Beruflich Dokumente
Kultur Dokumente
WALETZKO
Dept.
ACCELERATED
SHELF-LIFE
IN AIR AND
INTRODUCTION
IN THE PRODUCTION
of any new food, one important aspect is the knowledge of the shelf life. This life must at least
exceed the minimum distribution time required from processor to the consumer. The shelf life is controlled by:
1. The interaction of components of the system.
2. The process used.
3. The package permeability to light, moisture and gases.
4. The time-temperature-relative
humidity distribution
during
transportation and storage.
The processor must have a knowledge of all these factors as
well as a knowledge of the critical modes of failure of the
food. With this information, the processor can then choose the
best systems to maximize shelf life, put an open date on the
product indicating the maximum high quality life of the product, or insure the reliability of the nutrition label.
Unfortunately,
little or no information
is available for the
processor since most product development work does not consider the physcial-chemical
laws which could be used to predict the modes of deterioration and even the shelf life. Oswin
(1945) was the first to publish methodology which could be
used to predict the shelf life of a product. He developed an
equation to predict the rate of loss of moisture from cigarettes
in various packaging films. Charie et al. (1963) extended some
of this work to food products. In a major effort, Mizrahi et al.
(1970a) utilized these schemes to develop a simple mathematical model to predict the change in moisture of a dehydrated
food during storage as well as the extent of a chemical reaction, namely nonenzymatic
browning. Their equations could
be used to determine what packaging film should be used for a
given desired shelf life. The required factors were: the rate of
chemical deterioration of the product as a function of environmental conditions; the maximum extent of reaction that could
be tolerated; and the external conditions. This work was further extended to other food systems (Labuza et al., 1972;
Karel et al., 1971). Aguilera et al. (1975) and Davis (1970)
have also done similar work for dried potatoes and Harrington
(1973) extended it to storage of seed.
Simon et al. (1971) introduced the same concepts to the
prediction of the shelf life of a product which undergoes oxidation (freeze-dried, shrimp). Quast and Karel (1972a, b) extended this further to the study of potato chips which both
OF FOOD SCIENCE-Volume
Science
& Nutrition,
University
41 (1976)
and T. P. LABUZA
of Minnesota,
TESTING
OF AN INTERMEDIATE
MOISTURE
IN AN OXYGEN-FREE
ATMOSPHERE
ABSTRACT
An intermediate moisture food at water activity 0.85 was stored in air
and an oxygen-free atmosphere at 25, 35 and 45C. Various modes of
deterioration were studied including rancidity, nonenzymatic browning,
vitamin C loss, and organoleptic panel evaluation. It was found that all
modes of deterioration deviated from an Arrhenius relationship of log
(rate) vs OK when higher temperature data were projected to lower
temperature. These projections underestimate the true shelf life which
is of benefit to the processor. This deviation may be due to mechanism
changes, but most likely is a result of the heterogeneity of the system.
The major mode of organoleptic deterioration was related to browning.
Lysine and vitamin C losses were also very rapid. A special low oxygen
scavengerweb film increased shelf life significantly.
133%JOURNAL
of Food
FOOD
absorb water leading to sogginess and oxidize leading to rancidity. These latter studies showed the complexity of the problem but indicated short cuts for the solution.
Salwin and Salwson (1959), Hokoji et al. (1969) and Charie
et al. (1963) showed how to calculate moisture transfer between ingredients in a dehydrated food mix and use it to
predict stability. The major problem was that the ingredients
must all be kept at or near the monolayer to prevent deterioration. Labuza (1968, 1971) has reviewed the area of the
amount of moisture in a food in terms of stability.
Much work has been done in predicting the shelf life of
frozen foods during distribution
(Gaudagni, 1968). Olley and
Ratkowsky (1973) have studied the time-temperature distribution during transport using special indicators similar to defrost
indicators (Schoen and Byrne, 1972). In order to predict shelf
life, however, knowledge of the mode of deterioration
as a
function of temperature is needed. Some data have been collected by Dyer (1968) for fish, Jul (1968) for meat and
Kramer (1974) and Olson (1968) for various frozen foods.
