Dynamic headspace gas chromatography/mass spectrometry characterization of volatiles produced in fish oil enriched mayonnaise during storage

Protection against lipid oxidation and formation of unpleasant fishy and rancid off-flavors in oil-in-water food emulsions, such as fish oil enriched mayonnaise, is difficult to achieve. Volatile profiles from stored mayonnaises with different oil phase compositions were collected using a developed dynamic headspace sampling technique, in which interfering acetic acid was removed in situ with potassium hydroxide, and subsequently 148 volatiles were characterized and monitored by gas chromatography/mass spectrometry. Multivariate statistics showed correlation between the concentration of 62 volatiles and the fish oil and storage parameters, indicating the formation of lipid oxidation products, which impose fishy off-flavors. Further verification was obtained by gas chromatography/olfactometry, by which, among 78 odors, cis-4-heptenal and trans,cis-2,4-heptadienal were detected as distinct fishy notes. In total, 27 volatiles, including 1-penten-3-one, cis-2-penten-1-ol, cis-3-hexenal, cis-4-heptenal, 1-octen-3-one, 1,cis-5-octadien-3-one, 1-octen-3-ol, trans,cis-2, 4-heptadienal, and trans,cis-2,6-nonadienal, were suggested to contribute to the developed unpleasant fishy and rancid off-flavors.     

Lipid oxidation in milk, yoghurt, and salad dressing enriched with neat fish oil or pre-emulsified fish oil

This study compared the oxidative stabilities of fish-oil-enriched milk, yoghurt, and salad dressing and investigated the effects on oxidation of adding either neat fish oil or a fish-oil-in-water emulsion to these products. Milk emulsions had higher levels of a fishy off-flavor and oxidized faster, as determined by the peroxide value and volatile oxidation products, than fish-oil-enriched yoghurt and dressing, despite the fact that dressings had a higher fish oil content and were stored at room temperature. Additionally, fish-oil-enriched yoghurt generally had higher oxidative stability than fish-oil-enriched dressings, irrespective of the mode of fish oil addition. Yoghurt thus seemed to be a good delivery system of lipids containing n-3 polyunsaturated fatty acids. Different effects of adding fish oil either as neat fish oil or as a fish-oil-in-water emulsion were observed for milk, yoghurt, and dressing. Yoghurt and dressing enriched with neat fish oil were more stable than those enriched with a fish-oil-in-water emulsion, whereas milk enriched with neat fish oil was less stable than milk enriched with the fish-oil-in-water emulsion. Overall, it seemed that application of neat fish oil was a good option for preserving the final quality in yoghurt and dressings, but a pre-emulsion may still be considered for the fish oil enrichment of certain food products, for example, milk.     

Characterization of the antioxidant activity of sugars and polyhydric alcohols in fish oil emulsions

Polyols have been incorporated into fish oil emulsions as a means for the inhibition of lipid oxidation and suppression of fishy flavor. However, the role of sugars and polyhydric alcohols as antioxidants has not been clearly established. Selected polyols were evaluated for their performance as antioxidants and modifiers of oxidation pathways in a model system. Oil/water (O/W) emulsions were prepared with freshly steam-deodorized menhaden oil. A layer of emulsion in aluminum pans held at 5 degrees C was exposed to 2550 lx fluorescent lights for 24 h before peroxide values and volatile flavor compounds were analyzed by GC headspace entrainment procedure. Antioxidant activity was confirmed for fructose, sucrose, raffinose, sorbitol, or mannitol when incorporated at 16% of the aqueous phase into model fish oil-in-water emulsions. Peroxide values were suppressed 10-18% in treated samples compared to control samples. Viscosity data did not exclude possible contributions from a restricted oxygen diffusion mechanism in the antioxidant activity, but revealed that emulsion viscosity did not govern fish oil oxidation rates. Combining polyols with phenolic antioxidants (alpha-tocopherol, BHT, or TBHQ) frequently diminished the antioxidant activity compared to that for individual phenolic antioxidants, which was interpreted as indicating that the H-donating activity of phenolic antioxidants was hindered by the H-bonding activity of polyols. A viscosity-based inhibition of the retroaldol conversion of (E,Z)-2,6-nonadienal to (Z)-4-heptenal with a high fructose concentration (67%) was attributed to a restriction of molecular mobility of reactants, but the conversion was only slightly inhibited by the concentration of fructose (16%) used in experimental emulsions. The data supported a hypothesis that either or both free radical scavenging and transition state metal chelation activities were provided by polyols in fish oil emulsions. Also, polyols retarded the water-requiring retroaldol decomposition of (E,Z)-2,6-nonadienal to (Z)-4-heptenal in the model systems and the reaction may be involved in some suppression of fishy flavors in emulsions.     

