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Determination of volatile compounds in cows' milk using headspace GC-MS.

The composition of the volatile fraction of milk from cows was investigated in a survey of milk samples using a headspace sampling technique and gas chromatography coupled to mass spectrometry analysis (GC-MS). Milk samples were collected from 12 farms, selected for similar management, breed and level of production. Farms were also grouped according to the type of forage in the ration: (1) hay; (2) hay and maize silage; (3) hay, maize silage and grass silages. Forty-one compounds in milk were isolated and identified from GC-MS headspace analysis. Quantitatively, the most representative chemical class was ketones (eight compounds, 170 microg/kg), followed by aldehydes (nine compounds, 63 microg/kg), alcohols (eight compounds, 36 microg/kg), and lower amounts of hydrocarbons (six compounds), sulphur compounds (three compounds), esters (four compounds) and terpenes (three compounds). The novel headspace sampling technique, and the consequent reduction of sample pre-treatment, allowed the identification of low-molecular weight volatile compounds, and reduced the risk of producing artefacts during analysis. Discriminant analysis was used to identify a classification criterion for milk samples, using type of forage in the ration as a grouping variable. Posterior probability error rate indicated that aldehydes provided one of the best discriminant criteria for grouping milks according to ration composition. When all 41 identified volatile compounds were included, discriminant analysis selected nine compounds (acetone, 2,3-butanedione, 2-butanone, ethanol, acetaldehyde, ethylacetate, ethvlisovalerate, dimethylsulphone) that did not fail the tolerance test and which correctly classified 100% of the original cases.

Alcohols↗

Volatile fraction and sensory characteristics of Manchego cheese. 1. Comparison of raw and pasteurized milk cheese.

Manchego cheese can be manufactured from raw or pasteurized ewes' milk. An automatic purge and trap apparatus, coupled to a GC-MS was used to isolate. identify and compare the relative amounts of the volatile components of raw and pasteurized Manchego cheese during ripening. The majority of volatile compounds were more abundant in raw milk (RM) cheeses than in pasteurized milk (PM) cheeses. Alcohols and esters predominated in the profile of RM Manchego cheese, while methyl-ketones and 2,3-butanedione were quantitatively important in PM cheeses. Branched chain alcohols were much more abundant in RM cheeses. The discriminant analysis separated 100% samples into RM or PM cheeses by using only 16 volatile compounds. Aroma intensity was correlated with esters, branched chain aldehydes and branched chain alcohols in RM cheeses, and with esters, branched chain aldehydes, 2-methyl ketones and 2-alkanols in PM cheeses. Diacetyl was positively correlated with the aroma attribute 'toasted' and negatively correlated with aroma quality in PM cheeses.

Alcohols↗

Differentiation of Agaricus species and other homobasidiomycetes based on volatile production patterns using an electronic nose system.

Comparisons of the qualitative volatile production patterns between seven species of Agaricus, and between two of Volvariella and Pleurotus and one Coprinus species when grown at 25 degrees C on agar media for 14 d were made. There was good reproducibility between the volatile production patterns of the same species using an electronic nose unit with a 14 conducting sensor polymer array. Principle Component Analysis (PCA) showed that it was possible to discriminate between five of the seven Agaricus species, but that some overlap occurred between the others. Cluster analysis showed that there was also overlap between some species with the tropical collection of A. bitorquis separating out from the others. The volatile production profile of the commercial A. bisporus was close to that of a wild species, A. campestris. A. bisporus could be readily differentiated from other non-Agaricus species. This study demonstrates the potential for using electronic nose systems to rapidly differentiate mycelial cultures of homobasidiomycete mushrooms.

Agaricus↗

Sampling of trace volatile metal(loid) compounds in ambient air using polymer bags: a convenient method.

