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Turbulence effects on volatilization rates of liquids and solutes.

Volatilization rates of neat liquids (benzene, toluene, fluorobenzene, bromobenzene, ethylbenzene, m-xylene, o-xylene, o-dichlorobenzene, and 1-methylnaphthalene) and of solutes (phenol, m-cresol, benzene, toluene, ethylbenzene, o-xylene, and ethylene dibromide) from dilute water solutions have been measured in the laboratory over a wide range of air speeds and water-stirring rates. The overall transfer coefficients (K(L)) for individual solutes are independent of whether they are in single- or multi-solute solutions. The gas-film transfer coefficients (kG) for solutes in the two-film model, which have hitherto been estimated by extrapolation from reference coefficients, can now be determined directly from the volatilization rates of neat liquids through a new algorithm. The associated liquid-film transfer coefficients (kL) can then be obtained from measured K(L) and kG values and solute Henry law constants (H). This approach provides a novel means for checking the precision of any kL and kG estimation methods for ultimate prediction of K(L). The improved kG estimation enables accurate K(L) predictions for low-volatility (i.e., low-H) solutes where K(L) and kGH are essentially equal. In addition, the prediction of K(L) values for high-volatility (i.e., high-H) solutes, where K(L) approximately equal to kL, is also improved by using appropriate reference kL values.

Algorithms↗

Distribution of volatile organic compounds over a semiconductor Industrial Park in Taiwan.

This study examined volatile organic compounds (VOC) concentration in ambient air collected during the years 2000--2003 at several different locations of Hsinchu Science-based Industrial Park (HSIP) in Taiwan. A canister automated GC-MS system analyzed the volatile organics in ambient air grasp samples according to T0-15 method. Oxygenated volatiles were the most abundant VOC detected in HSIP followed by aromatics that are commonly used as solvents in the semiconductor industries. The major components measured in the ambient air are 2-propanol (29-135 ppbv), acetone (12-164 ppbv), benzene (0.7-1.7 ppbv), and toluene (13-20 ppbv). At some of the sampling locations, odorous compounds such as carbon disulfide and dimethyl sulfide levels exceed threshold values. The estimated toluene/benzene ratio is very high at most of the sites. However, the total amount of VOC is reduced over the years from 2000 to 2003 due to strict implementation on use and discharge of solvents in industries. There exists no definite seasonal pattern for sporadic occurrence of high levels of some of the volatile organics. Stagnant weather conditions with low wind speeds aid accumulation of toxic species at ground level. The results entail that hi-tech semiconductor industries are still a potential source for harmful organic substances to surrounding microenvironment.

2-Propanol↗

Measuring herbicide volatilization from bare soil.

A field experiment was conducted to measure surface dissipation and volatilization of the herbicide triallate after application to bare soil using micrometeorological, chamber, and soil-loss methods. The volatilization rate was measured continuously for 6.5 days and the range in the daily peak values for the integrated horizontal flux method was from 32.4 (day 5) to 235.2 g ha(-1) d(-1) (day 1), for the theoretical profile shape method was from 31.5 to 213.0 g ha(-1) d(-1), and for the flux chamber was from 15.7 to 47.8 g ha(-1) d(-1). Soil samples were taken within 30 min after application and the measured mass of triallate was 8.75 kg ha(-1). The measured triallate mass in the soil at the end of the experiment was approximately 6 kg ha(-1). The triallate dissipation rate, obtained by soil sampling, was approximately 334 g ha(-1) d(-1) (98 g d(-1)) and the average rate of volatilization was 361 g ha(-1) d(-1). Soil sampling at the end of the experiment showed that approximately 31% (0.803 kg/2.56 kg) of the triallate mass was lost from the soil. Significant volatilization of triallate is possible when applied directly to the soil surface without incorporation.

Air Movements↗

Simulating herbicide volatilization from bare soil affected by atmospheric conditions and limited solubility in water.