Freshness assessments of Moroccan sardine (Sardina pilchardus): comparison of overall sensory changes to instrumentally determined volatiles

Freshness of ice-stored sardine was assessed by two sensory methods, the quality index method (QIM) and the European Union freshness grading system, and by instrumental means using the method of aroma extract dilution analysis. Screening of sardine potent volatiles was carried out at three freshness stages. In the very fresh state, the plant-like fresh volatiles dominated the odor pattern, with the exception of methional. Overall odor changes in sardine throughout storage correlated with changes in the concentration of some potent volatiles: after 2 days of ice storage, (Z)-4-heptenal, (Z)-1,5-octadien-3-one, and methional imparted an overall "fishy" odor character to sardine, whereas at a lower sensory grade (B), the compounds (E)-2-nonenal and (E,Z)-2,6-nonadienal could be, in part, associated with the slightly rancid aroma top notes. Trimethylamine was detected as a highly volatile odorant using solid-phase microextraction (SPME) headspace analysis of refrigerator-stored sardine. Intensity and sensory characteristics of some SPME determined volatiles, for example, 3-methylnonane-2,4-dione, were closely related to overall odor changes. SPME headspace analysis may be useful in the characterization of off-flavors in fish.     

Comparison of the most odor-active compounds in fresh and dried hop cones (Humulus lupulus L. variety spalter select) based on GC-olfactometry and odor dilution techniques

Application of aroma extract dilution analysis on the volatiles obtained from dried cones of Spalter Select hops grown in the German hop-growing area of Hallertau revealed 23 odorants in the flavor dilution (FD) factor range of 16-4096, 20 of which could be identified. On the basis of high FD factors, trans-4, 5-epoxy-(E)-2-decenal, linalool, and myrcene were identified as the most potent odorants, followed by ethyl 2-methylpropanoate, methyl 2-methylbutanoate, (Z)-1,5-octadien-3-one, nonanal, (E,Z)-1,3, 5-undecatriene, 1,3(E),5(Z),9-undecatetraene, propyl 2-methylbutanoate, 4-ethenyl-2-methoxyphenol, and 1-octen-3-one. Ten of the high-impact hop aroma compounds had previously not been identified as hop constituents and, in particular, 1,3(E),5(Z), 9-undecatetraene has not yet been reported as a food odorant. In an extract obtained from fresh hops, in addition to the odorants found in dry hops, (Z)-3-hexenal was characterized as a further key odorant rendering an additional green aroma note to the fresh material.     

Gas chromatographic-olfactometric characterization of aroma compounds in two types of cashew apple nectar

Cashew apple nectar is a secondary product from the production of cashew nuts and possesses an exotic tropical aroma. Aroma volatiles in pasteurized and reconstituted (from concentrate) Brazilian cashew apple nectars were determined using GC-MS and split, time-intensity GC-olfactometry (GC-O)/GC-FID. Methional, (Z)-1,5-octadien-3-one, (Z)-2-nonenal, (E,Z)-2,4-decadienal, (E,E)-2,4-decadienal, beta-damascenone, and delta-decalactone were identified for the first time in cashew apple products. These compounds plus butyric acid, ethyl 3-methylbutyrate, 2-methylbutyric acid, acetic acid, benzaldehyde, homofuraneol, (E)-2-nonenal, gamma-dodecalactone, and an unknown were the most intense aroma volatiles. Thirty-six aroma volatiles were detected in the reconstituted sample and 41 in the pasteurized sample. Thirty-four aroma active components were common to both samples. Ethyl 3-methylbutyrate and 2-methylbutyric acid were character impact compounds of cashew apple (warm, fruity, tropical, sweaty). Using GC-pFPD, 2-methyl-3-furanthiol and bis(2-methyl-3-furyl) disulfide were identified for the first time in cashew apple. Both were aroma active (meaty).     