Gutschmidt (1974) reviewed the application of this to predicting shelf life. Rutgers (1970) in addition, published a major
survey of the shelf life of various foods including refrigerated,
frozen and dried, which also gives an idea of the modes of
deterioration.
Even if deterioration mode data can be collected, it would
be useful for the shelf life to be verified before the product
goes to market. This imposes a burden if the product has a
long shelf life so that some form of acceleration of deterioration would be desirable. With dehydrated foods, as was shown
by Mizrahi et al. (1970b), the water content can be used to
increase the reaction rate, since most reactions increase rapidly
above the monolayer moisture value.
Many researchers have used the oxygen bomb technique
which uses high oxygen pressure to accelerate rancidity (Pohle
et al., 1962, 1963, 1964). However, as shown by Labuza
(197 l), the oxidation rate does not change significantly
for
most foods other than oils at any level above about 5% oxygen. The major factor that accelerates the reaction is the high
temperature
used during the experiment.
Mizrahi et al.
(1970b) used high temperature in conjunction with high moisture to accelerate browning of cabbage. Different reactions are
affected to different extents by an increase in temperature.
This is usually measured by the Qr c of a reaction (the increase
in rate for a 10C increase), or the activation energy E, which
is the true function since Qr o is related to E, by:
log Qlo =
2.2 E,
(0 U+ 10)
SHELF-LIFE
Table
life study
l-Composition
of
intermediate
moisture
food
Table
for shelf-
Z-Peroxide
TESTING
%
15.44
15.44
30.87
4.08
1.67
11.24
21.26
0.85
Peanuts
Freeze-dried
chicken
Raisins
Skippy peanut butter
Honey
Nonfat dry milk
H,O
a,
Dav
Air
N, I-,
0
2
3
5
8
9
11
13
15
16
18
21
23
24
25
27
28
29
32
33
37
38
39
44
45
47
51
58
59
64
66
72
73
81
87
88
94
105
111
118
125
131
a -Indicates
0.39
(meq/kg
lipid)
45C
35 c
25 C
Component
OF AN IMF-1339
Air
I-,
Air
4.30
N, 1%
-
3.12
2.08
5.11
0.88
4.06
3.56
3.72
2.43
3.80
2.27
0.94
-
2.48
2.62
5.05
4.34
4.52
4.38
2.93
3.54
3.41
3.09
2.40
3.00
3.24
3.28
-
4.03
4.03
3.59
4.25
-
4.09
4.24
5.50
1.67
3.03
3.79
3.31
3.93
3.23
3.61
2.39
2.39
-
3.32
3.18
2.93
no
4.05
2.76
3.44
detectable
peroxides
when
measured.
& DISCUSSION
THE RESULTS of each individual test will be discussed separately. Moisture content checks of the samples at 25 and 35C
showed the packages to be adequate. Thus, no interference
with a change in moisture occurred during storage.
Rancidity
As seen in Table 2, the peroxide data illustrate that the
pouches with the oxygen-free environment have maintained a
protective action against lipid oxidation. This protection was
1340-JOURNAL
OF FOOD SCIENCE-Volume
41 (1976)
maintained even after 3 months storage at 35OC. Lipid oxidation is occurring in the systems stored in air (cans) but as
indicated by the low peroxide values, the rate is very slow.
There is no apparent difference in peroxide values among the
samples stored in air at the three different temperatures, implying that the antioxidants added are effective in this study.
Previous data (Labuza, 1973) for peroxide values in this same
IMF stored in vacuum sealed foil pouches at 35C without
antioxidants,
showed a rapid increase in PV and an onset of
rancidity at about 50 days. Thus, in this study, rancidity was
not the mode of deterioration
since the antioxidant
system
was effective for up to 4 months at 45OC. Based on a normal
activation energy of 26 kcal/mole or a Qre = 3, this would
mean about a 3 X 3 X 4 or 36 months shelf life at 25C with
respect to rancidity, compared to 45OC.
Ascorbic acid
As illustrated in Figure 1, ascorbic acid degraded rapidly
during storage of the IMF by a first order reaction mechanism.
