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Research article Institute of Brewing & Distilling

Received: 27 June 2013 Revised: 7 September 2013 Accepted: 9 October 2013 Published online in Wiley Online Library: 24 October 2013

(wileyonlinelibrary.com) DOI 10.1002/jib.100

SO2 reduction in distilled grape spirits by


three methods
Qingxuan Zhang, Jinhua Du,* Yuhong Jin, Zhiyun Zhao and Yingya Li
Sulphur dioxide (SO2) is the main additive in grape wine production and cannot be eliminated by simple distillation from the
base wine, lees or fermented pomace. This research was conducted to confirm the effectiveness of calcium oxide, powdered
activated charcoal and hydrogen peroxide on SO2 reduction in distilled grape spirits using a double distillation method.
Three treatments were conducted on the first distillate. Each method was assessed for its effectiveness on SO2 reduction
and its influence on the volatile compounds present, which were analysed both by GC and sensory evaluation. The total
residual SO2 content in the second distillate, which had been treated with calcium oxide, was about 2.00 mg L 1. The value
was below 1.00 mg L 1 for the activated charcoal and hydrogen peroxide treatments. The calcium oxide treatment was the
most convenient method, when compared with the other two treatments, but it also caused the largest decrease in acids and
esters. The activated charcoal-treated distillate had the highest sensory evaluation. However, there were some drawbacks,
such as the loss of esters and a higher cost for temperature maintenance (70°C for ~12 h). The hydrogen peroxide treatment
resulted in the lowest pH and most of the volatile compounds were retained, but the sensory evaluation was second to the
activated charcoal treatment. Copyright © 2013 The Institute of Brewing & Distilling

Keywords: sulphur dioxide reduction; distilled grape spirits; calcium oxide; activated charcoal; hydrogen peroxide

Introduction alcohol solution and can then be separated by distillation.


Activated charcoal has a wide range of applications owing to
Sulphur dioxide (SO2) is widely used in wine production as its large surface area. The SO2 can be adsorbed and oxidized
an additive, owing to its effective anti-microbial (1) and by AC in the presence of O2 and H2O (14), which provides the
anti-oxidant (2) functionalities at low concentrations. Previous potential to remove SO2 in the distillate. For H2O2 treatment,
studies have shown that the preservative activity of SO2 is the mechanism is that H2O2 can oxidize SO23 , the dissolved
decreased by binding with acetaldehyde and carbonyl form of SO2, to SO24 that will then be retained in the stillage.
compounds in the wine (3,4). Therefore, wines with high The aim of the study was to investigate the SO2 reduction
amounts of SO2 and binding compounds typically require effectiveness of CaO, AC and H2O2 in distilled grape spirits, and
increased SO2 additions. However, considering the possible to evaluate their influence on the spirit volatile compounds
health risks caused by excessive intake of SO2, such as and on the general quality of the sample. The results could
asthma (5,6) and cancer, exploration of SO2 reduction provide a more comprehensive understanding of each method
methods is highly desirable. Some studies have been for their practical application in the wine industry.
conducted aimed at reducing SO2 addition in the fermenta-
tion process, by reducing the SO2 binding power of the wine
by removing some of the carbonyl compounds (7), or seeking Materials and methods
new sterilization methods, such as high hydrostatic pressure
and ultraviolet radiation treatments (8,9), and so on (10,11). Base wine
However, SO2 remains an irreplaceable additive in enology The base wine used in the experiment was a Chardonnay wine,
for producing high-quality wines. with an alcohol content of 12.2% (v/v), pH 3.48, titratable acidity
In practice, fruits of poor quality are often used for making 6.2 g L 1 (tartaric acid equivalent) and a total SO2 of 176 mg L 1.
distilled fruit spirits and SO2 is inevitably added into the juices
or musts. Also, the lees and pomace collected in the process of
wine production and some low-quality wines could also be Reagents and standards
considered as a brandy base wine. The SO2 in base wines, lees Both the CaO 98% and the H2O2 99% used in the experiment
or fermented pomace not only cannot be eliminated, but it is were obtained from Kaitong (Tianjin, China). The AC was
also concentrated by distillation. Thus, SO2 reduction in distilled purchased from Begerow (Langenlonsheim, Germany).
spirits is a meaningful and important area of study.
Calcium oxide (CaO), powdered activated charcoal (AC) and
hydrogen peroxide (H2O2) are three widely used products in * Correspondence to: J. Du, College of Food Science and Engineering,
industry to reduce excess SO2. CaO has been extensively Shandong Agricultural University, Tai’an 271018, People’s Republic of
China. E-mail: djh@sdau.edu.cn
adopted to retain SO2 in waste gas pollution treatments
(12,13). To summarize its effect, it reacts with SO23 in the wine College of Food Science and Engineering, Shandong Agricultural
or the distillate to form CaSO3, which will precipitate in the
314

University, Tai’an 271018, People’s Republic of China

J. Inst. Brew. 2013; 119: 314–320 Copyright © 2013 The Institute of Brewing & Distilling
SO2 reduction in distilled grape spirits by three methods
Institute of Brewing & Distilling

