3.2 Phenolic compounds
The total polyphenols content increased from crushing until 30th day after crushing in all trials (Fig. 1a). Steel tank post fermentative maceration trial reached the value of 2330 mg/L of (+)-catechin on 40th day of maceration, whereas significantly higher values (about more than 20%) were observed in oak barrel post fermentative maceration trial, in which the mean value of 2900 mg/L ((+)-catechin) was kept from 30th to 70th day after crushing.
The evolution of total flavonoids followed almost the same trend of total polyphenols (Fig. 1b). The flavonoid content increased from crushing until the 40th day after crushing in steel tank post fermentative maceration trial, reaching the value of 2400 mg/L ((+)-catechin). Significantly higher values were observed in oak barrel post fermentative maceration trial, in which the mean value of 3000 mg/L ((+)-catechin) was kept from 20th to 70th day after crushing.
The content of total anthocyanins increased from crushing until 13th day, when the content of about 700 mg/L (malvidin-3-glucoside) was reached in all trials (Fig. 1c). Total anthocyanins content gradually decreased during post fermentative maceration, reaching the contents of 200 mg/L of malvidin-3-glucoside in steel tank trials and of 280 mg/L of malvidin-3-glucoside in oak barrel trials.
Monomer anthocyanins content increased from crushing, reaching the maximum value of 555 mg/L (malvidin-3-glucoside) on 8th day after crushing in steel tank trials and the mean value of 450 mg/L (malvidin-3-glucoside) between 8th and 13th day after crushing in oak barrel trials (Fig. 1d). Then, a strong reduction was observed during post fermentative maceration with a content of 100 mg/L of malvidin-3-glucoside in steel trial and 130 mg/L of malvidin-3-glucoside in oak barrel trial, with no significant differences.
Figure 2 shows the anthocyanin profiles (%) of Cabernet Sauvignon trials during the alcoholic fermentation and the post-fermentative maceration. The anthocyanin profile was characterized by the prevalence of trisubstituted anthocyanins (malvidin, petunidin and delphinidin-3-glucoside). The content of malvidin-3-glucoside, that is the compound most involved in the formation of the wine colour, is about 58% in steel tank trials, and about 65% in oak barrel trials, even though no significant differences were observed among the trials.
The contents of petunidin-3-glucoside and delphinidin-3-glucoside remained almost constant during the alcoholic fermentation and post-fermentative maceration (6.5% and 1.5%, respectively), with no significant differences among the trials.
Cyanidin-3-glucoside content was about 0.6% in steel tank trials, that is significantly higher than the oak barrel trial content (0.35%).
Peonidin-3-glucoside content is about 3.5% in all trials, with no significant differences among them.
Acylated anthocyanins were mainly represented by acetylated forms if compared to p-coumaroylated ones. Acetylated anthocyanins content remained almost constant during alcoholic fermentation and post fermentative maceration in all trials, with the mean value of 24% in steel tank trial and 20% in oak barrel trials, even though no significant differences were observed.
p-coumaroylated anthocyanins content was about 4.5% in all trials and remained constant during alcoholic fermentation and post fermentative maceration with no significant differences among the trials.
The ratio acetylated/p-coumaroylated anthocyanins ranged from 4 to 6.
Figure 3 shows the evolution of hydroxycinnamoyl tartaric acids in Cabernet Sauvignon trials during alcoholic fermentation and post-fermentative maceration.
All hydroxycinnamoyl tartaric acids (HCTA), shown as the sum of cis and trans configuration, followed almost the same evolution in all trials, with an increasing trend during alcoholic fermentation, followed by a decreasing trend during post fermentative maceration, with significantly higher values in oak barrel trials. In particular, cis and trans caffeoyl tartaric acid content reached the maximum value of 87 mg/L on 20th day after crushing in steel tank trials, and the maximum value of 117 mg/L on 20th day after crushing in oak barrel trials. Cis and trans p-coumaroyl tartaric acid content reached the maximum value of 47 mg/L on 13th day after crushing in steel tank trials, and the maximum value of 60 mg/L in oak barrel trials. Cis and trans feruloyl tartaric acid content reached the maximum value of 1.6 mg/L on 13th day after crushing in steel tank trials, and the maximum value of 3.2 mg/L on 13th day after crushing in oak barrel trials.
On 150th day the two isomer forms of caffeoyl tartaric acid showed values of 50 mg/L in steel trials and 86 mg/L in oak barrel trials; coumaroyl tartaric acid showed values of 20 mg/L in steel trials and 39 mg/L in oak barrel trials; feruloyl tartaric acid showed values of 1.2 mg/L in steel trials and 1.6 mg/L in oak barrel trials. The contents of HCTA in oak barrel trials remained significantly higher than the content in steel tank trials until the end of post fermentative maceration.
Caffeic acid content reached the maximum value of 3.1 mg/L on 13th day after crushing in steel tank trials, and the maximum value of 3.3 mg/L in oak barrel trials on the same date. Then, the content slightly decreased in all trials, even though the content in oak barrel trial remained significantly higher than that in steel tank trial.
Figure 4 shows the evolution of flavonols content in Cabernet Sauvignon wines during alcoholic fermentation and post-fermentative maceration.
Flavonols, compounds belonging to the class of flavonoids, are shown as the sum of 3-glucuronide and 3-glucoside forms except for the syringetin, that was determined only in the 3-glucoside form (Fig. 4).
Myricetin-3-glucuronide and 3-glucoside content increased during alcoholic fermentation reaching the maximum value of 4.5 mg/L on 20th day after crushing in steel tank trials and the maximum value of 6.4 mg/L on 8th day after crushing in oak barrel trials. Then, the content decreased during post fermentative maceration, even though the content in oak barrel trial was significantly higher than that in steel tank trial on 150th day after crushing.
Quercetin-3-glucuronide and 3-glucoside content reached the maximum value of 9.2 mg/L between 8th and 13th day after crushing in steel tank trials and the maximum value of 9.3 mg/L on 8th day after crushing in oak barrel trials. The content decreased during post fermentative maceration, reaching the value of 3.4 mg/L in steel tank post fermentative maceration trial and the value of 5.5 mg/L in oak barrel post fermentative maceration trial, that are significantly different.
