Professional Documents
Culture Documents
Edited by
M.L. ROONEY
Principal Research Scientist
CSIRO
Division of Food Science & Technology
North Ryde
New South Wales
Australia
Im
SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.
First edition 1995
© 1995 Springer Science+Business Media Dordrecht
Origina1ly published by Chapman & Hali in 1995
Softcover reprint ofthe hardcover lst edition 1995
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Acknowledgements
I extend my thanks to all the contributors, many of whom I have known and
all of whom I have respected for several years. I appreciate their
commitment in working within the tight schedule required. I also thank Lyn
Keen for her tolerant preparation and reorganization of much of the
manuscript, and Andrew Sennett for preparing so many versions of some of
the graphics. My thanks also go to Drs Bob Holland, Brian Patterson, Bob
Johnson, Mark Horsham, Alister Sharp, Candiera Albert and Michael
McNally for refereeing my contributions within CSIRO. I appreciate the
advice and forbearance of the staff at Blackie A&P. Finally, I thank my wife
Sally, and my children Helen, James and Kathy for their quiet patience and
active support during the preparation of this book.
M.L.R.
Contributors
2 Ethylene-removing packaging 38
D. ZAGORY
2.1 The chemistry of ethylene 38
2.1.1 Synthesis 38
2.1.2 Degradation 39
2.1.3 Adsorption and absorption 40
2.2 Deleterious effects of ethylene 41
2.2.1 Respiration 42
2.2.2 Fruit ripening and softening 42
2.2.3 Flower and lead abscission 42
2.2.4 Chlorophyll breakdown 43
2.2.5 Petal inrolling in carnations 43
2.2.6 Postharvest disorders 43
2.2.7 Susceptibility to plant pathogens 43
2.3 Interactions of ethylene and other gases 44
2.3.1 Oxygen 44
2.3.2 Carbon dioxide 44
2.3.3 Ozone 45
2.4 Ethylene sources in the environment 45
2.4.1 Combustion 45
2.4.2 Plant sources 45
2.4.3 Ripening rooms 46
2.4.4 Fluorescent ballasts and rubber materials 46
2.4.5 Microorganisms 46
2.5 Commercial applications in packaging 46
2.5.1 Potassium permanganate-based scavengers 46
2.5.2 Activated carbon-based scavengers 47
2.5.3 Activated earth-type scavengers 48
2.5.4 New and novel approaches to ethylene-removing packaging 50
Acknowledgements 51
References 51
CONTENTS IX
Index 256
1 Overview of active food packaging
M.L. ROONEY
Packaging may be termed active when it performs some role other than
providing an inert barrier to external conditions. Hotchkiss (1994) includes
the term 'desired' when describing the role, and this is important in that it
differentiates clearly between unwanted interactions and desired effects.
This definition reflects the element of choice in how active packaging
performs and the fact that it may play some single intended role and
otherwise be similar to other packaging in the remainder of its properties.
These latter two aspects also reflect that active packaging is something that
is designed to correct deficiencies which exist in passive packaging. A
simple example of this situation is when a plastics package has adequate
moisture barrier but an inadequate oxygen barrier. Active packaging
solutions could be the inclusion of an oxygen scavenger, or an antimicrobial
agent if microbial growth is the quality-limiting variable.
Active packaging has developed as a series of responses to unrelated
problems in maintenance of the quality and safety of foods. Accordingly a
range of types of active packaging has been developed. Each of these has a
range of descriptive terms. Horticultural produce has for some years now
been packaged in 'smart films', and oxygen has been removed from package
headspaces by oxygen scavengers, free-oxygen absorbers (FOAs) and
deoxidisers. Carbon dioxide can be released by emitters or can be absorbed
by getters, and microwaves can be controlled in packages by susceptors or
shields (Sacharow and Schiffman, 1992). Regional differences in terminol-
ogy are also seen. The terms 'freshness preservative' and 'functional' and
'avant garde' are also used to describe active packaging materials (Katsura,
1989; Louis and de Leiris, 1991). There has been a range of trade names for
those packages where a generic form has not been coined, with the result
that we have SmartCap (ZapatA - Advanced Oxygen Technologies) for
closures for beer bottles and Oxyguard for Toyo Seikan Kaisha Ltd. for caps
for similar use.
Smart packages have been defined by Wagner (1989) as 'doing more than
just offer protection. They interact with the product, and in some cases,
actually respond to changes'. In this sense, most packaging media are active
to some degree. However, there are forms of packaging which are clearly
distinct subclasses. The term equilibrium modified atmosphere (EMA)
2 ACTIVE FOOD PACKAGING
large indeed as with oxygen scavenging crown closures for bottled beer. In
some instances we see the need for application of two forms of active
packaging to achieve a goal. This has been demonstrated by Naito et al.
