## 3 Results  
### Semi-Quantitative Analysis of Volatiles in Wine  
Ethanol was present in all samples, including the matrix blank (model wine). The chromatographic peak at RT 3.9 min is ethanol in all total ion chromatograms (TIC). Since ethanol is present in all samples, it is not included in the further discussion. The signal-to-noise ratio of total ion chromatograms of \(\geq\)10 was considered acceptable. Percent spectral match of sample spectra to library spectra was acceptable at 65% or higher. 58 unique VOCs are detected in the headspace of Marquette and Frontenac wines produced from grapes harvested at 22\({}^{\circ}\) and 24\({}^{\circ}\) Brix (Table 2). Compounds including isoamyl alcohol, ethyl octanoate, 2,4-di-tert-butylphenol, ethyl acetate, ethyl hexanoate, ethyl decanoate, isocyanatomethane, and ethyl l lactate are present in wine samples at higher concentrations relative to 0.205 ppm of 3-nonanone IS and assuming equal detector response for all analytes. A full summary of retention times, published aroma descriptors, and relative concentrations of these 58 analytes detected in all samples are given in the Supplementary Materials, Table S1. Principal component analysis (PCA) was performed on the 58 VOCs found in all wine samples (Figure 2). Please refer to Table 2 for compound identification. Wine produced from Frontenac berries harvested at 22\({}^{\circ}\) Brix (F22-1, F22-2, and F22-3) is associated with higher levels of 1-octanol (compound **35**), ethyl laurate (compound **53**), methylbutanal (compound **8**), undecane (compound **31**), and ethyl \begin{table}
\begin{tabular}{c c c} \hline \hline
**No.** & **Compound** & **Relative Retention**1  \\ \hline
**1** & Acetaldehyde & 0.18 \\
**2** & Methyl acetate & 0.22 \\
**3** & 2-nitropropane & 0.22 \\
**4** & Isobutyraldehyde & 0.22 \\
**5** & Ethanol & 0.25 \\
**6** & Ethyl acetate & 0.27 \\
**7** & Acetic acid phenyl ester & 0.30 \\
**8** & Methylbutanal & 0.31 \\
**9** & 1,1-dimethyl-hydroazine & 0.33 \\
**10** & \(n\)-Propyl acetate & 0.38 \\
**11** & Isobutanol & 0.39 \\
**12** & Ethyl isobutyrate & 0.42 \\
**13** & 1-butanol & 0.46 \\
**14** & Isobutyl acetate & 0.46 \\
**15** & Ethyl butyrate & 0.51 \\
**16** & Isoamyl alcohol & 0.54 \\
**17** & 3-methylpentane & 0.55 \\
**18** & Isoyanatomymethane & 0.55 \\
**19** & Ethyl methylbutyrate & 0.58 \\
**20** & Ethyl 3-methylbutanoate & 0.59 \\
**21** & Isoamyl acetate & 0.65 \\
**22** & Ethyl lactate & 0.72 \\
**23** & Syrene & 0.73 \\
**24** & 1-hexanol & 0.76 \\
**25** & Acetic acid & 0.79 \\
**26** & 1,2-dimethyl alkylrazine & 0.79 \\
**27** & Ethyl hexanoate & 0.85 \\
**28** & 1-Heptonal & 0.92 \\
**29** & 2,3,4-trimethylpentane & 0.94 \\
**30** & Isoamyl butyrate & 0.94 \\
**31** & Undcane & 0.97 \\
**32** & Benzaldehyde & 0.97 \\
**33** & 3-Nonanone (IS) & 1.00 \\
**34** & Methyl octanoate & 1.06 \\
**35** & 1-Octanol & 1.06 \\
**36** & Octyl formate & 1.06 \\
**37** & Linalolol & 1.08 \\
**38** & Phenylethanal & 1.11 \\
**39** & Ethyl octanoate & 1.16 \\
**40** & 1-Nonanol & 1.20 \\
**41** & Pentanoic acid & 1.25 \\
**42** & Propyol octanoate & 1.28 \\
**43** & Ethyl nonanoate & 1.30 \\
**44** & Methyl salicylate & 1.30 \\
**45** & Methyl acetyls salicylate & 1.30 \\
**46** & Phenyl ethyl alcohol & 1.34 \\
**47** & Pheneethyl isobutyrate & 1.37 \\
**48** & Pheneyl phenyl acetate & 1.37 \\
**49** & Ethyl decanoate & 1.42 \\
**50** & Octanoic Acid & 1.47 \\
**51** & 9-damascone & 1.47 \\
**52** & Isoamyl octanoate & 1.49 \\
**53** & Ethyl laurate & 1.66 \\
**54** & 2,4-diet-butylphenol & 1.76 \\
**55** & Diethyl phthalate & 1.85 \\
**56** & Ethyl tetradecanoate & 1.89 \\
**57** & Ethyl hexadecanoate & 2.14 \\
**58** & Dibutyl phthalate & 2.37 \\ \hline \hline \end{tabular}
\end{table} 
Table 2: Compounds identified in the headspace of Marquette and Frontenac wines using AMDIS and a lab developed mass spectral library. tetradecanoate (compound **56**).