Solid-phase microextraction method development for headspace analysis of volatile flavor compounds

Solid-phase microextraction (SPME) fibers were evaluated for their ability to adsorb volatile flavor compounds under various conditions with coffee and aqueous flavored solutions. Experiments comparing different fibers showed that poly(dimethylsiloxane)/divinylbenzene had the highest overall sensitivity. Carboxen/poly(dimethylsiloxane) was the most sensitive to small molecules and acids. As the concentrations of compounds increased, the quantitative linear range was exceeded as shown by competition effects with 2-isobutyl-3-methoxypyrazine at concentrations above 1 ppm. A method based on a short-time sampling of the headspace (1 min) was shown to better represent the equilibrium headspace concentration. Analysis of coffee brew with a 1-min headspace adsorption time was verified to be within the linear range for most compounds and thus appropriate for relative headspace quantification. Absolute quantification of volatiles, using isotope dilution assays (IDA), is not subject to biases caused by excess compound concentrations or complex matrices. The degradation of coffee aroma volatiles during storage was followed by relative headspace measurements and absolute quantifications. Both methods gave similar values for 3-methylbutanal, 4-ethylguaiacol, and 2,3-pentanedione. Acetic acid, however, gave higher values during storage upon relative headspace measurements due to concurrent pH decreases that were not seen with IDA.     

Volatiles from roasted byproducts of the poultry-processing industry

Volatiles of roasted chicken breast muscle and byproducts, such as backbones, breastbones, spent bones, and skin, were investigated. Total volatile concentrations ranged from 2030 ppb in the roasted backbones to 4049 ppb in the roasted skin. The major classes of volatile compounds detected in roasted samples were aldehydes (648-1532 ppb) and alcohols (336-1006 ppb). Nitrogen- and/or sulfur-containing compounds were also detected in appreciable quantities (161-706 ppb) in all samples. For all samples, hexanal and 2-methyl-2-buten-1-ol were dominant among the aldehydes and alcohols, respectively. Among the nitrogen- and sulfur-containing compounds, Maillard reaction products, such as tetrahydropyridazines, piperidines, and thiazoles, were the major contributors to the total volatile content in all samples. The composition of volatiles observed in roasted byproducts was markedly different from that of the roasted breast muscle. Therefore, the blending of the byproducts in appropriate proportions or blending of volatile flavor extracts from different byproducts may be necessary to obtain an aroma that mimics roasted chicken aroma.     

Measurements of Some Volatile Compounds by Means of the Electronic Nose

Using an electronic nose, concentration ranges of volatile fatty acids(VFAs), methane and butane, NH₃, HCl, SO₂ andN₂O have been measured to establish the relation between theconcentration in the liquid or the gas sample and the electronic nosereading. A quantitative sensorial odor perception (SOP) was introduced,based on the average reaction of the twelve available sensors of theelectronic nose. The results of the different compounds showed that thesensors reach a saturation level with increasing concentration. In the lowerconcentration ranges, linearity between concentration and signal outputoccurred. This linear interval was situated for the VFAs between thedetection limit in the range of 5 to 15 g dissolved compound per L distilledwater and the upper limit of 60 g L^-1. For the gases, thedetection limit varied between 6 and 690 volumes of gas per million ofvolumes air (ppmv). The upper limit of the linear interval ranged from 100–3000 ppmv depending on the compound. For the olfactometry reference product n-butanol, with a reported olfactory lower threshold valueof 0.04 ppmv, the electronic nose was less sensitive and gave a detectionlimit around 975 ppmv. The different compounds could be visualized in radarplots, which had a specific profile for each compound. The higher theconcentration of the volatile compounds in the air, the larger the surfaceof the respective radarplot. A discriminant analysis showed clusters ofcompounds such as the VFAs, the non polar gaseous compounds methane andbutane and the other more polar gaseous compounds.     

