligopeptides, glucose and fructose react with each other during the roasting process to produce the typical cocoa flavour volatiles. Polyphenols are also oxidized by polyphenol oxidase during fermentation and drying which reduce the astringency and bitterness of the beans, thus, enhancing the flavour of cocoa beans. However, the extent to which other factors such as age of the cocoa tree and soil chemical compositions influence the formation of flavour precursors and their relationships with final flavour quality remains unclear. With increasing demand for sustainable production of high quality cocoa beans, greater understanding of factors contributing to the variations in flavour character would have significant commercial implications.     

The Precursors of Chocolate Aroma: Application of Gas Chromatography in Following Formation during Fermentation of Cocoa Beans

SUMMARY— An imporved method of roasting milligram order quantities of chocolate aroma precursors in a flash heater attached to a gas chromatograph has permitted semi-quantitative measurements of the aroma volatiles produced from samples withdrawn at intervals from fermenting heaps of cocoa beans. The observed increase in aroma concentration with increased duration of fermentation, and the time at which maximal concentration occurs, are in line with previous experience and with recent investigations on the production of free amino acids and reducing sugars, these substances being strongly suspected as aroma precursors.     

Precursors of Chocolate Aroma: Studies in the Degradation of Amino Acids during the Roasting of Accra Cocoa Beans

SUMMARY— A preliminary study of the Strecker degradation of amino acids by reducing sugars in cocoa beans has revealed an unexpected temperature effect on the extent of the reaction which might influence the flavor of the product. Model amino acid/sugar systems were studied and the results support the hypothesis that there exists a relationship between the temperature of reaction, the extent of amino acid degradation and the production of flavor volatiles during the roasting of cocoa beans. A factory experiment, in which Accra cocoa beans were roasted at three different temperatures, provided supporting evidence of the influence of temperature on total flavor and on the strength of basic chocolate flavor.     

Acidic Characteristics of Fermented and Dried Cocoa Beans from Different Countries of Origin

Thirty-nine fermented and dried cocoa bean samples from 13 countries were evaluated for pH, titratable acidity and concentrations of volatile and nonvolatile acids. The correlation coefficient between pH and log₁₀ titratable acidity was -0.94. Cocoa beans from Brazil and Far Eastern countries were highly acidic while those from Central American and South American countries were low in acidity. Samples from West African countries were intermediate with titratable acidity values from 0.12 to 0.15 meq NaOH/g sample and pH values from 5.20 to 5.49. Highly acidic beans were characterized by high concentrations of acetic and lactic acids. The high correlation between acetic acid and both pH (r=0.86) and titratable acidity (r = 0.91) indicated that this acid could be primarily responsible for high acidity in cocoa beans.     

Quantification of 3-aminopropionamide in cocoa, coffee and cereal products

Based on recent results confirming 3-aminopropionamide (3-APA) as a very effective precursor of acrylamide in the absence of further “catalysts”, this compound was quantified for the first time in cocoa masses, cocoa beans, coffee and cereal products by LC–MS–MS after derivatisation with dansyl chloride. Cocoa masses contained >3000 μg/kg of 3-APA, but varied significantly in its concentration. For the quantification of acrylamide (AA) in cocoa and coffee, an improved isolation procedure using charcoal was developed. In various samples of unroasted and roasted cocoa beans, the concentrations of AA were by a factor of >5 lower than those of 3-APA, but the concentrations of 3-APA and AA were more closely correlated as compared to the concentrations of AA and Asparagine. Experiments on authentic cocoa beans from Ghana and Sulawesi indicated that the thermal generation of 3-APA during roasting was much more pronounced as compared to its biochemical formation. By administering fermented cocoa beans with [¹³C₄ ¹⁵N₂]-asparagine before roasting, 3-APA was confirmed as transient intermediate in AA formation during cocoa roasting. Among the cereal products analysed, in particular popcorn contained quite high amounts of 3-APA, which were also well correlated with the AA concentration. Contrary, in coffee products, 3-APA was always lower than AA.     