(1991) who showed that use of an oxygen absorber alone suppressed growth
of bacteria and of yeast (Hansenula anomala) in packages of sponge cake
but that the inclusion of an ethanol or carbon dioxide emitter was even more
effective. The use of combined-effect sachets, for instance, is now
commonplace - see Chapter 6.
1.2.2.1 Iron-based oxygen scavengers. Since tinplate cans were the basic
packaging of processed foods for most of the past century, it is not
surprising that the next development was also targeted at canned food.
Tallgren (1938), in a patent, described the use of iron, zinc or manganese
powders to remove oxygen from the headspace of cans. This invention
paved the way for the subsequent development of the iron-based oxygen
scavengers of commerce today.
OVERVIEW 5
35
0
75/76 77/78 79/80 81/82 83/84 85/86 87/88 89/90 91/92 93/94
Years
Figure 1.1 Substrates described in patent applications for oxygen scavengers.
Mitsubishi Gas and Chemical Co. released Ageless sachets in 1978. The fall
in the number of patent applications in the mid-1980s is reflected in both the
number of metallic compositions and that of other compositions. The
subsequent, increasingly strong activity in both areas of chemistry reflects
the need for processes which overcome deficiencies in existing products.
If the preparation of an active packaging material or process is viewed as
a product development topic in its own right then there are two facets which
should be evident. The first is the composition and the second is the design
of the remainder of the product, including its packaging. Some active
packaging technologies have been based on the introduction of a sachet into
the package of food and thus have the characteristics of the protective and
functional packaging of any other sensitive product.
The results in Figure 1.2 show that, initially, innovation was directed
towards establishing claims for novel compositions and that the level of
activity between 1977 and 1982 was almost the same as that between 1989
and 1994. What has changed are the chemical reactions involved in these
compositions. Initially, greatest interest was shown in the reactions under-
gone by various sulfites in the presence of alkali powders which absorb the
sulfur dioxide formed. Subsequent developments were based on oxidation of
iron powder or ferrous compounds and this has continued with the growth in
the number of compositions based on organic reactions. Prominent among
these is oxidation of ascorbic acid or of ethylenically unsaturated com-
pounds such as fatty acids, squalene and rubbers.
OVERVIEW 7
70,-------------------------------------.
60 ......................................... .
10
o 75nS 77178 79/80 81/82 83184 85/86 87/88 89190 91/92 93194
Years
Figure 1.2 Patent applications for oxygen scavengers based on composition or design.
demonstrates the early success of this approach. The detail of the historical
development of research and commercial development of such processes is
described in Chapter 2.
The use of edible or otherwise non-toxic coatings on fruit skins as
vehicles for active chemicals has been known for several years. The
modification of the atmosphere close to the skins of fruit has been achieved
by shrink wrapping. Both these techniques assist in eliminating the build-up
of surface water as a cause of microbial growth on fruit surfaces. The recent
introduction of minimally processed fruits and vegetables in packaged form
has heightened awareness in this area. The importance of hygiene in the
preparation of sliced and diced produce has been discussed by Varoquaux
and Wiley (1994). The potential for antimicrobial edible films is reviewed in
Chapter 5.
Active packaging has developed as a series of topics which are related only
because they involve the package influencing the environment of the food.
The literature in this field consists very largely of patent applications,
technical leaflets and reviews. The latter have often been presented at
conferences where specialised audiences have been able to take up the ideas
presented. Reports of academic scientific investigation have been limited
largely to occasional assessments of the appropriateness of some of these
technologies. The literature in this field is therefore discussed in terms of the
reviews.
Sneller (1986) reported on the impact of smart films on controlled
atmosphere packaging although the first broadly based reviews were
presented in Iceland and Australia in 1987 (Labuza, 1987; Rooney, 1987).
The first use of the term active packaging was proposed at that time by
Labuza, who defined active packaging as a range of technologies, some of
which now represent the borderlines between active, 'intelligent', and
modified-atmosphere packaging (Labuza and Breene, 1989). The essential
features of these 'freshness enhancers' have been summarised in a short
review by Sacharow (1988).
Katsura (1989) reviewed the range of functional packaging materials
which had been commercialised with particular reference to Japan. He
demonstrated the attention that had been paid to freshness preservative
packaging. Wagner (1989) summarised the range of smart packages and
emphasised the role of microwaveable-food packaging. Rooney (1989a,b;
1990) concentrated on chemical effects, particularly oxygen scavenging. The
role of oxygen scavengers in maintaining the benefits of MAP for processed
foods was reviewed by Smith et al. (1990) following their own research into
suppression of microbial growth (see Chapter 6).