Ethanol (analytical grade) was purchased from Kermel diluted H2O2 was added slowly to the first distillate to avoid localized
(Tianjin, China). Chromatographic-grade standards including over oxidation. The first distillate was equilibrated for 3 h and then
1-propanol, 2-methyl-1-propanol, 1-butanol, 2-methyl-1-butanol, the total SO2 was analysed to confirm the success of the addition.
3-methyl-1-butnol, 1-pentanol, 1-hexanol, 2-phenethylethanol, The treatment was divided into several steps at room temperature
ethyl acetate, ethyl butyrate, isoamyl acetate, ethyl hexanoate, ethyl until the total SO2 did not decrease further.
oenanthate, ethyl lactate, butyl caproate, ethyl phenylacetate,
acetal, isovaleric aldehyde, acetaldehyde, isobutyraldehyde, furfural,
acetic acid, hexanoic acid, propanoic acid, isobutyric acid, butyric Analytical methods
acid, isovaleric acid, heptylic acid and octanoic acid were purchased
from Sigma and Aldrich (St Louis, MO, USA), and all had a purity Ethanol (%, v/v), titratable acidity and pH were determined
above 98%. according to OIV standard methods (16).
Stock solutions of references standards were prepared in
distilled water containing 50% (v/v) of ethanol. Tert-amyl alcohol,
n-butyl acetate and 2-ethyl butyrate were used as internal Analysis of SO2
standards. All other chemicals and solvents used in this research Total SO2 in the base wine and in the first distillate were mea-
were analytical grade. sured using an oxidation method according to OIV standard
(16), which has a detection limit of 10 mg L 1. Total SO2 in the
Distillation SD was measured by the pararosaniline hydrochloride method,
which has a detection limit of 1.00 mg L 1.
A double-distillation method was adopted from Satora and
Tuszynski (15) with some modifications. The distillation of the Volatile compound analysis. The volatile compounds were
base wine was carried out in a 5 L conical flask. First, the wine analysed by a GC method according to Diéguez et al. (17) and
was distilled to obtain the first distillate at an alcohol concentra- López-Vázquez et al. (18) with some modifications. The 10 μL
tion of 27–28% (v/v; pH 2.52, titratable acid 0.62 g L 1 acetic acid of internal standard, including tert-amyl alcohol and n-butyl ace-
equivalent, total SO2 292 mg L 1). Then the first distillate was tate at 162 mg L 1 and 2-ethyl butyrate at 186.6 mg L 1 in a 50%
treated with CaO, AC or H2O2 and then distilled again. During alcohol aqueous solution, was added to 1.0 mL of the SD and 1
the second distillation, three fractions were collected in se- μL of the sample was injected directly into the Shimadzu 2010
quence: the heads (1% of ethanol), the heart fraction (83%) chromatograph system with a free induction decay detector. A
and the tails (16%). An alcoholic concentration of 68%-72% capillary column CP-WAX 57CB (cross-linked polyethylene glycol
(v/v) was reached in the second distillate (heart fraction) (SD). stationary phase, 50 m × 0.2 mm × 0.25 μm) was used. The
In order to avoid losses of aroma, all samples were sealed and detector and injector temperatures were 260 and 240°C, respec-
kept at 4°C until analysis. tively. The oven temperature program was as follows: initial tem-
perature was 35°C, maintained for 4 min; increased to 60°C at
SO2 reduction the rate of 2°C min 1; followed by temperature ramp rates of
10°C min 1 to 130°C and 15°C min 1 to 205°C; and finally
Calcium oxide treatment. The CaO addition dosage was maintained at 205°C for 15 min. The carrier gas was nitrogen
based on the titratable acidity and content of total SO2. When with a flow rate of 1.35 ml min 1; the split ratio was 40:1.
1 mg of CaO was added to 1 L of the first distillate, the reduction The qualitative analyses of the volatile compounds (higher al-
of total acidity was about 0.987 mg according to a previous cohols, acids, aldehydes and acids) were based on the compari-
experiment. Considering the reaction efficiency, the actual addi- son of retention times that were read from the chromatograms
tion of CaO to 1 L of the first distillate should be greater than the of samples and standards. The quantitative analysis was
theoretical value of 628.2 mg. The CaO amount of 883.7, 927.9, according to internal standard method. All tests were carried
972.1 and 1060.4 mg L 1 was added to the first distillate and out in triplicate. The concentrations of volatile compounds were
mixed at room temperature. The mixture was subjected to SD recalculated on the basis of 100% (v/v) ethanol and expressed as
once the CaO was dissolved. The titratable acidity and total mg L 1 100°.
SO2 content in the SD were determined.
Activated carbon treatment. Treatment temperature and the Sensory analysis. Sensory analysis was an additional tech-
AC addition dosage are two important factors influencing the nique to evaluate the three methods. All samples were diluted
effectiveness of SO2 reduction. To determine the optimum with distilled water to an alcohol concentration of 40% (v/v)
temperature, samples with 1.0 g L 1 AC were sealed and placed before sensory evaluation, and then assessed by nine people,
into 20, 40 and 70°C water baths, and then shaken until there aged 25–30, who had sensory experience. During each session,
was no further decrease in total SO2 content. Afterwards, the four samples were evaluated in duplicate at 20°C.
effectiveness under each temperature treatment was evaluated.
The optimum AC addition dosage was selected from 0.5, 1.0, 1.5,
2.0 and 2.5 g L 1. Samples, with certain amounts of AC, were Statistical analysis
sealed and treated at the optimum temperatures determined
All data were the mean value of three parallel experiments and
above, and then the samples were shaken until the total SO2
expressed as mean values ± standard deviations. Statistical anal-
did not decrease.
ysis was carried out using Excel 2003 software. Differentiation
Hydrogen peroxide treatment. Hydrogen peroxide was di- analysis was carried out using DPS 7.05 statistical analysis
luted to a concentration below 1% before use and the concentration software with a confidence level of 95% (p = 0.05), the different
of diluted H2O2 was calibrated using potassium permanganate. The letters indicating significant differences (p < 0.05).
315

