Bioresource Technology 101 (2010) 1396–1398

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Short Communication

Influence of apple cultivar and juice pasteurization on hard cider

and eau-de-vie methanol content
Yong D. Hang *, Edward E. Woodams
Department of Food Science and Technology, Cornell University, 630 W. North Street, Geneva, NY 14456, USA

a r t i c l e i n f o a b s t r a c t

Article history: Apple eau-de-vie is a traditional alcoholic beverage produced in France by distillation of fermented apple
Received 7 November 2008 juice (hard cider). The current research was undertaken to determine the methanol content of hard cider
Received in revised form 18 September and apple eau-de-vie made from four apple cultivars grown in the Finger Lakes region of New York State.
2009
The methanol concentration of hard cider varied from 0.037% to approximately 0.091%, and the methanol
Accepted 18 September 2009
content of apple eau-de-vie ranged from below 200 mg to more than 400 mg/100 mL of 40% ethanol. The
United States legal limit of methanol for fruit brandy is 0.35% by volume or 280 mg/100 mL of 40% eth-
anol. Of the four apple cultivars examined, Crispin apples yielded significantly more methanol in hard
Keywords:
Methanol
cider and eau-de-vie than Empire, Jonagold or Pacific Rose apples. Pasteurization of Crispin apple juice
Hard cider prior to alcoholic fermentation significantly reduced the methanol content of hard cider and eau-de-vie.
Apple eau-de-vie Ó 2009 Elsevier Ltd. All rights reserved.
Distilled fruit spirit

1. Introduction
Eau-de-vie (water of life) is a French term for a colorless alco-
holic beverage produced in the Calvados region of Normandy,
France by the distillation of fermented apple juice or hard cider
(Subden et al., 1986; Andraous et al., 2004; Mattsson, 2004). Meth-
anol in fruit wines and distilled fruit spirits is a major health con-
cern, because it can exert adverse effects on human health (The
Merck Index, 2001). The United States Bureau of Alcohol, Tobacco,
Firearms and Explosives has set a tolerance methanol level of 0.35%
by volume or 0.28% by weight (280 mg/100 mL of 40% ethanol) for
brandy and other distilled fruit spirits (United States Code of Fed-
eral Regulations, 2003). Methanol is a product resulting during fer-
mentation from the hydrolysis of fruit pectin by pectin
methylesterase (EC 3.1.1.11) as follows (Dixon and Webb, 1964):
Pectin methylesterase
Pectin þ H2 O ƒƒƒƒƒƒƒƒƒƒ! Pectic acid þ Methanol
Commercial pectic enzymes produced by Aspergillus niger are
widely used in the production of apple juice to enhance the pro-
cessing efficiency and the product yield (Downing, 1989). Andra-
ous et al. (2004) reported that the distilled spirits made from
pectic enzyme-treated fruit mashes contained concentrations of
methanol significantly above the legal limit of 280 mg/100 mL of
40% ethanol, with the observed methanol concentrations in a range
* Corresponding author. Tel.: +1 315 787 2265; fax: +1 315 787 2284.
E-mail address: YDH1@cornell.edu (Y.D. Hang).
between 320 and 656 mg/100 mL of 40% ethanol. The objective of
the current study was to determine the methanol content of apple
eau-de-vie made from four apple varieties grown in the Finger
Lakes region of New York State.
2. Methods
2.1. Apples and apple juice extraction
Four apple cultivars (Empire, Jonagold, Crispin and Pacific Rose)
grown at Cornell University’s New York State Agricultural Experi-
ment Station in Geneva, NY, were hand picked and processed into
juice in the fruit and vegetable processing pilot plant located in the
Food Research Laboratory in Geneva, NY. Rapidase ADEX-D, a com-
mercial pectic enzyme preparation derived from A. niger (DSM
Food Specialities, USA Inc., Charlotte, NC), was added to apple
mashes (0.17 mL/kg), and the mixture was incubated at 50 °C. After
30 min of reaction, the treated apple mashes were passed through
a filter press to separate apple juice from apple pomace.
2.2. Pasteurization of apple juice
After 30 min of reaction at 50 °C, the treated apple mashes were
heated to about 85 °C to inactivate the commercial pectic enzyme
and passed through a filter press to separate pasteurized apple
juice from apple pomace.