Kampferol-3-glucuronide and 3-glucoside content reached the maximum value of 0.8 mg/L between 8th and 13th day after crushing in steel tank trials. Then, the content slightly decreased until 150th day after crushing reaching the value of 0.5 mg/L. In oak barrel trials the content of Kaempferol remained almost constant during the whole process and no significant differences were observed with the content of steel tank trial on 150th day.
Syringetin-3-glucoside content in steel tank trials reached the maximum value of 3.6 mg/L between 3rd and 8th day after crushing, followed by a decrease during post fermentative maceration, reaching the value of 0.5 mg/L on 150th day.
In oak barrel trials the content reached the minimum value of 2.2 mg/L on 8th day after crushing. However, the content increased during post fermentative maceration, and remained significantly higher than that observed in steel tank trials until the end of the process.
The evolution of the different classes of phenolic compounds during the long contact with the solid parts of the grapes suggested that the post fermentative maceration provide a higher content of these substances in wine, especially total polyphenols, and total flavonoids in oak barrel trials. The losses recorded were limited especially in oak barrel trials.
3.2.1 Modelized Anthocyanin first stage
As it is possible to observe from Fig. 5 and Table 2, the initial speed of anthocyanin extraction for PFMS resulted greater than PFMB (β parameter), also the decreasing in extraction speed resulted greater for PFMS (2α). The net effect was that PFMS reached the maximum concentration of anthocyanin after 8 days while PFMB after 13 days.
Table 2
parameters of the anthocyanins first stage
Anthocyanin first stage | PFMS | PFMB |
α | -4.71 | -4.59 |
β | 107.39 | 103.49 |
γ | 156.85 | 137.15 |
R2 | 1.0000 | 0.9951 |
Days max | 8 | 13 |
Max conc reached | 714.31 | 712.80 |
2α | -9.43 | -9.17 |
3.2.2 Modelized anthocyanin second stage
As it is possible to see from the Fig. 5 and from the Table 3 PFMS showed a greater “c” parameter and a delta a-b more negative than PFMB determining a faster decreasing in anthocyanin. At day 150 we still have registered a greater concentration of anthocyanin in PFMB.
Table 3
Parameter | PFMS | PFMB |
b | 962.97 | 780.82 |
c | 3.47∙ 10− 2 | 9.58 ∙ 10− 3 |
a (predicted horizontal asymptote) | 222.32 | 96.96 |
Concentration at 150 days | 202.99 | 276.51 |
R2 | 0.9303 | 0.9637 |
3.2.3 Modelized non-anthocyanic flavonoids
From the Fig. 6 and Table 4 it is possible to note that PFMS showed a slightly greater “c” parameter, or rather it approaches slightly faster to the asymptote of non-anthocyanic flavonoids (NAF) compared to PFMB, however PFMB showed a net greater concentration of NAF.
Table 4
non-anthocyanic flavonoids parameters
Parameter | PFMS | PFMB |
b | 221.85 | 165.52 |
c | 1.27 ∙ 10− 1 | 1.12∙ 10− 1 |
a | 1619.00 | 2179.70 |
Concentration at 150 days | 1671.78 | 2181.65 |
R2 | 0.9429 | 0.9811 |
3.3 Volatile organic compounds
Volatile organic compounds (VOCs) of wine belong to various chemical classes such as alcohols, ester, acids, aldehydes, and volatile phenols. Tables 5a and 5b show volatile organic compounds (mg/L) of Cabernet Sauvignon wines during alcoholic fermentation and post-fermentative maceration.
Table 5
a - Volatile organic compounds (g/L) of wine Cabernet Sauvignon during alcoholic fermentation and long post-fermentative maceration
Time and phase | Total Alcohols | Total Esters | Total Acids | Total Phenols |