It can also be seen that ascorbic acid is less stable in air than in
the N2/H2 pouch system and the rate of destruction of ascorbic acid in both systems was accelerated by an increase in
temperature. The calculated rate constants (0.693 f half-life)
were plotted on an Arrhenius type plot (Fig. 2) vs 1 /T. As seen
the data do not fit exactly on a straight line although one can
be drawn with a regression coefficient of 0.96. This deviation
is most likely due to error in sample heterogeneity, error in
sample preparation, and error in analysis. The data of Lee and
Labuza (1975) show similar deviation even for a pure system.
Based on this the mechanism of deterioration
presumably has
not changed with temperature. It is interesting to note that
projections from the high temperatures to 25OC give a shorter
k,
ASCORBIC
Table 3-Ascorbic
Temp
lC)
System
25
35
45
Air
25
35
45
acid results
Half-lifea
I Days)
IMF shelf-life
study
Half-lifeb
I Days)
(from
cl
k,Oplot)c
Air
10
5
2
12
5
2
1.70
1.67
N, 1%
N, h-4
N, 1%
69
21
6
52
18
6
3.74
3.44
Air
a Based
on best stright
line through
three
b Based on straighi.
line thru
45 and 35OC
c E, = 9.93
kcal/mole
in air; E, = 24.04
lo-20
kcal/mole
(literature)
points
kcal/mole
in
N,/H,
; E,
ACID
0.:
i-
45 C
35 C
25 C
>\
0.
I-
03
%
O
O.Oi
r-
0.05
i-
T-
0
A
I
15
0
24
TIME
48
25c
35c
45c
,-
AIR
---
N2/H2(0PEN
I
72
(CLOSED
I96
(days)
Fig. I-Loss
of ascorbic
acid in the intermediate
moisture
food at
three temperatures
stored either in air or in a scavenger web pouch
with an N, /H, atmosphere.
3.1
OK- x IO3
Fig. 2-Arrhenius
relationship
for ascorbic acid destruction
rate constant K for samples stored in air and in a scavenger
web with an
N, /H, atmosphere.
SHELF-LIFE
Table 4-Accelerated
Temp
PC)
System
Visual
shelf life
(Days)
Days to reach
6 = 0.35
25
35
Air
Air
85
140
30
30
45
Air
10
11
25
N, Hz
N, H,
N, H,
215
217
JO
45
15
35
45
a Based
on
b Browning:
E, = 17.0
actual
data
E, = 23.2
kcallmole-air
19
kc&mole
panel;
E,
in air;
= 20.9
E, = 24.8
kcal/mole-N,
kcal/mole
in
H, panel.
shelf-life
textural
Q 10 a
protective against ascorbic acid degradation than the air system, its effectiveness is reduced with this food at the higher
temperatures. As seen, the activation energies are not the same
for both conditions, indicating that a different mechanism for
ascorbate destruction is occurring in the N2/H2 system. This
should be expected based on the many different pathways for
ascorbate destruction. Thus, one cannot extrapolate from one
system to another. The Qr es indicate an overall accelerating
factor of 2.84 (air) and 12.9 (Nz/H2) for studies at 4S compared to 25%. Since ascorbic acid is usually the most reactive
of the vitamins, it would be the limiting one in terms of nutritional labeling and could be considered as one major mode of
deterioration. Lee and Labuza (1975) also found a rapid degradation rate for ascorbate at high a,. Table 3 also indicates the
half-life at 25OC based on drawing a Line through the 35 and
4SC data. As seen, the error compared to the actual results is
20-25s
which is probably within the experimental limits that
can be done in these types of studies.
Nonenzymatic browning
Figure 3 shows the degree of nonenzymatic
browning as
detected by pigment formation. The browning rate increases
with temperature and occurs by a zero order reaction since the
lines are linear with time. The increased rate and the greater
amount of pigment formed in the air system as compared to
the Nz /Hz system may be due to the increased rate of ascorbic
acid degradation in the air system which can eventually lead to
the formation of furfurals which react with amino compounds
to produce brown pigments.
= 20-25
Days to reach
unacceptabilityb
date
Panel
kcal/mole
110
105
45
45
2.3
11
15
3.0
(literature).