The sampling of volatile metal(loid) compounds (VOMs) such as hydrides, methylated, and permethylated species of arsenic, antimony, and tin is described using Tedlar bags. Advantages as well as limitations and constraints are discussed and compared to other widely used sampling techniques within this area, namely, stainless steel canisters, cryotrapping, and solid adsorbent cartridges. To prove the suitability of Tedlar bags for the sampling of volatile metal(loid) compounds, series of stability tests have been run using both laboratory synthetic and real samples analyzed periodically after increasing periods of storage. The samples have been stored in the dark at 20 degrees C and at 50 degrees C. Various volatile arsenic species (AsH3, MeAsH2, Me2AsH, Me3As), tin species (SnH4, MeSnH3, Me2SnH2, Me3SnH, Me4Sn, BuSnH3), and antimony species (SbH3, MeSbH2, Me2SbH, Me3Sb) have been generated using hydride generation methodology and mixed with moisturized air. Three static gaseous atmospheres with concentrations of 0.3-18 ng/L for the various compounds have been generated in Tedlar bags, and the stability of the VOMs has been monitored over a period of 5 weeks. Sewage sludge digester gas samples have been stored only at 20 degrees C for a period of 48 h. Cryotrapping GC/ICPMS has been used for the determination of the VOMs with a relative standard deviation of 5% for 100 pg. After 8 h, the recovery rate of all the compounds in the air atmospheres was better than 95% at 20 and 50 degrees C, whereas the recovery after 24 h was found to be between 81 and 99% for all VOMs at 20 and 50 degrees C except for Me3Sb and Me3As. These species show a loss between 48 and 73% at both temperatures. After 5 weeks at 20 degrees C, a loss of only 25-50% for arsine and stibine and the above-mentioned tin compounds was determined. Only Me3Sb, Me3Bi, and Me2Te were present in the digester gas sample. After 24 h, losses of 44, 10, and 12%, respectively, could be determined. Given these results, Tedlar bags could even be used, with some limitations, for long-term sampling of air containing traces of VOMs. The loss is more pronounced at higher temperatures.

Air↗

Vapor phase transport and biodegradation of volatile fuel compounds in the unsaturated zone: a large scale lysimeter experiment.

The vapor phase transport and biodegradation of typical fuel compounds including volatile petroleum hydrocarbons and methyl tert-butyl ether (MTBE) was studied in a large scale field lysimeter representing a 2.3 m thick sandy unsaturated zone over a gravel aquifer. A mixture of 13 fuel compounds with MTBE (5%) was placed at a defined depth in the unsaturated zone to obtain a homogeneous source zone with a residual NAPL saturation. The upward and downward transport of fuel vapors and the biodegradation by indigenous microorganisms were monitored during 70 days. Using tracers in water and NAPL, it was shown that fuel compounds were transported by vapor phase diffusion only. All fuel compounds except MTBE disappeared from the lysimeter below the analytical detection limits within 70 days. MTBE accumulated in groundwater but volatilized from the unsaturated zone. First-order biodegradation rates were estimated in the unsaturated zone to range from <0.05 d(-1) for MTBE up to 8.7 d(-1) for octane. Aerobic biodegradation of degradable fuel compounds to CO2 started without any lag phase and removed about 3 times more fuel mass than volatilization. The study illustrates the recalcitrance of MTBE vapors compared to other fuel vapors, leading to a significant groundwater pollution with MTBE.

Air Pollutants↗

Characterization of diesel particles: effects of fuel reformulation, exhaust aftertreatment, and engine operation on particle carbon composition and volatility.

Diesel exhaust particles are the major constituent of urban carbonaceous aerosol being linked to a large range of adverse environmental and health effects. In this work, the effects of fuel reformulation, oxidation catalyst, engine type, and engine operation parameters on diesel particle emission characteristics were investigated. Particle emissions from an indirect injection (IDI) and a direct injection (DI) engine car operating under steady-state conditions with a reformulated low-sulfur, low-aromatic fuel and a standard-grade fuel were analyzed. Organic (OC) and elemental (EC) carbon fractions of the particles were quantified by a thermal-optical transmission analysis method and particle size distributions measured with a scanning mobility particle sizer (SMPS). The particle volatility characteristics were studied with a configuration that consisted of a thermal desorption unit and an SMPS. In addition, the volatility of size-selected particles was determined with a tandem differential mobility analyzer technique. The reformulated fuel was found to produce 10-40% less particulate carbon mass compared to the standard fuel. On the basis of the carbon analysis, the organic carbon contributed 27-61% to the carbon mass of the IDI engine particle emissions, depending on the fuel and engine operation parameters. The fuel reformulation reduced the particulate organic carbon emissions by 10-55%. In the particles of the DI engine, the organic carbon contributed 14-26% to the total carbon emissions, the advanced engine technology, and the oxidation catalyst, thus reducing the OC/EC ratio of particles considerably. A relatively good consistency between the particulate organic fraction quantified with the thermal optical method and the volatile fraction measured with the thermal desorption unit and SMPS was found.

