You are on page 1of 16

2646_ch16_Frame Page 39 Wednesday, October 23, 2002 5:29 PM

chapter sixteen

Technologies to extend
the refrigerated shelf life
of fresh fruits
Adel A. Kader, R. Paul Singh, and Jatal D. Mannapperuma

Contents
Controlled atmosphere storage
Effects of controlled atmospheres
Potential beneficial effects
Potential harmful effects
Requirements and recommendations
Modified atmosphere packaging
Design of modified atmosphere packages
Development of a mathematical model
Influence of permeability ratio
Influence of respiratory quotient
Influence of package design parameters
Influence of temperature
Influence of holes, micropores, and water layers in a package
Dynamic behavior of gas concentrations inside a package
Observations on designing modified atmosphere packages
Bibliography

Controlled atmosphere storage


Modified atmospheres (MA) or controlled atmospheres (CA) mean removal or addition
of gases resulting in an atmospheric composition around the commodity that is different
from that of air (78.08% N2, 20.95% O2, 0.03% CO2). Usually this involves reduction of
oxygen (O2) and/or elevation of carbon dioxide (CO2) concentrations. MA and CA differ
only in the degree of control; CA is more exact. The use of MA or CA should be considered
as a supplement to proper temperature and relative humidity management.

©1998 CRC Press LLC


2646_ch16_Frame Page 40 Wednesday, October 23, 2002 5:29 PM

Effects of controlled atmospheres


The potential for benefit or hazard from atmospheric modification depends upon the
commodity, variety, physiological age, atmospheric composition, and temperature and
duration of storage. This helps explain the wide variability in results among published
reports for a given commodity.

Potential beneficial effects


Used properly, MA or CA can supplement proper temperature management and can
result in one or more of the following benefits, which translate into reduced quantitative
and qualitative losses during postharvest handling and storage of some horticultural
commodities:

1. Retardation of senescence (ripening) and associated biochemical and physiological


changes, i.e., slowing down respiration and ethylene production rates, softening,
and compositional changes.
2. Reduction of fruit sensitivity to ethylene action at O2 levels below about 8% and/or
CO2 levels above 1%.
3. Alleviation of certain physiological disorders such as chilling injury of various
commodities, russet spotting in lettuce, and some storage disorders of apples.
4. MA/CA can have a direct or indirect effect on postharvest pathogens and conse-
quently decay incidence and severity. For example, elevated CO2 levels (10% to
15%) significantly inhibit development of botrytis rot on strawberries, cherries, and
other fruits.
5. Low O2 (0–5% or lower) can be a useful tool for insect control in some commodities.

Potential harmful effects


In most cases, the difference between beneficial and harmful MA combinations is relatively
small. Also, MA combinations that are necessary to control decay or insects, for example,
cannot always be tolerated by the commodity and may result in faster deterioration.
Potential hazards of MA to the commodity include the following:

1. Initiation and/or aggravation of certain physiological disorders such as blackheart


in potatoes, brown stain on lettuce, and brown heart in apples and pears.
2. Irregular ripening of fruits such as banana, pear, and tomato can result from O2
levels below 2% or CO2 levels above 5%.
3. Development of off-flavors and off-odors at very low O2 concentrations as a result
of anaerobic respiration.
4. Increased susceptibility to decay when the commodity is physiologically injured
by too-low O2 or too-high CO2 concentrations.
5. Stimulation of sprouting and retardation of periderm development in some root
and tuber vegetables such as potatoes.

Requirements and recommendations


During the past 50 years, uses of CA and MA has increased steadily and has contributed
significantly to extending the postharvest life and maintaining the quality of several fruits
and vegetables. This trend is expected to continue as technological advances are made in
attaining and maintaining CA and MA during transport, storage, and marketing of fresh
produce. Several refinements in CA storage include low O2 (1.0–1.5%) storage, low ethyl-
ene CA storage, rapid CA (rapid establishment of the optimum levels of O2 and CO2),

©1998 CRC Press LLC


2646_ch16_Frame Page 41 Wednesday, October 23, 2002 5:29 PM

Table 1 Classification of Fruits and Vegetables According to Their Tolerance of


Low O2 Concentrations
Minimum O2
Concentration
Tolerated (%) Commodities
0.5 Tree nuts, dried fruits, and vegetables.
1.0 Some cultivars of apples and pears, broccoli, mushroom, garlic, onion, most cut or
sliced (minimally processed) fruits and vegetables.
2.0 Most cultivars of apples and pears, kiwifruit, apricot, cherry, nectarine, peach,
plum, strawberry, papaya, pineapple, olive, cantaloupe, sweet corn, green bean,
celery, lettuce, cabbage, cauliflower, brussels sprouts
3.0 Avocado, persimmon, tomato, pepper, cucumber, artichoke
5.0 Citrus fruits, green pea, asparagus, potato, sweet potato