J. Inst. Brew. 2013; 119: 314–320 Copyright © 2013 The Institute of Brewing & Distilling wileyonlinelibrary.com/journal/jib
Q. Zhang et al.
Institute of Brewing & Distilling

Results and discussion and these two indices showed no significant differences among
the five treatments. To evaluate the effectiveness of SO2 reduc-
SO2 reduction effectiveness tion, 72, 24, 17, 12 and 12 h were tested for the five AC treatment
concentrations. The required treatment period decreased signif-
Calcium oxide treatment. The residual SO2 content after CaO
icantly with increases in the AC dosage. The addition of 1.0 and
treatment is shown in Table 1. The amount of residual SO2 was
2.0 g L 1 deserved attention as there was a sharp decrease of
3.12 mg L 1 when the dosage was 883.7 mg L 1, while it was
time, from 72 to 24 h, when the AC dosage was increased. By in-
2.07 mg L 1 when the dosage was 927.9 mg L 1. When the
creasing the AC dosage to 2.5 g L 1, no significant decrease in
CaO dosage was increased to 972.1 and 1060.4 mg L 1, only
time was observed in comparison to the 2.0 g L 1. In consider-
1.12 and 1.05 mg L 1 SO2 was detected, respectively, but a
ation of the cost of maintaining a temperature of 70°C, the 2.0
distinct alkali smell was identified in these two distillates. The
g L 1 addition dosage was chosen in order to decrease the treat-
conclusion could be drawn that the more CaO that was added,
ment time.
the less SO2 remained. Correspondingly, a lower titratable acid-
ity and higher pH were acquired. However, in consideration of Hydrogen peroxide treatment. The content of SO2 in the SD-
the effectiveness of SO2 reduction and the effect on flavour, H2O2 treated product was less than 1.00 mg L 1 SO2, as shown
927.9 mg L 1 was chosen as a suitable dosage. in Table 4, in comparison to the 654 mg L 1 SO2 in the control
sample. The reduction in the SO2 resulted in a significant reduc-
Activated carbon treatment. As shown in Table 2, the treat- tion in the titratable acidity (from 757.7 to 69.0 mg L 1) and a
ment temperature with AC played an important role in the effec- corresponding increase in the pH value (from 2.42 to 4.43) in
tiveness of SO2 reduction. The times needed for SO2 decreased the SD-H2O2.
lower than 1.00 mg L 1 with 24 h and 30 days for 70 and 40°C
treatments, respectively. However, for the 20°C treatment, there
was still 98 mg L 1 residual SO2 after 120 days. It was concluded Volatile compounds in the second distillate
that, the higher the temperature was, the shorter the treatment Volatile compounds, including higher alcohols, esters, aldehydes
period needed for SO2 reduction. Since there was no significant and acids in the SDs were identified and quantified by the GC
difference in the pH and titratable acidity between SD-ACs method. The variety and concentration of the volatile
treated at 40 and 70°C, the temperature of 70°C was selected compounds in all of samples are given in Table 5. Different
for further experiments to determine the addition dosages SO2 reduction methods resulted in significant differences in
of AC. the concentrations of the volatile compounds (p < 0.05).
As seen in Table 3, all of the total SO2 content values were be-
low 1.00 mg L 1 when 0.5, 1.0, 1.5, 2.0 or 2.5 g L 1 AC was added Higher alcohols. Higher alcohols dominated the volatile com-
to the samples. The pH value of the SD-ACs was in the range of pounds in the SDs. There were no significant differences in the
5.12–5.26 and the titratable acidity was from 39.1 to 43.2 mg L 1, total amount of higher alcohols amongst the CaO, AC treatment

Table 1. General composition of second distillate with different calcium oxide additions (SD-CaO)

Addition of CaO (mg L 1) Control 883.7 927.9 972.1 1060.4

Alcohol (%,v/v) 68.9 ± 0.1a 68.7 ± 0.1a 68.8 ± 0.1a 68.8 ± 0.1a 68.7 ± 0.1a
pH 2.42 ± 0.06a 5.50 ± 0.05b 6.05 ± 0.11c 7.06 ± 0.10d 7.45 ± 0.12e
Titratable aciditya (mg L 1) 757.3 ± 12.3a 7.0 ± 0.0b 5.5 ± 0.0c n.d. n.d.
Total SO2 (mg L 1) 654 ± 11a 3.12 ± 0.05b 2.07 ± 0.04c 1.12 ± 0.04d 1.05 ± 0.05d
All values are expressed as mean values ± standard deviations (n = 3). Different lower-case letters in the same row indicate signif-
icant differences (p < 0.05).
a
Described as acetic acid.
n.d., Not detected.