OVERVIEW 11
Respiring Produce
Dry
Foods
active
Bakery
Products
FOOD CLASS
Some of these are quite complicated and they are set out in Chapter 3 to
provide an easy-to-use model. This form of packaging is commonly termed
modified atmosphere packaging (MAP) or more appropriately equilibrium
modified atmosphere (EMA) packaging.
EMA packaging involving selection of polymer films is, as mentioned
previously, the borderline between active and passive packaging. Chapter 3
shows how modelling can indicate quickly whether available packaging
plastics are going to be suitable for maintaining EMA over the temperature
range chosen. Several approaches to overcoming the limitations of these
films have been reported. One which is still in its infancy is the use of liquid-
crystal polymers which undergo a phase change at a characteristic
temperature. The permeability of the polymer to oxygen sharply increases as
this temperature is exceeded, thus providing the oxygen necessary to prevent
packaged horticultural produce from switching from aerobic to anaerobic
respiration. The present state of the art is not sufficiently advanced to cover
EMA films which match produce over a wide temperature range, but
research has opened up this possibility.
An alternative involves pores in portions of a package which open when
the temperature exceeds a precisely set value. This has been achieved by
filling pores in a patch on a package with a wax which melts appropriately
(Cameron and Patterson, 1992). This wax, when liquid, is drawn away by a
wick such as a microporous film to leave the pore open to gas exchange.
This type of high-temperature emergency valve is applicable to packages
over a wide range of sizes. Microporous patches are already used
commercially on retail trays of some fruit.
The use of pores in packaging materials to actually balance the
atmosphere in packages of respiring fruit has been the subject of some
research and a large amount of marketing. Several forms of crushed rock,
coral and synthetic zeolites have been incorporated into extruded film but
there has been very little disinterested scientific evaluation done. Such films
extend the range of gas permeability values of the commodity films in
current use. Some results for P-Plus, a porous film currently manufactured
by Sidlaw Packaging, Bristol (UK), have been presented (Gill, 1990).
Predictive research and some experimental verification of the effects of
single pores in produce packages have been reported (Mannapperuma and
Singh, 1994). The effects of changes in temperature on gas composition
need to be evaluated.
Extension of the post-harvest life of fruits and vegetables requires more
than EMA packaging. The water relations between the horticultural
foodstuff and its atmosphere need to be balanced both to prevent
dehydration and to avoid condensation induced by temperature abuse. Since
the RH of such packages exceeds 95%, a temperature drop from 12°C to
11°C at the pack surface can cause condensation. The visually unpleasant
appearance in retail packs is frequently overcome by antifogs in the plastic
OVERVIEW 15
areas such as closures and to areas of close contact of product and package
as found with meats, cheeses and wet foods generally.
The ability of polymers to act where there is close contact opens the way
to provide a variety of food additives via a diffusive mechanism. This
includes antimicrobial action (Halek and Garg, 1988) or antioxidant (Han et
aI., 1987) effects. To date, the use of such packaging has been restricted to
controlled release of antioxidant into cereal products (Miltz et al., 1989).
The benefit of slow release of antimicrobial agents and antioxidants is the
potential for maintenance of the requisite high concentration at wet food
surfaces. This applies especially to high-water-content foods in which
diffusion from the surface into the bulk can deplete surface concentrations
(Torres et al., 1985). This effect has been noted by Smith et al. (1990) who
investigated the effectiveness of ethanol-emitting sachets on the growth of
Saccharomyces cerevisiae on apple turnovers. For active packaging to fulfil
a useful role in this field it will be necessary for it to provide controllable,
slow release matched to the needs of the food. Water-triggered sachets of
silica containing ethanol are very much a first generation approach to this
form of packaging. The role of edible food coatings in release of food
additives is discussed in Chapter 5.
Besides antimicrobials and antioxidants there is a wide variety of other agents
that can be added to foods or which can act on them. Thus flavours can be
added to offset degradation on storage, enzymes can remove oxygen or other
undesirable food components, and insecticides can repel insects or kill them
with permitted fumigants. There is a potential ethical dilemma which may arise
from the application of such approaches to food packaging. There is also the
potential for foods to be self-promoting via the aroma of their packaging. Thus a
desirable flavour might be generated by an outer layer of a package to attract
customers rather than being released from an inner layer to offset scalping or
processing losses. In an extreme case, supermarkets might become a confusing
garden of unbalanced aromas competing for the organoleptic senses of the
customer in much the same way as package print attracts the customer visually.