Table 2 Classification of Fruits and Vegetables According to Their Tolerance of


Elevated CO2 Concentrations
Minimum CO2
Concentration
Tolerated (%) Commodities
2 Apple (Golden Delicious), Asian pear, European pear, apricot, grape, olive,
tomato, pepper (sweet), lettuce, endive, Chinese cabbage, celery, artichoke, sweet
potato.
5 Apple (most cultivars), peach, nectarine, plum, orange, avocado, banana, mango,
papaya, kiwifruit, cranberry, pea, pepper (chili), eggplant, cauliflower, cabbage,
brussels sprouts, radish, carrot.
10 Grapefruit, lemon, lime, persimmon, pineapple, cucumber, summer squash, snap
bean, okra, asparagus, broccoli, parsley, leek, green onion, dry onion, garlic,
potato.
15 Strawberry, raspberry, blackberry, blueberry, cherry, fig, cantaloupe, sweet corn,
mushroom, spinach, kale, Swiss chard.

and programmed or sequential CA storage (e.g., storage in 1% O2 for 2 to 6 weeks followed


by storage in 2–3% O2 for the remainder of the storage period). Other developments that
may expand use of MA during transport and distribution include using edible coatings
or polymeric films to create a desired MA within the commodity.
Fresh fruits and vegetables vary greatly in their relative tolerance to low O2 concen-
tration (Table 1) and elevated CO2 concentrations (Table 2). These are the levels beyond
which physiological damage would be expected. These limits of tolerance can be different
at temperatures above or below recommended temperatures for each commodity. Also, a
given commodity may tolerate brief exposures to higher levels of CO2 or lower levels of
O2 than those indicated. The limit of tolerance to low O2 would be higher as storage
temperature or duration increases, because O2 requirements for aerobic respiration of the
tissue increases with higher temperatures. Depending on the commodity, damage associ-
ated with CO2 may either increase or decrease with an increase in temperature. CO2
production increases with temperature, but its solubility decreases; thus, CO2 in the tissue
can be increased or decreased by an increase in temperature. Further, the physiological
effect of CO2 could be temperature dependent. Tolerance limits to elevated CO2 decrease
with a reduction in O2 level, and similarly the tolerance limits to reduced O2 increase with
the increase in CO2 level.
Current MA/CA recommendations are summarized in Table 3 (fruits) and Table 4
(vegetables). Also included is an estimate of potential benefits and extent of current

©1998 CRC Press LLC


2646_ch16_Frame Page 42 Wednesday, October 23, 2002 5:29 PM

Table 3 Summary of recommended CA or MA conditions


during transport and/or storage of selected fruits
Temp.
range CAb Potential
Commodity (°C)a %O2 %CO2 for benefitc Remarksd
Deciduous Tree Fruits
Apple 0–5 1–3 1–5 A About 50% of production is
stored under CA
Apricot 0–5 2–3 2–3 C No commercial use
Cherry, sweet 0–5 3–10 10–15 B Some commercial use
Fig 0–5 5–10 15–20 B Limited commercial use
Grape 0–5 2–5 1–3 C Incompatible with SO2
fumigation
Kiwifruit 0–5 1–2 3–5 A Some commercial use; C2H4 must
be maintained below 20 ppb
Nectarine 0–5 1–2 3–5 B Limited commercial use
Peach 0–5 1–2 3–5 B Limited commercial use
Pear, Asian 0–5 2–4 0–1 B Limited commercial use
Pear, European 0–5 1–3 0–3 A Some commercial use
Persimmon 0–5 3–5 5–8 B Limited commercial use
Plum and prune 0–5 1–2 0–5 B Limited commercial use
Raspberry and other 0–5 5–10 15–20 A Increasing use during transport
cane berries
Strawberry 0–5 5–10 15–20 A Increasing use during transport
Nuts and dried fruits 0–25 0–1 0–100 A Effective insect control method

Subtropical and tropical fruits


Avocado 5–13 2–5 3–10 B Limited commercial use
Banana 12–15 2–5 2–5 A Some commercial use during
transport
Grapefruit 10–15 3–10 5–10 C No commercial use
Lemon 10–15 5–10 0–10 B No commercial use
Lime 10–15 5–10 0–10 B No commercial use
Olive 5–10 2–3 0–1 C No commercial use
Orange 5–10 5–10 0–5 C No commercial use
Mango 10–15 3–5 5–10 C Limited commercial use
Papaya 10–15 3–5 5–10 C No commercial use
Pineapple 8–13 2–5 5–10 C No commercial use
a Usual and/or recommended range. A relative humidity of 90% to 95% is recommended.
b Best CA combination may vary among cultivars and according to storage temperature and duration.
c A = excellent, B = good, C = fair.
d Comments about use refer to domestic marketing only; many of these commodities are shipped under MA
for export marketing.

commercial use. There is no doubt that some of these MA combinations will change as
more research is completed. The possibility of adding carbon monoxide to MA/CA for
some commodities may change its potential for benefit.
Current CA use for long-term storage of fresh fruits and vegetables is summarized in
Table 5. Its use on nuts and dried commodities (for insect control and quality maintenance,
including prevention of rancidity) is increasing as it provides an excellent substitute for
chemical fumigants, (such as methyl bromide) used for insect control. Also the use of CA
on commodities listed in Table 5 other than apples and pears is expected to increase as
international market demands for year-round availability of various commodities expand.