1
Table 2. Comparison of second distillate with 1.0 g L of activated carbon at different temperatures (SD-AC)

Temperature Control 20°C 40°C 70°C


Treatment period — 120 d 30 d 24 h
Alcohol (%, v/v) 68.9 ± 0.1a — 69.1 ± 0.1a 69.1 ± 0.1a
pH 2.42 ± 0.03a — 5.16 ± 0.09b 5.16 ± 0.09b
Titratable aciditya (mg L 1) 757.3 ± 12.3a — 40.0 ± 1.0b 43.2 ± 2.0b
Total SO2 (mg L 1) 654 ± 11a 98 ± 2.0b <1.00c <1.00c
All values are expressed as mean values ± standard deviations (n = 3). Different lower-case letters in the same row indicate signif-
icant differences (p < 0.05).
a
Described as acetic acid.
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wileyonlinelibrary.com/journal/jib Copyright © 2013 The Institute of Brewing & Distilling J. Inst. Brew. 2013; 119: 314–320
SO2 reduction in distilled grape spirits by three methods
Institute of Brewing & Distilling

Table 3. General composition of second distillate with different additions of activated carbon (SD-AC) at 70°C

Addition of activated carbon (g, L 1) Control 0.5 1.0 1.5 2.0 2.5
Treatment period (h) — 72a 24b 17c 12d 12d
Alcohol (%, v/v) 68.9 ± 0.1a 69.0 ± 0.1a 69.1 ± 0.1a 68.9 ± 0.1a 69.1 ± 0.1a 69.1 ± 0.1a
pH 2.42 ± 0.03a 5.12 ± 0.10b 5.16 ± 0.09b 5.20 ± 0.03b 5.14 ± 0.06b 5.26 ± 0.10b
Titratable aciditya (mg L 1) 757.3 ± 12.3a 41.3 ± 2.0b 43.2 ± 2.0b 39.1 ± 2.0b 39.1 ± 2.0b 40.5 ± 2.0b
Total SO2 (mg L 1) 654 ± 11a <1.00 b <1.00b <1.00b <1.00b <1.00b
All values are expressed as mean values ± standard deviations (n = 3). Different lower-case letters in the same row indicate signif-
icant differences (p < 0.05).
a
Described as acetic acid.

(24). In some alcoholic beverages, such as whisky, the ratios of


Table 4. General composition of the second distillate with 3-methyl-1-butanol/isobutanol and isobutanol/propanol are
hydrogen peroxide treatment ( SD-H2O2) used as a quality index and these should be greater than unity
(25). The values of 3-methyl-1-butanol/2-methyl-1-propanol ratio
were 4.7, 4.9, 4.9 and 5.0 for control, SD-CaO, SD-AC and
Control SD-H2O2
SD-H2O2 respectively, while the values of 2-methyl-1-propanol/
Alcohol (%v/v) 68.9 ± 0.1a 68.7 ± 0.2a 1-propanol ratio were 1.06, 1.07, 1.04 and 0.93, respectively
pH 2.42 ± 0.06a 4.43 ± 0.06b (Table 5). These results indicate that the CaO treatment and
Titratable aciditya (mg L 1) 757.3 ± 12.3a 69.0 ± 2.0b the AC treatment changed the character of SDs less than the
Residual SO2 (mg L 1) 654 ± 11a <1.00b H2O2 treatment.
The compound 1-hexanol is considered to have a positive
All values are expressed as mean values ± standard devia- influence on the aroma of the distillate up to a concentration
tions (n = 3). Different lower-case letters in the same row of 20 mg L 1 (26). Elevated concentrations (generally accepted
indicate significant differences (p < 0.05). as up to 100 mg L 1 100°) impart a grass-like and hot flavour
a
Described as acetic acid. to alcoholic beverages (15). The amount of 1-hexanol in the
SDs was at a low level (14.8–17.5 mg L 1 100°). The compound
2-phenyl ethanol contributes a rose aroma to the distillate
and the control, while the H2O2 method caused a significant (27,28). It was also present at a lower level in all samples
reduction because of its oxidizing property (p < 0.05). (6.1–8.8 mg L 1 100°).
No significant differences were found in levels of 1-propanol
and 1-pentanol amongst the different treatments. The 1-hexanol Esters. In the control, total esters of the SDs were character-
content decreased after H2O2 treatment and increased slightly ized by ethyl esters (C4–C10) and ethyl acetate was the major es-
after the AC and CaO treatments. Generally, the content of most ter in the distillate, similar to many other distilled alcoholic
of the higher alcohols with the SD-CaO treatment showed no drinks (25,29). A significant decrease in the ester levels in the
significant differences from the control. The content of 1-buta- SDs from the three treatment methods was found (p < 0.05;
nol, 2-methyl-1-butanol and 2-phenylethanol decreased Table 5), except for butyl caproate, which did not change signif-
significantly (p<0.05) after the AC treatment. The H2O2 icantly. The total ester level was reduced by about 91% in the
treatment yielded the lowest 2-methyl-1-propanol, 1-butanol SD-CaO and 24% in the SD-AC treatments. Only small changes
and 1-hexanol content; however, results for 2-methyl-1-butanol were observed in the SD-H2O2, at about 9%. In the SD-CaO, the
and 2-phenylethanol were similar to that seen with the AC individual esters decreased sharply and ethyl phenylacetate
treatment. was not detected (owing to a saponification reaction).
Previous investigations have suggested that a concentration Isoamyl acetate, ethyl butyrate, ethyl oenanthate, ethyl lactate
of higher alcohols greater than 3.50 g L 1 100° would lead to and ethyl phenylacetate were reduced significantly by the differ-
poor quality product (19). The total higher alcohol content of ent methods (p < 0.05), while others did not change signifi-
the samples shown in Table 5 was about 1.9 g L 1 100°, cantly, such as ethyl hexanoate and butyl caproate, which may
suggesting high quality to some extent. The compound 2- have been due to the different adsorption capacity of the AC.
methyl-1-propanol, which contributes flavour to the spirit (20), Compared with CaO and AC, the H2O2 method altered the ester
was usually found at higher concentrations than 1-propanol content less extensively. For example, the contents of ethyl bu-
(Table 5), which was consistent with the data from the Cortés tyrate and butyl caproate were similar to that of the control,
et al. study (21). while others had a moderate reduction, and the ethyl
The amyl alcohols (3-methyl-1-butanol and 2-methyl-1-buta- oenanthate was reduced sharply from the control with all three
nol) were predominant in all of the samples, and they accounted methods.
for about 74% of the total higher alcohols. These are character- Esters contribute to the fruity aroma and flavour of spirits and
ized by aromatic notes such as ‘alcoholic’, ‘sweet’ and ‘choking’ are widely used to evaluate a spirit’s quality (20,30,31). For exam-
(22) and reinforce the structure of the distillates in the mouth ple, the ratio of total esters/ethyl acetate is used to evaluate sen-
(19,23). However, a further increase in amyl alcohol content sory characteristics: the higher the ratio, the higher the quality of
would contribute to a negative flavour in the overall aroma the spirit (32). The ratio was 1.19, 2.34, 1.14 and 1.18 in the
317