Alcoholic fermentation | PFMS | PFMB | PFMS | PFMB | PFMS | PFMB | PFMS | PFMB |
Day 30 | 36.52 ± 1.43 A,a | 125.46 ± 4.93 E,b | 4.43 ± 0.17 A,a | 6.19 ± 0.24 A,b | 6.19 ± 0.24 E,b | 3.78 ± 0.15 A,a | 0.97 ± 0.04 I, b | 0.51 ± 0.02 E |
Day 8 | 75.86 ± 2.98 B,a | 164.20 ± 6.45 H,b | 10.37 ± 0.41 B | 11.66 ± 0.46 B | 4.25 ± 0.17 B,a | 5.36 ± 0.21 B,b | 0.53 ± 0.02 D | 0.58 ± 0.02 F |
Day 13 | 94.74 ± 3.72 D,a | 173.47 ± 6.81 I,b | 25.13 ± 0.99 C,b | 20.37 ± 0.80 C,a | 8.45 ± 0.33 G,a | 13.61 ± 0.53 EF,b | 0.84 ± 0.03 H,b | 0.61 ± 0.02 GH |
Post-fermentation maceration | | | | | | | | |
Day 20 | 86.17 ± 3.38 C,a | 155.75 ± 6.12 G,b | 23.29 ± 0.91 C | 24.84 ± 0.98 D | 7.36 ± 0.29 F,a | 13.28 ± 0.52 E,b | 0.45 ± 0.02 C | 0.65 ± 0.02 IJ,b |
Day 30 | 87.87 ± 3.45 CD,a | 137.75 ± 5.41 F,b | 34.31 ± 1.35 D,b | 24.32 ± 0.96 D,a | 5.69 ± 0.22 D,a | 12.95 ± 0.51 E,b | 0.58 ± 0.02 E,b | 0.39 ± 0.02 D |
Day 40 | 171.46 ± 6.74 G,b | 138.72 ± 5.45 F,a | 45.83 ± 1.80 F,b | 29.30 ± 1.15 FG,a | 9.43 ± 0.37 H,a | 16.71 ± 0.66 G,b | 0.71 ± 0.03 G | 0.68 ± 0.03 J |
Day 50 | 200.11 ± 7.86 H | 139.99 ± 5.50 F,a | 45.21 ± 1.78 F,b | 36.06 ± 1.42 I,a | 10.36 ± 0.41 I,a | 19.86 ± 0.78 H,b | 0.64 ± 0.02 F | 0.58 ± 0.02 FG |
Day 60 | 140.17 ± 5.51 F | 122.83 ± 4.82 E | 36.67 ± 1.44 E | 34.57 ± 1.36 I | 6.27 ± 0.25 E,a | 14.35 ± 0.56 F,b | 0.58 ± 0.02 E | 0.64 ± 0.02 HI |
Day 70 | 110.62 ± 4.35 E | 93.89 ± 3.69 D | 36.27 ± 1.42 DE | 32.24 ± 1.27 H | 5.46 ± 0.21 D,a | 10.83 ± 0.43 D,b | 0.51 ± 0.02 D,b | 0.42 ± 0.02 D |
Day 90 | 81.07 ± 3.18 BC,b | 64.95 ± 2.55 A,a | 35.88 ± 1.41 DE,b | 29.92 ± 1.18 G,a | 4.65 ± 0.18 C,a | 7.30 ± 0.29 C,b | 0.44 ± 0.02 C,b | 0.20 ± 0.01 AB |
Day 110 | 85.66 ± 3.36 C,b | 72.15 ± 2.83 A,a | 36.33 ± 1.43 DE,b | 27.29 ± 1.07 E,a | 5.49 ± 0.22 D,b | 2.81 ± 0.11 A,a | 0.39 ± 0.01 B,b | 0.18 ± 0.01 A |
Day 130 | 82.90 ± 3.26 BC | 79.34 ± 3.12 C | 34.47 ± 1.35 D,b | 27.92 ± 1.10 EF,a | 3.15 ± 0.12 A,a | 4.96 ± 0.19 B,b | 0.24 ± 0.01 A | 0.23 ± 0.01 BC |
Day 150* | 87.75 ± 3.45 CD | 83.79 ± 3.29 C | 35.04 ± 1.38 DE,b | 27.56 ± 1.08 E,a | 4.07 ± 0.16 B,b | 3.43 ± 0.13 A,a | 0.24 ± 0.01 A | 0.23 ± 0.01 C |
PFMS: post-fermentative maceration in steel; PFMB: post-fermentative maceration in barrel; |
* racking PFMS and PFMB trials |
n.d.: not detected |
Values are expressed as mean ± standard deviation (n = 3). |
Uppercase letters indicate differences over time within a single column (post hoc), lowercase letters indicate differences between samples, PFMS and PFMB, (t test). |
Table 5
b - Volatile organic compounds (mg/L) of wine Cabernet Sauvignon during alcoholic fermentation and post-fermentative maceration
| | | Alcoholic fermentation | | | Post-fermentation maceration | | | | | | | | |
| | | Day 3 | Day 8 | Day 13 | | Day 20 | Day 30 | Day 40 | Day 50 | Day 60 | Day 70 | Day 90 | Day 110 | Day 130 | Day 150* |
1-hexanol | | PFMS | 1.73 ± 0.07 D | 2.10 ± 0.08 E,b | 2.95 ± 0.11 H,b | | 2.78 ± 0.11 G,b | 2.70 ± 0.10 FG,b | 2.63 ± 0.10 F | 3.05 ± 0.12 H,b | 1.76 ± 0.07 D,b | 1.59 ± 0.06 C | 1.43 ± 0.05 B | 2.20 ± 0.08 E,b | 1.65 ± 0.06 CD,b | 1.16 ± 0.04 A |
| PFMB | 1.69 ± 0.06 DE | 1.77 ± 0.07 E,a | 1.89 ± 0.07 F,a | | 1.99 ± 0.08 G,a | 2.10 ± 0.08 H,a | 2.35 ± 0.09 I | 2.49 ± 0.10 J,a | 2.09 ± 0.08 H,a | 1.66 ± 0.06 D | 1.23 ± 0.05 C | 1.15 ± 0.04 B,a | 1.07 ± 0.04 A,a | 1.18 ± 0.05 BC |
trans-3-Hexenol | | PFMS | 0.12 ± 0.00 B,a | 0.19 ± 0.01 C | 0.20 ± 0.01 CD | | 0.26 ± 0.01 E,b | 0.19 ± 0.01 C | 0.12 ± 0.00 B,a | 0.33 ± 0.01 F,b | 0.31 ± 0.01 F,b | 0.22 ± 0.01 D,b | 0.12 ± 0.00 B,b | 0.03 ± 0.00 A,a | 0.03 ± 0.00 A,a | 0.03 ± 0.00 A,a |