©1998 CRC Press LLC


2646_ch16_Frame Page 43 Wednesday, October 23, 2002 5:29 PM

Table 4 Summary of Recommended CA or MA Conditions during Transport and/or Storage


of Selected Vegetables
Temp. Potential
range CAb for
Commodity (°C)a %O2 %CO2 benefitc Remarksd
Artichokes 0–5 2–3 2–3 B No commercial use
Asparagus 0–5 air 5–10 A Limited commercial use
Beans, snap 5–10 2–3 4–7 C Potential for use by processors
Beets 0–5 None D 98–100% rh is best
Broccoli 0–5 1–2 5–10 A Limited commercial use
Brussels sprouts 0–5 1–2 5–7 B No commercial use
Cabbage 0–5 2–3 3–6 A Some commercial use for long-term
storage of certain cultivars
Cantaloupes 3–7 3–5 10–15 B Limited commercial use
Carrots 0–5 None D 98–100% rh is best
Cauliflower 0–5 2–3 2–5 C No commercial use
Celery 0–5 1–4 0–5 B Limited commercial use in mixed loads
with lettuce
Corn, sweet 0–5 2–4 5–10 B Limited commercial use
Cucumbers 8–12 3–5 0 C No commercial use
Honeydews 10–12 3–5 0 C No commercial use
Leeks 0–5 1–2 3–5 B No commercial use
Lettuce 0–5 1–3 0 B Some commercial use with 2–3% CO
added
Mushrooms 0–5 air 10–15 C Limited commercial use
Okra 8–12 3–5 0 C No commercial use; 5–10% CO2 is
beneficial at 5–8°C
Onions, dry 0–5 1–2 0–5 B No commercial use; 7% rh
Onions, green 0–5 1–2 10–20 C Limited commercial use
Peppers, bell 8–12 3–5 0 C Limited commercial use
Peppers, chili 8–12 3–5 0 C No commercial use; 10–15% CO2 is
beneficial at 5–8°C
Potatoes 4–12 None D No commercial use
Radish 0–5 None D 98–100% rh
Spinach 0–5 air 0–20 B No commercial use
Tomatoes, mature 12–20 3–5 0–3 B Limited commercial use
Tomatoes, green- 8–12 3–5 0–5 B Limited commercial use
partially ripe
a Usual and/or recommended range. A relative humidity of 90% to 98% is recommended unless otherwise
indicated under “Remarks.”
b Best CA combination may vary among cultivars and according to storage temperature and duration.
c A = excellent, B = good, C = fair, D = slight or none.
d Comments about use refer to domestic marketing only; many of these commodities are shipped under MA for
export marketing.

CA/MA use for short-term storage and transport of fresh horticultural crops (Table 6)
will continue to increase supported by technological developments in transport containers,
MA packaging, and edible coatings. Carbon monoxide at 5–10%, when added to O2 levels
below 5%, is an effective fungistat that can be used for decay control on commodities that
do not tolerate 15% to 20% CO2. However, CO is very toxic to humans, and special
precautions must be taken.
CA/MA conditions, including MA packaging (MAP), can replace certain postharvest
chemicals used for control of some physiological disorders, such as scald on apples. Proper

©1998 CRC Press LLC


2646_ch16_Frame Page 44 Wednesday, October 23, 2002 5:29 PM

Table 5 Summary of CA Use for Long-Term Storage of Fresh Fruits and Vegetables
Storage Duration
(months) Commodities
More than 12 Almond, filbert, macadamia, pecan, pistachio, walnut, dried fruits and
vegetables
6–12 Some cultivars of apples and European pears
3–6 Cabbage, Chinese cabbage, kiwifruit, some cultivars of Asian pears
1–3 Avocado; olive; some peach, nectarine, and plum cultivars; persimmon;
pomegranate

Table 6 Summary of CA/MA Use for Short-Term Storage and/or Transport of


Fresh Horticultural Crops
Primary benefit of CA/MA Commodities
Delay ripening and avoid chilling temperatures Avocado, banana, mango, melons, nectarine,
papaya, peach, plum, tomato (picked mature-
green or partially ripe)
Control decay Blackberry, blueberry, cherry, fig, grape,
raspberry, strawberry
Delay senescence and undesirable compositional Asparagus, broccoli, lettuce, sweet corn, fresh
changes (including tissue brown discoloration) herbs, minimally processed fruits and
vegetables

use of CA can also eliminate the need for using daminozide on apples. Furthermore, some
postharvest fungicides and insecticides can be reduced or eliminated where CA/MA
provides adequate control of postharvest pathogens or insects.
CA/MA may facilitate picking and marketing more mature (better flavor) fruits by
slowing their postharvest deterioration to permit transport and distribution. Another poten-
tial use for CA/MA is in maintaining quality and safety of lightly processed fruits and
vegetables, which are increasingly being marketed as value-added convenience products.
The residual effects of CA/MA on fresh commodities after transfer to air (during mar-
keting) may include reduction of respiration and ethylene production rates, maintenance of
color and firmness, and delayed decay. Generally, the lower the concentration of O2 and the
higher the concentration of CO2 (within the tolerance limits of the commodity), and the
longer the exposure to CA/MA conditions, the more prominent are the residual effects.

