Norisoprenoids, Sesquiterpenes and Terpenoids Content of Valpolicella Wines During Aging: Investigating Aroma Potential in Relationship to Evolution of Tobacco and Balsamic Aroma in Aged Wine

Abstract

During wine aging, tobacco and balsamic aroma notes appear. In this paper, volatile compounds directly or potentially related to those aromas have been investigated in Corvina and Corvinone wines during aging. Corvina and Corvinone are two northern-Italy autochthonous red grape varieties, used to produce Valpolicella Classico and Amarone wines, both characterized by tobacco and balsamic aroma notes. Wines were analyzed shortly after bottling or following model aging at 60°C for 48, 72, and 168 h. Volatile compounds were analyzed by HS-SPME-GC-MS. Results showed that compounds related to tobacco aroma [β-damascenone, 3-oxo-α-ionol, (E)-1-(2,3,6-Trimethylphenyl)-buta-1,3-diene (TPB), and megastigmatrienones] increased in relationship to storage time with different patterns. β-Damascenone and 3-oxo-α-ionol rapidly increased to reach a plateau in the first 48–72 h of model aging. Instead, TPB and megastigmatrienones concentration showed a linear correlation with aging time. During model aging, several cyclic terpenes tended to increase. Among them 1,8-cineole and 1,4-cineole, previously reported to contribute to red wine eucalyptus notes increased proportionally to storage time, and this behavior was clearly associated with reactions involving α-terpineol, limonene, and terpinolene, as confirmed by studies with model wine solutions. Among other relevant volatile compounds, sesquiterpenes appear to contribute potentially balsamic and spicy aroma notes. In this study, linear sesquiterpenes (nerolidol, farnesol) underwent acid hydrolysis during long wine aging, while cyclic sesquiterpenes seemed to increase with time. The chemical pathways associated with evolution of some of the compounds investigated have been studied in model wine.

The Actual and Potential Aroma of Winemaking Grapes

“…Additionally, recent evidence has shown that the molecule can be found in unripe berries of Cabernet Sauvignon and Merlot [119], contributing to the green perception via perceptual interaction with IBMP. A third formation route of 1,8-cineole in wine as product of the reaction of limonene and other terpenols has been also reported [66,121].…”

“…formed very soon, sharp decrease [15,66] Geraniol Always found; up to 10% of total terpenes in Shiraz, 14% in Muscat [144] No [138]; 3-30% of levels found in enzymatic [12] Maxima in fermentation, sharp decrease in aging [14,143]; formed very soon, sharp decrease [15,66] (Z)-Rose oxide 11-29 ppb in Muscat, depending on maturity [145]; unrelated to free form in raisins [23] 0.04 ppb in Muscat, 0.01 ppb in Grenache; not found in Verdejo, Tempranillo, Chardonnay, Cabernet Sauvignon, or Merlot [12] Geranic acid Up to 2-3 ppm [146,147]; also found in raisins [23]; <4 ppb [145]; up to 7.5% total terpenes in Shiraz, 18% in Muscat [144] Not found [138]; 0.5-50% of levels found in enzymatic [12] 1.5 ppb in Chardonnay juices [148] Piperitone Derived from limonene, unknown accumulation pattern [149]; limonene accumulates in the first periods of aging, then slight decrease [66] n.d.: Not detected. Table 7.…”

“…formed soon and stable, maxima 17 ppb [15]; idem, with maxima 7 ppb [66] β-Ionone Not found; yes in frozen grapes [136]; not in wines [137]; <0.11 ppb in frozen grapes [12] Generally yes; not found in [12] Maxima (1.9 ppb) after short aging, stable with time [14]; formed soon, stable for a while, maxima 7.7 ppb [15] TDN Not found; yes in frozen grapes [136]; not in wines [137]; 1-6 ppb (5-30% of levels found in harsh acid hydrolysis) in frozen grapes [12] 8 ppb [138]; detected by GCO [12] 3 ppb [138]; 2-23 ppb depending varieties [12] Continuously formed, maxima 9 ppb [66] Terpenes Linalool Generally present; not found in Portuguese reds [140]; not found in Melon B [141]; not found in Shiraz [144]; found at low levels (less than 7% geraniol 1% total terpenes) [144] 3% levels found in enzymatic [138]; 10-50% of levels found in enzymatic [12] Found only in mild acid hydrolysis [141]; maxima after fermentation, sharp decrease in aging [14]; in Grenache, maxima after short aging [143];…”

“…Its structure and odor properties, together with those of other important aroma compounds from the same family, can be seen in Table 2. Different studies confirm that β-damascenone tends to accumulate in grapes in the last periods of maturation [60][61][62][63], particularly in the case of late season berry dehydration (or raisining) [64,65], during the storage of the raisins [58], or even during the aging of wines made with raisins [66]. Its levels, however, have no clear relationship with sun exposure on the vine [67,68].…”

“…Some others, such as volatile phenols or vanillin derivatives, rather exert a cooperative effect on wine aroma. Mint lactones, recently identified at low levels in red wines from Bordeaux [135], limonene and 1,4-and 1,8-cineol, as well as some megastigmatrienones, may also play a role in minty, balsamic, and tobacco notes [66], but evidence about their implication is yet weak.…”