Effect of ethanol, temperature, and gas flow rate on volatile release from aqueous solutions under dynamic headspace dilution conditions

On the basis of a mechanistic model, the overall and liquid mass transfer coefficients of aroma compounds were estimated during aroma release when an inert gas diluted the static headspace over simple ethanol/water solutions (ethanol concentration = 120 mL x L(-1)). Studied for a range of 17 compounds, they were both increased in the ethanol/water solution compared to the water solution, showing a better mass transfer due to the presence of ethanol, additively to partition coefficient variation. Thermal imaging results showed differences in convection of the two systems (water and ethanol/water) arguing for ethanol convection enhancement inside the liquid. The effect of ethanol in the solution on mass transfer coefficients at different temperatures was minor. On the contrary, at different headspace dilution rates, the effect of ethanol in the solution helped to maintain the volatile headspace concentration close to equilibrium concentration, when the headspace was replenished 1-3 times per minute.     

Retronasal transport of aroma compounds

A comparison was made between the amounts of volatiles in the headspace above a solution and the breath volatile content (exhaled from the nose or mouth) after consumption of the same solution. The amounts of volatiles in the breath were lower than those in the headspace, with breath exhaled via the mouth containing, on average, 8-fold more volatiles than breath exhaled via the nose. Dilution of the sample by saliva in-mouth did not appear to be a major factor affecting volatile delivery. Instead, the rate of in vivo equilibration (mass transfer) appeared to be the most significant factor, principally affecting volatile delivery from the solution to the gas phase. Thereafter, gas-phase dilution of the volatile as it passed through the upper airway resulted in a further decrease in volatile concentration. The final factor affecting the volatile concentration exhaled from the nose was absorption of volatiles to the nasal epithelia, which was greatest for those compounds with the lowest air/water partition coefficients.     

Computerized apparatus for measuring dynamic flavor release from liquid food matrices

A fully computer-controlled apparatus was designed. It combines a glass reactor with a temperature-controlled hood, in which headspace volatiles are captured. Flavored liquids can be introduced into the reactor and exposed to conditions of temperature, air flow, shear rate, and saliva flow as they occur in the mouth. As the reactor is completely filled before measurements are started, creation of headspace just before sampling start prevents untimely flavor release resulting in real time data. In the first 30 s of flavor release the concentrations of the volatiles can be measured up to four times by on-line sampling of the dynamic headspace, followed by off-line trapping of the samples on corresponding Tenax traps and analysis using GC-TDS-FID. Flavor compounds from different chemical classes were dissolved in water to achieve concentrations typically present in food (micrograms to milligrams per liter). Most of the compounds showed constant release rates, and the summed quantities of each volatile of three 10 s time intervals correlated linearly with time. The entire method of measurement including sample preparation, release, sampling, trapping, thermodesorption, and GC analysis showed good sensitivity [nanograms (10 s)(-1)] and reproducibility (mean coefficient of variation = 7.2%).     

Dynamic headspace analysis of the release of volatile organic compounds from ethanolic systems by direct APCI-MS

Static equilibrium headspace was diluted with a stream of nitrogen to study the stability of the volatile headspace concentration. The headspace dilution profile of 18 volatile compounds above aqueous and ethanolic solutions was measured in real time using atmospheric pressure chemical ionization-mass spectrometry. Under dynamic conditions the volatiles headspace concentration above water solutions decreased readily upon dilution. The presence of ethanol helped to maintain the volatile headspace concentration when the ethanol solution concentration was above 50 mL/L. This effect was such that under dynamic conditions the absolute volatile concentration above an ethanolic solution was higher than that above an aqueous solution, contrary to results observed in equilibrium studies. The ratio of the headspace concentration of volatiles above ethanolic 120 mL/L and water solutions was correlated to their air/water partition coefficient.     