Influence of water on the generation of Strecker aldehydes from dry processed foods

Completeness of extraction, losses during isolation and, in particular, the formation of new constituents are challenges during the enrichment of volatiles for GC analysis. Especially the isolation of volatiles by simultaneous steam distillation/extraction has long been known to generate artifacts due to the hot water treatment. However, even a simple treatment of dry foods with cold water may already lead to the release of odour-active volatiles. After treatment of chocolate or cocoa beans with water, the concentrations of the four Strecker aldehydes 2- and 3-methylbutanal, 3-(methylthio)propanal and phenylacetaldehyde were increased by factors between 10 and 100. Also in other dry processed foods, such as malt or crackers, the concentrations of the Strecker aldehydes were substantially increased upon water addition. Although a physical release of the aldehydes weakly bound to, e.g. proteins or starch is possible, in a further experiment, it could be shown that a yet unknown precursor of 3-(methylthio)propanal and phenylacetaldehyde could be isolated by solvent extraction from caramalt and Munich malt. As a consequence, the presence or absence of water during the work-up procedure might either lead to an over- or underestimation of the relevance of the respective aroma compounds, which might also effect aroma formation and perception during the process of eating.     

Extraction and determination of methylpyrazines in cocoa beans using coupled steam distillation-microdistillator

The formation of methylpyrazines was determined in fermented cocoa beans (Ivory Coast), in laboratory and industrially roasted samples. The determination of these methylpyrazines was studied by coupled steam distillation-microdistillation as the extraction method and gas chromatography using capillary column and a thermionic detector. The monomethyl-; 2,3-dimethyl-; 2,5-dimethyl-; 2,6-dimethyl-; trimethyl- and the tetramethylpyrazine were detected in non-roasted cocoa beans. Their concentration increased rapidly in laboratory roasted cocoa beans and industrial samples, only the tetramethylpyrazine showed a maximum peak of concentration. The principal compound was the tetramethylpyrazine in fermented and roasted cocoa beans. The determination of the different methylpyrazines in cocoa beans would permit both the evaluation of cocoa mass quality and the control of the cocoa roasting process.     

Antioxidant Properties of Cocoa Beans (Theobroma cacao L.): Influence of Cultivar and Roasting Conditions

Effects of various roasting conditions on antioxidant properties of five Theobroma cacao L. varieties were investigated. The cocoa beans were roasted at four different temperatures (110–150°C) and three different air humidities (0.3–5.0%). The raw cocoa beans were characterized by high antioxidant activities. The antioxidant properties of the roasted cocoa beans varied markedly among the analyzed cultivars and geographical regions and were affected by roasting conditions. Generally, cocoa beans of the cv. Forastero from Brazil exhibited higher total phenolic content, free radical scavenging activity, and metal chelating ability than samples of the other analyzed cocoa varieties. Roasting at 110°C caused negligible changes in total phenolics content and antioxidant activity of cocoa beans, while almost all samples tended to have lower antioxidant potential when roasting temperature increased. The air humidity used in roasting did not affect the total phenolics content and antioxidant activity for lowest roasting temperature (110°C). Moreover, the obtained results revealed that thermal processing at the higher temperatures and elevated air humidity resulted in the higher antioxidant capacities. It was also found that the ferrous ion chelating activity of cocoa beans increased with the roasting temperature (in the range from 110 to 150°C), with the exception of cv. Trinitario from Papua New Guinea. The data showed that roasting at lower temperatures with humid air are more favorable in terms of preserving the bioactivity of roasted cocoa beans.     

Aroma precursors and methylpyrazines in underfermented cocoa beans induced by endogenous carboxypeptidase

Cocoa-specific aroma precursors and methylpyrazines in underfermented cocoa beans obtained from fermentation induced by indigenous carboxypeptidase have been investigated. Fermentation conditions and cocoa bean components were analyzed during 0 to 3 d of fermentation. Underfermented cocoa beans were characterized as having hydrophilic peptides and free hydrophobic amino acids much higher than unfermented ones. These 2 key components of cocoa aroma precursors may be produced from the breakdown of proteins and polypeptides by endogenous carboxypeptidase during the fermentation process. The enzyme was activated during fermentation. Polypeptides of 47, 31, and 19 kDa were observed in the samples throughout the 3-d fermentation period; however, only the first 2 polypeptides were remarkably reduced during fermentation. Since the 1st day of fermentation, underfermented cocoa beans contained methylpyrazines, a dominant group of cocoa-specific aroma. This might be due to microbial activities during fermentation, observed through a decrease of pH value and an increase of temperature of cocoa beans. The concentration of tetramethylpyrazines was significantly increased during the 3 d of fermentation. This may increase the cocoa-specific flavor to the beans.     