Aroma content of fresh basil (Ocimum basilicum L.) leaves is affected by light reflected from colored mulches

Sweet basil (Ocimum basilicum L.) is an herb that is used to add a distinct aroma and flavor to food. Volatile compounds emitted from fully expanded fresh leaves grown in drip-irrigated plots that were covered with six colors of mulch were compared. The colors reflected a range of photosynthetic photon flux, far-red, red, and blue light from the soil surface to developing leaves. Our objective was to determine whether reflection from the different colors could influence concentrations of volatile compounds emitted from the fresh leaves. Volatile compounds were isolated by headspace sampling and quantified by gas chromatography. Twenty-six compounds were identified, of which the terpenoids linalool and 1,8-cineole comprised more than 50% of the total yield. Concentrations of volatile compounds from leaves that developed over green, blue, yellow, white, and red mulches followed the same patterns as they did for air-dried leaves of the same cultivar. However, the concentration of volatile compounds from fresh leaves was about 50-fold higher than those found in the previous study of air-dried leaves.     

Comparison of nosespace,headspace, and sensory intensity ratings for the evaluation of flavor absorption by fat

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 panelists. These same panelists 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.     

The Potted-Plant Microcosm Substantially Reduces Indoor Air VOC Pollution: II. Laboratory Study

Indoor air-borne loads of volatile organic compounds (VOCs) are usually significantly higher than those outdoors, and chronic exposures can cause health problems. Our previous laboratory studies have shown that the potted-plant microcosm, induced by an initial dose, can eliminate high air-borne VOC concentrations, the primary removal agents being potting-mix microorganisms, selected and maintained in the plant/root-zone microcosm. Our office field-study, reported in the preceding paper, showed that, when total VOC (TVOC) loads in reference offices (0 plants) rose above about 100 ppb, levels were generally reduced by up to 75% (to < 100 ppb) in offices with any one of three planting regimes. The results indicate the induction of the VOC removal mechanism at TVOC levels above a threshold of about 100 ppb. The aims of this laboratory dose-response study were to explore and analyse this response. Over from 5 to 9 days, doses of 0.2, 1.0, 10 and 100 ppm toluene and m-xylene were applied and replenished, singly and as mixtures, to potted-plants of the same two species used in the office study. The results confirmed the induction of the VOC removal response at the lowest test dosage, i.e in the middle of the TVOC range found in the offices, and showed that, with subsequent dosage increments, further stepwise induction occurred, with rate increases of several orders of magnitude. At each dosage, with induction, VOC concentrations could be reduced to below GC detection limits (< 20 ppb) within 24 h. A synergistic interaction was found with the binary mixtures, toluene accelerating m-xylene removal, at least at lower dosages. The results of these two studies together demonstrate that the potted-plant microcosm can provide an effective, self-regulating, sustainable bioremediation or phytoremediation system for VOC pollution in indoor air.     

Which impact for beta-damascenone on red wines aroma?

beta-Damascenone, a C-13 norisoprenoid compound, is usually presented as an impact odorant in red wines. Its direct contribution to their aroma was investigated. Both free beta-damascenone and beta-damascenone precursors were isolated from various French red wines and then analyzed by gas chromatography-mass spectrometry, revealing concentrations in the vicinity of 1 and 2 microg/L for free compounds and both forms, respectively. Gas chromatography-olfactometry analyses were also performed on dilutions of both red wine extracts and pure beta-damascenone. The very low detection threshold in olfactometry for this compound explains why it is found at the highest dilution factor in aroma extract dilution analysis methods. Moreover, determination of beta-damascenone's odor thresholds confirmed the huge importance of the matrix: beta-Damascenone is characterized by a very low perception threshold in hydroalcoholic solution as compared to red wine, where it is over 1000-fold higher. In hydroalcoholic solution, beta-damascenone enhanced fruity notes of ethyl cinnamate and caproate and masked the herbaceous aroma of IBMP. Globally, these results suggested that beta-damascenone has more an indirect than a direct impact on red wine aroma.     

Sorption behavior of volatile phenols at the oak wood/wine interface in a model system

The sorption in a model system of aroma compounds of enological interest (mixture of the eight derivatives from guaiacol, 4-ethylphenol, and whiskylactone) onto wood was investigated to assess the influence of wood on the concentration of these volatiles during the aging of wine. To evaluate the influence of the solubility of aroma compounds in sorption phenomena, this parameter was determined for each volatile compound in model wine at 10 and 25 degrees C. The solubility is significantly higher in the model wine than in water and remains constant in the range of temperatures studied, except for guaiacol and vanillin. Kinetic and equilibrium sorptions were investigated. Sorption kinetics showed that the sorption equilibrium for all aroma compounds was reached after 6-7 days. From the study of the individual sorption isotherms, two distinct kinds of sorption behavior were observed depending on the presence or not of an ethylenic para substituent conjugated to the phenyl ring. K(ww) partition coefficients between the wood and the model wine were determined, which exhibited an unusual positive variation with temperature.     