Modified atmosphere packaging


The positive effects of film packaging, other than creation of MA/CA conditions, can
include:

1. maintenance of high relative humidity and reduction of water loss;


2. improved sanitation by reducing contamination of the commodity during handling;
3. minimized surface abrasions by avoiding contact between the commodity and the
material of the shipping container;
4. reduced spread of decay from one unit to another;
5. possible exclusion of light, when needed, for commodities such as potato and
Belgian endive;
6. use of the film as carrier of fungicides, sprout inhibitors, scald inhibitors, or other
chemicals;
7. facilitation of brand identification.

©1998 CRC Press LLC


2646_ch16_Frame Page 45 Wednesday, October 23, 2002 5:29 PM

The negative effects include slowing down cooling of the packaged commodity and
increased potential for water condensation within the package, which may encourage
fungal growth.
Modified atmospheres can be created either passively by the commodity or intention-
ally. With commodity-generated or passive MA, if commodity and film permeability charac-
teristics are properly matched, an appropriate atmosphere can passively evolve within a
sealed package through consumption of O2 and production of CO2 by respiration. The gas
permeability of the selected film must allow O2 to enter the package at a rate offset by the
consumption of O2 by the commodity. Similarly, CO2 must be vented from the package to
offset the production of CO2 by the commodity. Furthermore, this atmosphere must be
established rapidly and without creating anoxic conditions or injuriously high levels of CO2.
Because of the limited ability to regulate a passively established atmosphere, it is likely
that atmospheres within MAP will be actively established and adjusted known as active
modified atmosphere. This can be done by pulling a slight vacuum and replacing the
package atmosphere with the desired gas mixture. This mixture can be further adjusted
through the use of absorbing or adsorbing substances in the package to scavenge O2, CO2,
or C2H4.
Although active modification implies some additional costs, its main advantage is
that it ensures the rapid establishment of the desired atmosphere. Ethylene absorbers can
help delay the climacteric rise in respiration for some fruits. Carbon dioxide absorbers
can prevent the buildup of CO2 to injurious levels, which can occur for some commodities
during passive modification of the package atmosphere.
Many plastic films are available for packaging, but relatively few have been used to
wrap fresh produce. Low-density polyethylene and polyvinyl chloride are the main films
used in packaging fruits and vegetables. Polystyrene has been used, but Saran™ and
polyester have such low gas permeabilities that they would be suitable only for commod-
ities with very low respiration rates.

Design of modified atmosphere packages


The design of modified atmosphere packages involves the use of mass transport properties
of packages and respiration rates of produce placed inside the package. In this section we
will examine how simple mathematical models may be developed for this purpose. The
design methodology presented in this chapter is based largely on a paper presented by
Mannapperuma and Singh (1994).
The basic principles involved in the design of modified atmospheric packages can be
illustrated by plotting the recommended modified atmospheric compositions, such as
those listed in Tables 3 and 4, on a two-dimensional chart with O2 concentration as the
x axis and CO2 concentration as the y axis. Figures 1 and 2 are such plots for some common
fruits and vegetables (Mannapperuma and Singh, 1994).
Most of the recommended modified atmospheres contain lower O2 concentrations and
higher CO2 concentrations compared to the ambient. In such cases, these concentration
gradients create a flux of O2 into the package and a flux of CO2 out of the package. Under
steady-state conditions these two fluxes should be equal to the O2 consumption and the
CO2 generation by the produce in the package. The design parameters of the package are
determined using these equalities.

Development of a mathematical model


Using the quantities shown in Figure 3, a mathematical model for the package may be
formulated. The gas flow rate through the package is expressed as the product of film

©1998 CRC Press LLC


2646_ch16_Frame Page 46 Wednesday, October 23, 2002 5:29 PM

Figure 1 Recommended modified atmospheres for storage of fruits (numbers within parenthesis
are oxygen and carbon dioxide ranges).

permeability, film area, and the concentration gradient. Multiplying the weight of the
produce by the specific respiration rate, we obtain the respiration rate of the produce.
Thus the mathematical model is expressed as follows:

{
WR1 = P1 A (c1 ± x1 ) b } (1)

{ }
WR2 = P2 A ( x 2 ± c2 ) b , (2)

where A = area of the film (m2), b = thickness of the film (m), c = gas concentrations in
ambient (mol/m3), P = permeability (m2/s), R = respiration rate (mol/kg⋅s), W = weight
of produce in the package (kg), and x = gas concentrations in package atmosphere
(mol/m3); suffixes 1 and 2 denote O2 and CO2 gases.
In Equations (1) and (2), there are 11 different variables. By rearranging these equations
and introducing relating terms, we can show the effect of these variables on the package
design.

©1998 CRC Press LLC


2646_ch16_Frame Page 47 Wednesday, October 23, 2002 5:29 PM

Figure 2 Recommended modified atmospheres for storage of vegetables (numbers within paren-
thesis are oxygen and carbon dioxide ranges).

Figure 3 Schematic of a modified atmosphere package.