Effect of polyphenol and pH on cocoa Maillard-related flavour precursors in a lipidic model system

Polyphenol and pH influence the flavour quality of cocoa beans during roasting. Amino acids and reducing sugars are flavour precursors in cocoa beans, which develop into cocoa-specific aroma through Maillard reactions during roasting. A central composite design was applied to determine the combined effect of polyphenol and pH on the flavour precursors during cocoa roasting at 120 °C for 45 min using a lipidic model system. Polyphenol was added at 40, 80 and 120 g kg⁻¹ and pH was adjusted to 4.5, 6 and 7.5. The response surface methodology revealed that a lower concentration of amino acids and reducing sugars was obtained at higher polyphenol concentration (120 g kg⁻¹) and lower pH value (4.5). Based on the constraints set, the best polyphenol concentration of 43–58 g kg⁻¹ and pH of 7.0–7.5 was found to be optimum for the formation of flavour precursors in this lipidic model study.     

Application of various methods for determination of the color of cocoa beans roasted under variable process parameters

Cocoa beans of Forastero variety from Togo were subjected to roasting under either constant or variable process parameters. The variable process parameters were roasting air flow rate, temperature and relative humidity. The color of roasted cocoa beans was determined by pigment extraction under various conditions followed by either their spectrophotometric assays or CIE L*a*b measurements. Also the Maillard compounds index and total polyphenols content correlated with progress of the browning of beans were determined. It was found that an increase in the roasting air relative humidity stimulated formation of brown pigments, while elevated temperature caused worsening of color parameters of roasted cocoa beans. The most suitable method of color characterization of roasted cocoa beans was found to be pigments extraction combined with either separation of their fractions or CIE L*a*b measurements. These assays revealed that cocoa beans roasted under variable roasting air flow rate were characterized by improved color parameters. The relatively simple and inexpensive CIE L*a*b measurements ensured fast analysis of color parameters, while total polyphenols in roasted cocoa beans were quickly estimated by using F–C reagent. Furthermore, quantification of melanoid pigments in roasted cocoa beans can be based on determination of the index of nonenzymatic browning products content, which is relatively simple and inexpensive.     

The Effect of pH and Temperature on Cabbage Volatiles During Storage

During storage of shredded cabbage, characteristic sulfurous volatile compounds are formed affecting cabbage aroma both negatively and positively. Selected ion flow tube‐mass spectrometry (SIFT‐MS) was used to measure the concentration of cabbage volatiles during storage. The volatile levels of cabbage samples were measured at pH 3.3 to 7.4 at 4 °C for 14 d, and pH 3.3 at 25 °C for 5 d in order to determine the effect of pH and temperature. Aroma intensity, best aroma, freshness, and off odor were evaluated in a sensory test of the samples at 4 °C. The desirable volatile allyl isothiocyanate was lower in high pH samples (pH 7.4 and 6.4), whereas higher concentrations were detected in low pH samples (pH 3.3 and 4.6). Lipoxygenase volatiles, which produce a fresh green and leafy aroma in cabbage, were generated in very low amounts at any pH value. High pH samples generated significantly higher concentrations of off odors such as dimethyl sulfide, dimethyl disulfide, dimethyl trisulfide, and methanethiol. Sensory tests showed that higher pH samples had significantly stronger off odor and lower desirable cabbage aroma than lower pH samples. Thus, sensory results matched the volatile results in that samples at higher pH levels formed the highest amount of undesirable volatiles and the least amount of desirable volatiles. Storage at 25 °C produced similar concentrations of allyl isothiocyanate, but significantly higher levels of off odors, than at 4 °C. Shredded cabbage products should be stored in low pH dressings to minimize formation of off odors and maximize formation of characteristic, desirable cabbage odor.     