Characterization of volatile aroma compounds in cooked black rice

Black rice ( Oryza sativa L.), an aromatic specialty rice popular in Asia, has a unique flavor, the volatile chemistry of which has not been reported. The objectives of this research were to study volatile profiles of cooked black rice and to characterize the odor-active compounds. Thirty-five volatile compounds were identified by gas chromatography-mass spectrometry using a dynamic headspace system with Tenax trapping. Aldehydes and aromatics were quantitatively in the greatest abundance, accounting for 80.1% of total relative concentration of volatiles. The concentration of 2-acetyl-1-pyrroline (2-AP) was high, exceeded only by hexanal, nonanal, and 2-pentylfuran. A total of 25 odor-active compounds, determined by gas chromatography-olfactometry, were applied to principal component analysis, demonstrating significant differences between a black and a traditional white rice cultivar in terms of aroma and explaining 93.0% of the total variation. 2-AP, guaiacol, indole, and p-xylene largely influenced the difference between the aroma in cooked black and white rice. 2-AP and guaiacol were major contributors to the unique character of black rice based on odor thresholds, relative concentrations, and olfactometry.     

Volatile Profiles of 13 Foxtail Millet Commercial Cultivars (Setaria italica Beauv.) from China

The volatile components from 13 commercially valuable foxtail millets from China were investigated by means of gas chromatography–mass spectrometry combined with simultaneous distillation extraction. A total of 52 volatile compounds were identified in all of the samples: 19 aldehydes, 5 alcohols, 10 ketones, 9 hydrocarbons, 6 benzene derivatives, and 3 others. Here, 23 common constituents were found in all samples. Aldehydes were the predominant volatile components in various cultivars. The importance of each volatile was assessed on the basis of odor thresholds and odor activity values (OAVs). Here, 35 volatile compounds were described using aroma character, and 24 volatile compounds were found to be odor‐active compounds. Another 11 common constituents were found in all samples. The components with the highest OAVs in most cultivars were (E )‐2‐nonenal and (E,E )‐2,4‐decadienal. Most of the other aldehydes also had high OAVs. Some of the ketones, alcohols, benzene derivatives, and other compounds were found to contain an odor‐active compound in several cultivars of foxtail millet. Principal component analysis was employed to evaluate the differences among cultivars. The results demonstrated that the volatile profile based on the OAVs of aroma compounds enabled good differentiation of most cultivars.     

Calculated sulfur dioxide equilibria at low concentrations between air and water

Low concentration equilibria of SO₂ between air and water have been calculated for temperatures in the range 0 to 60°C and air concentrations of 2 ppb to 100 ppm incorporating the best currently available theory to define this process. The data showed negative, non-regular deviations of from less than 1 to about 12% lower than the limited experimental aqueous concentration data available at these levels. Log-log plots of these equilibrium data were linear over a four decade concentration span in air and provided a format which may be readily interpolated for data access. Linear plots of the fraction of the total aqueous SO₂ present as unreacted SO₂ presented here for the first time, show a more marked rise with concentration than was expected, which is used to qualitatively explain biological and corrosion activity of dilute solutions of SO₂.     

Effect of copper on the volatility of aroma compounds in a model mouth system

Copper is thought to influence aroma perception by affecting volatility of aroma compounds in the mouth through interaction with salivary components, especially proteins. Our objective was to identify the effect of copper on the volatility of aroma compounds and the role of copper-protein interaction in volatile chemistry in the mouth. Copper (2.5 mg/L) and four aroma compounds (hexanal, butyl acetate, 2-heptanone, and ethyl hexanoate, 0.5 microL/L each) were added to model systems containing water, electrolytes, and artificial saliva at different pH levels. Headspace concentration of each volatile was measured using SPME-GC analysis. Copper in the model systems increased headspace concentration of volatiles at pH 6.5, but no change in volatility was observed at pH 7.0. At pH 7.5, the presence of copper in the artificial saliva system containing mucin and alpha-amylase decreased headspace volatile concentration, whereas histatin did not cause any changes in volatility. Effect of copper on volatiles at pH 6.5 may be due to increased solubility of copper at lower pH. Salivary proteins seem to interact with copper at pH 7.5. The interaction may change configuration of binding sites for aroma compounds in mucin.     