Influence of lambda-carrageenan on the release of systematic series of volatile flavor compounds from viscous food model systems

The effect of lambda-carrageenan addition level (0.1, 0.25, 0.4, and 0.5% w/w) and viscosity on the release of systematic series of aroma compounds (aldehydes, esters, ketones, and alcohols) was studied in thickened viscous solutions containing lambda-carrageenan and 10 wt % of sucrose. Air-liquid partition coefficients K (37 degrees C) of a total of 43 aroma compounds were determined in pure water and in the lambda-carrageenan solutions by static headspace gas chromatography. Mass transfer of the aroma compounds in water and in the thickened lambda-carrageenan solutions which had a wide viscosity range was assessed by dynamic headspace gas chromatography. K (37 degrees C) increased as the carbon chain increased within each homologous series. Esters exhibited the highest volatility, followed by aldehydes, ketones, and alcohols. Under equilibrium, no overall effect of lambda-carrageenan was found, except with the most hydrophobic compounds. Analysis of flavor release under nonequilibrium conditions revealed a suppressing effect of lambda-carrageenan on the release rates of aroma compounds, and the extent of decrease in release rates was dependent on the physicochemical characteristics of the aroma compounds, with the largest effect for the most volatile compounds. However, none of the effects was of a magnitude similar to the obtained changes in the macroscopic viscosity, and the suppressing effects are therefore attributable to the thickener and not the physical properties of the increasingly viscous systems.     

Effect of preparation conditions on release of selected volatiles in tea headspace

The release of volatile compounds from infused tea was monitored using on-line atmospheric pressure chemical ionization (APCI) mass spectrometry. Assignment of the APCI ions to particular compounds was achieved using gas chromatography of tea headspace with dual electron ionization and APCI-MS detectors. Six ions in the APCI spectrum could be assigned to individual compounds, five ions were associated with isobaric compounds (e.g., 2- and 3-methylbutanal and pentanal) or stereoisomers (e.g., heptenals or heptadienals), and a further four ions monitored were identified compounds but with some unknown impurities. Reproducibility of infusion preparation and the analytical system was good with percentage variation values generally below 5%. The analysis was used to study the effect of infusion and holding temperatures on the volatile profile of tea headspace samples, and this was found to be compound-dependent. Both the extraction of volatiles from leaf tea and the release of volatiles into the headspace play a role in creating the aroma profile that the consumer experiences.     

Aroma-active components in fermented bamboo shoots.

Bamboo shoots (Phyllostachys pubescens) were fermented and prepared in a traditional Taiwanese manner. Static and dynamic headspace extractions of volatile compounds were conducted by solid phase microextraction (SPME) and by cryogenic focusing purge and trap, respectively. Volatile analysis was conducted with gas chromatography and mass spectrometry. Gas chromatography-olfactometry (GCO) was conducted utilizing the Osme time-intensity method. Of 70 volatile compounds detected, 29 possessed aroma activity, and the most odor active included p-cresol (barn-like), 2-heptanol (mushroom), acetic acid (vinegar), and 1-octen-3-ol (mushroom). SPME extracted 66 compounds, purge and trap extracted 14 compounds, and 12 compounds were common to both methods. The Osme GCO technique coupled with SPME is an effective tool for the extraction and evaluation of aroma-active headspace volatiles.     

Effect of xanthan on flavor release from thickened viscous food model systems

The influence of xanthan concentration (0, 0.02, 0.1, 0.4, and 0.8% w/w) and bulk viscosity on the release of 20 aroma compounds of different chemical classes (5 aldehydes, 4 esters, 5 ketones, 3 alcohols, and 3 terpenes) was evaluated in xanthan-thickened food model systems having different viscosities. Interactions between flavor compounds and xanthan were assessed by measuring air-liquid partition coefficients, K, of aroma compounds in pure water and in the xanthan solutions by static headspace gas chromatography. Mass transfer of aroma compounds was estimated by dynamic headspace gas chromatography. Notably, limonene and some of the esters and aldehydes exhibited decreased K values in the presence of xanthan, indicating that the release of these volatile aroma compounds was reduced due to interaction with the xanthan matrix. The degree of interaction depended on the physicochemical characteristics of the aroma compounds. A similar tendency was observed at nonequilibrium with the decreases in release rates being most pronounced for limonene, followed by the esters and aldehydes, with no effect for ketones and an apparent "salting out" effect for alcohols. The reduction in flavor release by xanthan was thus dependent on the physicochemical properties of the aroma compounds and was apparently a result of the aroma-xanthan interactions and not influenced by the viscosity of the system itself.     