Aerosols↗

Volatile metals and metalloids in hydrothermal gases.

Volatile metals and metalloids were sampled from hot springs, fumaroles, and a hydrothermally influenced wetland in Yellowstone National Park. The sampling was based on diffusion through gas sampling chambers. Collected gases were stabilized by dissolution and oxidation in 1:100 diluted NaOCl. Special procedures were developed to analyze the oxidized samples by GF-AAS and HG-AAS. For ICP-MS, samples had to be blank-corrected for polyatomic isotope interferences, especially by 23Na35Cl+ and 23Na37Cl+ on 58Ni and 60Ni and by 40Ar23Na+ on 63Cu. From the concentrations trapped in solution, net diffusion rates were calculated by Fick's first law. The highest concentrations reached a maximum of 8 g/m3 for volatile silicon. Volatile nickel, tungsten, zinc, copper, and molybdenum, previously only known from anthropogenic sources, occurred naturally in the hydrothermal gases in ranges of tens to hundreds of microg/m3. Replicate measurements indicated significant temporal variations in concentrations, probably the result of complex changes in the hydrothermal regime as well as varying microbial activity. Global correlations between gaseous and superficial aqueous phases were missing.

Air Pollutants↗

Volatile chemicals identified in extracts from leaves of Japanese mugwort (Artemisia princeps pamp.).

Extracts from leaves of Japanese mugwort (Artemisia princeps Pamp.) were obtained using two methods: steam distillation under reduced pressure followed by dichloromethane extraction (DRP) and simultaneous purging and extraction (SPSE). A total of 192 volatile chemicals were identified in the extracts obtained by both methods using gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). They included 47 monoterpenoids (oxygenated monoterpenes), 26 aromatic compounds, 19 aliphatic esters, 18 aliphatic alcohols, 17 monoterpenes (hydrocarbon monoterpenes), 17 sesquiterpenes (hydrocarbon sesquiterpenes), 13 sesquiterpenoids (oxygenated sesquiterpenes), 12 aliphatic aldehydes, 8 aliphatic hydrocarbons, 7 aliphatic ketones, and 9 miscellaneous compounds. The major volatile constituents of the extract by DRP were borneol (10.27 ppm), alpha-thujone (3.49 ppm), artemisia alcohol (2.17 ppm), verbenone (1.85 ppm), yomogi alcohol (1.50 ppm), and germacren-4-ol (1.43 ppm). The major volatile constituents of the extract by SPSE were 1,8-cineole (8.12 ppm), artemisia acetate (4.22 ppm), alpha-thujone (3.20 ppm), beta-caryophyllene (2.39 ppm), bornyl acetate (2.05 ppm), borneol (1.80 ppm), and trans-beta-farnesene (1. 78 ppm).

Artemisia↗

Formation of volatile branched chain esters in bananas (Musa sapientum L.).

Substrates controlling the formation of branched chain volatile esters in ripening bananas were investigated by the application of alcohol and amino acid precursors to whole fruit and tissue samples. The resulting changes in the profile of the volatile esters were determined using SPME and GC. These changes revealed the selectivity characteristics of the esterification enzyme AAT, the availability of acyl CoA's for ester formation, and the role of substrate supply on volatile production. The results obtained suggest that substrate supply is a major determinant of the quantitative and qualitative composition of the resulting aroma profile.

Esterification↗

Effects of olive, canola, and sunflower oils on the formation of volatiles from the Maillard reaction of lysine with xylose and glucose.