Identification of the medicinal off-flavor compound formed from ascorbic acid and (E)-hex-2-enal

A test apple beverage made up of apple juice (20%), high-fructose corn syrup (11.5%), citric acid (0.43%), trisodium citrate (0.02%), apple-odor flavor (0.1%), and ascorbic acid (0.02%) was stored at 40 °C and then analyzed for the change of odor in the beverage. Although no thermoacidophilic bacteria (TAB) were detected, a medicinal off-flavor was perceived after the 8 weeks of storage. Model experiments on the ingredients of the test apple beverage revealed that the off-flavor compound had been formed by ascorbic acid and (E)-hex-2-enal. Synthesis and NMR (1H, 13C, HMQC, and HMBC) analyses identified the compound as 6-propylbenzofuran-7-ol. The odor quality, retention index (RI), and mass spectrum of synthetic 6-propylbenzofuran-7-ol were identical with those of the medicinal odor compound from the test apple beverage. Sensory evaluation revealed the recognition thresholds for medicinal odor were 31.4 ppb in water and 24.0 ppb in apple beverage, and the detection thresholds were 19.6 ppb in water and 8.6 ppb in apple beverage, respectively. The quantified concentration of 6-propylbenzofuran-7-ol formed in test apple beverage was 90 ppb, approximately. This concentration was well above the odor threshold, so it was concluded that the compound was the source of the medicinal off-flavor.     

Comparison of odor-active compounds from six distinctly different rice flavor types

Using a dynamic headspace system with Tenax trap, GC-MS, GC-olfactometry (GC-O), and multivariate analysis, the aroma chemistry of six distinctly different rice flavor types (basmati, jasmine, two Korean japonica cultivars, black rice, and a nonaromatic rice) was analyzed. A total of 36 odorants from cooked samples were characterized by trained assessors. Twenty-five odorants had an intermediate or greater intensity (odor intensity >or= 3) and were considered to be major odor-active compounds. Their odor thresholds in air were determined using GC-O. 2-Acetyl-1-pyrroline (2-AP) had the lowest odor threshold (0.02 ng/L) followed by 11 aldehydes (ranging from 0.09 to 3.1 ng/L), guaiacol (1.5 ng/L), and 1-octen-3-ol (2.7 ng/L). On the basis of odor thresholds and odor activity values (OAVs), the importance of each major odor-active compound was assessed. OAVs for 2-AP, hexanal, ( E)-2-nonenal, octanal, heptanal, and nonanal comprised >97% of the relative proportion of OAVs from each rice flavor type, even though the relative proportion varied among samples. Thirteen odor-active compounds [2-AP, hexanal, ( E)-2-nonenal, octanal, heptanal, nonanal, 1-octen-3-ol, ( E)-2-octenal, ( E, E)-2,4-nonadienal, 2-heptanone, ( E, E)-2,4-decadienal, decanal, and guaiacol] among the six flavor types were the primary compounds explaining the differences in aroma. Multivariate analysis demonstrated that the individual rice flavor types could be separated and characterized using these compounds, which may be of potential use in rice-breeding programs focusing on flavor.     

Precursors of chicken flavor. II. Identification of key flavor precursors using sensory methods

Sensory evaluation was used to identify flavor precursors that are critical for flavor development in cooked chicken. Among the potential flavor precursors studied (thiamin, inosine 5'-monophosphate, ribose, ribose-5-phosphate, glucose, and glucose-6-phosphate), ribose appears most important for chicken aroma. An elevated concentration (added or natural) of only 2-4-fold the natural concentration gives an increase in the selected aroma and flavor attributes of cooked chicken meat. Assessment of the volatile odor compounds by gas chromatography-odor assessment and gas chromatography-mass spectrometry showed that ribose increased odors described as "roasted" and "chicken" and that the changes in odor due to additional ribose are probably caused by elevated concentrations of compounds such as 2-furanmethanethiol, 2-methyl-3-furanthiol, and 3-methylthiopropanal.     