Modeling the secondary shelf life of ground roasted coffee

This work was addressed to study the secondary shelf life of ground roasted coffee. To this purpose, fresh dark-roasted ground coffee samples were equilibrated at increasing water activity (aw) values up to 0.44 and stored at 30 degrees C for up to 1 month. To simulate home storage conditions, the headspace atmosphere was periodically perturbed by opening for a short time and then closing the packaging. The changes of some chemical and physicochemical indexes of coffee staling were studied, and sensory analysis was carried out to determine the end point of coffee acceptability. The results showed that the volatile compounds in the headspace are representative indexes of the quality depletion of roasted ground coffee during home usage. The sensory and instrumental results were used to develop a mathematical model allowing to simply and quickly calculate the secondary shelf life of coffee on the basis of its aw value at a given temperature.     

Study of both sunflower oil and its headspace throughout the oxidation process. Occurrence in the headspace of toxic oxygenated aldehydes

The static headspace composition of sunflower oil throughout the oxidation process at 70 degrees C with circulating air is studied by means of solid-phase microextraction followed by gas chromatography-mass spectrometry (SPME-GC-MS); at the same time the liquid phase of the same oil is studied by means of Fourier transform infrared (FTIR) spectroscopy. Each technique provides complementary information about the process; FITR spectroscopy detects changes in the functional groups of the liquid matrix in a global way and SPME/GC-MS provides information about the different components present in the volatile phase during the oxidation process. Concordance between the timing of the changes produced in both liquid and gaseous phases is observed, as well as agreement and complementarity in the results obtained from both phases. The formation of some well-known genotoxic and cytotoxic oxygenated aldehydes in this process and their presence in the oil headspace are proved.     

Optimization of multiple headspace solid-phase microextraction for the quantification of volatile compounds in dry fermented sausages

Multiple headspace solid-phase microextraction (HS-SPME) is a stepwise method that eliminates the influence of the matrix sample on the quantitative analysis of solid samples. The process was optimized for the analysis of volatile compounds in dry fermented sausages by gas chromatography and mass spectrometry. Different amounts of fermented sausages and different vial volumes were studied to obtain the theoretical exponential decay of the peak area of the four successive extractions in order to calculate the total area in the sausage. The highest number of volatile compounds analyzed by multiple HS-SPME in dry fermented sausages was obtained in a 10 mL headspace vial with 0.07 g of sample in the presence of water, 0.75 mg butylated hydroxytoluene, and 0.5 g sodium chloride. Finally, the method was characterized in terms of linearity and detection limits and applied to analyze the volatile compounds present in fermented sausages manufactured with either nitrate or nitrite.     

Use of fiber interface direct mass spectrometry for the determination of volatile flavor release from model food systems.

Described in this paper is a fiber interface direct headspace mass spectrometric system for the real-time measurement of flavor release. The system was optimized for the detection of the garlic aroma volatile, diallyl disulfide, from water. Parameters investigated included interface temperature, flow rate through the fiber, flow rate through the sample vessel, and sample stir rate. The delay time for detection of sample after introduction into the sample vessel was determined as 43 s. The system proved to be reliable and robust with no loss in sensitivity or contamination of the mass spectrometer over a 6 month period. The technique was applied to a homologous series of aliphatic alcohols from C(2) to C(7). Results showed that as polarity decreased with increasing chain length the release of volatile into the headspace was faster and gave a higher maximum intensity. Release of the garlic aroma volatile from different commercial mayonnaise products clearly showed a decrease in the release of diallyl disulfide as fat content increased. These results demonstrate the potential of using this technique as a tool for understanding the complex interactions that occur between flavor compounds and the bulk food matrix.     

