Analysis of acrylamide in green tea by gas chromatography-mass spectrometry

Optimization of the solid-phase extraction cleanup procedure enabled the GC-MS analysis of acrylamide in tea samples without the interference of bromination by tea catechins. Although polyvinylpolypyrrolidone (PVPP) is available for removing tea catechins from tea extract, the peaks derived from PVPP had the same retention time as brominated acrylamide in mass chromatograms obtained by GC-MS. A considerable amount of acrylamide was formed at roasting temperatures of > or =120 degrees C; the highest acrylamide level was observed when tea samples were roasted at 180 degrees C for 10 min. Higher temperatures and longer processing times caused a decrease in the acrylamide content. Furthermore, an analysis of 82 tea samples showed that rather than the reducing sugar content, the asparagine content in tea leaves was a significant factor related to acrylamide formation in roasted products. The acrylamide level in roasted tea products was controlled by asparagine in the presence of reducing sugars.     

Studies on the key odorants formed by roasting of wild mango seeds (Irvingia gabonensis)

Application of the aroma extract dilution analysis on a concentrate of volatiles obtained by solvent extraction and high vacuum distillation from roasted seeds (180 degrees C; 15 min) of wild mango (Irvingia gabonensis) revealed 32 odor-active compounds with flavor dilution (FD) factors ranging from 8 (low odor activity) to 2048 (high odor activity). The identification experiments based on the use of reference odorants revealed methional (cooked potato-like) followed by 2-acetyl-1-pyrroline (roasty, popcorn-like), butan-2,3-dione, pentan-2,3-dione, 2-ethyl-3,5-dimethylpyrazine, and 2,3-diethyl-5-methylpyrazine as the key aroma compounds among the 27 odorants identified. All odorants are reported for the first time as components of roasted wild mango seeds.     

Effects of roasting on pyrazine contents and oxidative stability of red pepper seed oil prior to its extraction

Red pepper seeds were roasted with constant stirring for 6, 9, 10, and 12 min at 210 degrees C, and oils were extracted from the roasted red pepper seeds using an expeller. The iodine values and fatty acid compositions of red pepper seed oils did not change with roasting time. The fatty acid composition of the oil obtained from the red pepper seeds roasted for 6 min was 0.24% myristic acid, 13. 42% palmitic acid, 0.33% palmitoleic acid, 2.07% stearic acid, 10. 18% oleic acid, 73.89% linoleic acid, and 0.37% linolenic acid, showing a fatty acid composition similar to that of high-linoleate safflower oil. Thirteen alkylpyrazines were identified in the roasted red pepper seed oils: 2-methylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2-ethylpyrazine, 2-ethyl-6-methylpyrazine, 2-ethyl-5-methylpyrazine, trimethylpyrazine, 2,6-diethylpyrazine, 2-ethyl-3,5-dimethylpyrazine, tetramethylpyrazine, 2, 3-diethyl-5-methylpyrazine, 2-isobutyl-3-methylpyrazine, and 3, 5-diethyl 2-methylpyrazine. The pyrazine content increased markedly as the roasting time increased, showing 2.63, 5.01, 8.48, and 13.10 mg of total pyrazine/100 g of oils from the red pepper seeds roasted for 6, 8, 10, and 12 min, respectively, at 210 degrees C. 2, 5-Dimethylpyrazine in the roasted red pepper seed oil seemed to be the component most responsible for the pleasant nutty aroma of the oils. The oxidative stabilities of oils increased greatly as the roasting time increased.     

Effect of roasting conditions on the polycyclic aromatic hydrocarbon content in ground Arabica coffee and coffee brew

Roasting is a critical process in coffee production as it enables the development of flavor and aroma. At the same time, roasting may lead to the formation of nondesirable compounds, such as polycyclic aromatic hydrocarbons (PAHs). In this study, Arabica green coffee beans from Cuba were roasted under controlled conditions to monitor PAH formation during the roasting process. Roasting was performed in a pilot spouted bed roaster, with the inlet air temperature varying from 180 to 260 degrees C, using both dark (20 min) and light (5 min) roasting conditions. Several PAHs were determined in both roasted coffee samples and green coffee samples. Also, coffee brews, obtained using an electric coffee maker, were analyzed for final estimation of PAH transfer coefficients to the infusion. Formation of phenanthrene, anthracene, and benzo[a]anthracene in coffee beans was observed at temperatures above 220 degrees C, whereas formation of pyrene and chrysene required 260 degrees C. Low levels of benzo[g,h,i]perylene were also noted for dark roasting under 260 degrees C, with simultaneous partial degradation of three-cycle PAHs, suggesting that transformation of low molecular PAHs to high molecular PAHs occurs as the roasting degree is increased. The PAH transfer to the infusion was quite moderate (<35%), with a slightly lower extractability for dark-roasted coffee as compared to light-roasted coffee.     