Comparison of three lychee cultivar odor profiles using gas chromatography-olfactometry and gas chromatography-sulfur detection

Odor volatiles in three major lychee cultivars (Mauritius, Brewster, and Hak Ip) were examined using gas chromatography-olfactometry, gas chromatography-mass spectrometry, and gas chromatography-pulsed flame photometric detection. Fifty-nine odor-active compounds were observed including 11 peaks, which were associated with sulfur detector responses. Eight sulfur volatiles were identified as follows: hydrogen sulfide, dimethyl sulfide, diethyl disulfide, 2-acetyl-2-thiazoline, 2-methyl thiazole, 2,4-dithiopentane, dimethyl trisulfide, and methional. Mauritius contained 25% and Brewster contained 81% as much total sulfur volatiles as Hak Ip. Cultivars were evaluated using eight odor attributes: floral, honey, green/woody, tropical fruit, peach/apricot, citrus, cabbage, and garlic. Major odor differences in cabbage and garlic attributes correlated with cultivar sulfur volatile composition. The 24 odor volatiles common to all three cultivars were acetaldehyde, ethanol, ethyl-3-methylbutanoate, diethyl disulfide, 2-methyl thiazole, 1-octen-3-one, cis-rose oxide, hexanol, dimethyl trisulfide, alpha-thujone, methional, 2-ethyl hexanol, citronellal, (E)-2-nonenal, linalool, octanol, (E,Z)-2,6-nonadienal, menthol, 2-acetyl-2-thiazoline, (E,E)-2,4-nonadienal, beta-damascenone, 2-phenylethanol, beta-ionone, and 4-vinyl-guaiacol.     

Aroma of fresh oysters Crassostrea gigas: composition and aroma notes

In contrast to many foods, very little is known about the aroma of fresh oysters. This study deals with the relationship between extracted volatiles of oysters and their olfactory properties. Nearly 50 volatiles were identified: most of them were principally related to fatty acid oxidation (86%) and particularly to n-3 polyunstaturated fatty acid oxidation (66%). Only one volatile arose from amino acid degradation. Panelists detected 42 odors by sniffing. Among them, only 12 odors were definitely attributed to identified volatile. These odors were green/sulfur/crustacean, mushroom/citrus, and marine/cucumber notes and were attributed to dimethyl sulfide, 1-penten-3-one, hexanal, (2,4)-E,E-heptadienal, 1-octen-3-one, 1-octen-3-ol, 6-methyl-5-hepten-3-one, octanal, (E,Z)-2,6-nonadienal, (E)-2-octenal, and decanal, respectively.     

Impact odorants contributing to the fungus type aroma from grape berries contaminated by powdery mildew (Uncinula necator); incidence of enzymatic activities of the yeast Saccharomyces cerevisiae

Powdery mildew due to the fungus Uncinula necator is an important disease for the vineyard. The development of the fungus at the surface of the berries leads to the occurrence of a very characteristic and sometimes intense mushroom-type odor cited as an important default for grapes quality. Gas chromatography/olfactometry, gas chromatography, and multidimensional gas chromatogaphy/mass spectrometry techniques were used to investigate the most important odorants of grapes diseased by powdery mildew. Among 22 odorants detected, strongly odorant compounds were identified or tentatively identified in purified extracts obtained from grapes diseased by powdery mildew. Aroma extraction dilution analysis (AEDA) analysis revealed that 1-octen-3-one (mushroom odor), (Z)-1,5-octadien-3-one (geranium-leaf odor), and an unidentified odorous zone (fishy-mushroom like odor) were the most potent volatiles of the diseased grapes. In the presence of nonproliferating Saccharomyces cerevisiae yeast cells, and consequently during alcoholic fermentation, the enzymatic reduction of 1-octen-3-one and (Z)-1,5-octadien-3-one to much less odorant compounds, namely 3-octanone and (Z)-5-octen-3-one, was shown. Those results explain to some extent the disappearance of the fungal aroma specific to powdery mildew grapes during alcoholic fermentation.     