105
45
Texture:
E,
.
.
o6o.
= 17.0
kcal/mole-instron;
0.
om-
2.3
3.0
15
d
2 IOIONON-ENZYMATIC
Q 10
lnstron
215
60
19
4.8
3.0
E,
OF AN IMF-1341
results
4.6
2.7
N,H,;
TESTING
9B-
BROWNING
APPEARANCE
OVERALL
TEXTURE
25c
35c
AIR
*
20
TIME
Fig. 3-Extent
samples stored
phere.
40
IdeYs)
60
80
100
120
140
of nonenzymatic
browning
at three temperatures
for
in air and in a scavenger web with an N, /Hz atmos-
20
80
40
100
,
120
DnvS
Fig. I-Average
panel scores for appearance,
texture
and overall
acceptability
for samples held at 35C in air and in an N, /H, atmosphere.
1342-JOURNAL
Of FOOD SCIENCE-Volume
47 (79761
TOUGHNESS
/
12r
AIR Nz/Hz
0
20
40
TIME
60
Closed Symbol
- Open Symbol
60
loo
(days)
Fig. 6-increase
in toughening
(hardness)
for samples held at three
temperatures
and in air and a scavenger web with an N, /H, atmosphere.
BROWNING
.-AIR
3.10
315
320
325
3.30
335
340
IO
3.1
OK-X IO
Fig. 5-Arrhenius
relationship
for browning
stored in air and in a scavenger web with
(solid line). Dashed line represents projection
atures (45 C, 35 Cl to 25 C.
endpoint
for samples
an N,/H,
atmosphere
of two higher temper-
Fig. 7-Arrhenius
and for lnstron
3.2
OK-
relationship
data. Samples
3.3
X
34
IO*
of texture endpoint
from panel
held in air and N, /H, atmosphere.
data
SHELF-LIFE
textural basis. It should be noted that initially the product has
a soft, moist texture and becomes harder with age without any
moisture loss.
The end-point values from the Instron for toughness are
plotted in Figure 7 and fit a straight line fairly well. The
straight lines in Figure 6 fit a zero order reaction as with the
browning results. Thus the end-point analysis can be used for
Figure 7. The Q I 0 s and activation energies are listed in Table
4. The values are somewhat less than that for browning, but
can be considered to be within experimental error and thus the
two reactions are definitely related. As with the visual data
previously, the panel textural data for the N2/H2 system do
not correlate with the mechanical measurements made. The
reasons for this are not clear, but must be based on a different
set of reactions leading to the same end-point.
Overall, it can be seen that browning development with
Table
lysine/l6
G-Available
mg protein
lysine
nitrogen)
content
26C
Day
0
4
6
N, 2
Air
4.88
t3.75
4.88
4.88
3.00
3.91
13
3.50
27
(mg
45 c
N, Hz
Air
N,H,
0.35
0.98
0.75
0.75
1.05
0.70
0.3
1.05
SUMMARY
3.25
2.25
2.63
2.50
2.25
2.00
2.38
2.00
1 .a8
3.63
4.00
3.38
3.50
32
34
36
3.22
2.88
39
2.63
1.25
2.13
1.72
2.13
1.58
1 .J5
3.25
2.50
3.38
58
60
3.06
a E, = 24.04
kcal/mole;
Q, ,, = 3.8 25-35C;
Table 6-Overall
Q, o = 3.5 35-45C
evaluation:
Subjective
Temp
PC)
25
Visual
browning
System
45
Air
Air
Air
25
35
45
"'2 I'-',
N, 1%
f", 4
35
Hennican
shelf-life
tests
Thoughening
& CONCLUSION
4.50
2.25
OF AN IMF-1343
4.88
3.25
29
43
44
52
55
in storagea
35C
Air
7
10
15
17
18
20
21
24
of Hennican
TESTING
study.