J. Inst. Brew. 2013; 119: 314–320 Copyright © 2013 The Institute of Brewing & Distilling wileyonlinelibrary.com/journal/jib
Q. Zhang et al.
Institute of Brewing & Distilling

1
Table 5. Volatile compounds in the second distillate after treatment using different products (mg L 100°)a

Compounds Control SD-CaO SD-AC SD-H2O2


Higher alcohols
1-Propanol 226.3 ± 1.8a 221.7 ± 1.2a 212.7 ± 10.7a 234.4 ± 10.5a
2-Methyl-1-propanol 252.5 ± 3.0a 246.1 ± 4.0a 245.8 ± 0.6a 229.0 ± 8.7b
1-Butanol 5.1 ± 0.1a 5.5 ± 0.0a 4.8 ± 0.0b 3.8 ± 0.1c
2-Methyl-1-butanol 238.9 ± 4.0a 236.5 ± 1.3a 220.7 ± 3.8b 218.5 ± 6.9b
3-Methyl-1-butanol 1192.0 ± 11.3ab 1207.1 ± 4.0a 1194.5 ± 13.2ab 1160.5 ± 24.2b
1-Pentanol 0.3 ± 0.0a 0.4 ± 0.0a 0.3 ± 0.1a 0.3 ± 0.0a
1-Hexanol 16.0 ± 0.1a 17.1 ± 0.2b 17.5 ± 0.2b 14.8 ± 0.2c
2-Phenylethanol 8.2 ± 0.4a 8.8 ± 0.3a 6.5 ± 0.3b 6.1 ± 0.2b
Alcohols subtotal 1939.3 ± 10.0a 1943.2 ± 6.8a 1902.8 ± 24.9a 1864.7 ± 17.9b
Esters
Ethyl acetate 387.7 ± 8.8a 17.1 ± 0.5d 316.1 ± 2.0c 361.0 ± 14.1b
Ethyl butyrate 8.2 ± 0.5a 7.5 ± 0.2ab 7.2 ± 0.4b 8.1 ± 1.5a
Isoamyl acetate 40.7 ± 1.2a 3.5 ± 0.2d 11.5 ± 0.2c 35.0 ± 1.6b
Ethyl hexanoate 16.8 ± 1.0a 9.5 ± 0.5c 17.6 ± 1.2a 11.8 ± 1.7b
Ethyl oenanthate 2.3 ± 0.1a 0.1 ± 0.0b 0.1 ± 0.0b 0.1 ± 0.0b
Ethyl lactate 12.4 ± 0.1a 0.5 ± 0.0d 5.3 ± 0.2c 11.2 ± 0.8b
Butyl caproate 1.7 ± 0.1a 1.8 ± 0.1a 1.5 ± 0.0a 1.4 ± 0.2a
Ethyl phenylacetate 0.6 ± 0.05a n.d. n.d. 0.3 ± 0.0b
Esters subtotal 470.4 ± 10.3a 40.0 ± 1.1d 359.3 ± 2.6c 428.9 ± 17.3b
Aldehydes
Acetal 26.0 ± 1.2a 318.4 ± 1.0c 199.8 ± 2.8b 362.2 ± 11.1d
Isovaleric aldehyde 96.0 ± 5.9a 77.3 ± 1.9b 99.7 ± 3.8a 76.5 ± 3.7b
Acetaldehyde 373.7 ± 17.8a 86.7 ± 5.9c 190.0 ± 12.4b 89.9 ± 6.2c
Isobutyraldehyde 2.2 ± 0.1a 1.9 ± 0.1b 1.8 ± 0.2b 1.4 ± 0.1c
Furfural 3.0 ± 0.3a 1.4 ± 0.1b 2.9 ± 0.0a 0.7 ± 0.1c
Aldehyde subtotal 500.9 ± 7.9a 485.7 ± 7.1a 494.2 ± 12.8a 530.7 ± 17.4b
Acids
Acetic acid 52.6 ± 1.3a 4.8 ± 0.1d 39.0 ± 2.1b 33.2 ± 0.6c
Hexanoic acid 16.2 ± 0.5a 1.7 ± 0.0d 11.1 ± 0.0c 12.0 ± 0.1b
Propanoic acid 0.4 ± 0.0a n.d. 0.2 ± 0.0b 0.4 ± 0.0a
Isobutyric acid 0.9 ± 0.1a n.d. 1.0 ± 0.1a 0.7 ± 0.1b
Butyric acid 2.7 ± 0.1a 0.7 ± 0.0c 2.7 ± 0.2a 1.8 ± 0.2b
Isovaleric acid 1.1 ± 0.0a 0.4 ± 0.1c 0.9 ± 0.1a 0.7 ± 0.0b
Heptylic acid 0.5 ± 0.0a 0.5 ± 0.0a 0.4 ± 0.0a 0.6 ± 0.1a
Octanoic acid 33.3 ± 0.5a 3.0 ± 0.3d 8.7 ± 0.5c 28.2 ± 2.6b
Acids subtotal 107.7 ± 1.8a 11.1 ± 0.4d 64.0 ± 2.6c 77.6 ± 3.3b
All values are expressed as mean values ± standard deviations (n = 3). Different lower-case letters in the same row indicate signif-
icant differences (p < 0.05).
a
mg L 1 100° means that the concentration of the volatile compounds were recalculated on the basis of 100% (v/v) ethanol.
n.d.= not detected.