Identification of potent odorants formed during the preparation of extruded potato snacks

Extrusion cooking processing followed by air-drying has been applied to obtain low-fat potato snacks. Optimal parameters were developed for a dough recipe. Dough contained apart from potato granules 7% of canola oil, 1% of salt, 1% of baking powder, 5% of maltodextrin, and 15% of wheat flour. After the extrusion process, snacks were dried at 85 degrees C for 15 min followed by 130 degrees C for 45 min. The potent odorants of extruded potato snacks were identified using aroma extract dilution analysis and gas chromatography-olfactometry. Among the characteristic compounds, methional with boiled potato flavor, benzenemethanethiol with pepper-seed flavor, 2-acetyl-1-pyrroline with popcorn flavor, benzacetaldehyde with strong flowery flavor, butanal with rancid flavor, and 2-acetylpyrazine with roasty flavor were considered to be the main contributors to the aroma of extruded potato snacks. Several compounds were concluded to be developed during extrusion cooking, such as ethanol, 3-methylbutanal, (Z)-1,5-octadien-3-one with geranium flavor, and unknown ones with the flavor of boiled potato, cumin, candy, or parsley root. Compounds such as methanethiol, 2,3-pentanedione, limonene, 2-acetylpyrazine, 2-ethyl-3,5-dimethylpyrazine, 4-hydroxy-2,5-dimethyl-3(2H)-furanone, 3-hydroxy-4,5-dimethyl-2(5H)-furanone, 2-methyl-3,5-diethylpyrazine, 5-methyl-2,3-diethylpyrazine, and (E)-beta-damascenone were probably developed during air-drying of the potato extrudate.     

Kinetic study of the thermal stability of tea catechins in aqueous systems using a microwave reactor

Tea catechins may undergo complex reactions such as oxidation, polymerization, and epimerization during thermal processing. The thermal stability of tea catechins in an aqueous system, including degradation and epimerization reactions, was investigated using a microwave reactor. Reactions were controlled at high temperatures ranging from 100 to 165 degrees C with various durations up to 120 min. Three sources of tea catechins containing different levels of (-)-epigallocatechin gallate (EGCG), (-)-epicatechin gallate (ECG), and their epimers were studied. Kinetic models for the degradation/epimerization of tea catechins were developed and validated by the reactions at 145 degrees C. It was shown that the epimerization and degradation of tea catechins followed first-order reactions and the rate constants of reaction kinetics followed the Arrhenius equation. Values of the activation energy (E(a)) for the epimerization of EGCG from epi- to nonepi-structures, the epimerization of GCG from nonepi- to epi-structures, and the total degradation of EGCG and its epimer GCG were 117.6, 84.2, and 42.8 kJ/mol, respectively. For ECG and CG, the E(a) values were 119.3, 96.2, and 41.6 kJ/mol, respectively. The mathematical models may provide a useful prediction for the loss of tea catechins during any thermal processing.     

Acrylamide formation in almonds (Prunus dulcis): influences of roasting time and temperature, precursors, varietal selection, and storage

Acrylamide is a probable human carcinogen that is found in many roasted and baked foods. This paper describes two sensitive and reliable LC-(ESI)MS/MS methods for the analysis of (1) acrylamide and (2) common acrylamide precursors (i.e., glucose, fructose, asparagine, and glutamine) in raw and roasted almonds. These methods were used to evaluate the impact of roasting temperatures (between 129 and 182 °C) and times on acrylamide formation. Controlling the roasting temperature at or below 146 °C resulted in acrylamide levels below 200 ppb at all roasting times evaluated. Six varieties of almonds collected in various regions of California over two harvest years and roasted at 138 °C for 22 min had acrylamide levels ranging from 117 ± 5 μg/kg (Sonora) to 221 ± 95 μg/kg (Butte) with an average of 187 ± 71 μg/kg. A weak correlation between asparagine content in raw almonds and acrylamide formation was observed (R(2) = 0.6787). No statistical relationship was found between acrylamide formation and almond variety, orchard region, or harvest year. Stability studies on roasted almonds indicated that acrylamide levels decreased by 12.9-68.5% (average of 50.2%) after 3 days of storage at 60 °C. Short-term elevated temperature storage may be another approach for mitigating acrylamide levels in roasted almonds.     