Overall
tests
Nonenzymatic
browning
B = 0.35
lnstron
6.5 kg
Vitamin C
half-life
Lysine
half-life
(Days)
(Days)
76
85
30
IO
110
45
11
85
30
10
140
30
11
105
45
15
IO
5
2
24
5
215
JO
19
215
60
19
215
60
19
217
105
45
15
JO
18
6
76
24
5
45
15
1344-JOURNAL
OF FOOD SCIENCE-Volume
41 (19761
REFERENCES
Acott, K. and Labuza, T.P. 1975, Inhibition
of A. niger in an intermediate moisture
food svstem. J. Food Sci. 40: 137.
Aguilera,
J.M.. Chlrife,
J.. Fllnk,
J. and Karel, M. 1975. Computer
simulation
of nonenzymatic
browning
during potato dehydration.
Lebensm. Wiss. U-Tecbnol.
8: 128.
Booth,
V.H. 1971. Problems in the determination
of FDNB available
lysine. J. Sci. Food Agr. 22: 658.
Charie, H.J., East, E. and Van der Veen, W. 1963. Effect of moisture
on
storage properties
of dehydrated
food products.
Proc. 1st Intl Congress on Food Science & Technol.
1: 45.
Choi, R.P.. Koncus. A.F.. OMalley,
C.M. and Fairbanks,
B.W. 1949. A
proposed
method for the determination
of color of dry products
of
milk J. Dairy Sci. 32: 580.
Davis, E. 1970. Evaluation
and selection
of flexible
films for food
packaging
Food Technol. in Australia.
22: 62.
Dyer, W.J. 1968. Deterioration
and storage life of frozen fish. In Low
Temperature
Biology of Foodstuffs.
Pergamon Press, New York.
Guadagni.
D.G. 1968. Cold storage life of frozen fruits and vegetables
as a function
of time and temperature.
In Low
Temperature
Biology of Foodstuffs.
Pergamon Press, New York.
Gutschmidt.
J. 1974. The storage life of frozen chicken with regard to
the temperature
in the cold chain. Lebensm.
Wiss. PTechnol.
1:
137.
Harrington.
J.F. 1973. Packaging seed for storage and shipment.
Seed
Sci. & Technol.
1973: 701.Hokoii.
H.. Kaaa. S. and Takeva.
Y. 1969. Water vanor transfer
between caps&es and powders.~Ckem
Pharm. Bull. (Japan) 17: 1134.
Jul. M. 1968. Frozen meat. In Low
Temperature
Biology
of Foodstuffs. Pergamon Press, New York.
Karel, M. 1972. Calculation
of storage stability
of foods on the basis of
analysis of kinetics
of deteriorative
reactions
of foods and of mass
transfer rates throwb - uackaaing
materials.
Int
l Svmuosium
on Heat
_
and Mass Transfer Problems &I Food Engineering.Karel, M., Mizrahi.
S. and Labuza, T.P. 1971. Computer
prediction
of
food storage. Mod. Packag Aug.
Kram.er, A. 1974. Storage retention
of nutrients.
Food Technol. 28: 50.
Labuza,
T.P. 1968. Sorption
phenomena
ln foods. Food Technol.
22:
263.
Labuza, T.P. 1971. Kinetics
of lipid oxidation
in foods. CRC Crit. Rev.
Food Technol.
2: 355.
Labuza, T.P. 1972. Nutrient
losses during drying and storage of dehydrated foods. CRC Crit. Rev. Food Technol.
3: 217.
Labuza, T.P. 1973. Storage stability
and improvement
of intermediate
moisture
foods. Contract
NAS #9-12560.
NASA. Lyndon
Johnson
.
Space Center, Houston,
Texas.
Labuxa. T.P., Mizrahi,
S. and Karel, M. 1972. Mathematical
models of
optimization
of flexible
film packaging
of foods for storage. Trans.
ASAE 15: 50,
Labuza.
T.P.. Tannenbaum.
S.R. and Karel. M. 1970. Water content
and. stability
of low-mdisture
and inter&diate-moisture
foods. J.
Food Sci. 36: 850.
Supported
in part by the University
of Minnesota
Agricultural
Experiment
Station,
Project
18-72HM
and NAS Contract
#B-12560,
Lyndon
Johnson Space Center. Houston,
Texas. Scientific
paper series
#B476 from the University
of Minnesota
Agricultural
Experiment
Station.