Model studies on the release of aroma compounds from structured and nonstructured oil systems using proton-transfer reaction mass spectrometry

Relative retention, volatility, and temporal release of volatile compounds taken from aldehyde, ester, and alcohol chemical classes were studied at 70 degrees C in model systems using equilibrium static headspace analysis and real time dynamic headspace analysis. These systems were medium-chain triglycerides (MCT), sunflower oil, and two structured systems, i.e., water-in-oil emulsion and L2 phase (water-in-oil microemulsion). Hydrophilic domains of the emulsion type media retained specifically the hydrophilic compounds and alcohols. Four kinetic parameters characterizing the concentration- and time-dependent releases were extracted from the aroma release curves. Most of the kinetic parameter values were higher in structured systems than in oils particularly when using MCT. The oil nature was found to better control the dynamic release profiles than the system structures. The release parameters were well-related (i) to the volatile hydrophobicity as a function of the oil used and (ii) to the retention data in the specific case of the L2 phase due to a specific release behavior of alcohols.     

Model studies on volatile release from different semisolid fat blends correlated with changes in sensory perception

The effect of dispersed aqueous droplets in water-in-oil (W/O)-emulsion semisolid fats on aroma release and sensory perception was investigated on margarine models where model aroma substances were added. Aroma release from W/O-emulsion fat blends and bulk fat blends with added monoglycerides combining different fatty acids of various short-chain free fatty acids, methylketones, esters, and lactones were measured using headspace solid phase microextraction-gas chromatography/mass spectrometry (SPME-GC/MS), and their perception profiles were evaluated by sensory analysis. The presence of aqueous phase in a fat blend significantly reduced the headspace concentrations of butanoic acid and hexanoic acid, and also decreased the perceived intensity of total aroma and cheesy aroma. The aroma release of methylketones, esters, and lactones from the W/O-emulsion fat blends increased with increasing carbon chain length of the volatile molecules. The intensity of aroma perception in a W/O-emulsion fat blend depended on the melting point of the fatty acids (oleic, palmitic, stearic, and behenic) of the monoglyceride used as an emulsifier. Thus, aroma release from a W/O-emulsion semisolid fat blend was influenced by interactions between aroma volatiles and the dispersed aqueous droplets and by their viscoelastic properties.     

Amelioration of odorous components in spent mushroom compost

Volatile sulfur compounds, as well as other volatiles found in the headspace above spent mushroom compost (SMC), were analyzed by gas chromatography and mass spectrometry. Data from these techniques as well as organoleptic evaluation of both the SMC and the chromatographic eluant indicated that the volatile sulfur compounds and cresol were important odorous components in SMC; cresol was reported as a musty, cattle-feces aroma. Samples consisted of headspaces from untreated SMC as well as SMC stirred with 1% (by weight) powered activated carbon (PAC). SMC stirred with and without PAC reduced headspace volatile concentrations, but the stirred with added PAC further decreased concentrations of important malodorants such as volatile sulfur compounds and cresol.     

Effect of beta-cyclodextrin on aroma release and flavor perception

Binding and release of volatile compounds to and from beta-cyclodextrin were measured in model aqueous systems using static equilibrium headspace and dynamic headspace dilution. Beta-cyclodextrin decreased the static equilibrium headspace for some volatiles (e.g., ethyl octanoate and decanone) due to binding, but dilution studies demonstrated that binding was readily reversible. Dynamic release of hydrophobic volatile compounds was similar to that observed from emulsions. When beta-cyclodextrin was added to fat free yogurt, the release of a commercial lemon flavoring was modified and was similar to release from a regular fat yogurt. Sensory difference testing confirmed the release results. The data demonstrate that beta-cyclodextrin can be used to modify flavor delivery in both model and real systems; the effects in the latter are sensorially significant.     