Influence of permeability ratio


It is well known that the gas permeabilities of commercially available polymers vary over
a wide range. However, the ratio of the permeability of any two gases falls within a very
narrow range for all the polymers (Stannett, 1968). For most of the polymers used in
commercial practice, the ratio of permeability of CO2 to O2 (permeability ratio, β) falls
between 4 and 6. This narrow range in permeability ratio causes numerous limitations in

©1998 CRC Press LLC


2646_ch16_Frame Page 48 Wednesday, October 23, 2002 5:29 PM

the design of polymeric packages for fresh produce. We may combine Equations (1) and (2)
and the permeability ratio, β, to illustrate this limitation.

x 2 = c2 + β ±1 (c1 ± x1 ) R2 R1 . (3)

From Equation (3), when the permeability ratio is close to 5, as for low-density
polyethylene (LDPE), we obtain a straight line with a slope of 1/5 on the plot of
recommended modified atmospheres. In Figures 1 and 2, this line is shown as A-B. This
analysis indicates that in a package made of LDPE film, we can generate only those
modified atmospheres that are represented by points along the line A-B. For example,
we can obtain a modified atmosphere of 2% CO2 and 11% O2 or 1% CO2 and 16% O2,
and so on.
We can then relate the modified atmospheres generated by the LDFE film with prod-
ucts that have recommended requirements of specific modified atmospheres. For example,
from Figure 1, the recommended modified atmosphere conditions for cauliflower, celery,
and pepper, and those of kiwifruit, nectarine, peach, cranberry, plum, orange, banana, and
avocado from Figure 2 lie along the line A-B. Thus for the aforementioned commodities,
packages made of LDPE film are suitable, as they can create the recommended modified
atmospheres. Conversely, packages made of LDPE film are not appropriate for other
commodities that do not lie along the A-B line on Figures 1 and 2.

Influence of respiratory quotient


The slope of line A-B is influenced also by the ratio of carbon dioxide generation to oxygen
consumption. This ratio, known as respiratory quotient, α, is close to unity when substrate
used in the metabolic process is carbohydrate and sufficient amount of oxygen is available.
This ratio is <1 when the substrate is a lipid and >1 when the substrate is an organic acid.
When anaerobic conditions prevail, the respiratory quotient is >1 even when the substrate
is a carbohydrate.
The influence of respiratory quotient on the package atmosphere can be illustrated
by introducing the symbol in Equation (3), as follows:

x 2 = c2 + (α β)(c1 ± x1 ) . (4)

In Equation (4), it is obvious that the effect of the permeability ration, β, is opposed by
the respiratory quotient, α. Therefore, respiratory quotients greater than unity will result
in slopes greater than l/β and vice versa.

Influence of package design parameters


When designing packages for modified atmosphere, the values of R1, R2, and α are deter-
mined by the type of produce placed inside a package. Similarly, the produce also deter-
mines the recommended modified atmospheric composition x1 and x2, and therefore the
value of β. With the preceding quantities, a certain type of film is identified, therefore,
fixing the values of P1 and P2. As a result of this selection process, the package designer
is left with the choice of only three variables: thickness of the film, area of the package,
and weight of the produce in the package. The criterion for the selection of these three
variables can be illustrated by rewriting Equations (1) and (2), and by introducing a new
parameter, φ.

©1998 CRC Press LLC


2646_ch16_Frame Page 49 Wednesday, October 23, 2002 5:29 PM

x1 = c1 ± ( R1 P1 )φ (5)

x 2 = c2 + ( R2 P2 )φ, (6)

where

φ = Wb A . (7)

From Equations (6) and (7), we can examine the influence of increasing φ. As φ increases,
the package atmosphere moves toward point B along line A-B in Figures 1 and 2, and vice
versa. The quantity φ increases by decreasing the area, A, or by increasing the weight of
the produce, W, or thickness of the film, b.
The package atmosphere affects the respiration rates of fresh produce. In most cases,
the respiration rate increases with increasing oxygen content. And, the respiration rate
decreases with increasing carbon dioxide content or as a package atmosphere moves
toward B along the A-B line. This relationship between the package atmosphere and the
respiration rate tends to moderate the effect of φ. An increase in φ increases x2 and decreases
x1. This will decrease respiration rates R1 and R2. Therefore, the final value of x1 will be
higher and x2 will be lower than those predicted by Equations (5) and (6) where constant
values of R1 and R2 were used. These relationships are helpful to a package designer. Any
errors in values available for respiration rate and film permeability data will result in
smaller deviations of package atmospheres. In addition, the effect of temperature on the
respiration rate and film permeability will be moderated to a large extent.

Influence of temperature
The respiration rates of produce and the film permeability are influenced by the temper-
ature. Both these effects can be expressed as Arrhenius-type relations in the temperature
range encountered in modified atmosphere packages of fresh produce. These relationships
are shown as follows:

[
P = P0 exp ±Ep R′T ] (8)

R = R0 exp[ ±ER R′T ] , (9)

where R = universal gas constant (J/mole⋅K), T = temperature (K), and E = activation


energy (J/mol).
The effect of a change in temperature on package atmosphere can be illustrated by
combining Equations (8) and (9) and using two temperatures, Tref and T, as follows:

( ) 
( ) .
R1 P1 = R1,ref P1,ref exp  –  ( E R1 – E P1 ) R ′  (1 T) – (1 Tref )
  
(10)

The difference in activation energy of respiration and permeation governs the change
in package atmosphere due to change in temperature. The activation energy of perme-
ability of some films are listed in Table 7. When the activation energy of respiration of
some fresh produce in modified atmosphere conditions are within the same range, the