A numerical model that simulates pesticide fate was developed to predictthe behavior of triallate after application to a field soil. The model has options that allow water and/ or heat transport and can limit simulated aqueous-phase concentrations to triallate solubility in water. Several methods for describing the volatilization boundary condition were tested to assess the accuracy in predicting the volatilization rate, including an approach that requires no atmospheric information and an approach that couples soil and atmospheric processes. Four scenarios were constructed and simulated, to compare with measured volatilization rates. The peak measured volatilization rate (168 g ha(-1) h(-1)) was most accurately predicted with the scenario that included the most complex model (100 g ha(-1) h(-1)). The simplest model overpredicted the peak rate (251 g ha(-1) h(-1)), and the others underpredicted the peak rate (16-67 g ha(-1) h(-1)). The simulations that limited aqueous solubility provided relatively similar values for the total emissions (21-37% of applied triallate), indicating that simplified models may compare well with measurements (31% of applied). A prospective simulation over a period of 100 days showed that applying triallate to the soil surface would ultimately lead to atmospheric emissions of 80% of the applied material with 6% remaining in soil. Incorporating triallate to a depth of 10 cm would reduce emissions to less than 5% and lead to 41% remaining in soil.

Air Pollution↗

Volatile components of green walnut husks.

Volatiles were isolated from whole green mature walnuts (Hartley variety) with husks still intact using dynamic headspace sweeping with trapping on Tenax. A total of 45 volatile compounds were identified by GC-MS. Major volatiles identified included (E)-4, 8-dimethyl-1,3,7-nonatriene, pinocarvone, pinocarveol, myrtenal, myrtenol, (E,E)-4,8,12-trimethyl-1,3,7,11-tridecatetraene, caryophyllene epoxide, verbenol, verbenone, and terpinolene. Green walnuts that had been infested with codling moth showed appreciably higher amounts emitted for (E)-4,8-dimethyl-1,3,7-nonatriene, (E, E)-4,8,12-trimethyl-1,3,7,11-tridecatetraene, alpha- and beta-pinenes, sabinene, (E)-beta-ocimene, (E,E)-alpha-farnesene, and linalool. The infested nuts also emitted benzyl methyl ether, isobutyl cyanide, and 1-nitro-3-methylbutane, compounds not found with the healthy nuts. Volatiles from uninfested green walnuts at the maturity stage where the husk was just beginning to split were also analyzed and compared.

Gas Chromatography-Mass Spectrometry↗

Impacts of ionizing radiation on volatile production by ripening gala apple fruit.

Apple (Malus x domestica Borkh., cv. Gala) fruit treated with 0.5 microL x L(-1) 1-methylcyclopropene (MCP) or air (non-MCP) for 12 h at 20 degrees C were exposed to gamma radiation at doses of 0, 0.44, 0.88, or 1.32 kGy at 23 degrees C and then stored at 20 degrees C. Production of volatile compounds was measured on the day of irradiation and 1, 3, 7, 14, and 21 days after irradiation. Both MCP treatment and irradiation inhibited ethylene production. MCP treatment reduced production of all volatile esters and alcohols detected, whereas irradiation inhibited production of most, but not all, esters and some alcohols by non-MCP-treated fruit. The inhibition of volatile production following irradiation increased with dose. Production of methyl and propyl esters was inhibited more than that of other esters following irradiation or MCP treatment. The impact of irradiation on production of esters and alcohols by MCP-treated fruit was minimal. Non-MCP-treated fruit irradiated at 0.44 kGy produced the most esters during the 21-day period at 20 degrees C following irradiation, and the ester production rate in these fruit was comparable to that of the nonirradiated fruit 21 days after irradiation. Fruit treated with doses higher than 0.44 kGy did not recover their ability to produce volatile compounds. These results indicate both MCP and ionizing radiation inhibit production of many aroma compounds produced by ripening apple fruit.

Alcohols↗

Plant odor analysis of apple: antennal response of codling moth females to apple volatiles during phenological development.

Volatile compounds were collected from apple branches (Malus domestica) at different developmental stages, and the antennal response of codling moth females (Cydia pomonella) to these compounds was recorded by electroantennography coupled to gas chromatography. Presence of a range of terpenoid compounds, many of which had antennal activity, was characteristic for volatile collections from branches with leaves, and from small green apples. Nine compounds from branches with leaves and green fruit consistently elicited an antennal response: methyl salicylate, (E)-beta-farnesene, beta-caryophyllene, 4,8-dimethyl-1,3(E),7-nonatriene, (Z)3-hexenol, (Z,E)-alpha-farnesene, linalool, germacrene D, and (E,E)-alpha-farnesene. The bouquet emitted from flowering branches contained in addition several benzenoid compounds which were not found after bloom. Small green apples, which are the main target of codling moth oviposition during the first seasonal flight period, released very few esters. In comparison, fully grown apples released a large number of esters, but fewer terpenoids. The study of apple volatiles eliciting an antennal response, together with a survey of the seasonal change in the release of these compounds, is the first step toward the identification of volatiles mediating host-finding and oviposition in codling moth females.