| PFMB | 0.16 ± 0.01 E,b | 0.18 ± 0.01 G | 0.20 ± 0.01 I | | 0.13 ± 0.01 D,a | 0.18 ± 0.01 FG | 0.19 ± 0.01 H,b | 0.17 ± 0.01 F,a | 0.15 ± 0.01 E,a | 0.12 ± 0.00 C,a | 0.09 ± 0.00 A,a | 0.10 ± 0.00 B,b | 0.12 ± 0.00 C,b | 0.11 ± 0.00 B,b |
cis-3-Hexenol | | PFMS | 0.06 ± 0.00 D,b | 0.04 ± 0.00 C,b | 0.02 ± 0.00 A,b | | 0.08 ± 0.00 F | 0.09 ± 0.00 G,b | 0.11 ± 0.00 H,b | 0.16 ± 0.01 I,b | 0.07 ± 0.00 EF,b | 0.07 ± 0.00 DE,b | 0.06 ± 0.00 D,b | 0.04 ± 0.00 C,b | 0.05 ± 0.00 C | 0.03 ± 0.00 B,a |
| PFMB | 0.03 ± 0.00 BC,a | 0.03 ± 0.00 D,a | 0.03 ± 0.00 B,a | | 0.08 ± 0.00 H | 0.06 ± 0.00 G,a | 0.04 ± 0.00 E,a | 0.06 ± 0.00 F,a | 0.04 ± 0.00 E,a | 0.03 ± 0.00 BCD,a | 0.02 ± 0.00 A,a | 0.03 ± 0.00 CD,a | 0.04 ± 0.00 E | 0.04 ± 0.00 E,b |
2-Phenylethanol* | | PFMS | 35.41 ± 1.35 A,a | 75.30 ± 2.88 B,a | 93.56 ± 3.58 D,a | | 84.73 ± 3.24 C,a | 86.54 ± 3.31 CD,a | 172.36 ± 6.5 G,b | 200.98 ± 7.6 H,b | 141.12 ± 5.3 F | 111.18 ± 4.2 E,b | 81.25 ± 3.11 BC,b | 85.04 ± 3.25 C | 82.87 ± 3.17 BC | 88.35 ± 3.38 CD |
| PFMB | 126.56 ± 4.8 E,b | 166.33 ± 6.3 H,b | 175.69 ± 6.7 I,b | | 157.16 ± 6.0 G,b | 138.63 ± 5.3 F,b | 139.22 ± 5.3 F,a | 140.30 ± 5.3 F,a | 123.20 ± 4.7 E D | 94.09 ± 3.60 D,a | 64.98 ± 2.48 A,a | 72.38 ± 2.77 BAB | 79.78 ± 3.05 CBC | 84.20 ± 3.22 CBC |
Benzyl alcohol* | | PFMS | 0.21 ± 0.01 A,a | 0.33 ± 0.01 B,a | 0.64 ± 0.02 D,b | | 0.71 ± 0.03 E | 0.78 ± 0.03 FG,b | 1.01 ± 0.04 H,b | 1.14 ± 0.04 I,b | 0.80 ± 0.03 G | 0.63 ± 0.02 D | 0.46 ± 0.02 C | 0.74 ± 0.03 EF,b | 0.60 ± 0.02 D | 0.62 ± 0.02 D |
| PFMB | 0.51 ± 0.02 B,b | 0.46 ± 0.02 A,b | 0.49 ± 0.02 B,a | | 0.71 ± 0.03 F | 0.62 ± 0.02 E,a | 0.78 ± 0.03 G,a | 0.86 ± 0.03 H,a | 0.75 ± 0.03 G | 0.59 ± 0.02 D | 0.43 ± 0.02 A | 0.48 ± 0.02 B,a | 0.53 ± 0.02 C | 0.59 ± 0.02 D |
Ethyl 3-hydroxy-butanoate | | PFMS | 0.01 ± 0.00 A,a | 0.06 ± 0.00 BC,a | 0.07 ± 0.00 CD,b | | 0.11 ± 0.00 F,b | 0.16 ± 0.01 H,b | 0.15 ± 0.01 G,b | 0.18 ± 0.01 I,b | 0.08 ± 0.00 E | 0.07 ± 0.00 DE,b | 0.07 ± 0.00 CD,b | 0.06 ± 0.00 B,b | 0.07 ± 0.00 BC,b | 0.07 ± 0.00 CD,b |
| PFMB | 0.11 ± 0.00 GH,b | 0.11 ± 0.00 G,b | 0.05 ± 0.00 D,a | | 0.06 ± 0.00 DE,a | 0.06 ± 0.00 DE,a | 0.10 ± 0.00 F,a | 0.11 ± 0.00 H,a | 0.09 ± 0.00 F | 0.06 ± 0.00 E,a | 0.03 ± 0.00 A,a | 0.03 ± 0.00 B,a | 0.04 ± 0.00 C,a | 0.04 ± 0.00 C,a |
Ethyl 4-hydroxy-butyrate | | PFMS | 0.53 ± 0.02 A,b | 3.67 ± 0.14 E | 15.81 ± 0.60 H,b | | 11.39 ± 0.44 G,b | 11.07 ± 0.42 G,b | 11.36 ± 0.43 G,b | 9.82 ± 0.38 F,b | 1.17 ± 0.04 AB,a | 1.76 ± 0.07 BC,a | 2.34 ± 0.09 CD,a | 2.35 ± 0.09 CD,a | 2.39 ± 0.09 CD,a | 2.85 ± 0.11 DE |
| PFMB | 0.00 ± 0.00 A,a | 3.87 ± 0.15 D | 10.08 ± 0.39 H,a | | 6.64 ± 0.25 F,a | 3.20 ± 0.12 C,a | 6.78 ± 0.26 FG,a | 7.16 ± 0.27 G,a | 6.38 ± 0.24 F,b | 5.30 ± 0.20 E,b | 4.23 ± 0.16 D,b | 2.09 ± 0.08 B B | 3.02 ± 0.12 C,b | 2.46 ± 0.09 B |
γ-nonalactone | | PFMS | 0.00 ± 0.00 A,a | 0.05 ± 0.00 E,b | 0.07 ± 0.00 G,b | | 0.06 ± 0.00 F,b | 0.04 ± 0.00 D,b | 0.07 ± 0.00 G,b | 0.09 ± 0.00 I,b | 0.11 ± 0.00 J,b | 0.08 ± 0.00 H,b | 0.04 ± 0.00 D,b | 0.02 ± 0.00 B | 0.03 ± 0.00 C,b | 0.03 ± 0.00 C,b |
| PFMB | 0.07 ± 0.00 H,b | 0.04 ± 0.00 DE,a | 0.03 ± 0.00 DE,a | | 0.03 ± 0.00 C,a | 0.02 ± 0.00 B,a | 0.05 ± 0.00 G,a | 0.04 ± 0.00 F,a | 0.04 ± 0.00 EF,a | 0.03 ± 0.00 D,a | 0.03 ± 0.00 C,a | 0.02 ± 0.00 B | 0.01 ± 0.00 A,a | 0.02 ± 0.00 B,a |