Characterization of the odor-active volatiles in citrus Hyuganatsu (Citrus tamurana Hort. ex Tanaka)

The volatile components of Hyuganatsu (Citrus tamurana Hort. ex Tanaka) peel oil, isolated by cold-pressing, were investigated by chemical and sensory analyses. According to chemical analysis by GC and GC-MS, limonene (84.0%) was the most abundant compound, followed by gamma-terpinene (6.9%), myrcene (2.2%), alpha-pinene (1.2%), and linalool (1.0%). Monoterpene hydrocarbons were predominant in Hyuganatsu peel oil. The odor-active volatiles in Hyuganatsu flavor were studied by GC-olfactometry and omission tests. The characteristic flavor was present in the oxygenated fraction. Flavor dilution (FD) factors of the volatile flavor components of the Hyuganatsu cold-pressed oil were determined by aroma extraction dilution analysis (AEDA). Furthermore, relative flavor activity was investigated by means of FD factor and weight percent. Ten kinds of odor compounds having Hyuganatsu-like aroma were detected by AEDA: limonene, linalool, octanol, neral, neryl acetate, tridecanal, trans-carveol, cis-nerolidol, trans,trans-farnesyl acetate, and trans,trans-farnesol. Linalool and octanol were regarded as the most odor-active or key compounds of Hyuganatsu aroma. Diluted solutions of linalool and octanol of approximately 2 ppm gave a fresh and fruity aroma note similar to Hyuganatsu flavor.     

Sublethal effects of insect growth regulators upon crab larval behavior

Both swimming speeds and phototaxis by the four larval stages of the crab Rhithropanopeus harrisii were monitored upon chronic exposure to sublethal concentrations of the insect growth regulators methroprene (Altosid^R: ZR-515), hydroprene (Altozar^R: ZR-512) and dimiline (TH-6040). Larvae were reared under conditions of salinity (20orbo) and temperature (25°C) which produce the greatest developmental success. Sublethal concentrations of methroprene had no effect on swimming rates or phototaxis as compared to the acetone control larvae. For hydroprene, swimming rates by stage I, II and III zoeae were unaffected while a significant increase in swimming speeds occurred in Stage IV zoeae exposed to concentrations of 0.05 and 0.1 ppm. Only Stage III zoeae exposed to 0.l ppm showed a significant decrease in the level of positive phototaxis. Dimilin was much more potent, as significant increases in swimming speeds occurred in Stage I, II and III zoeae, with 0.3 ppb being the lowest effective concentration. Although swimming by Stage IV zoeae was unaffected, phototaxis was altered at concentrations as low as 0.1 ppb. Concentrations, which alter behavior, are related to levels which are reported to control mosquitoe larvae.     

Analysis of volatile compounds from various types of barley cultivars

We identified volatile compounds of barley flour and determined the variation in volatile compound profiles among different types and varieties of barley. Volatile compounds of 12 barley and two wheat cultivars were analyzed using solid phase microextraction (SPME) and gas chromatography. Twenty-six volatiles comprising aldehydes, ketones, alcohols, and a furan were identified in barley. 1-Octen-3-ol, 3-methylbutanal, 2-methylbutanal, hexanal, 2-hexenal, 2-heptenal, 2-nonenal, and decanal were identified as key odorants in barley as their concentration exceeded their odor detection threshold in water. Hexanal (46-1269 microg/L) and 1-pentanol (798-1811 microg/L) were the major volatile compounds in barley cultivars. In wheat, 1-pentanol (723-748 microg/L) was a major volatile. Hulled barley had higher total volatile, aldehyde, ketone, alcohol, and furan contents than hulless barley, highlighting the importance of the husk in barley grain aroma. The proanthocyanidin-free varieties generally showed higher total volatile and aldehyde contents than wild-type varieties, potentially due to decreased antioxidant activity by the absence of proanthocyanidins.