Determination of olive oil oxidative status by selected ion flow tube mass spectrometry

The emergence of primary and secondary oxidation products in New Zealand extra virgin olive oil during accelerated thermal oxidation was measured and correlated with the concentrations of 13 headspace volatile compounds measured by selected ion flow tube mass spectrometry (SIFT-MS). SIFT-MS is a mass spectrometric technique that permits qualitative and absolute quantitative measurements to be made from whole air, headspace, or breath samples in real-time down to several parts per billion (ppb). It is well-suited to high-throughput analysis of headspace samples. Propanal, hexanal, and acetone were found at high concentrations in a rancid standard oil, while propanal, acetone, and acetic acid showed marked increases with oxidation time for the oils used in this study. A partial least-squares (PLS) regression model was constructed, which allowed the prediction of peroxide values (PV) for three separate oxidized oils. Sensory rancidity was also measured, although the correlations of headspace volatile compounds with sensory rancidity score were less satisfactory, and too few results were available for the construction of a PLS regression model. A fast (approximately 1 min), reliable method for prediction of olive oil PVs by SIFT-MS was developed.     

Partition and release of 21 aroma compounds during storage of a pectin gel system

The increasing popularity of low-fat products increases the need for a better understanding of how flavor release is affected by partial substitution of fat with hydrocolloids. Partitioning and release of aroma compounds from four pectin gels with different compositions were studied with static headspace and with a model mouth. Air/product partition coefficients determine the potential extent of aroma release, and mass transfer determines the rate at which aroma compounds are released to the vapor phase. This study showed that the gel network had large effects on the partition of aroma compounds between the gel and vapor phase. The specific properties of the aroma compounds were also of importance for the air/gel partition. Storage of the four gels showed that one of the weaker gels was influencing the concentration of aroma compounds in the headspace, probably caused by formation of a denser network over time.     

In vitro measurement of volatile release in model lipid emulsions using proton transfer reaction mass spectrometry

The presence of fat in food plays an important role in the way aroma is released during consumption and in the creation of the overall sensory impression. Fat acts as a reservoir for lipophilic volatile compounds and modulates the timing and delivery of aroma compounds in a unique manner. Despite considerable research, reproducible in vitro methods for measuring the effect of fat on volatile release are lacking. An open in vitro cell was used to simulate the open human naso-oropharygeal system and was interfaced with a proton transfer reaction mass spectrometer (PTR-MS) to examine some of the fundamental effects of fat on dynamic volatile release in liquid fat emulsions. Lipid emulsions with various fat contents (0-20%) and droplet sizes (0.25, 0.5, and 5.0 μM) were spiked with flavor volatiles representing a range of lipophilicity (K(o/w) = 1-1380). Preloaded syringes of spiked emulsion were injected into the cell, and temporal changes in release were measured under dynamic conditions. Significant differences in release curves were measured according to the lipid content of emulsions, the vapor pressure, and K(o/w) values of the volatile compounds. With increasing addition of fat, the critical volatile release parameters, maximum concentration (I(max)), time to maximum concentration (T(max)), and the integrated area under the concentration curve (AUC), were affected. The in vitro curves were reproducible and in agreement with theory and correlated with the preswallow phase of in vivo release data. An exponential model was used to calculate changes in mass transfer rates with increased fat addition.     

Influence of rearing conditions on the volatile compounds of cooked fillets of Silurus glanis (European catfish)

Volatile compounds of cooked fillets of Silurus glanis reared under two conditions occurring in France were studied. They were extracted by dynamic headspace, identified by gas chromatography/mass spectrometry, and quantified by gas chromatography-flame ionization detection. Odor active volatile compounds were characterized by gas chromatography-olfactometry. Sixty volatile compounds were detected in dynamic headspace extracts, among which 33 were odor active. Rearing conditions affected their estimated concentrations and their odor intensities, but very few qualitative differences were exhibited (only seven volatile compounds were concerned). A good correlation between quantitative and olfactometric results is shown. 2-Methylisoborneol and (E)-2-hexenal were less represented in OUTDOOR extracts, while 2-butanone was less represented in INDOOR extracts. In addition, olfactometric results can be closely related to those previously obtained by sensory analysis. Boiled potato sensory odor of the silurus cooked fillets can be related to (Z)-4-heptenal and methional, and buttery odor can be related to 2,3-butanedione, an unknown compound (RI = 1010), and 2,3-pentadione.