©1998 CRC Press LLC


2646_ch16_Frame Page 50 Wednesday, October 23, 2002 5:29 PM

Table 7 Permeability Data of Some Polymeric Films, Air, and Water


Permeability Activation Energy
(std ml⋅mil/m2⋅h⋅atm) (J/mol) Permeability
O2 CO2 O2 CO2 Ratio
Polyethylene (density 0.914) 310 1360 42,400 38,900 4.44
Polypropylene 180 780 47,700 38,100 4.33
Polyvinyl chloride 4.9 16.9 55,600 56,900 3.46
Polyvinylidene chloride (Saran) 0.57 3.23 66,500 51,400 5.66
Air 2.6 × 109 2.0 × 109 3,600 3,600 0.8
Water 9.3 × 103 2.2 × 105 15,800 15,800 23.3

Note: Data from Mannapperuma, J.D., et al. 1989. In: Proceedings of the Fifth International Controlled
Atmosphere Research Conference, vol. 2, Other Commodities and Storage Recommendations, ed.
J. K. Fellman, p. 225-233, June 14-16, 1989; Wenatchee, WA.

changes in temperature do not cause any large changes in the package atmosphere (Man-
napperuma et al., 1989).

Influence of holes, micropores, and water layers in a package


Packages made of polymeric films are susceptible to puncturing during handling. Some-
times, special microporus films and labels are used in modified atmosphere packaging.
The presence of holes in the film allows the flow of gases by diffusion as well as by
convection. The analysis of these phenomena is extremely complicated. However, the
relative effect of diffusive flow through holes on package atmosphere can be studied by
comparing the permeability of gases in air with permeability of the gases in polymers. As
seen in Table 7, the air is much more permeable than polymeric films. Therefore, even a
very small hole in a polymeric package can affect the package atmosphere very signifi-
cantly. However, this phenomenon can be used as an advantage by using carefully intro-
duced micropores in the package film.
The permeability ratio β for air may be calculated as 0.8. This represents line A-C in
Figures 1 and 2. This implies that an otherwise impermeable package, with a few small
holes, can be used to create atmospheres along this line, such as in the requirement for
berries and figs in Figure 2. The carbon-dioxide–oxyen atmospheres that lie between lines
A-B and A-C may be created by using packages that use LDPE film with pinholes or
microporus windows (Mannapperuma and Singh, 1994).
It is common to see an accumulation of water on the interior surface of the film as a
thin layer or as droplets due to condensation in fresh produce packages. The effect of such
water layers on the package atmosphere may be studied by converting the data on diffusion
of gases in water to the same basis as film permeability using the convention proposed by
Yasuda (1975). The converted values (Table 7) show that the permeability of gases in water
is much higher than in polymers. Therefore, thin layers and droplets of water forming
inside polymeric packages do not affect the package atmosphere significantly.

Dynamic behavior of gas concentrations inside a package


In this chapter, the method presented to design a modified atmosphere package described
earlier was based entirely on the steady-state or equilibrium behavior of the package and
its contents. Normally, when produce is packaged, the internal gas atmosphere may not
reach the design conditions for a certain period of time which may be a few hours or a
few days. The gas composition inside the package during this initial period may be studied

©1998 CRC Press LLC


2646_ch16_Frame Page 51 Wednesday, October 23, 2002 5:29 PM

using a dynamic model. Of course, if the gas atmosphere is flushed with the design
conditions at the time of packaging, then the following analysis is not necessary.
In order to study the dynamic behavior of the package, the free volume inside the
package must be known. The time required by the package to reach the equilibrium
conditions is closely related to the free volume inside the package, V. Three mathematical
equations of the dynamic model consist of three equations describing the rate of change
of the concentrations of the three gases, oxygen, carbon dioxide, and nitrogen. For oxygen,

V (dx1 dt) = ( P1 A b)(c1 ± x1 ) ± WR1 , (11)

for carbon dioxide,

V (dx 2 dt) = ( P2 A b)(c2 ± x 2 ) + WR2 , (12)

and for nitrogen,

V (dx 3 dt) = ( P3 A b)(c 3 ± x 3 ) . (13)

In addition to the above equations, the ideal gas equation relation has to be obeyed by
the gases inside the package. This provides a restriction on total pressure, p, of the package,
as follows:

p = ( x1 + x2 + x3 )R′T . (14)

The solution to this set of equations depends on the nature of the dependence of R1
and R2 on x1 and x2. When the relationship is simple, an analytical solution can be obtained.
A numerical technique such as Runge–Kutta or predictor–corrector method may be
employed when the relationship is complicated.
Analytical solutions of Equations (11) and (12) were obtained by Deily and Rizvi
(1981), assuming that R1 and R2 were constant in the case of peaches. Hayakawa et al.
(1975) assumed R1 and R2 to be piecewise multilinear functions of x1 and x2 and obtained
analytical solutions using the Laplace transformation method. However, both of these
studies do not include Equations (13) and (14). A number of models for packages with
constraints on volume and pressure were presented by Mannapperuma and Singh (1987).
In these models, the gas concentrations inside a product were considered as a separate
set of variables.
According to Equation (14), the sum of three gas concentrations remains invariant
in spite of unequal changes in x1 and x2. This equality will hold only by changing the
volume of the package. In fact, this phenomenon is often observed as a contraction of
polymeric packages when a modified atmosphere is established inside a package. Because
Equation (14) imposes a change in volume, the system of equations becomes nonlinear,
therefore requiring numerical methods to obtain solutions.
It is important to note that the solution of a dynamic model will always converge to
a steady-state solution. However, the behavior during the initial stages depends on free
volume in the package and the initial gas concentrations. Of course, the steady-state
conditions are obtained faster when free volume is smaller and when the initial gas
concentrations are closer to the steady state concentrations.