0960-8524/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.09.069
 Y.D. Hang, E.E. Woodams / Bioresource Technology 101 (2010) 1396–1398 1397

2.3. Cider fermentation
All cider fermentation experiments were conducted in triplicate
in 500 mL fermenters, each containing 400 mL of apple juice. After
inoculation with about 0.2 g/fermenter Red Star dry active wine
yeast (Presque Isle Wine Cellars, North East, PA, USA), all the apple
juice samples were incubated at room temperature (16–19 °C) for
7 days. The three different batches of cider fermentation were
made with each apple cultivar.
2.4. Distillation
Samples of hard cider were distilled using a laboratory distilla-
tion apparatus (Andraous et al., 2004). The distillations were per-
formed on three different batches of hard cider made with each
apple cultivar.
2.5. Analytical methods
The concentrations of methanol and ethanol in samples of hard
cider produced from the four New York State apple cultivars are gi-
ven in Table 2. The ethanol concentrations of hard cider ranged
from nearly 7% to greater than 10% and were dependent on the ap-
ple variety fermented. The methanol concentrations of hard cider
varied considerably and ranged from 0.03 to 0.091% v/v (0.221–
0.507% v/v 40% ethanol). Crispin apples produced the largest
amount of methanol (0.091% v/v or 0.507% v/v 40% ethanol) in hard
cider. The methanol concentrations of the hard cider made with
Pacific Rose and Empire apples were 0.074% v/v (0.305% v/v 40%
ethanol) and 0.064% v/v (0.355% v/v 40% ethanol), respectively.
The hard cider made with Jonagold apples had the lowest amount
of methanol (0.037% v/v or 0.221% v/v 40% ethanol). The acetic acid
concentrations in the samples of hard cider produced from the four
apple cultivars ranged from nearly 0.015% to more than 0.030%.
Table 2
Influence of apple cultivar on the methanol content of hard cider.

Cultivar Methanol Methanol (% v/v Ethanol

Methanol, ethanol and acetic acid were analyzed by HPLC under (% v/v) 40% ethanol) (% v/v)
the following conditions (Bio-Rad Laboratories, 1993; Hang and Empire
Woodams, 2008): Column, Bio-Rad Aminex HPX 87H; Eluant, EP1 0.063 0.361 6.94
0.005 M H2SO4; flow rate, 0.6 mL/min; temperature, 50 °C; detec- EP2 0.060 0.341 7.03
tor, a refractive index detector (Knauer K-2300, Sonntek Inc., Upper EP3 0.068 0.364 7.44
Mean ± SD 0.064 ± 0.004 0.355 ± 0.012B 7.14 ± 0.27
Saddle River, NJ). °Brix was measured with a Carl Zeiss refractom-
eter (Jena, Germany). The titratable acidity, expressed as % malic Jonagold
JG1 0.036 0.222 6.44
acid, was determined by titrating the samples with 0.02 N NaOH
JG2 0.039 0.225 6.93
to pH 8.2 (Sadler and Murphy, 2003), and pH was analyzed with JG3 0.036 0.216 6.66
a Fisher pH meter Model 230 (www.fishersci.com). Mean ± SD 0.037 ± 0.002 0.221 ± 0.004C 6.68 ± 0.25
Crispin
2.6. Statistical analysis CR1 0.104 0.581 7.08
CR2 0.084 0.446 7.50
CR3 0.085 0.495 6.96
All experiments were conducted in triplicate, and the experi- Mean ± SD 0.091 ± 0.011 0.507 ± 0.068A 7.18 ± 0.28
mental data were expressed as mean ± SE (standard deviation).
Pacific Rose
The SAS statistical computer package was used to analyzed the PR1 0.076 0.335 9.04
data (SAS Institute, Cary, NC, USA). The values that have no com- PR2 0.076 0.302 10.12
mon superscript are significantly different according to Duncan’s PR3 0.071 0.277 10.20
multiple range test. The Student’s t-test was used to determine if Mean ± SD 0.074 ± 0.003 0.305 ± 0.029B 9.65 ± 0.76