Diethyl malate* | | PFMS | 0.00 ± 0.00 A,a | 0.03 ± 0.00 B,a | 0.10 ± 0.00 D,b | | 0.05 ± 0.00 C,a | 0.23 ± 0.01 J,b | 0.21 ± 0.01 I,b | 0.24 ± 0.01 J,b | 0.19 ± 0.01 H,b | 0.17 ± 0.01 G,b | 0.15 ± 0.01 F,b | 0.17 ± 0.01 G,b | 0.12 ± 0.00 E,b | 0.14 ± 0.01 F,b |
| PFMB | 0.09 ± 0.00 F,b | 0.04 ± 0.00 B,b | 0.05 ± 0.00 B,a | | 0.08 ± 0.00 E,b | 0.11 ± 0.00 H,a | 0.12 ± 0.00 I,a | 0.10 ± 0.00 G,a | 0.08 ± 0.00 E,a | 0.05 ± 0.00 C,a | 0.03 ± 0.00 A,a | 0.04 ± 0.00 B,a | 0.06 ± 0.00 D,a | 0.06 ± 0.00 D,a |
Isoamyl lactate | | PFMS | 0.19 ± 0.01 B,b | 0.15 ± 0.01 A,a | 0.23 ± 0.01 C,a | | 0.15 ± 0.01 A,a | 0.39 ± 0.01 F,a | 0.49 ± 0.02 I,a | 0.44 ± 0.02 H,a | 0.35 ± 0.01 E,a | 0.38 ± 0.01 F,a | 0.41 ± 0.02 G | 0.29 ± 0.01 D,a | 0.39 ± 0.02 FG,a | 0.55 ± 0.02 J |
| PFMB | 0.14 ± 0.01 A,a | 0.42 ± 0.02 B,b | 0.66 ± 0.03 D,b | | 0.82 ± 0.03 E,b | 0.67 ± 0.03 D,b | 0.84 ± 0.03 E,b | 0.96 ± 0.04 F,b | 0.95 ± 0.04 F,b | 0.68 ± 0.03 D,b | 0.42 ± 0.02 B | 0.54 ± 0.02 C,b | 0.65 ± 0.02 D,b | 0.51 ± 0.02 C |
Butyrolactone | | PFMS | 0.05 ± 0.00 A,a | 0.52 ± 0.02 D,a | 0.95 ± 0.04 I,b | | 0.99 ± 0.04 I | 0.72 ± 0.03 F,a | 0.69 ± 0.03 F,b | 0.88 ± 0.03 H,b | 0.78 ± 0.03 G,b | 0.56 ± 0.02 DE,b | 0.33 ± 0.01 B B | 0.60 ± 0.02 E,b | 0.43 ± 0.02 C,b | 0.35 ± 0.01 B |
| PFMB | 0.11 ± 0.00 A,b | 0.99 ± 0.04 H,b | 0.64 ± 0.02 F,a | | 0.91 ± 0.03 G | 1.62 ± 0.06 I,b | 0.48 ± 0.02 E,a | 0.42 ± 0.02 DE,a | 0.43 ± 0.02 DE,a | 0.40 ± 0.02 D,a | 0.38 ± 0.01 D D | 0.30 ± 0.01 C,a | 0.21 ± 0.01 B,a | 0.38 ± 0.01 D |
Isoamyl 4-hydroxybutyrate | | PFMS | 0.20 ± 0.01 A,b | 0.37 ± 0.01 D | 0.29 ± 0.01 BC,a | | 0.21 ± 0.01 A,a | 0.39 ± 0.01 D,a | 1.02 ± 0.04 G,b | 0.63 ± 0.02 F,a | 0.45 ± 0.02 E,a | 0.35 ± 0.01 D,a | 0.26 ± 0.01 B,b | 0.31 ± 0.01 C,b | 0.17 ± 0.01 A,a | 0.21 ± 0.01 A |
| PFMB | 0.13 ± 0.01 A,a | 0.35 ± 0.01 D | 1.16 ± 0.04 I,b | | 0.90 ± 0.03 H,b | 0.79 ± 0.03 G,b | 0.67 ± 0.03 F,a | 0.86 ± 0.03 H,b | 0.88 ± 0.03 H,b | 0.52 ± 0.02 E,b | 0.16 ± 0.01 AB,a | 0.20 ± 0.01 BC,a | 0.25 ± 0.01 C,b | 0.22 ± 0.01 C |
Ethyl lactate* | | PFMS | 0.03 ± 0.00 A,a | 0.14 ± 0.01 A,a | 0.21 ± 0.01 A,a | | 0.28 ± 0.01 A,a | 0.23 ± 0.01 A,a | 0.18 ± 0.01 A,a | 2.01 ± 0.08 B,a | 3.84 ± 0.15 C,a | 3.80 ± 0.15 C,a | 3.75 ± 0.14 C | 4.80 ± 0.18 D,b | 5.17 ± 0.20 D,b | 5.60 ± 0.21 E,b |
| PFMB | 1.39 ± 0.05 A,b | 1.59 ± 0.06 AB,b | 1.79 ± 0.07 B,b | | 5.22 ± 0.20 G,b | 4.26 ± 0.16 DE,b | 4.83 ± 0.18 F,b | 6.18 ± 0.24 H,b | 6.09 ± 0.23 H,b | 4.96 ± 0.19 FG,b | 3.83 ± 0.15 C | 4.02 ± 0.15 CD,a | 4.22 ± 0.16 DE,a | 4.43 ± 0.17 E,a |
Monoethyl succinate* | | PFMS | 0.00 ± 0.00 A,a | 0.50 ± 0.02 AB,b | 0.97 ± 0.04 B,b | | 0.93 ± 0.04 B,b | 10.94 ± 0.42 H,b | 9.54 ± 0.36 G,b | 7.04 ± 0.27 F,b | 4.39 ± 0.17 E,b | 3.07 ± 0.12 D,b | 1.75 ± 0.07 C,b | 2.58 ± 0.10 D,b | 0.90 ± 0.03 B,b | 1.67 ± 0.06 C,b |
| PFMB | 0.11 ± 0.00 E,b | 0.16 ± 0.01 H,a | 0.21 ± 0.01 K,a | | 0.20 ± 0.01 J,a | 0.19 ± 0.01 I,a | 0.11 ± 0.00 EF,a | 0.12 ± 0.00 F,a | 0.13 ± 0.01 G,a | 0.09 ± 0.00 D,a | 0.04 ± 0.00 A,a | 0.05 ± 0.00 AB,a | 0.06 ± 0.00 B,a | 0.08 ± 0.00 C,a |
Diethyl succinate* | | PFMS | 0.02 ± 0.00 A,a | 0.10 ± 0.00 A,a | 2.94 ± 0.11 B,b | | 4.72 ± 0.18 BC,a | 6.51 ± 0.25 C,a | 18.86 ± 0.72 D,b | 21.24 ± 0.81 E,b | 22.98 ± 0.88 EFG,b | 23.83 ± 0.91 FG,b | 24.68 ± 0.94 G,b | 23.42 ± 0.90 FG,b | 23.42 ± 0.90 FG,b | 22.61 ± 0.86 EF,b |
| PFMB | 0.12 ± 0.00 A,b | 0.21 ± 0.01 A,b | 1.88 ± 0.07 B,a | | 6.35 ± 0.24 C,b | 10.83 ± 0.41 D,b | 12.72 ± 0.49 E,a | 18.42 ± 0.70 FG,a | 17.48 ± 0.67 F,a | 18.66 ± 0.71 FGH,a | 19.84 ± 0.76 H,a | 19.22 ± 0.73 GH,a | 18.59 ± 0.71 FGH,a | 18.40 ± 0.70 FG,a |