Effects of heat processing and storage on flavanols and sensory qualities of green tea beverage

This research was conducted to understand the effects of heat processing and storage on flavanols and sensory qualities of green tea extract. Fresh tea leaves were processed into steamed and roasted green teas by commercial methods and then extracted with hot water (80 degrees C) at 1:160 ratio (tea leaves/water by weight). Green tea extracts were heat processed at 121 degrees C for 1 min and then stored at 50 degrees C to accelerate chemical reactions. Changes in flavanol composition and sensory qualities of green tea extracts during processing and storage were measured. Eight major flavanols (catechin, epicatechin, gallocatechin, epigallocatechin, epicatechin gallate, catechin gallate, epigallocatechin gallate, and gallocatechin gallate) were identified in the processed tea extract. Among them, epigallocatechin gallate and epigallocatechin appeared to play the key role in the changes of sensory qualities of processed green tea beverage. The steamed tea leaves produced a more desirable quality of processed green tea beverage than the roasted ones.     

Influence of manufacturing conditions and crop season on the formation of 4-mercapto-4-methyl-2-pentanone in Japanese green tea (sen-cha)

4-Mercapto-4-methyl-2-pentanone is one of the most strongly contributing odorants in the volatile fraction of a Japanese green tea (sen-cha) infusion, and on the basis of the results of an aroma extract dilution analysis, the contribution of this compound to the flavor of the sen-cha infusion varied according to the degree of heating of the tea leaves during the roasting process. The concentration of this odorant in the sen-cha infusion, as with other roasty odorants, increased with the increasing roasting temperature. However, the slope of the increase curve differed with the odor compound, and even if roasting was done at a low temperature, at which the other roasty odorants hardly increased, 4-mercapto-4-methyl-2-pentanone still increased and reached a maximum at 112 degrees C. On the other hand, the amount of 4-mercapto-4-methyl-2-pentanone in sen-cha was a maximum in the first crop, then decreasing in the order of the second and third crops. These results suggested that the amount of 4-mercapto-4-methyl-2-pentanone was closely involved with the quality of sen-cha and that the concentration was dependent on the roasting conditions for the green tea leaves, which might be accompanied by an enzymatic reaction.     

Effect of citric acid and glycine addition on acrylamide and flavor in a potato model system

Acrylamide levels in cooked/processed food can be reduced by treatment with citric acid or glycine. In a potato model system cooked at 180 degrees C for 10-60 min, these treatments affected the volatile profiles. Strecker aldehydes and alkylpyrazines, key flavor compounds of cooked potato, were monitored. Citric acid limited the generation of volatiles, particularly the alkylpyrazines. Glycine increased the total volatile yield by promoting the formation of certain alkylpyrazines, namely, 2,3-dimethylpyrazine, trimethylpyrazine, 2-ethyl-3,5-dimethylpyrazine, tetramethylpyrazine, and 2,5-diethyl-3-methylpyrazine. However, the formation of other pyrazines and Strecker aldehydes was suppressed. It was proposed that the opposing effects of these treatments on total volatile yield may be used to best advantage by employing a combined treatment at lower concentrations, especially as both treatments were found to have an additive effect in reducing acrylamide. This would minimize the impact on flavor but still achieve the desired reduction in acrylamide levels.     

Detection of gamma-irradiated sesame seeds before and after roasting by analyzing photostimulated luminescence, thermoluminescence, and electron spin resonance

Sesame seeds were irradiated using a (60)Co irradiator (0-4 kGy) and then roasted (220 degrees C for 10 min). To identify the irradiation treatment, physical detection methods like photostimulated luminescence (PSL), thermoluminescence (TL), and electron spin resonance (ESR) have been investigated before and after roasting. The photon counts of the irradiated samples (nonroasted and roasted) were higher than those of nonirradiated ones, making it possible to distinguish the two samples. The threshold values of nonroasted and roasted samples increased linearly with the irradiation dose, respectively. The TL for the nonirradiated nonroasted and roasted samples presented a lower peak at about 300 degrees C, but irradiated samples showed a higher peak at around 150 degrees C. The areas of TL glow curves were 15 times higher in nonroasted as compared with roasted samples. TL ratio [integrated area of TL 1 (the first glow)/TL 2 (the second glow)] obtained by the reirradiation step was 0 in nonirradiated samples and more than 0.15 in irradiated samples. The radiation-induced ESR signals originating from cellulose were determined in irradiated samples before and after roasting.     