©1998 CRC Press LLC


2646_ch16_Frame Page 52 Wednesday, October 23, 2002 5:29 PM

Observations on designing modified atmosphere packages


The permeability ratio of films determines the range of modified atmospherses that may
be obtained in MAP applications. As noted in this chapter, this ratio is within a very
narrow range for all the polymers. By careful introduction of pinholes or microporous
windows, one can extend the range of attainable atmospheres considerably. The atmo-
spheres that lie outside this extended range cannot be attained by the equilibrium inter-
action of produce respiration and package permeability. Therefore, injecting the required
atmosphere into a relatively impermeable package can be expected to maintain a favorable
atmosphere for a considerable length of time. This particular concept is frequently used
in the air shipment of stawberries. This problem can be analyzed by using the dynamic
model as presented in this chapter.
The respiration rate and film permeability are influenced by temperature. However,
the change in respiration rate is usually much greater than the change in gas permeability.
This can result in anaerobic conditions inside optimally designed packages when subjected
to temperature abuse. To avoid such conditions, one may rely on suboptimal designs. It
may be noted that the respiration activity is only one of the factors that influences the
shelf life. There is a direct correlation between the cummulative respiration activity and
the shelf life during storage of some commodities.
Another important factor to consider in MAP applications is the water vapor transfer.
When the vapor pressure surrounding a product is too low it causes wilting of the produce.
This is often observed in packages where holes are made to allow for respiration. On the
other hand, when the vapor pressure is too high then condensation of water occurs.
Antifog films prevent accummulation of droplets on the film but not the spoilage effects
of free water. The water vapor transfer may be controlled by selective permeation or by
the use of absorbers.
In summary, the design of modified atmosphere packages requires the knowledge of
mass transport properties of polymeric films and the respiration rates of fresh produce
placed inside the packages. Mathematical models are useful in determining the changes
in gas concentrations in a package caused by the respiring fruits and vegetables inside
the package during storage.

Bibliography
1. Ben-Yehoshua, S. 1985. Individual seal-packaging of fruits and vegetables in plastic film.
A new postharvest technique. HortScience 20:32-37.
2. Ben-Yehoshua, S. and A. C. Cameron. 1989. Exchange determination of water vapor, carbon
dioxide, oxygen, ethylene, and other gases of fruits and vegetables. In: Modern Methods of
Plant Analysis, New Series, vol. 9, Gases in Plant and Microbial Cells, eds. H.F. Linskens
and J.F. Jackson, 177-193. Berlin: Springer-Verlag.
3. Blankenship, S. M., ed. 1985. Controlled atmospheres for storage and transport of perishable
agricultural commodities. Proc. Fourth Natl. Controlled Atmos. Res. Conf. July 23-26, 1985,
Dept. of Hortic., Univ. of North Carolina, Raleigh, NC.
4. Brecht, P. E. 1980. Use of controlled atmospheres to retard deterioration of produce. Food
Technol. 34(3):45-50.
5. Brody, A. L., ed. 1989. Controlled Modified Atmosphere Vacuum Packaging of Foods. Trum-
bull, CT: Food & Nutrition Press.
6. Calderon, M. and R. Barkai-Golan, eds. 1990. Food Preservation by Modified Atmospheres.
Boca Raton, FL: CRC Press.
7. Cameron, A. C., Boylan-Pett, W. E. and Lee, J. 1989. Design of modified atmosphere systems:
Modeling oxygen concentrations within sealed packages of tomato fruits. J. Food Sci.
54(6):1413