Some important edible oils (extra virgin olive oil, canola oil, and sunflower oil) were added to aqueous glucose-lysine or xylose-lysine model systems to investigate their effect on the formation of volatiles from the Maillard reaction (MR). The volatile compounds were extracted by a Likens-Nickerson apparatus and quantified. Pyrazines, Maillard reaction products with an important impact on food flavor, appeared to be particularly sensitive to the presence of the oils in both the xylose-lysine and glucose-lysine model systems. The unsubstituted pyrazine was formed more with olive oil, less with canola oil, and even less with sunflower oil, whereas 2-methylpyrazine, 2,5-methylpyrazine, and 2,3-dimethylpyrazine were formed less with olive oil, more with canola oil, and even more with sunflower. The oxidative states of the oils and their fatty acid fingerprints were determined: the results indicated that the relative amounts of the pyrazines are sensitive to the degree of unsaturation of the oil. The autoxidation of the volatile compounds generated from the MR, investigated by the addition of free radical modulators (antioxidants alpha-tocopherol, 2,6-di-tert-butyl-4-methylphenol, and rosemary extract; or pro-oxidant alpha,alpha'-azobis-isobutyronitrile, a free radical initiator), was limited in respect to aqueous model systems.

Fatty Acids↗

Inhibitory effect of betel quid on the volatility of methyl mercaptan.

Betel quid, a popular natural masticatory in Taiwan, is mainly composed of fresh areca fruit, Piper betle (leaf or inflorescence), and slaked lime paste. People say that halitosis disappears during betel quid chewing. In this study, the removal of mouth odor during betel quid chewing was discussed by using a model system which measured its inhibition on the volatility of methyl mercaptan. Results showed that crude extracts of betel quid (the mixture of areca fruit, Piper betle, and slaked lime paste) and extracts of the mixture of areca fruit and slaked lime paste exhibited marked effects on the volatility of methyl mercaptan, and the inhibition function increased when increasing amounts of slaked lime paste were added. The same condition (increased inhibition) was also found by replacing the slaked lime paste with alkaline salts (calcium hydroxide, potassium hydroxide, or sodium hydroxide). Areca fruit, the major ingredient of betel quid, contained abundant phenolics. However, the crude phenolic extract of areca fruit did not show any inhibitory activity on the volatility of methyl mercaptan. Great inhibitory activity occurred only when the crude phenolic extract of areca fruit was treated with alkali. Further studies by using gel filtration determined that the effect probably came from the oxidative polymerization of phenolics of areca fruit after alkaline treatment.

Areca↗

Free volatile components of passion fruit puree obtained by flash vacuum-expansion.

Purple passion fruits were processed by the flash vacuum-expansion process. Volatile components were analyzed in purees from steam-heated fruits, steam-heated then vacuum-expanded fruits and their aromatic liquors, and fruit rind, in comparison with a reference single-strength juice. After steam heating, the puree was enriched in esters arising from the rind. Steam-heated then vacuum-expanded fruits yielded a puree impoverished in volatiles due to evaporation of approximately 10% of water. These volatile compounds were mostly recovered in aromatic liquors.

Food Handling↗

Free and bound volatile composition and characterization of some glucoconjugates as aroma precursors in melón de olor fruit pulp (Sicana odorifera).

Free and glycosidically bound volatiles obtained from the fruit pulp of Sicana odorifera by liquid-liquid extraction and by chromatography, followed by enzymatic hydrolysis with Rohapect D5L, respectively, were analyzed by capillary gas chromatography (HRGC), HRGC-mass spectrometry (HRGC-MS), and HRGC-Olfatometry (HRGC-O) analyses. A total of 37 free volatiles was detected, with the major components being 3-methyl-2-butanol, 3-hydroxy-2-butanone, ethyl 3-hydroxybutanoate, and (Z)-3-hexenol. Among the 22 detected glycosidically bound compounds, 4-hydroxybenzyl methyl ether, 4-hydroxybenzyl alcohol, and 2-phenylethanol were found to be the major constituents. Additionally, two glucoconjugates were isolated in pure form by multilayer coil countercurrent chromatography (MLCCC) of the glycosidic extrac and further purification. Their structures were elucidated by MS and NMR analyses to be the novel [4-(beta-D-glucopyranosyloxy)benzyl] 2,3-dihydroxy-3-methylbutanoate 2, and the known 4-(beta-D-glucopyranosyloxy)benzyl alcohol 1. Compounds 1 and 2 are precursors of 4-hydroxybenzyl alcohol, one of the major volatiles generated by enzymatic hydrolysis of the glycosidic fraction.