Identification of fruity/fermented odorants in high-temperature-cured roasted peanuts

Gas chromatography/olfactometry on a concentrate of volatiles obtained by solvent-assisted flavor evaporation (SAFE) from roasted peanuts containing a fruity/fermented off-note was used to identify the odorants responsible for the flavor defect. Freshly dug peanuts were divided into two classes, mature and immature, using pod mesocarp color, and subjected to normal (27 degrees C) and high (40 degrees C) temperature curing. Sensory evaluation of the roasted peanuts found that immature peanuts cured at high temperature contained the fruity/fermented off-note. Mature peanuts cured at high temperature and both immature and mature peanuts cured at low temperature were free of the off-note. Peanuts with the off-flavor were found to contain fruit-like esters (ethyl 2-methylpropanoate, ethyl 2-methylbutanoate, and ethyl 3-methylbutanoate) along with increased levels of short chain organic acids (butanoic, 3-methylbutanoic, and hexanoic). These findings were confirmed by sensory evaluation of models, where the addition of these compounds produced the fruity/fermented flavor defect in a control peanut paste. This is the first time that the odorants responsible for this off-note in roasted peanuts have been identified.     

Antioxidant properties of water extracts from Cassia tora L. in relation to the degree of roasting

The antioxidant properties of water extracts from Cassia tora L. (WECT) prepared under different degrees of roasting were investigated. The water extracts of unroasted C. tora L. (WEUCT) showed 94% inhibition of peroxidation of linoleic acid at a dose of 0.2 mg/mL, which was higher than that of alpha-tocopherol (82%). Water extracts prepared from C. tora L. roasted at 175 degrees C for 5 min and at 200 degrees C for 5 min exhibited 83% and 82%, respectively, inhibition of linoleic acid peroxidation. This result indicated that the antioxidant activities of WECT decreased with longer roasting time or higher roasting temperature. The IC(50) of WEUCT in liposome oxidation induced by the Fenton reaction was 0.41 mg/mL, which was higher than that of alpha-tocopherol (IC(50) = 0.55 mg/mL). WEUCT also exhibited good antioxidant activity in enzymatic and nonenzymatic microsome oxidative systems. The water extracts of roasted C. tora L. increased in the degree of browning and produced chemiluminescence when compared with the unroasted sample. However, the total polyphenolic compounds of WECT decreased after the roasting process finished. In conclusion, the decrease in the antioxidant activity of water extracts from roasted C. tora L. might have been due to the degradation of Maillard reaction products and the decrease of polyphenolic compounds.     

Effects of carnosine on volatile generation from Maillard reaction of ribose and cysteine

Carnosine occurs naturally in meat and meat products in significant quantity, and it possesses strong antioxidant activity that inhibits lipid oxidation and enhances shelf life. In this study, the effects of carnosine on thermal flavor generation were investigated using the model system of cysteine and ribose, which was heated to the roasting temperature of 180 degrees C for 2 h at pH 5 and pH 8.5. The results indicated that carnosine affected volatile formation in a complex manner. Volatiles identified from the liquid phase of the reaction systems of ribose and cysteine showed that the sulfur-containing compounds such as thiophenes, thiazoles, and polysulfides were the most abundant compounds. The addition of carnosine into the reaction mixtures in general caused a reduction in contents of thiophenes and some important meaty flavor compounds such as 2-methyl-3-furanthiol, 2-furfurylthiol, and their associated dimers. On the other hand, it facilitated the generation of several important nitrogen-containing volatiles such as pyrazine, methylpyrazine, 2,6-dimethylpyrazine, and other alkyl pyrazines and thiazoles, which are known to elicit roasty and nutty flavor notes. The results suggested that carnosine acts as a nitrogenous source to facilitate the formation of nitrogen-containing compounds, possibly by degradation to form ammonia.     

Identification of potent odorants in different green tea varieties using flavor dilution technique

Two kinds of pan-fired green teas (Japanese Kamairi-cha and Chinese Longing tea) were compared with the common Japanese green tea (Sen-cha). Application of the aroma extract dilution analysis (AEDA) using the volatile fraction of the Sen-cha, Kamairi-cha and Longing tea infusions revealed 32, 51, and 52 odor-active peaks with flavor dilution factors between 16 and 1024, respectively. (Z)-1,5-Octadien-3-one (metallic, geranium-like), 4-mercapto-4-methyl-2-pentanone (meaty, black currant-like), methional (potato-like), (E,Z)-2,6-nonadienal (cucumber-like), and 3-methylnonane-2,4-dione (green, fruity, hay-like) showed high flavor dilution factors in all varieties. In addition, 2-acetyl-1-pyrroline (popcorn-like), 2-ethyl-3,5-dimethylpyrazine (nutty), 2,3-diethyl-5-methylpyrazine (nutty), and 2-acetyl-2-thiazoline (popcorn-like) belonged to the most potent odorants only in the pan-fired green teas. Among these odorants, 2-acetyl-1-pyrroline and 2-acetyl-2-thiazoline were identified for the first time among the tea volatiles.     