Animals↗

New device for direct extraction of volatiles in solid samples using SPME.

A new device that allows extraction of volatiles from solid materials by SPME, avoiding preparation of the sample, was designed and tested in two different food products. Volatiles from dry-cured ham and canned liver sausage were analyzed by headspace SPME (HS SPME) and by using a new device that protects the SPME fiber in the core of the solid material. Volatile profiles generated by using both methods of extraction were very similar in both products. Compounds that have been previously highlighted as quality markers, such as products from oxidative degradation of lipids, products from Strecker degradation of amino acids, or terpenes, were satisfactorily extracted by SPME coupled to the device for direct extraction. In addition, by using this method no laboratory contaminants were extracted, whereas some major laboratory solvents were presented in the chromatogram using the HS SPME method. However, coefficients of variation were higher when performing the direct sampling procedure. This new device appears to have potential as a simple method for extracting volatiles in solid materials while at the same time avoiding taking samples.

Chromatography, Liquid↗

Effect of pH, temperature, and moisture on the formation of volatile compounds in glycine/glucose model systems.

Mixtures of glycine, glucose, and starch were extrusion cooked using sodium hydroxide at 0, 3, and 6 g/L of extruder water feed, 18% moisture, and 120, 150, and 180 degrees C target die temperatures, giving extrudates with pH values of 5.6, 6.8, and 7.4. Freeze-dried equimolar solutions of glucose and glycine were heated either dry or after equilibration to approximately 13% moisture at 180 degrees C in a reaction-tube system designed to mimic the heating profile in an extruder. Volatile compounds were isolated onto Tenax and analyzed by gas chromatography-mass spectrometry. For the extrudates, total yields of volatiles increased with decreasing pH at 180 degrees C, reached a maximum at pH 6.8 at 150 degrees C, and increased with increasing pH at 120 degrees C. Amounts increased with temperature at all pH values. Pyrazines were the most abundant class for all sets of conditions (54-79% of total volatiles). Pyrroles, ketones, furans, oxazoles, and pyridines were also identified. Yields of volatiles from the reaction-tube samples increased by >60% in the moist system. Levels of individual classes also increased in the presence of moisture, except pyrazines, which decreased approximately 3.5-fold. Twenty-one of the compounds were common to the reaction-tube samples and the extrudates.

Cooking↗

Effect of salivary components on volatile partitioning from solutions.

Partition of fourteen volatile compounds, representing the diverse physicochemical properties of aroma compounds, was measured by static equilibrium headspace in solutions containing the components of artificial saliva, either singly or in mixtures. Comparison of a bovine salivary mucin and pig gastric mucin showed no significant difference in partition behavior of the volatiles, so gastric mucin was used. Mucin viscosity changed with pH, but binding of volatile compounds did not show a marked dependence on pH. All combinations of the salivary components were tested for their effect on partition. Three types of behavior were noted. Partition of some compounds was unaffected by mucin, and with other compounds mucin decreased partition, whereas another group showed a decrease with mucin that was affected by the presence of salivary salts and sugar. When volatiles or sugar were added to a mucin solution, the final headspace concentration depended on the order of addition, indicating some competition for binding. These solute-mucin effects are discussed in relation to mucin structure and behavior in solution.

Animals↗

Maturing wines in oak barrels. Effects of origin, volume, and age of the barrel on the wine volatile composition.

The influence of the oak origin, volume, and age of the barrel on the volatile composition of a red wine after six months of maturation have been studied. Major volatile compounds in wine were determined using liquid-liquid extraction with dichloromethane, and those volatiles being due to the oak were determined by extraction with pentane-ether using deuterated analogues as internal standards. The results show that there is little difference between the volatile composition of wines matured in French oak barrels and those matured in American oak barrels. The concentration of cis-oak lactone was the most significant difference. The greatest instrumental and sensory differences were found between new and used barrels, with important decreases in lactones and vanillin concentration in used barrels. When studying the effect of the volume of the barrel, the characteristics of the wine matured in 220-L new barrels versus those matured in 1000-L new barrels were very different. In new barrels, the larger the volume of the barrel, the lower the concentrations of those compounds responsible for the oaky aroma. These differences were less evident when comparing wines matured in used barrels with different capacities.