茶叶挥发物对鞍形花蟹蛛觅食行为的影响

为了探明茶叶挥发物在鞍形花蟹蛛(Xysticus ephippiatus Simon)搜寻猎物——茶尺蠖(Ectropis obliqua Prout)过程中的作用,采用固相微萃取气相色谱质谱联用技术研究了茶尺蠖取食对茶树叶片挥发物释放的影响,并通过蜘蛛行为观测平台研究了蟹蛛在不同味源侧(觅食斑块)的活动行为。结果表明:对照叶片没有释放出挥发物,经茶尺蠖幼虫取食后的叶片能释放31种挥发物,其中有12种绿叶挥发物、9种萜类及其衍生物、4种芳香族挥发物和6种未知化合物。行为观测表明,雌、雄蟹蛛进入处理味源侧(茶尺蠖取食后的茶树叶片)和对照味源侧(未损伤茶树叶片)的初次选择均不存在差别(P>0.05),雌蛛进入处理味源侧和对照味源侧的频次分别为3.37±0.18和3.43±0.15,二者无明显区别(P>0.05);雄蛛进入两侧的频次分别为3.86±0.21和3.66±0.20,也无明显区别(P>0.05);雌蛛在处理味源侧和对照味源侧的停留时间分别为(922.57±19.59)s和(818.89±29.63)s,有极显著差异(P<0.01),雄蛛在两侧的停留时间分别为(937.97±18.05)s和(814.83±18.97)s,也有极显著差异(P<0.01),表明雌蛛、雄蛛在处理侧的停留时间明显延长。这说明,猎物取食诱导改变了茶树叶片挥发物的释放,而鞍形花蟹蛛能感知挥发物的变化并由此调整在不同觅食斑块中的停留时间。另外,本文还讨论了挥发物在蟹蛛搜寻猎物过程中的生态学意义。     

Effect of milk protein concentrate on lipid oxidation and formation of fishy volatiles in herring mince (Clupea harengus) during frozen storage

The effect of milk protein concentrate (MPC) at 0, 2, 4, and 6% on lipid oxidation and volatile formation in frozen stored herring mince (-18 degrees C) was evaluated by analyzing samples at 0, 2, and 4 months for fatty acid composition, volatiles, and thiobarbituric acid reactive substances (TBARS). Sensory evaluation was also conducted to assess the intensity of fishy odor, and the volatiles were analyzed using static headspace gas chromatography-mass spectrometry (SHGC-MS). The addition of 4 and 6% MPC to herring mince resulted in a 33% and 50% reduction of TBARS, respectively, at month 4 and lessened the intensity of fishy odor throughout storage. However, MPC did not protect fatty acids from enzymatic degradation unless it was added immediately after mincing. Volatile analysis using SHGC-MS showed that 4% MPC was able to reduce headspace volatiles associated with fishy odor. MPC is most effective for reducing 4-heptenal, 3-methyl-1-butanol, 2-hexenal, and 1-penten-3-ol, which are known to be potent odorants associated with lipid oxidation.     

Protection against oxidation of fish-oil-enriched milk emulsions through addition of rapeseed oil or antioxidants

The ability of rapeseed oil and/or different antioxidants (alpha- and gamma-tocopherol mixture, ascorbyl palmitate, and EDTA) to protect fish-oil-enriched milk emulsions against oxidation was investigated. Tocopherol isomers in concentrations similar to those found in natural rapeseed oil were added to rapeseed oil stripped of natural tocopherols. The rapeseed oil with added tocopherols significantly inhibited oxidation in the fish-oil-enriched milk emulsions. In contrast, the emulsions with only fish oil and added alpha- and gamma-tocopherol were less stable than the emulsions with fish oil alone. When added individually, the gamma-tocopherol seemed to inhibit oxidation more efficiently than alpha-tocopherol. Ascorbyl palmitate (AP) almost completely retarded oxidation in the fish-oil-enriched milk emulsions, as determined by PV, volatile oxidation products, and sensory evaluation. AP also prevented the otherwise prooxidant effect of tocopherols added to fish oil before emulsification. No interactions between AP, tocopherols, and EDTA were observed, and EDTA added alone to fish oil did not show antioxidant properties in the milk emulsions. Overall, the results showed that addition of AP or rapeseed oil containing natural tocopherols to fish oil was equally efficient in inhibiting oxidation in the fish-oil-enriched milk emulsions.     