©1998 CRC Press LLC


2646_ch16_Frame Page 53 Wednesday, October 23, 2002 5:29 PM

8. Deily, K. H. and Rizvi, S. S. H. 1981. Optimization of parameters for packaging of fresh


peaches in polymeric films. J. Food Process Eng. 5:23.
9. Dewey, D. H., ed. 1977. Controlled atmospheres for the storage and transport of perishable
agricultural commodities (Proc. 2nd Natl. CA Res. Conf., April 1977). Mich. State Univ. Dept.
Hortic. Rept. 28.
10. Dewey, D. H., R. C. Herner, and D. R. Dilley, eds. 1969. Controlled atmospheres for the
storage and transport of horticultural crops (Proc. 2nd Natl. CA Res. Conf, January 1969).
Mich. State Univ. Dept. Hortic. Rept. 9.
11. El-Goorani, M. A. and N. F. Sommer. 1981. Effects of modified atmospheres on postharvest
pathogens of fruits and vegetables. Hortic. Rev. 3:412-61.
12. Fellman, J.K., ed. 1989. Proceedings of the ffth international controlled atrnosphere research
conference. June 14-16, 1989, Washington State Univ. Research and Extension Center,
Wenatchee, WA). Vol. 1, 515 pp.; vol. 2, 374 pp.
13. Hardenburg, R.E., A.E. Watada, and C-Y. Wang. 1986. The commercial storage of fruits,
vegetables, and florist and nursery stocks. USDA, Agric. Hb. No. 66.
14. Hayakawa, K. I., Henig, Y. S. and Gilbert, S. G. 1975. Formulae for predicting gas exchange
of fresh produce in polymeric film package. J. Food Sci. 40:187.
15. Henig, Y. S. and Gilbert, S. G. 1975. Computer analysis of the variables affecting respiration
and quality of produce packaged in polymeric films. J. Food Sci. 40: 1033.
16. Jurin V. and Karel. M. 1963. Studies on control of respiration of McIntosh apples by packaging
methods. Food Technol. 17(782).
17. Kader, A. A. 1980. Prevention of ripening in fruits by use of controlled atmospheres. Food
Technol. 34(3):51-54.
18. Kader, A. A. 1986. Biochemical and physiological basis for effects of controlled and modified
atmospheres on fruits and vegetables. Food Technol. 40(5):99-100, 102-104.
19. Kader, A. A., D. Zagory, and E. L. Kerbel. 1989. Modified atmosphere packaging of fruits
and vegetables. CRC Crit. Rev. Food Sci. Nutr. 28(1):1-30.
20. Lougheed, E. C. 1987. Interactions of oxygen, carbon dioxide, temperature, and ethylene that
may induce injuries in vegetables. HortScience 22:791-94.
21. Mannapperuma, J. D. and Singh, R. P. 1987. A computer-aided model for gas exchange in
fruits and vegetables in polymeric packages. Presented at the 1987 International Meeting of
the American Society of Agricultural Engineers, Chicago, IL, December 15-18.
22. Mannapperuma, J. D. and Singh, R. P. 1994. Modeling of gas exchange in polymeric
polymeric packages of fresh fruits and vegetables. In Minimal Processing of Foods and Process
Optimization — An Interface. Eds. Singh, R. P. and F. A. R. Oliveira. pp. 437–458. CRC Press,
Boca Raton, FL.
23. Mannapperuma, J. D. and R. P. Singh. 1994. Modeling of gas exchange in polymeric packages
of fresh fruits and vegetables. In: Minimal Processing of Foods and Process Optimiza-
tion — An Interface, eds. R. P. Singh and F. A. R. Oliverira, p. 437-458, June 14-16, 1989; CRC
Press, Boca Raton, FL.
24. O’Beirne, D. 1990. Modified atmosphere packaging of fruits and vegetables. In: Chilled Foods:
the State of the Art, ed. T.R. Gromley, 183-199. New York: Elsevier Science Publishers.
25. Richardson, D. G. and M. Meheriuk, eds. 1982. Controlled atmospheres for storage and
transport of perishable agricultural commodities (Proc. 3rd Natl. CA Res. Conf., July 1981).
Beaverton, OR: Timber Press.
26. Rizvi, S. S. H. 1981. Requirements for foods packaged in polymeric films. CRC Crit. Rev.
Food Sci. Nutr. 14(2): 111.
27. Smith, S., J. Geeson, and J. Stow. 1987. Production of modified atmospheres in deciduous
fruits by the use of films and coatings. HortScience 22:772-76.
28. Solomos, T. 1987. Principles of gas exchange in bulky plant tissues. HortScience 22:766-71.
29. Stannett, V. 1968. Simple gases. In: Diffusion of Cases in Polymers, ed. Crank, J. and Park,
G. S., London: Academic Press.
30. Veeraju, P. and Karel, M. 1966. Controlling atmosphere in a fresh fruit package. Modern
Packaging 40(2):166.

©1998 CRC Press LLC


2646_ch16_Frame Page 54 Wednesday, October 23, 2002 5:29 PM

31. Wade, N. L. and Graham, D. 1987. A model to describe the modified atmospheres developed
during the storage of fruit in plastic films. ASEAN Food J. 3:(3&4):105.
32. Weichmann, J. 1986. The effect of controlled atmosphere storage on the sensory and nutri-
tional quality of fruits and vegetables. Hortic. Rev. 8: 101-27.
33. Yasuda, H. 1975. Units of gas permeability constants. J. Appl. Polymer Sci. 19:2529.
34. Zagory, D. and A. A. Kader. 1988. Modified atmospheres packaging of fresh produce. Food
Technol. 42(9):70-74, 76-77.
35. Zagory, D. and A. A. Kader. 1989. Quality maintenance in fresh fruits and vegetables by
controlled atmospheres. In Q~ y Factors of Fruits and Vegetables—Chemistry and Technol-
ogy, ed. J. J. Jen, 174-188. Washington, D.C.: American Chemical Society.
36. Zagory, D., J. D. Mannapperuma, A. A. Kader and R. P. Singh. 1989. Use of computer model
in the design of modified atmosphere packages for fresh fruits and vegetables. In: Proceed-
ings of the Fifth International Controlled Atmosphere Research Conference, vol 1, Pome
Fruits, ed. J. K. Fellman, p. 479-486, June 14-16, 1989; Wenatchee, WA.

©1998 CRC Press LLC

Related Interests