Benzaldehydes↗

Investigation of volatiles evolution during the alcoholic fermentation of grape must using free and immobilized cells with the help of solid phase microextraction (SPME) headspace sampling.

A biocatalyst was prepared by immobilization of Saccharomyces cerevisiae strain AXAZ-1 on delignified cellulosic material (DCM). Repeated batch fermentations were conducted using these biocatalysts and free cells, separately, at temperatures of 20, 15, and 10 degrees C. Solid phase microextraction (SPME) was used in monitoring the formation of volatile alcohols, acetate esters, and ethyl esters of fatty acids. The kinetics of volatile production were similar for free and immobilized cells. In all cases immobilized cells showed a better rate of volatile production, which was directly connected to sugar consumption. The main difference observed was in propanol production, which increased with temperature decrease for the immobilized cells, whereas it remained constant for the free ones. In the case of immobilized cells significant amounts of esters were also produced. It is well-known that esters contribute to the fruity aroma of wine. It was also established that SPME is a very sensitive, accurate, and reliable technique and can be used without any reservation in the characterization of volatile constituents of wine.

Acetaldehyde↗

Volatile sulfur compounds in irradiated precooked turkey breast analyzed with pulsed flame photometric detection.

Ionizing radiation is an effective processing technology for pathogen inactivation on various foods. However, the generation of off-odor is a concern for some irradiated meats. This study was conducted to investigate volatile sulfur compounds of precooked ready-to-eat turkey breast as functions of radiation dose and subsequent storage. Precooked turkey breast was exposed to 0, 1, 2, 3, 4, and 5 kGy of gamma radiation and stored for 14 days at 5 degrees C. Volatile sulfur compounds were extracted using solid phase microextraction (SPME), followed by gas chromatographic separation and pulsed flame photometric detection. Irradiation dramatically increased concentrations of hydrogen sulfide, sulfur dioxide, methanethiol, and dimethyl disulfide. The rate of increase was higher at low doses (0-2 kGy) than at higher doses of 3-5 kGy. Carbon disulfide was the only volatile sulfur compound that was reduced by irradiation. Concentrations of all volatile sulfur compounds decreased in both irradiated and nonirradiated samples stored at 5 degrees C.

Animals↗

Volatile chemicals identified in extracts from newly hybrid citrus, dekopon (Shiranuhi mandarin Suppl. J.).

Extracts from the peel and flesh of a citrus fruit, dekopon (Shiranuhi mandarin Suppl. J.), were obtained under reduced pressure followed by dichloromethane extraction. A total of 127 volatile chemicals were identified in the extracts using gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). They included 11 monoterpenes, 32 monoterpenoids, 9 sesquiterpenes, 5 sesquiterpenoids, 20 aliphatic alcohols, 14 aliphatic esters, 15 aliphatic aldehydes and ketones, 7 aliphatic acids, and 10 miscellaneous compounds. The major volatile constituents of the extract from the peel were d-limonene (2380.33 mg/kg), myrcene (36.54 mg/kg), bisabolene (30.03 mg/kg), sabinene (21.12 mg/kg), trans-beta-ocimene (16.96 mg/kg), valencene (12.84 mg/kg), decanal (8.14 mg/kg), beta-phellandrene (4.53 mg/kg), citronellol (4.51 mg/kg), 4-terpineol (4.50 mg/kg), linalool (4.13 mg/kg), and citronellyl acetate (3.63 mg/kg). The major volatile constituents of the extract from the flesh were ethyl acetate (21.54 mg/kg), acetoin (7.23 mg/kg), 3-methylbutanol (2.79 mg/kg), p-mentha-cis-2,8-dien-1-ol (1.01 mg/kg), 3-methylbutanoic acid (0.95 mg/kg), isobutanol (0.59 mg/kg), trans-isopiperitenol (0.58 mg/kg), p-mentha-trans-2,8-dien-1-ol, and trans-carveol (0.44 mg/kg). Compositions of volatile chemicals in peel and flesh extract were considerably different: the peel extract was rich in terpenes, whereas the flesh extract was rich in aliphatic compounds.

Alcohols↗

Changes in volatile compounds of gamma-irradiated fresh cilantro leaves during cold storage.