Ethyl hexanoate | | PFMS | 0.55 ± 0.02 B | 1.52 ± 0.06 G,b | 0.57 ± 0.02 B,a | | 0.85 ± 0.03 D | 0.93 ± 0.04 E | 1.01 ± 0.04 F,a | 0.96 ± 0.04 EF | 0.84 ± 0.03 D,a | 0.83 ± 0.03 D,b | 0.82 ± 0.03 D,b | 0.75 ± 0.03 C,b | 0.56 ± 0.02 B | 0.47 ± 0.02 A,a |
| PFMB | 0.52 ± 0.02 C | 0.74 ± 0.03 E,a | 0.82 ± 0.03 F,b | | 0.91 ± 0.03 G | 1.00 ± 0.04 H | 1.37 ± 0.05 I,b | 0.88 ± 0.03 G | 1.00 ± 0.04 H,b | 0.67 ± 0.03 D,a | 0.34 ± 0.01 A,a | 0.42 ± 0.02 B,a | 0.50 ± 0.02 C | 0.72 ± 0.03 DE,b |
Ethyl octanoate | | PFMS | 0.52 ± 0.02 D,b | 0.55 ± 0.02 F,b | 0.53 ± 0.02 DE,b | | 0.69 ± 0.03 J,b | 0.60 ± 0.02 H,b | 0.57 ± 0.02 G,b | 0.54 ± 0.02 EF,b | 0.62 ± 0.02 I | 0.54 ± 0.02 DEF | 0.45 ± 0.02 B | 0.50 ± 0.02 C,b | 0.50 ± 0.02 C,b | 0.27 ± 0.01 A,b |
| PFMB | 0.25 ± 0.01 D,a | 0.15 ± 0.01 B,a | 0.40 ± 0.02 F,a | | 125.46 ± 4.93 E,b | 0.11 ± 0.00 A,a | 0.44 ± 0.02 G,a | 0.20 ± 0.01 C,a | 0.56 ± 0.02 I | 0.48 ± 0.02 H | 0.40 ± 0.02 F | 0.32 ± 0.01 E,a | 0.34 ± 0.01 E,a | 0.21 ± 0.01 C,a |
Ethyl decanoate | | PFMS | 0.10 ± 0.00 B,a | 0.21 ± 0.01 CD | 0.18 ± 0.01 C,a | | 0.51 ± 0.02 G,b | 0.46 ± 0.02 F,b | 0.60 ± 0.02 H,b | 0.43 ± 0.02 F,b | 0.27 ± 0.01 E,a | 0.23 ± 0.01 D | 0.19 ± 0.01 C | 0.10 ± 0.00 B,b | 0.10 ± 0.00 B | 0.06 ± 0.00 A,a |
| PFMB | 0.26 ± 0.01 GH,b | 0.19 ± 0.01 C | 0.24 ± 0.01 EF,b | | 0.23 ± 0.01 DE,a | 0.22 ± 0.01 D,a | 0.27 ± 0.01 H,a | 0.29 ± 0.01 I,a | 0.31 ± 0.01 J,b | 0.25 ± 0.01 FG | 0.18 ± 0.01 C | 0.05 ± 0.00 A,a | 0.09 ± 0.00 B | 0.09 ± 0.00 B,b |
Ethyl octadecanoate | | PFMS | 0.00 ± 0.00 A,a | 0.18 ± 0.01 D,b | 0.33 ± 0.01 E,b | | 0.45 ± 0.02 G,b | 0.43 ± 0.02 G,b | 0.62 ± 0.02 H,b | 0.40 ± 0.02 F,b | 0.18 ± 0.01 D,b | 0.17 ± 0.01 D,b | 0.17 ± 0.01 D,b | 0.08 ± 0.00 BC,b | 0.05 ± 0.00 B,b | 0.10 ± 0.00 C,b |
| PFMB | 0.04 ± 0.00 A,b | 0.08 ± 0.00 D,a | 0.13 ± 0.00 F,a | | 0.17 ± 0.01 G,a | 0.20 ± 0.01 H,a | 0.13 ± 0.00 F,a | 0.06 ± 0.00 C,a | 0.11 ± 0.00 E,a | 0.08 ± 0.00 D,a | 0.05 ± 0.00 B,a | 0.05 ± 0.00 AB,a | 0.04 ± 0.00 A,a | 0.05 ± 0.00 B,a |
Isoamyl acetate | | PFMS | 1.86 ± 0.07 I,b | 1.61 ± 0.06 H,a | 1.82 ± 0.07 I,a | | 2.31 ± 0.09 J,b | 1.88 ± 0.07 I,b | 1.38 ± 0.05 G,b | 1.19 ± 0.05 F,b | 1.06 ± 0.04 E,b | 0.91 ± 0.03 D,b | 0.76 ± 0.03 C,b | 0.49 ± 0.02 A | 0.61 ± 0.02 B,b | 0.57 ± 0.02 AB,b |
| PFMB | 0.50 ± 0.02 AB,a | 2.24 ± 0.09 H,b | 2.02 ± 0.08 G,b | | 2.00 ± 0.08 G,a | 1.30 ± 0.05 F,a | 0.84 ± 0.03 D,a | 0.96 ± 0.04 E,a | 0.70 ± 0.03 C,a | 0.65 ± 0.02 C,a | 0.60 ± 0.02 BC,a | 0.53 ± 0.02 AB | 0.46 ± 0.02 A,a | 0.47 ± 0.02 A,a |
Hexyl acetate | | PFMS | 0.16 ± 0.01 AB,a | 0.16 ± 0.01 A,a | 0.16 ± 0.01 A,a | | 0.17 ± 0.01 AB,a | 0.19 ± 0.01 BC,a | 0.21 ± 0.01 C,a | 0.22 ± 0.01 C,b | 0.30 ± 0.01 D,b | 0.46 ± 0.02 G,b | 0.62 ± 0.02 H,b | 0.64 ± 0.02 H,b | 0.39 ± 0.01 F,b | 0.33 ± 0.01 E,b |
| PFMB | 0.32 ± 0.01 F,b | 0.33 ± 0.01 F,b | 0.32 ± 0.01 F,b | | 0.40 ± 0.02 G,b | 0.24 ± 0.01 E,b | 0.18 ± 0.01 D,a | 0.08 ± 0.00 C,a | 0.06 ± 0.00 BC,a | 0.05 ± 0.00 B,a | 0.05 ± 0.00 AB,a | 0.04 ± 0.00 AB,a | 0.04 ± 0.00 AB,a | 0.03 ± 0.00 A,a |
2-phenylethyl acetate | | PFMS | 0.34 ± 0.01 E,a | 0.84 ± 0.03 G,b | 0.60 ± 0.02 F,b | | 0.08 ± 0.00 A,a | 0.09 ± 0.00 ABC,a | 0.14 ± 0.01 D,a | 0.15 ± 0.01 D,a | 0.08 ± 0.00 A,a | 0.08 ± 0.00 AB,a | 0.09 ± 0.00 ABC,a | 0.16 ± 0.01 D,b | 0.13 ± 0.00 CD | 0.12 ± 0.00 BCD |
| PFMB | 2.21 ± 0.08 E,b | 0.47 ± 0.02 D,a | 0.43 ± 0.02 CD,a | | 0.34 ± 0.01 C,b | 0.18 ± 0.01 AB,b | 0.19 ± 0.01 AB,b | 0.21 ± 0.01 AB,b | 0.22 ± 0.01 B,b | 0.18 ± 0.01 AB,b | 0.14 ± 0.01 AB,b | 0.13 ± 0.00 AB,a | 0.12 ± 0.00 A | 0.14 ± 0.01 AB |
