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1 Sensory profile analysis: Preliminary characterization of wine aroma profiles using solid phase microextraction and simultaneous chemical and sensory analyses Iowa State University and South Dakota State University Ames, IA Somchai Rice*, Jacek Koziel*, Devin Maurer*, Anne Fennell** *Department of Agricultural and Biosystems Engineering, Iowa State University **Department of Plant Science, South Dakota State University Background and Rationale: Sensory profile analysis (iv) is part of Obj. 1a Evaluate cold climate cultivar performance under a wide range of climates throughout the Upper Midwest and Northeast to match cultivar with site. Wine aroma profiles from three wine varieties (Marquette, Frontenac, and St. Croix, 2012 SDSU) were characterized. Results will be compared with the development of volatiles in crushed berries, and volatiles emitted by maturing grapes to inform how grape growing and processing can affect wine aroma. Treatments/Methods: Wine aroma profiles from a selection of the sites will be characterized using solid phase microextraction coupled with multidimensional gas chromatography-mass spectrometry-olfactometry for simultaneously chemical and sensory analysis. This method couples identification of flavor and aroma-active compounds with detection and description by humans. Preliminary work has been completed with 2012 Marquette, Frontenac, and St. Croix wine in anticipation of the major effort with wine aroma analyses in years 2 to 4. An aromagram was recorded by a panelist utilizing the human trained panelist using nose as a detector. Aroma events resulting from separated compounds eluting from the gas chromatography column were characterized for aroma descriptor with a 64-descriptor panel and aroma intensity with Aromatrax software (MOCON Texas Laboratory, Round rock, TX). The olfactory responses of a panelist were recorded using AromaTrax software by applying an aroma tag to a peak or a region of the chromatographic separation.

2 Results: Examples of simultaneous chemical and sensory analyses of Marquette, Frontenac, and St. Croix wine are presented in the following figures and tables. Simultaneous chemical and sensory analysis of 2012 Marquette wine (Fennell, SDSU) Figure 1 Example of a typical overlay of total ion chromatogram (TIC) and aromagram showing simultaneous chemical and sensory analysis of Marquette wine using multidimensional gas chromatography-mass spectrometry-olfactometry. Red signal is TIC from mass selective detector, black signal is aromagram generated by trained human panelist. Details for each signal are given in Table 1. Simultaneous chemical and sensory analysis of 2012 Frontenac wine (Fennell, SDSU) Figure 2 Example of a typical overlay of total ion chromatogram (TIC) and aromagram showing simultaneous chemical and sensory analysis of Frontenac wine using multidimensional gas chromatography-mass spectrometry-olfactometry. Red signal is TIC from mass selective detector, black signal is aromagram generated by trained human panelist. Details for each signal are given in Table 2.

3 Simultaneous chemical and sensory analysis of 2012 St. Croix wine (Fennell, SDSU) Figure 3 Example of a typical overlay of total ion chromatogram (TIC) and aromagram showing simultaneous chemical and sensory analysis of St. Croix wine using multidimensional gas chromatography-mass spectrometry-olfactometry. Red signal is TIC from mass selective detector, black signal is aromagram generated by trained human panelist. Details for each signal are given in Table 3. What the results mean: Preliminary simultaneous chemical and sensory analysis of Marquette, Frontenac, and St. Coix wine shows 60+ chemical compounds of which more than 20+ produce distinct flavor aroma as detected by human nose. Many of the aromas are desirable for enhanced wine aroma. There is no data comparing cold climate wine aromas with wines currently marketed. Comparisons and benchmarking of aromas in wines made from cold hardy grapes is warranted.

4 Table 1 Summary of compounds detected using simultaneous chemical and sensory analysis of Marquette wine. Peak # RT(min) Compound CAS % Match Published Aroma Descriptor 1 Detected Aroma Descriptor 3.32 Methyl acetate Propylene glycol n-propyl acetate Fruit, Apple, Banana Butter pentanol Fruit 6.37 Ethyl isobutyrate Sweet, Rubber 6.38 Propyl butyrate Pineapple, Solvent Fruity Neutral 6.97 Isobutyl acetate butanol Medicine, Fruit 7.64 Ethyl butyrate Apple Neutral 0/ Fruity Unpleasant -1/Skunk/Fruity 8.71 Amyl alcohol Balsamic methylpentane Ethyl 3-methylbutanoate Fruit Neutral 0/ Cut Grass/ Floral 9.80 Isoamyl acetate Banana 9.80 Amyl acetate Neutral 0/ Cut Grass Neutral 0/ Cut Grass Ethyl lactate Fruit Neutral Hexanol Resin, Flower, Green Acetic acid Sour Ethyl hexanoate Apple peel, Fruit Floral/Skunk Pleasant Neutral Heptanol Chemical, Green Methacrolein Isobutyric acid Rancid, Butter, Cheese Neutral 0/ Burnt match Ethyl heptanoate Fruit γ-butyrolactone Caramel, Sweet Octanol Chemical, Metal, Burnt