control, SD-CaO, SD-AC and SD-H2O2, respectively. Isoamyl ace- and there was a substantial increase in all of the treated samples.
tate with its fruity notes of ‘banana’ and ‘apple’ (33) contributes This could be because more acetaldehyde was released during
to the aroma of spirits and ethyl lactate is considered to stabilize treatment, which then reacted with ethanol.
the flavour of the distillate and to soften the harsh flavour char- Acetaldehyde was the major carbonyl compound in the spirit
acteristics when present in low concentrations (26). In general, a (373.7 mg L 1 100°) and it contributes to aroma (35). Its level de-
decrease in the ester content will cause a loss of spirit aroma. creased significantly (p < 0.05) after treatment. No significant
difference was detected between the levels in the SD-CaO and
Aldehydes. A significant increase in the amount of total alde- SD-H2O2 treatments, which were 86.7 and 89.9 mg L 1 100°,
hydes was observed with the SD-H2O2 (p < 0.05) treatment; respectively.
however, it did not drop notably in the SD-CaO and SD-AC treat- The isovaleric aldehyde content in the SD-AC was similar
ment compared with the control. Acetal contributes a pungent to that in the control, whereas the amount in the SD-CaO
and unpleasant note to spirit aroma (34), and it forms during dis- and SD-H2O2 decreased. Isobutyraldehyde, which has a
tillation and favours high temperatures and a high ethanol content. banana–melon aroma note, decreased significantly after the
It presented at a low concentration in the control (26.0 mg L 1 100°) H2O2 treatment.
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SO2 reduction in distilled grape spirits by three methods
Institute of Brewing & Distilling

Table 6. Comparison of the three different treatment methods for SO2 reduction
1 1
Additive H2O2 927.9 mg L CaO 2.0 g L AC
Treatment period (h) About 48 h Immediately 12 h
Treatment temperature (°C) RT RT 70°C
Alcohol (%, v/v) 68.7 ± 0.2a 68.8 ± 0.1a 69.1 ± 0.1a
pH value 4.43 ± 0.06a 6.05 ± 0.11c 5.14 ± 0.06b
Titratable aciditya (mg L 1) 69.0 ± 2.0a 5.5 ± 0.0c 39.1 ± 2.0b
Residual total SO2 (mg L 1) <1.00b 2.07 ± 0.04a <1.00b
All values are expressed as mean values ± standard deviations (n = 3). Different lower-case letters in the same row indicate
significant differences (p < 0.05).
a
Described as acetic acid.
RT, Room temperature.