Fluidized bed roasting of cocoa nibs speeds up processing and favors the formation of pyrazines

Roasting is an important step in cocoa processing causing water loss and generating volatile compounds responsible for chocolate aroma like nitrogen-heterocycles. In this study, the comparison of two techniques, oven roasting, and fluidized bed roasting, in terms of effective water diffusivity (De) and activation energies of formation (Ea) of nitrogen-heterocycles was achieved with cocoa nibs. Fluidized bed roasting, recognized for its energy efficiency and low-footprint synthesis, was 16 times faster than oven roasting. The order of magnitude of De in fluidized-bed-roasted nibs was −8, while it was −9 in the oven-roasted nibs. Moreover, the a_w was 50% higher in fluidized-bed-roasted nibs than in the oven-roasted ones. The Ea of nitrogen-heterocycles ranged roughly between 40 and 80 kJ/mol. Those values were lower under fluidized bed roasting than under oven roasting. The more effortless water mobility within fluidized-bed-roasted cocoa demanded lower Ea, and favored the formation of nitrogen-heterocyclics.Industrial relevanceThis study can inspire cocoa manufacturers and equipment designers to pursue the formation of nitrogen-heterocycles during the roasting process of cocoa. It can be done either by adapting and scaling the current fluidized bed coffee roasters to cocoa beans or nibs; or by exploring other alternatives capable of leading enough water diffusivity and water activity in the cocoa nibs, as reported here. These physicochemical conditions undoubtedly boosted the formation of volatile compounds responsible for chocolate aroma, e.g., the pyrazines, without carrying the formation of typical-burn volatile compounds. This natural way of favoring the generation of pyrazines in cocoa nibs could contribute to clean labels by reducing or avoiding the subsequent use of flavorings. The implementation of efficient heat-transfer techniques during roasting, e.g., fluidized bed roasting, could reduce the processing cost and improve sustainability. Studies in the matter of sensory profile, and energy consumption/conversion are called for future research.     

Tocopherols in cocoa butter obtained from cocoa bean roasted in different forms and under various process parameters

Obtaining good quality chocolate strongly depends on raw material, i.e. cocoa beans. The processing of cocoa beans consists of some important steps, including fermentation, drying fermented beans and roasting. Traditionally roasting is performed on whole beans but currently, roasting crushed cocoa beans or cocoa liquor becomes more and more popular. Many biologically active compounds may be found in the cocoa beans, including tocopherols. This work investigates the influence of the constant or variable roasting process parameters (temperature, velocity and relative humidity of roasting air) on the tocopherol concentration in cocoa butter (CB) extracted from cocoa beans originating from Togo and roasted in two different forms, namely as whole and crushed beans. Whole cocoa beans were roasted to a 2% moisture content and crushed cocoa beans were firstly partially dried which further enables easier dehusking, then ground, dehusked and roasted until their humidity decreased to around 2%. Roasting resulted in lowering the content of individual tocopherols in analyzed material. The degree of degradation of tocopherols in CBs was different, depending on the form of roasted beans from which these CBs were extracted. Higher concentrations were determined in CBs extracted from beans roasted in the form of crushed samples comparing to CBs obtained from beans roasted as a whole. The study investigates different roasting parameters of crushed beans, none of which drastically lowered the concentration of tocopherols in extracted CBs. Their concentration in CBs extracted from whole beans was, on the other hand, influenced by roasting air parameters. In case of whole beans roasted under constant parameters, application of 150 °C proved to be more favorable than roasting at 135 °C, as well as application of “dry” air and 1 m/s roasting air velocity. Discussing the variable roasting process parameters, in case of applied roasting temperature it is more favorable to change it from 150 °C to 135 °C, than the other way round. Changing the relative humidity of roasting air from 5 to 0.3%, lower degradation of tocopherols in CB occurs when the process is conducted at 150 °C. It may be further concluded that a direct dependence between the velocity of roasting air varied during the process and the concentration of tocopherols in extracted CB may not be indicated. In conclusion, it is stated that the temperature of the air applied during the roasting process has the decisive influence on the tocopherol content in CBs extracted from cocoa beans subjected to the process.     