Isovalerianic acid | | PFMS | 0.47 ± 0.02 B | 0.61 ± 0.02 C,a | 0.76 ± 0.03 D,a | | 0.45 ± 0.02 B,a | 1.11 ± 0.04 F,b | 1.19 ± 0.05 G,b | 1.85 ± 0.07 H,b | 0.27 ± 0.01 A,a | 0.46 ± 0.02 B | 0.65 ± 0.02 C,b | 0.98 ± 0.04 E,b | 0.58 ± 0.02 C,b | 0.61 ± 0.02 C,b |
| PFMB | 0.56 ± 0.02 D | 0.90 ± 0.03 FG,a | 1.32 ± 0.05 I,b | | 1.08 ± 0.04 H,b | 0.85 ± 0.03 F,a | 0.95 ± 0.04 G,a | 1.10 ± 0.04 H,a | 0.76 ± 0.03 E,b | 0.48 ± 0.02 C | 0.20 ± 0.01 A,a | 0.34 ± 0.01 B,a | 0.48 ± 0.02 C,a | 0.46 ± 0.02 C,a |
Hexanoic acid | | PFMS | 2.53 ± 0.10 E,b | 1.33 ± 0.05 B,b | 2.70 ± 0.10 F,b | | 2.28 ± 0.09 D,b | 1.85 ± 0.07 C,b | 3.31 ± 0.13 G,b | 3.71 ± 0.14 H,b | 2.50 ± 0.10 E,b | 1.89 ± 0.07 C,b | 1.29 ± 0.05 B,b | 1.77 ± 0.07 C,b | 0.98 ± 0.04 A,b | 1.20 ± 0.05 B,b |
| PFMB | 1.16 ± 0.04 E,a | 0.92 ± 0.03 CD,a | 1.38 ± 0.05 F,a | | 1.11 ± 0.04 E,a | 0.85 ± 0.03 C,a | 2.03 ± 0.08 G,a | 1.96 ± 0.07 G,a | 1.44 ± 0.05 F,a | 1.19 ± 0.05 E,a | 0.94 ± 0.04 D,a | 0.44 ± 0.02 A,a | 0.72 ± 0.03 B,a | 0.72 ± 0.03 B,a |
Octanoic acid | | PFMS | 1.92 ± 0.07 E | 1.40 ± 0.05 C,a | 4.13 ± 0.16 I | | 3.87 ± 0.15 H | 1.55 ± 0.06 CD,a | 3.29 ± 0.13 G,b | 3.17 ± 0.12 G,b | 2.27 ± 0.09 F | 1.83 ± 0.07 E | 1.38 ± 0.05 C,b | 1.59 ± 0.06 D,b | 0.70 ± 0.03 A,a | 1.01 ± 0.04 B,a |
| PFMB | 1.66 ± 0.06 C | 2.80 ± 0.11 FG,b | 3.94 ± 0.15 I | | 3.30 ± 0.13 H | 2.65 ± 0.10 EF,b | 2.56 ± 0.10 E,a | 2.99 ± 0.11 G,a | 2.30 ± 0.09 D | 1.55 ± 0.06 C | 0.80 ± 0.03 B,a | 0.54 ± 0.02 A,a | 0.89 ± 0.03 B,b | 0.79 ± 0.03 B,a |
Decanoic acid | | PFMS | 0.58 ± 0.02 D,b | 0.51 ± 0.02 C,b | 0.44 ± 0.02 B,a | | 0.26 ± 0.01 A,a | 0.46 ± 0.02 B,b | 0.72 ± 0.03 E | 0.79 ± 0.03 F | 0.62 ± 0.02 D | 0.76 ± 0.03 F,b | 0.91 ± 0.03 H,b | 1.02 ± 0.04 I,b | 0.86 ± 0.03 G,b | 1.03 ± 0.04 I,b |
| PFMB | 0.12 ± 0.00 B,a | 0.29 ± 0.01 C,a | 1.54 ± 0.06 G,b | | 0.82 ± 0.03 F,b | 0.11 ± 0.00 AB,a | 0.74 ± 0.03 E | 0.81 ± 0.03 EF | 0.62 ± 0.02 D | 0.33 ± 0.01 C,a | 0.03 ± 0.00 A,a | 0.15 ± 0.01 B,a | 0.26 ± 0.01 C,a | 0.18 ± 0.01 B,a |
9-Decenoic acid | | PFMS | 0.85 ± 0.03 I,b | 0.41 ± 0.02 DE,a | 0.33 ± 0.01 C,a | | 0.30 ± 0.01 C,a | 0.40 ± 0.02 D,a | 0.54 ± 0.02 FG,a | 0.71 ± 0.03 H,a | 0.57 ± 0.02 G,a | 0.51 ± 0.02 F,a | 0.44 ± 0.02 E,a | 0.22 ± 0.01 B,a | 0.06 ± 0.00 A,a | 0.25 ± 0.01 B,a |
| PFMB | 0.38 ± 0.01 A,a | 0.60 ± 0.02 A,b | 5.82 ± 0.22 D,b | | 7.34 ± 0.28 E,b | 8.85 ± 0.34 F,b | 10.89 ± 0.42 H,b | 13.54 ± 0.52 I,b | 9.63 ± 0.37 G,b | 7.58 ± 0.29 E,b | 5.52 ± 0.21 D,b | 1.41 ± 0.05 B,b | 2.74 ± 0.10 C,b | 1.37 ± 0.05 B,b |
Dodecanoic acid | | PFMS | 0.00 ± 0.00 A | 0.11 ± 0.00 D | 0.32 ± 0.01 G | | 0.42 ± 0.02 H | 0.47 ± 0.02 I | 0.64 ± 0.02 J | 0.43 ± 0.02 H | 0.21 ± 0.01 F | 0.16 ± 0.01 E | 0.11 ± 0.00 D | 0.07 ± 0.00 BC | 0.04 ± 0.00 B | 0.08 ± 0.00 CD |
| PFMB | NA | NA | NA | | NA | NA | NA | NA | NA | NA | NA | NA | NA | NA |
Benzaldehyde | | PFMS | 0.07 ± 0.00 F,b | 0.06 ± 0.00 D,b | 0.05 ± 0.00 B,b | | 0.05 ± 0.00 AB,b | 0.05 ± 0.00 C,b | 0.05 ± 0.00 A,a | 0.07 ± 0.00 F | 0.09 ± 0.00 G | 0.09 ± 0.00 G | 0.09 ± 0.00 G | 0.07 ± 0.00 E | 0.07 ± 0.00 E | 0.05 ± 0.00 B,a |
| PFMB | 0.05 ± 0.00 D,a | 0.04 ± 0.00 C,a | 0.03 ± 0.00 A,a | | 0.04 ± 0.00 BC,a | 0.04 ± 0.00 B,a | 0.06 ± 0.00 E,b | 0.09 ± 0.00 I | 0.09 ± 0.00 J | 0.09 ± 0.00 J | 0.09 ± 0.00 J | 0.08 ± 0.00 H | 0.07 ± 0.00 F | 0.07 ± 0.00 G,b |
Guaiacol | | PFMS | 0.16 ± 0.01 D,b | 0.14 ± 0.01 C,a | 0.21 ± 0.01 E | | 0.24 ± 0.01 F | 0.26 ± 0.01 G,b | 0.36 ± 0.01 I,b | 0.23 ± 0.01 F,b | 0.34 ± 0.01 H,b | 0.23 ± 0.01 EF,b | 0.12 ± 0.00 C,b | 0.05 ± 0.00 A,b | 0.07 ± 0.00 B,b | 0.08 ± 0.00 B,b |