Furfural contributes ‘coconut’, ‘almond’ and ‘nutty’ notes to caused the greatest decrease in acids and esters, while the AC
distillates (36). There was a high content in the control method caused little decrease in the acids and esters. The
(3.0 mg L 1 100°) and a reduced content in the SD-H2O2 H2O2 method retained most of the aromatic components. How-
(0.7 mg L 1 100°) and SD-CaO (1.4 mg L 1 100°). Different ever, the sensory evaluation was not in full accord with the con-
methods caused significant differences in the content of the tent of the analysed volatile compounds. The sensory evaluation
furfural levels (p < 0.05). of the SD-AC was prior to the others and followed that of the SD-
H2O2. The treatment period was about 48 h with the H2O2 at
Acids. The total acids in the control were mainly characterized room temperature and about 12 h at 70°C by AC, while almost
by acetic acid (52.6 mg L 1 100°, 50% of total acid), octanoic acid no time was consumed by the CaO with the room temperature
(33.3 mg/L, 30% of total acid) and hexanoic acid (16.2 mg L 1, treatment (Table 6).
15% of total acid). Compared with the control, the total acid
content decreased significantly in all three treated samples
(p < 0.05). The acid level was reduced about 90% in SD-CaO ow-
ing to the neutralization reaction, while the value in SD-AC was Conclusions
about 40%, because of the adsorption of aliphatic acids. The All the three methods could reduce SO2 effectively. However,
least decrease was seen in the SD-H2O2 treatment. there were significant differences in their cost and in the flavour
Although acetic acid was dominant in the spirit, its content of the corresponding distillates. The SD-AC treatment gave the
was far below its perception threshold of 200 mg L 1 (17). best quality but at the highest cost. The SD-CaO treatment had
Octanoic acid, which supplies caprylic odours to the spirit, was the lowest cost but there were quality issues. The cost of the
found at a concentration higher than its perception threshold SD-H2O2 treatment was lower than that of the SD-AC treatment
of 8.8 mg L 1 (17), in both the SD-H2O2 and in the control. and the quality was superior to the SD-CaO treatment. Thus, the
AC method could be used for producing a high-grade distillate
Sensory evaluation in the wine industry, while the CaO method could be used for
a general distillate, especially when the base wine had a high
The control was characterized by a strong pungent matchstick volatile acid content. The H2O2 method was an effective way
taste owing to its high concentration of SO2. The SD-CaO treated to reduce the SO2 quantitatively for the wine industry. In conclu-
sample was described as oil, cooked sweet potato and stale tast- sion, the AC method is the recommended method to use in the
ing, owing to its low acidity and total ester content, along with wine industry to produce distillates of high quality.
its higher content of aldehydes and alcohols (as shown in
Table 5). The SD-AC treated sample was characterized by a pure,
sweet taste, a clear fruit flavour owing to its low acid content
and higher content of esters. The SD-H2O2 sample had a smoky, References
paper flavour and a more noticeable aroma, probably owing to 1. Carreté, R., Vidal, M. T., and Bordons, A. M. (2002) Inhibitory effect of
the higher content of esters and some acids, such as octanoic sulfur dioxide and other stress compounds in wine on the ATPase
acid, whose content was higher than the taste threshold, and activity of Oenococcus oeni, FEMS Microbiol. Lett., 211, 155–159.
2. Danilewicz, J. C. (2003) Review of reaction mechanisms of oxygen
so would bring a caprylic odour. and proposed intermediate reaction products in wine: central role
of iron and copper, Am. J. Enol. Viticult., 54, 73–85.
3. Jackowetz, J. N., and Mira de Orduña, R. (2012) Metabolism of SO2
Comparison of the different methods for SO2 reduction binding compounds by Oenococcus oeni during and after malolactic
fermentation in white wine, Int. J. Food Microbiol., 155, 153–157.
The residual total SO2 levels in the SD-AC and SD-H2O2 were be- 4. Jackowetz, J. N., and Orduña, R. M. D. (2013) Survey of SO2 binding
low 1.00 mg L 1, while in the SD-CaO they were about 2.00 mg carbonyls in 237 red and white table wines. Food Control, 32, 687–692.
L 1. There were significant differences between pH and titrat- 5. Arellano, V. M., Martos, M. R., Cabreros, M. R., Fernández, A. B., Loria,
able acidity (p < 0.05). The SD-H2O2 had the lowest pH (4.43) J. G., and Mosquera, M. R. (2011) Sulfite sensitivity in a patient with
allergic asthma, Allergol. Immunopathol., 5, 306–307.
and the SD-CaO had the highest pH (6.05). In contrast, the 6. Vally, H., and Thompson, P. (2001) Role of sulfite additives in wine in-
SD-H2O2 had the highest titratable acidity (69.0 mg L 1) and duced asthma: single dose and cumulative dose studies, Thorax, 56
the SD-CaO had the lowest (5.5 mg L 1). The CaO method (10), 763–769.
319

J. Inst. Brew. 2013; 119: 314–320 Copyright © 2013 The Institute of Brewing & Distilling wileyonlinelibrary.com/journal/jib
Q. Zhang et al.
Institute of Brewing & Distilling