Change in the flavor of black tea drink during heat processing.

Heat processing during canning is responsible for the change in flavor of black tea infusion. The quantitative change in the volatile components of the black tea infusion during heat processing is not sufficient for explaining the sensory evaluation. In this study, application of aroma extract dilution analysis using the volatile fraction before and after black tea (Darjeeling) samples were heat processed resulted in the detection of 10 odor-active peaks for which flavor dilution (FD) factors changed. Seven potent odorants were identified from these peaks by gas chromatography-mass spectrometry. Among these components, 3-methylbutanal (stimulus), methional (potato-like), beta-damascenone (sweet), dimethyl trisulfide (putrid), and 2-methoxy-4-vinylphenol (clove-like) showed the highest FD factors after heat processing of the black tea sample. Therefore, these odorants were the most important components involved in changing the black tea odor during heat processing. In addition, the precursor of beta-damascenone in black tea infusion was investigated, and 3-hydroxy-7,8-didehydro-beta-ionol was determined to be one of the beta-damascenone-generating compounds for the first time.     

Changes in volatile flavor components of guava juice with high-pressure treatment and heat processing and during storage.

The changes in volatile flavor components of guava juice during pressure processing (25 degrees C, 600 MPa, 15 min), heat processing (95 degrees C, 5 min), and storage at 4 and 25 degrees C were evaluated by purge and trap/gas chromatography/mass spectrometry. Esters were the major volatile fraction in guava juice, and alcohols were the second. Pressure processing could maintain the original flavor distribution of the juice. Heat processing (95 degrees C, 5 min) caused decreases in the majority of flavor components in the juice when compared with freshly extracted juice. High-pressure treatment at 600 MPa for 15 min can effectively sterilize microbes but partially inactivate enzymes of guava juice; therefore, volatile components in pressure-treated juice gradually changed during storage periods. Pressure-treated guava juice showed increases in methanol, ethanol, and 2-ethylfuran with decreases in the other components during storage period. Nevertheless, the volatile distribution of 600 MPa treated guava juice was similar to that of freshly extracted juice when stored at 4 degrees C for 30 days.     

Factors affecting the formation of alkylpyrazines during roasting treatment in natural and alkalinized cocoa powder

The cocoa roasting process at different temperatures (at 125 and 135 degrees C for 3 min, plus 44 and 52 min, respectively, heating-up times) was evaluated by measuring the initial and final free amino acids distribution, flavor index, formol number, browning measurement, and alkylpyrazines content in 15 cocoa bean samples of different origins. These samples were also analyzed in manufactured cocoa powder. The effect of alkalinization of cocoa was studied. Results indicated that the final concentration and ratio of tetramethylpyrazine/trimethylpyrazine (TMP/TrMP) increased rapidly at higher roasting temperatures. The samples roasted with alkalies (pH between 7.20 and 7.92), such as sodium carbonate, or potassium plus air injected in the roaster during thermal treatment, exhibited a greater degree of brown color formation, but the amount of alkylpyrazines generated was adversely affected. The analysis of alpha-free amino acids at the end of the roasting process demonstrated the importance of the thermal treatment conditions and the pH values on nibs (cocoa bean cotyledons), liquor, or cocoa. Higher pH values led to a lower concentration of aroma and a higher presence of brown compounds.     

Modeling the formation of some polycyclic aromatic hydrocarbons during the roasting of Arabica coffee samples

Roasting is a critical process in coffee production, as it enables the development of flavor and aroma. At the same time, roasting may lead to the formation of nondesirable compounds, such as polycyclic aromatic hydrocarbons (PAHs). In this study, Arabica green coffee beans from Cuba were roasted under controlled conditions to monitor PAH formation during the roasting process. Roasting was performed in a pilot-spouted bed roaster, with the inlet air temperature varying from 180 to 260 degrees C, for roasting conditions ranging from 5 to 20 min. Several PAHs were determined in both roasted coffee samples and green coffee samples. Different models were tested, with more or less assumptions on the chemical phenomena, with a view to predict the system global behavior. Two kinds of models were used and compared: kinetic models (based on Arrhenius law) and statistical models (neural networks). The numbers of parameters to adjust differed for the tested models, varying from three to nine for the kinetic models and from five to 13 for the neural networks. Interesting results are presented, with satisfactory correlations between experimental and predicted concentrations for some PAHs, such as pyrene, benz[a]anthracene, chrysene, and anthracene.