Cucurbitaceae↗

Solid-phase microextraction of volatile components from natural grassland plants.

The volatile components from nine plants growing on natural grasslands in Auvergne, central France, selected for the broad qualitative and quantitative diversity of their terpenoid fractions, were analyzed by high-resolution gas-phase chromatography and mass spectrometry (HRGC-MS) after static headspace solid-phase microextraction (SHS-SPME). SHS-SPME allowed all the plant material to be analyzed under the same conditions despite its wide-ranging composition. This is not always possible with other extraction methods. Using an apolar poly(dimethylsiloxane) (PDMS) phase, numerous terpenoid hydrocarbons, together with alcohols, cyclic ethers, and esters, were extracted. Its ease of use and the high resolution of the chromatographic profiles obtained make SHS-SPME well suited to the rapid characterization of the main components of the volatile fraction of plants. Of the nine plants studied, four (Meum athamanticum, Pimpinella saxifraga, Achillea millefolium, and Thymus pulegioides) exhaled more than 60 different volatile components. Certain terpenes present in large amounts in these plants might help link dairy products to grazing pasture, thus improving food traceability.

Alcohols↗

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.

Chromatography, Gas↗

Volatile flavor components of stored nonfat dry milk.

Nonfat dry milk (NDM) is widely used both as an ingredient in other preparations and for direct consumption. Flavor quality of NDM is a critical parameter because it can directly impact final product quality. Flavors can be formed in NDM during subsequent storage. Identification of compounds responsible for storage-induced flavors is necessary to correlate sensory quality with potential sources of the flavors. Six NDM samples were selected for volatile flavor analysis based on sensory analysis and storage time. Volatile components were extracted by direct solvent extraction/high vacuum distillation. Volatile extracts were separated into neutral/basic and acidic fractions and analyzed by gas chromatography-olfactometry (GCO) and aroma extract dilution analysis (AEDA). A variety of aldehydes, ketones, and free fatty acids were responsible for generation of flavors in stored NDM. The following compounds exhibited high aroma impact by AEDA: 3-(methylthio)propanal (boiled potato); o-aminoacetophenone (corn tortilla); 2,5-dimethyl-4-hydroxy-3(2H)-furanone and 2-methyl-3-hydroxy-4H-pyran-4-one (burnt sugar); butanoic acid (cheesy); pentanoic acid (sweaty); acetic and hexanoic acids (sour/vinegar); octanoic, decanoic, and dodecanoic acids (waxy); p-cresol (cowy/barny); 3-methylindole (fecal); dimethyl trisulfide (cabbage); (E,E)-2,4-decadienal (fried/fatty); furfuryl alcohol (rubber/vitamin); phenylacetic acid (rose-like); and 1-octen-3-one (mushroom).

Animals↗

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.

Antioxidants↗

Comparison of volatile compounds in water- and oil-soluble annatto (Bixa orellana L.) extracts.

Annatto is a natural food colorant extracted from the seeds of the Bixa orellana L. plant. Annatto is used in Latin American cuisine to add a deep red color as well as distinctive flavor notes to fish, meat, and rice dishes. In the United States, annatto extracts are primarily used to impart orange/yellow hues to cheese and other dairy foods. The objective of this study was to identify and compare volatile compounds present in water- and oil-soluble annatto extracts. Volatile compounds were recovered using dynamic headspace-solvent desorption sampling and analyzed using GC-MS. Compounds were identified by comparison to a mass spectral database, Kovats indexes, and retention times of known standards. Of the 107 compounds detected, 56 compounds were tentatively identified and 51 were positively identified. Volatile profile differences exist between water- and oil- soluble extracts, and annatto extracts contain odorants with the potential to influence food aroma.

Alcohols↗