5 16.97 Linalool Flower, Lavender Pleasant +1/ Floral Unpleasant -3/ Unpleasant Ethyl octanoate Fruit, Fat Pleasant +3/ Floral Cyclohexane Nonanol Fat, Green octanolide Peach Isopentyl acetate (+)-4-Carene α-terpineol Oil, Anise, Mint Ethyl nonanoate Heptanoic acid Pentanoic acid Sweat Citronellol Rose Methyl salicylate Peppermint Neutral 0/ Smokey/ Rubber Benzyl alcohol Phenylethyl alcohol Honey, Spice, Rose, Lilac Phenethyl isobutyrate Ethyl salicylate Wintergreen, Mint Neutral 0/ Burnt Match Ethyl decanoate Grape ,3,4-trimethylpentane Isoamyl octanoate Floral β-damascenone Apple, Rose, Honey Octanoic Acid Sweat, Cheese Neutral 0/ Berry Octyl formate Butylated Hydroxytoluene Neutral 0/ Berry Eugenol Clove, Honey Ethyl laurate Leaf Nerolidol Wood, Flower, Wax Ethylhydroxyhexanoate Fresh n-decanoic acid Rancid, Fat β-irone Ethyl tetradecanoate Ether Ethyl undecanoate Cognac, Coconut undecanol Mandarin

6 32.45 Ethyl hexadecanoate Wax Methyl linoleate Ethyl stearate Camphene Camphor Peak # corresponds to numbered peaks in aromagram (black signal) of Figure 1. RT = retention time in minutes. % Match = net probability match of mass spectra of sample to target specialty mass spectral library. Published Aroma Descriptor compiled from Flavornet 1. Detected Aroma Descriptor is generated by trained human panelist. Table 2 Summary of compounds detected using simultaneous chemical and sensory analysis of Frontenac wine. Peak # RT(min) Compound CAS % Match Published Aroma Descriptor 1 Detected Aroma Descriptor 2.67 Acetaldehyde Pungent, Ether Unpleasant Ethanol 3.91 Propylene glycol n-propyl acetate Fruit, Apple, Banana Pentanone Ether, Fruit Butter pentanol Fruit Floral 5.56 Propyl propanoate Pineapple Neutral 6.26 Methyl acetate Sweaty/Floral methyl-3-pentanone Mint 6.96 Butyl acetate Pear 6.98 Isobutyl acetate Fruit, Apple, Banana butanol Medicine, Fruit 7.65 Ethyl butyrate Apple Pleasant +1/ Sherry 8.71 Amyl alcohol Balsamic Sweaty/Floral/Strawberry methylpentane Methyl propionate Ethyl 3-methylbutanoate Fruit 9.80 Isoamyl acetate Banana Banana Medicinal Ethyl lactate Fruit Taco Shell hexanol Resin, Flower, Green

7 12.91 Acetic acid Sour Ethyl hexanoate Apple peel, Fruit Cherry/Fruity Garlic Heptanol Chemical, Green methyl-3-heptanone Ethyl heptanoate Fruit methylvaleric acid Methylbutyric acid Cheese, Sweat γ-butyrolactone Caramel, Sweet Octanol Chemical, Metal, Burnt Ethyl octanoate Fruit, Fat Unpleasant ethyl-1-butanol octanolide Peach Propyl octanoate ethyl butyric acid Ethyl nonanoate Heptanoic acid Pentanoic acid Sweat Methyl salicylate Peppermint Methyl decanoate Wine Hexanoic acid, methyl ester Fruit, Fresh, Sweet Octyl formate Phenylethyl alcohol Honey, Spice, Rose, Lilac Phenethyl isobutyrate Ethyl decanoate Grape Fruity methyl naphthalene Isoamyl octanoate β-damascenone Apple, Rose, Honey Octanoic Acid Sweat, Cheese Spicy Raspberry Strawberry Strawberry Jam Nonanol Fat, Green Ethyl laurate Leaf γ-hexalactone Coumarin, Sweet Nerolidol Wood, Flower, Wax ,3,4-trimethylpentane