Aroma components of cooked tail meat of American lobster (Homarus americanus)

Key aroma components of cooked tail meat of American lobster (Homarus americanus) were studied by gas chromatography-olfactometry (GCO) techniques. Components of low and intermediate volatility were evaluated by aroma extract dilution analysis of solvent extracts prepared by direct solvent extraction-high vacuum distillation and vacuum steam distillation-solvent extraction, whereas headspace volatile components were assessed by GCO of decreasing headspace (static and dynamic modes) samples. Forty-seven odorants were detected by all techniques. 3-Methylbutanal (chocolate, malty), 2,3-butanedione (buttery), 3-(methylthio)propanal (cooked potato), 1-octen-3-one (mushroom), 2-acetyl-1-pyrroline (popcorn), and (E,Z)-2,6-nonadienal (cucumber), were identified as predominant odorants by all four isolation methods. The highly volatile compounds methanethiol (rotten, sulfurous) and dimethyl sulfide (canned corn) were detected by headspace methods only. These eight odorants along with three unknown compounds with crabby, amine, fishy odors were found to predominate in the overall aroma of cooked lobster tail meat.     

Light-induced off-flavor development in cloudy apple juice

Cloudy apple juice has been found to develop off-flavors during storage in daylight. The development of off-flavors and volatile compounds was monitored in reconstituted juice prepared from 'Golden Delicious' and 'Fuji' apple concentrates stored in glass bottles under fluorescent light (3000 lx, 8 degrees C). A strong metallic off-flavor was formed by photooxidation. A major contributor to the off-flavor was identified as 1-octen-3-one by gas chromatography-olfactometry. In addition, six volatile compounds, pentanal, 2-methyl-1-penten-3-one, hexanal, (E)-2-heptenal, 6-methyl-5-hepten-2-one, and (E)-2-octenal, increased significantly after light exposure and could contribute to the off-flavor. Except for pentanal and hexanal, these volatiles were found only after light exposure. Higher levels of volatiles were observed in juice from 'Golden Delicious' apples than in juice from 'Fuji' apples, and this difference was consistent with higher levels of suspended solids. When the suspended solids were removed by centrifugation, the development of volatiles on exposure to light was reduced significantly.     

Ascorbyl palmitate, gamma-tocopherol, and EDTA affect lipid oxidation in fish oil enriched salad dressing differently

The aim of the study was to investigate the ability of gamma-tocopherol, ethylenediaminetetraacetate (EDTA), and ascorbyl palmitate to protect fish oil enriched salad dressing against oxidation during a 6 week storage period at room temperature. The lipid-soluble gamma-tocopherol (220 and 880 microg g-1 of fish oil) reduced lipid oxidation during storage by partly retarding the formation of lipid hydroperoxides (PV) and by decreasing the concentrations of individual volatile oxidation products by 34-39 and 42-66%, respectively. EDTA (10 and 50 microg g-1 of dressing) was the most efficient single antioxidant, and overall peroxide values and volatiles were reduced by approximately 70 and 77-86%, respectively. Conversely, prooxidant effects were observed with a high concentration of ascorbyl palmitate (300 microg g-1 of fish oil), whereas a low concentration was slightly antioxidative (50 microg/g of fish oil). Finally, a combination of all three antioxidants completely inhibited oxidation during storage, indicating that the prooxidant effects of ascorbyl palmitate were reverted or overshadowed by EDTA and gamma-tocopherol.     

Comparison of odor-active volatile compounds of fresh and smoked salmon

The odorant volatile compounds of raw salmon and smoked salmon have been investigated by two gas chromatography-olfactometry methods (frequency detection and odorant intensity) and gas chromatography-mass spectrometry. After simultaneous steam distillation-solvent extraction with diethyl ether and the recovery of the aromatic extract in ethanol, qualitative olfactometric characterization and identification followed by a quantitative assessment of the odorant volatile compounds were carried out. The origin of many odorant compounds of smoked salmon can be attributed to wood smoke. Another part of smoked salmon aroma is due either to the odorant compounds of the raw fish flesh or to an evolution of fish flesh aroma thanks to the smoking process conditions. Forty-nine odorant compounds have been identified in fresh salmon and 74 in smoked salmon. Carbonyl compounds, such as heptanal or (E,Z)-2,6-nonadienal, show a high detection frequency and odorant intensity in unsmoked fish, giving the flesh its typical fishy odor. For smoked salmon, phenolic compounds, such as cresol or guaiacol, and furanic compounds seem to be responsible for the smoked odor.     