7. Blasi, M., Barbe, J. C., Dubourdieu, D., and Deleuze, H. (2008) New the major volatile compounds of Tsipouro a traditional Greek distil-
method for reducing the binding power of sweet white wines. late, Food Sci. Technol. Int., 9, 371–378.
J. Agr. Food Chem., 56, 8470–8474. 23. Silva, M. L., Malcata, F. X., and Revel, G. D. (1996) Volatile contents of
8. Buzrul, S. (2012) High hydrostatic pressure treatment of beer and grape marcs in Portugal, J. Food Compos. Anal., 9, 72–80.
wine: A review, Innov. Food Sci. Emerg., 13, 1–12. 24. Falque, E., Fernandez, E., and Dubourdieu, D. (2001) Differentiation
9. Fredericks, I. N., du Toit, M., and Krügel, M. (2011) Efficacy of ultravi- of white wines by their aromatic index, Talanta, 54, 271–281.
olet radiation as an alternative technology to inactivate microorgan- 25. Cortés, S., Gil, L., and Fernandez, E. (2005) Volatile composition of tra-
isms in grape juices and wines, Food Microbiol., 28, 510–517. ditional and industrial Orujo spirits, Food Control, 16, 383–388.
10. Sonni, F., Chinnici, F., Natali, N., and Riponi, C. (2011) Pre-fermentative 26. Apostolopoulou, A. A., Flouros, A. I., Demertzis, P. G., and Akrida-
replacement of sulphur dioxide by lysozyme and oenological tannins: Demertzi, K. (2005) Differences in concentration of principal vola-
Effect on the formation and evolution of volatile compounds during tile constituents in traditional Greek distillates, Food Control, 16,
the bottle storage of white wines, Food Chem., 129, 1193–1200. 157–164.
11. Salaha, M. I., Kallithraka, S., Marmara, I., Koussiss, E., and Tzourou, 27. Ferrari, G., Lablanquie, O., Cantagrel, R., Ledauphin, J., Payot, T.,
I. (2008) A natural alternative to sulphur dioxide for red wine produc- Fournier, N., and Guichard, E. (2004) Determination of key odorant
tion: Influence on colour, antioxidant activity and anthocyanin con- compounds in freshly distilled cognac using GC-O, GC-MS, and sen-
tent, J. Food Compos. Anal., 21, 660–666. sory evaluation, J. Agric. Food Chem., 52(18), 5670–5676.
12. Macías-Pérez, M. C., Bueno-López, A., Lillo-Ródenas, M. A., Salinas- 28. Cortés, S., Fernández, A., Otero, C., and Salgado, I. (2009) Application
Martínez de Lecea, C., and Linares-Solano, A. (2008) SO2 retention of sensory descriptive analysis to complete the current official card
on CaO/activated carbon sorbents. Part III. Study of the retention of the Galician Orujo spirits, J. Sens. Stud., 24, 317–331.
and regeneration conditions, Fuel, 87, 3170–3175. 29. Nonato, E. A., Carazza, F., Silva, F. C., Carvalho, C. R., and Cardeal, Z. L.
13. Lee, K. T., Mohamed, A. R., Bhatia, S., and Chu, K. H. (2005) Removal of sul- (2001) A headspace solid-phase microextraction method for the de-
fur dioxide by fly ash/CaO/CaSO4 sorbents, Chem. Eng. J., 114, 171–177. termination of some secondary compounds of Brazilian sugar cane
14. Gaur, V., and Asthana, R. (2006) Removal of SO2 by activated carbon spirits by gas chromatography, J. Agric. Food Chem., 49, 3533–3539.
fibers in the presence of O2 and H2O, Carbon, 44, 46–60. 30. Selli, S., Cabaroglu, T., Canbas, A., Erten, H., Nurgel, C., Lepoutre, J. P.,
15. Satora, P., and Tuszynski, T. (2010) Influence of indigenous yeasts on and Gunata, Z. (2004) Volatile composition of red wine from cv.
the fermentation and volatile profile of plum brandies, Food Kalecik Karasi grown in central Anatolia, Food Chem., 85, 207–213.
Microbiol., 27, 418–424. 31. King, E. S., Kievit, R. L., Curtin, C., Swiegers, J. H., Pretorius, I. S., and
16. OIV. International Oenological Codex, Edition 2006. (2006) Compen- Bastian, S. (2004) The effect of multiple yeasts co-inoculations on
dium of International Methods of Wine and Must Analysis, Office Sauvignon blanc wine aroma composition, sensory properties and
International de la Vigne et du Vin: Paris. consumer preference, Food Chem., 122, 618–626.
17. Diéguez, S. C., Dı́az, L. D., Luisa, M., De La Peña, G., and Gómez, E. F. 32. Guichard, H., Lemesle, S., Ledauphin, J., Barillier, D., and Picoche,
(2002) Variation of volatile organic acids in spirits during storage at B. (2003) Chemical and sensorial aroma characterization of freshly
low and room temperatures, LWT-Food Sci. Technol., 35, 452–457. distilled Calvados. 1. Evaluation of quality and defects on the basis
18. López-Vázquez, C., Bollaín, M. H., Berstsch, K., and Orriols, I. (2010) of key odorants by olfactometry and sensory analysis, J. Agric. Food
Fast determination of principal volatile compounds in distilled Chem., 51, 424–432.
spirits, Food Control, 21, 1436–1441. 33. Francis, I. L., and Newton, J. L. (2005) Determining wine aroma from
19. Cortés, S., Rodríguez, R., Salgado, J. M., and Domínguez, J. M. (2011) compositional data, Aust. J. Grape Wine Res., 11, 114–126.
Comparative study between Italian and Spanish grape marc spirits 34. Masino, F., Montevecchi, G., Riponi, C., and Antonelli, A. (2009) Com-
in terms of major volatile compounds, Food Control, 22, 673–680. position of some commercial grappas (grape marc spirit): the anom-
20. Silva, M. L., Macedo, A. C., and Malcata, F. X. (2000) Review: steam alous presence of 1,1-diethoxy-3-methylbutane a case study, Eur.
distilled spirits from fermented grape pomace, Food Sci. Technol. Food Res. Technol., 228, 565–569.
Int., 6, 285–300. 35. Porto, C. D., Cordaro, F., and Marcassa, N. (2006) Effects of carbohy-
21. Cortés, S., Salgado, J. M., Rodríguez, N., and Domínguez, J. M. (2010) drate and noncarbohydrate sweeteners on the orange spirit volatile
The storage of grape marc: Limiting factor in the quality of the dis- compounds, LWT-Food Sci. Technol., 39, 159–165.
tillate, Food Control, 22, 673–680. 36. Monica-Lee, K. Y., Paterson, A., and Piggot, J. R. (2000) Perception of
22. Flouros, A. I., Apostolopoulou, P. G., Demertzis, P. G., and Akrida- whisky flavor reference compounds by Scottish distillers, J. Inst.
Demertzi, K. (2003) Note: Influence of the packaging material on Brew., 106, 203–208.
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