8 26.76 n-decanoic acid Rancid, Fat Fruity undecanol Mandarin Ethyl tetradecanoate Ether Decanol Fat Ethyl hexadecanoate Wax Methyl oleate Methyl linoleate Ethyl stearate Perillaldehyde Spice (1R)-(+)-trans-isolimonene Camphene Camphor Caryophyllene oxide Herb, Sweet, Spice Peak # corresponds to numbered peaks in aromagram (black signal) of Figure 2. RT = retention time in minutes. % Match = net probability match of mass spectra of sample to target specialty mass spectral library. Published Aroma Descriptor compiled from Flavornet 1. Detected Aroma Descriptor is generated by trained human panelist. Table 3 Summary of compounds detected using simultaneous chemical and sensory analysis of St. Croix wine. Peak # RT(min) Compound CAS % Match Published Aroma Descriptor 1 Detected Aroma Descriptor Sweet 2.67 Acetaldehyde Pungent, Ether Unpleasant Methyl acetate Alcoholic/Sweet 4.03 n-propyl acetate Fruit, Apple, Banana Buttery pentanol Fruit Fruity Body Odor Pleasant +1/Unpleasant -1/Fruity 6.38 Ethyl isobutyrate Sweet, Rubber 6.97 Isobutyl acetate Fruit, Apple, Banana 6.98 Butyl acetate Pear butanol Medicine, Fruit 7.64 Ethyl butyrate Apple Strawberry Spicy Body Odor/Woody/Body Odor/Chocolate/Cherry

9 8.75 Amyl alcohol Balsamic methylpentane Ethyl 3-methylbutanoate Fruit ,2-Dimethylvaleric acid Ethyl (E)-2-crotonate Isoamyl acetate Banana Strawberry Jam Sweet Ethyl lactate Fruit Unpleasant -1/Medicinal hexanol Resin, Flower, Green Fruity Nutty Acetic acid Sour Methyl formate Ethyl hexanoate Apple peel, Fruit Floral/Fruity Spicy Taco Shell Heptanol Chemical, Green Butyl formate Propylene glycol Ethyl 3-hydroxybutanoate Marshmallow Isobutyric acid Rancid, Butter, Cheese Ethyl heptanoate Fruit Methyl octanoate Orange Octanol Chemical, Metal, Burnt ,3,4-trimethylpentane Linalool Flower, Lavender Isovaleric acid Sweat, Acid, Rancid Methylbutyric acid Cheese, Sweat Ethyl octanoate Fruit, Fat Rusty/Metallic/Medicinal Woody Nonanol Fat, Green Ethyl nonanoate Pentanoic acid Sweat Citronellol Rose Citronellyl butyrate Fruit, Sweet, Rose Citronellolformate Methyl salicylate Peppermint

10 20.65 Benzyl alcohol Sweet, Flower Octyl formate Dimethyl octanol Ethyl phenylacetate Fruit, Sweet Phenylethyl alcohol Honey, Spice, Rose, Lilac Phenethyl isobutyrate Geraniol Rose, Geranium Ethyl decanoate Grape Isoamyl octanoate β-damascenone Apple, Rose, Honey Octanoic Acid Sweat, Cheese Sweet Sweet/Floral Honey/Pear Sweet/Strawberry Phenethyl isovalerate Phenethyl phenyl acetate undecanol Mandarin Butylated Hydroxytoluene Fruity Eugenol Clove, Honey Ethyl laurate Leaf Woody γ-hexalactone Coumarin, Sweet Ethyl cinnamate Honey, Cinnamon Nerolidol Wood, Flower, Wax Ethylhydroxyhexanoate Fresh n-decanoic acid Rancid, Fat Ethyl tetradecanoate Ether (-)-β-citronellene Ethyl undecanoate Cognac, Coconut Ethyl hexadecanoate Wax Methyl linoleate Ethyl stearate Peak # corresponds to numbered peaks in aromagram (black signal) of Figure 3. RT = retention time in minutes. % Match = net probability match of mass spectra of sample to target specialty mass spectral library. Published Aroma Descriptor compiled from Flavornet 1. Detected Aroma Descriptor is generated by trained human panelist. References 1 Acree, T., and H. Arn Flavornet. Available at (verified 03 Jan 2014).

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