Identification of aroma-active compounds in Jiashi muskmelon juice by GC-O-MS and OAV calculation

To identify aromatic compounds in Jiashi melon juice, gas chromatography-mass spectrometry-olfactometry (GC-MS-O) analysis was used. Odor activity values (OAVs) were also calculated on the basis of the qualitative and quantitative analysis of volatile compounds. Results showed that 42 volatiles were identified, among which 4 compounds, namely, diethyl carbonate, isophorone, 2-butoxyethyl acetate, and menthol, were identified or tentatively identified for the first time as volatiles in melon fruit. Twelve compounds, namely, (2E,6Z)-nona-2,6-dienal, (3Z,6Z)-nona-3,6-dien-1-ol, ethyl butanoate, ethyl 2-methylbutyrate, ethyl 2-methylpropanoate, (Z)-non-6-enal, (E)-2-nonenal, heptanal, methyl 2-methylbutyrate, nonanal, hexanal, and 2-methylpropyl acetate, were identified as the potent odorants of Jiashi melon juice by both OAV and detection frequency analysis (DFA). In addition, seven odorants were detected by all of the panelists and showed higher OAVs, indicating that DFA and OAV resulted in relatively similar "Jiashi" melon aroma patterns.     

Characterization of volatiles and aroma-active compounds in honeybush (Cyclopia subternata) by GC-MS and GC-O analysis

Volatile organic compounds (VOCs) in fermented honeybush, Cyclopia subternata, were sampled by means of a high-capacity headspace sample enrichment probe (SEP) and analyzed by gas chromatography-mass spectrometry (GC-MS). Stereochemistry was determined by means of enantioselective GC-MS with derivatized β-cyclodextrin columns as chiral selectors. A total of 183 compounds, the majority of which are terpenoids (103; 56%), were identified by comparing their mass spectra and retention indices with those of reference compounds or tentatively identified by comparison with spectral library or literature data. Of these compounds, 37 were determined by gas chromatography-olfactometry (GC-O), using detection frequency (DF) and aroma extract dilution analysis (AEDA), to be odor-active (FD ≥ 2). (E)-β-Damascenone, (R/S)-linalool, (E)-β-damascone, geraniol, (E)-β-ionone, and (7E)-megastigma-5,7,9-trien-4-one were identified with the highest FD factors (≥512). The odors of certain compounds, that is, (6E,8Z)-megastigma-4,6,8-trien-3-one, (6E,8E)-megastigma-4,6,8-trien-3-one, (7E)-megastigma-5,7,9-trien-4-one, 10-epi-γ-eudesmol, epi-α-muurolol, and epi-α-cadinol, were perceived by GC-O assessors as typically honeybush-like.     

Identification of potent odorants formed by autoxidation of arachidonic acid: structure elucidation and synthesis of (E,Z,Z)-2,4,7-tridecatrienal.

The aroma composition of autoxidized arachidonic acid was characterized by aroma extract dilution analysis. The most potent odorant was trans-4,5-epoxy-(E)-2-decenal followed by 1-octen-3-one, (E,Z)-2,4-decadienal, (E,Z,Z)-2,4,7-tridecatrienal, (E,E)-2,4-decadienal, and hexanal. (E,Z,Z)-2,4,7-Tridecatrienal was unequivocally identified by mass spectrometry and nuclear magnetic resonance (NMR) data. The stereochemistry of its extended double-bond system was elucidated on the basis of NMR measurements. The target compound was synthesized in four steps starting with bromination of 2-octyn-1-ol, followed by copper-catalyzed coupling of the bromide with ethylmagnesium bromide and (E)-2-penten-4-yn-1-ol. Partial hydrogenation of the resulting C(13)-compound with triple bonds in the positions C-4 and C-7 gave rise to (E,Z,Z)-2,4,7-tridecatrien-1-ol, which was finally oxidized to the target compound. It exhibits a typical egg-white-like, marine-like odor at low concentrations, and an intense orange-citrus, animal-like odor at higher concentrations. Its odor threshold was estimated by gas chromatography-olfactometry to be 0.07 ng/L air, which is of the same order of magnitude as that reported for 1-octen-3-one and (E,E)-2,4-decadienal.