| PFMB | 0.13 ± 0.00 E,a | 0.19 ± 0.01 F,b | 0.22 ± 0.01 G | | 0.26 ± 0.01 H | 0.11 ± 0.00 D,a | 0.30 ± 0.01 I,a | 0.19 ± 0.01 F,a | 0.20 ± 0.01 F,a | 0.11 ± 0.00 D,a | 0.02 ± 0.00 A,a | 0.04 ± 0.00 AB,a | 0.05 ± 0.00 BC,a | 0.06 ± 0.00 C,a |
4-vinylguaiacol | | PFMS | 0.73 ± 0.03 H,b | 0.33 ± 0.01 F | 0.57 ± 0.02 G,b | | 0.16 ± 0.01 B,a | 0.27 ± 0.01 E | 0.30 ± 0.01 EF | 0.33 ± 0.01 F | 0.16 ± 0.01 B,a | 0.19 ± 0.01 C | 0.23 ± 0.01 D,b | 0.27 ± 0.01 E,b | 0.10 ± 0.00 A | 0.11 ± 0.00 A |
| PFMB | 0.33 ± 0.01 FG,a | 0.34 ± 0.01 GH | 0.37 ± 0.01 I,a | | 0.35 ± 0.01 HI,b | 0.24 ± 0.01 E | 0.32 ± 0.01 FD | 0.31 ± 0.01 F | 0.35 ± 0.01 HI,b | 0.22 ± 0.01 D | 0.09 ± 0.00 B,a | 0.07 ± 0.00 A,a | 0.11 ± 0.00 C | 0.10 ± 0.00 BC |
PFMB: post-fermentative maceration in barrel |
* racking PFMS and PFMB trialsn.d.: not detected Values are expressed as mean ± standard deviation (n = 3). |
Uppercase letters indicate differences over time within a single column (ANOVA), lowercase letters indicate differences between samples, PFMS and PFMB, (t test). |
Higher alcohols content increased during alcoholic fermentation in all trials, because of pre-fermentative enzymatic activities (lipoxygenase) and yeast activity (Nicolini et al., 1996; Houtman and Du Plessis, 1986). In PFMS the maximum content of alcohols was 200.11 mg/L on 50th day after crushing. Then, the content decreases to 87.75 mg/L on 150th day after crushing.
In PFMB the maximum content of alcohols was 173.47 mg/L on 13th day after crushing. Then, the content gradually decreased to the value 83.79 mg/L, with no significant differences with the content of steel tank trial.
The esters content showed an increasing trend during alcoholic fermentation in all trials especially given by the ethyl esters of hydroxyacids (aging esters). In steel tank trial the maximum value of 45.83 mg/L was observed between 40th and 50th day after crushing. Then, the content decreased to 35.04 mg/L on 150th day after crushing. In oak barrel trial the maximum value of 36.05 mg/L was observed between 50th and 60th day after crushing. Then, the content decreased to 27.56 mg/L on 150th day after crushing, that is significantly different from the content of PFMS.
The acids content increased during alcoholic fermentation in all trials. PFMS trial the maximum value of 10.36 mg/L was observed on 50th day after crushing. Then, the content decreased to 3.15 mg/L on 130th day after crushing. In oak barrel trial the maximum value of 16,71 mg/L was observed between 50th day after crushing. Then, the content decreased to 3.43 mg/L on 150th day after crushing, that is significantly different from the content of steel tank trial.
The decreasing evolution of hexanoic and octanoic acid content is not significatively negatively correlated with ethyl hexanoate and octanoate concentration (Pearson’s R acid-ester PFMS 0.1038, 0.537; Pearson’s R acid-ester PFMB 0.7001, -0.1455) that indicates us that this disappearance is not due by esters chemical formation as also confirmed by the decreasing in these esters concentration. We suppose that an adsorbing phenomenon of these molecules on grape solids or yeast cells could be involved.
During maceration, the concentrations of the different chemical classes were higher in PFMB and then became similar on day 150 (racking), except for esters, which were present in larger quantities in steel samples.