Acidification,proteolysis and flavour potential in fermenting cocoa beans

Cocoa fermentations in Ghana and Trinidad as well as anaerobic fermentation-like incubations of fresh cocoa beans in Germany were carried out under controlled conditions. Samples of beans were taken during the course of these treatments and determinations were made as to acidification (pH, acetic acid content), proteolysis (free α-amino nitrogen, peptide nitrogen and SDS electrophoresis of the protein peptides) and flavour potential (gas chromatography of the highly volatile compounds, in particular isopentanal and organoleptic analysis after thin layer roasting). A positive correlation between acidification, proteolysis and the development of flavour potential during anaerobic fermentation can be demonstrated in principle. However, the flavour potential is increased if the temperature rise is comparatively slow in both normal fermentation and laboratory incubation. Strong acidification and high accumulation of amino acids and peptides were not essential for a good flavour potential. The isopentanal content proved to be a useful indicator of the progress of normal fermentation in the tropics. These findings can be interpreted on the basis of earlier results about germination-like processes in the protein vacuoles, pre- and post-mortem subcellular structures and the special characteristics of acetic acid diffusion. Conclusions which are relevant to the practice of cocoa fermentation are discussed in more detail.     

Physicochemical properties,antioxidant content,volatile organic compounds and sensory profile of cocoa beans fermented with yeast starter cultures

This study determined the influence of selected yeast starters on the antioxidant content, volatile organic compounds and sensory qualities of fermented cocoa beans. Cocoa beans fermented with Hanseniaspora thailandica (MH979675), Pichia kudriazevii (MH979681), or a mixture of both species in fermentation (20 kg) were highly reproducible based on the physicochemical parameters (temperature, pH of nibs, fermentation index and cut test). The usage of H. thailandica improved the total polyphenols content of cocoa beans with fermentation index around 1.24 and 1.33. The correlation analyses suggested that phenolics and flavonoids compounds may not be the main constituents that led to the antioxidant activities of the fermented samples. Principal Component Analysis showed distinct differences in VOC profiles between spontaneous and fermentation using yeast. Sweet and spicy notes were only found in sample fermented with yeast. The inoculation of yeast in fermentation influenced the sensorial and antioxidant properties of cocoa beans.     

Evaluation of sensory attributes of coffee brews from robusta coffee roasted under different conditions

Robusta coffee beans with a different initial moisture of 5, 7.5 and 10% were convectively roasted at 230 °C, microwaved at 700 W, and roasted by the coupled convective-microwave method. Sensory attributes of brews prepared from these coffee samples were evaluated. Final temperature of microwaved coffee beans was lower than that of the beans processed by the two other methods, which resulted in a higher content of volatile aroma compounds and a lesser degree of charring of their surface. Lower initial humidity of coffee beans shortened the time of roasting. However, the aroma developed upon roasting of the moistest beans was the most intense and pleasant. Modification of roasting conditions increased shifting of the overall acceptability of coffee infusions by 2 points in a 10-point hedonic scale, which implies that, if roasting conditions are adequate to the type of coffee, its sensory characteristics can be improved. Thus, optimization of roasting parameters can increase the share of robusta in well-accepted commercial coffee blends, a convenient fact because of the significant difference in price between the latter and arabica coffee.     

Analysis and stereodifferentiation of linalool in Theobroma cacao and cocoa products using enantioselective multidimensional gas chromatography

Contents and enantiomeric distributions of linalool (3,7-dimethyl-1,6-octadien-3-ol) were investigated in raw and roasted cocoa beans (seeds of Theobroma cacao) of defined origin as well as in commercial products, such as cocoa powders or chocolates. The stereodifferentiation of linalool was achieved by enantioselective multidimensional gas chromatography using heptakis (2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin as chiral stationary phase. Simultaneous steam distillation–extraction at pH 7 allowed sample preparation without racemization of linalool. Cocoa beans contain linalool primarily as (S)-enantiomer. Model experiments and analyses of commercial products such as cocoa powders and chocolates revealed that technological procedures employed in the manufacturing of cocoa products do not result in significant changes of the original enantiomeric distribution of linalool.