there was a significant difference between unpasteurized and pas- The values of methanol that have no common superscript are significantly different
teurized samples of hard cider and apple eau-de-vie. The level of at the 95% confidence level according to Duncan’s multiple range test.
confidence used in the statistical analysis of the data was 95%.
Table 3
Influence of apple cultivar on the methanol content of eau-de-vie.
3. Results and discussion
Cultivar Batch Methanol content
The chemical composition of the four apple cultivars (Crispin, (mg/100 mL of 40% ethanol)
Empire, Jonagold and Pacific Rose) grown in the Finger Lakes re- Empire
gion of New York Stat is shown in Table 1. The values of °Brix, E1 285
E2 270
pH, and titratable acidity varied widely with the apple variety. Pa-
E3 287
cific Rose apples were found to have the highest °Brix value (17.3), Mean ± SD 281 ± 9B
whereas Empire apples have the lowest value of °Brix (13.0). The
Jonagold
values of pH varied from 3.26 to 3.83, and the malic acid ranged J1 176
from 0.21% to 0.38%. The °Brix, pH, acidity, and other constituents J2 178
can be significantly influenced by location, season, maturity, post- J3 171
harvest handling and processing (Way and McLellan, 1989). Mean ± SD 175 ± 4C
Crispin
C1 459
Table 1 C2 352
Chemical composition of New York State apple cultivar. C3 390
Mean ± SD 400 ± 54A
Cultivar °Brix pH Acidity %
Pacific Rose
Crispin 14.5 ± 1.2a 3.83 ± 0.03 0.21 ± 0.04b P1 265
Empire 13.0 ± 0 3.45 ± 0.02 0.26 ± 0.01 P2 238
Jonagold 14.3 ± 0.1 3.44 ± 0.01 0.35 ± 0 P3 219
Pacific Rose 17.3 ± 0.3 3.63 ± 0.08 0.38 ± 0.04 Mean ± SD 241 ± 23B
a
Values are the means of six determinations for each apple cultivar. The values of methanol that have no common superscript are significantly different
b
Titratable acidity was expressed as % malic acid. at the 95% confidence level according to Duncan’s multiple range test.
1398 Y.D. Hang, E.E. Woodams / Bioresource Technology 101 (2010) 1396–1398

Table 4 tent of the eau-de-vie from the pasteurized Crispin apple juice was
Influence of apple juice pasteurization on the methanol content of eau-de-vie. only 217 ± 11 mg/100 mL of ethanol (N = 3). The Student’s t-test of
Cultivar Pasteurization Methanol content the experimental data yielded a value of 5.87 at the 95% confidence
(mg/100 mL of 40% ethanol) level indicating that the pasteurized Crispin apple juice produced a
Crispin significantly smaller amount of methanol in the eau-de-vie than
C1 No 459 the unpasteurized Crispin apple juice. The United States legal limit
C2 No 352 of methanol is 0.35% by volume or 280 mg/100 mL of brandy with
C3 No 390
Mean ± SD 400 ± 54A
an ethanol content of 40% (80 proof). However, Student’s t-test of
the unpasteurized and pasteurized samples of eau-de-vie made
HC4 Yes 214
HC5 Yes 208
with Pacific Rose apples yielded a value of 2.91 at the 95% confi-
HC6 Yes 229 dence level indicating pasteurization had no significant influence
Mean ± SD 217 ± 11B on the methanol content of eau-de-vie made with Pacific Rose ap-
ples. As shown in Table 4, the methanol concentrations of eau-de-
Pacific Rose
vie produced from the pasteurized or the unpasteurized Pacific
P1 No 265
P2 No 238 Rose apple juice were well below the United States legal limit of
P3 No 219 280 mg/100 mL of 40% ethanol for brandy.
Mean ± SD 241 ± 23C It is concluded from the results of the present investigation that
HP4 Yes 154 the pasteurization of apple juice prior to alcoholic fermentation
HP5 Yes 136 could significantly reduce the methanol content of hard cider and
HP6 Yes 194 eau-de-vie.
Mean ± SD 161 ± 30C

The values of methanol that have no common superscript are significantly different Acknowledgements
(p < 0.05) according to Student’s t-test at the 95% confidence level.

This investigation was supported in part by the Federal Formula

As shown in Table 3, the methanol concentrations of apple eau-
de-vie made with the four apple cultivars grown in New York State
ranged from less than 200 mg to more than 400 mg/100 mL of eau-
de-vie containing 40% ethanol. According to the United States Code
of Federal Regulations (2003), the legal limit on methanol in bran-
dy and other distilled fruit spirits is 0.35% by volume or 0.28% by
weight (280 mg/100 mL of 40% ethanol). Of the four New York ap-
ple cultivars examined in the current study, only the methanol
content of apple eau-de-vie made from Crispin apples was signifi-
cantly higher (400 ± 54 mg/100 mL of 40% ethanol) than the United
States legal limit of 280 mg/100 mL of 40% ethanol. The apple eau-
de-vie made with Jonagold apples had the lowest concentration of
methanol content (174 ± 4 mg/100 mL of 40% ethanol). The con-
centrations of apple eau-de-vie made from Empire and Pacific Rose
apples were 281 ± 9 mg and 241 ± 23 mg/100 mL of 40% ethanol,
respectively.
Methanol is a product resulting from the hydrolysis of apple
pectin by pectic enzymes (Dixon and Webb, 1964). To minimize
the presence of methanol in hard cider and apple eau-de-vie, it is
important to inactivate the commercial pectic enzymes used in
the extraction of apple juice prior to cider fermentation. As shown
in Table 4, the methanol concentration of the eau-de-vie made
with unpasteurized Crispin apple juice, for example, was
400 ± 54 mg/100 mL of 40% ethanol (N = 3), but the methanol con-
Fund Project NE-1008.
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