Consumption of salsas and dishes containing cilantro has been linked to several recent outbreaks of food-borne illness due to contamination with human pathogens. Ionizing irradiation can effectively eliminate food-borne pathogens from various vegetables including cilantro. However, the effect of irradiation on aroma of fresh cilantro is unknown. This study was conducted to investigate the effect of irradiation on volatile compounds of fresh cilantro leaves. Fresh cilantro leaves (Coriandrum sativum L) were irradiated with 0, 1, 2, or 3 kGy gamma radiation and then stored at 3 degrees C up to 14 days. Volatile compounds were extracted using solid-phase microextraction (SPME), followed by gas chromatographic separation and mass spectra detection at 0, 3, 7, and 14 days after irradiation. Most of the volatile compounds identified were aldehydes. Decanal and (E)-2-decenal were the most abundant compounds, accounting for more than 80% of the total amount of identified compounds. The amounts of linalool, dodecanal, and (E)-2-dodecenal in irradiated samples were significantly lower than those in nonirradiated samples at day 14. However, the most abundant compounds [decanal and (E)-2-decenal] were not consistently affected by irradiation. During storage at 3 degrees C, the amount of most aldehydes peaked at 3 days and then decreased afterward. Our results suggest irradiation of fresh cilantro for safety enhancement at doses up to 3 kGy had minimal effect on volatile compounds compared with the losses that occurred during storage.

Acyclic Monoterpenes↗

Antioxidant activity and characterization of volatile constituents of Taheebo (Tabebuia impetiginosa Martius ex DC).

Volatiles were isolated from the dried inner bark of Tabebuia impetiginosa using steam distillation under reduced pressure followed by continuous liquid-liquid extraction. The extract was analyzed by gas chromatography and gas chromatography-mass spectrometry. The major volatile constituents of T. impetiginosa were 4-methoxybenzaldehyde (52.84 microg/g), 4-methoxyphenol (38.91 microg/g), 5-allyl-1,2,3-trimethoxybenzene (elemicin; 34.15 microg/g), 1-methoxy-4-(1E)-1-propenylbenzene (trans-anethole; 33.75 microg/g), and 4-methoxybenzyl alcohol (30.29 microg/g). The antioxidant activity of the volatiles was evaluated using two different assays. The extract exhibited a potent inhibitory effect on the formation of conjugated diene hydroperoxides (from methyl linoleate) at a concentration of 1000 microg/mL. The extract also inhibited the oxidation of hexanal for 40 days at a level of 5 microg/mL. The antioxidative activity of T. impetiginosa volatiles was comparable with that of the well-known antioxidants, alpha-tocopherol, and butylated hydroxytoluene.

Allylbenzene Derivatives↗

Optimization of solid phase microextraction analysis for the headspace volatile compounds of parmesan cheese.

Optimum conditions of solid phase microextraction (SPME) analysis of the headspace volatile compounds of Parmesan cheese in airtightly sealed 100-mL bottles were developed. The coefficient of variation of SPME analysis on the headspace volatile compounds of Parmesan cheese was 2%. The reproducibility of SPME was improved by a combination of sampling at -10 degrees C, controlling the sample temperature, and uniform magnetic stirring of samples during equilibrium and isolation steps. The sensitivity of SPME increased by 125% in total peak areas by a combination of 40 min of sonication and 25% (w/v) sodium phosphate solution, compared with that of samples containing deionized water only (P < 0.05). The addition of salt solution or sonication treatment in samples increased the headspace volatile compounds of cheese quantitatively without producing any new volatile compounds.

Cheese↗

Identification of volatile compounds in soybean at various developmental stages using solid phase microextraction.

Soybean (Glycine max) seed volatiles were analyzed using a solid phase microextraction (SPME) method combined with gas chromatography-mass spectrometry (GC-MS). Thirty volatile compounds already reported for soybean were recovered, and an additional 19 compounds not previously reported were identified or tentatively identified. The SPME method was utilized to compare the volatile profile of soybean seed at three distinct stages of development. Most of the newly reported compounds in soybean seed were aldehydes and ketones. During early periods of development at maturity stage R6, several volatiles were present at relatively high concentrations, including 3-hexanone, (E)-2-hexenal, 1-hexanol, and 3-octanone. At maturity stage R7 and R8, decreased amounts of 3-hexanone, (E)-2-hexenal, 1-hexanol, and 3-octanone were observed. At maturity stage R8 hexanal, (E)-2-heptenal, (E)-2-octenal, ethanol, 1-hexanol, and 1-octen-3-ol were detected at relatively high concentrations. SPME offers the ability to differentiate between the three soybean developmental stages that yield both fundamental and practical information.

Aldehydes↗