At this point the packaging ceases to be active in the sense of the present
definition and can be described as intelligent in the definition of the CEST
report (Summers, 1992). Introduction of many of these forms of active or related
packaging technologies will necessitate serious consideration of explanatory
labelling. In some cases this may require regulation, as with oxygen-scavenging
sachets in Japan, the USA and Australia where the "Do not eat label" is required.
In Australia at least, minimum sizes are specified to reduce risk of
ingestion.
21
18
--
~
c
15
12
CD
C)
>-
><
0
6
3
........ _---
0
0 5 10 15 20 25
Time (hours)
Figure 1.4 Oxygen scavenging from loosely packed biscuits packs (.) compared to tightly packed
packets (A) (simulating domestic use).
20 ACTIVE FOOD PACKAGING
The fact that active packaging has developed as a series of responses to the
needs of niche markets should not hide the small number of underlying
principles being applied (successfully) thus far. Table 1.3 summarises the
use to which these principles have been applied either commercially or in
patent applications or other publications.
such novel ways that they deserve attention. Labuza and Breene (1989)
reviewed novel two-layer packages both with and without an intermediate
layer such as a chillable gel which imparts an increased thermal load. The
use of labels which expand to give an insulating foam when plastics lunch-
cups are retorted is a novel example.
A higher level of sophistication is found in the inclusion of selective
shielding of portions of microwaveable meals by appropriate placement of
metallised strips in the top dome of packs. This makes possible the
engineering of food products with mixtures of components with very
different heating requirements (see Chapter 9).
The concept of shielding the food from energy applied externally can also
be applied to shock absorption by layers of foam. One such laminate is
described by Yoshizaki (1976). This approach is not substantially different
from the application of shrinkable foamed sleeves to glass soft-drink
bottles.
1.5.1.10 Hydrolysis. To date, very little use has been made of hydrolytic
reactions. The desorption of ethanol mentioned above may involve some
hydrolysis. Use has been made of the release of sulfur dioxide from sodium
metabisulfite in quilted pads of microporous material which are placed in
cartons on top of table grapes. Water vapour from the grapes is absorbed and
releases the gas which is required to act as a fungicide to prevent attack at
OVERVIEW 25
the stem junction of the fruit. Thus far, there has been no satisfactory method
of controlling the rate of hydrolysis, with the result that excessive rates of
release can cause partial bleaching of the grapes.
An unintended hydrolytic reaction appears to have been found by Halek
and Garg (1988) who set out to bind Benomyl fungicide to a carboxylic-
acid-containing film, Surlyn (Dupont). The fungal inhibition results obtained
when the film was placed in contact with inoculated agar indicated
detachment of the fungicide from the polymer and diffusion into the
agar.
between the active one and the food is sufficiently permeable. This is the
basis of the ethanol-releasing sachets Ethicap and Negamold (both from
Freund Ltd., Tokyo) and of the CO 2-releasing sachets manufactured by
Mitsubishi Gas and Chemical Co., Toppan Printing Co. (both of Tokyo) and
Multiform Desiccants Inc. of Buffalo, NY. The permeability of the sachet
material to water vapour or ethanol is of critical importance in the
application of these sachets. Most frequently, microporosity of a hydro-
phobic film material has been made use of to achieve this.
Similar considerations to the above apply when active packaging is
chosen to remove a foodlheadspace component such as oxygen, carbon
dioxide or odours. The need to separate the scavengers from the food by a
layer impermeable to the scavenger has thus far been relatively simple, as
inorganic substances such as iron powder have been used both commercially
(Koyama and Oda, 1992) and in proposed systems (Teijin, 1981; Toyobo,
1981). The choice of film materials permeable to oxygen, carbon dioxide or
organic off-flavours has been relatively simple as polyolefins serve this
purpose well. Where concurrent permeation of the barrier layer to water is
also required, problems are encountered with the polyolefins which are
highly permeable to non-polar gases and vapours but are not sufficiently
permeable to water vapour. This problem is overcome in sachet manufacture
by use of microporous films which are hydrophobic and resist liquid water
penetration (Mitsubishi, 1983). Substantial numbers of patents describe
methods of achieving the requisite permeabilities to water and oxygen using
this approach. The careful choice of food contact layer plastics for retortable
packages by Toyo Seikan (Koyama and Oda, 1992) and American Can
Company has resulted in the development of heat-triggered oxygen
scavengers which function when the water vapour transmission rate of the
laminate reaches the necessary value. The premature oxidation of the
reduced iron scavenger in the Toyo Seikan Oxyguard process at extrusion
temperatures of around 220°C is minimised by keeping the plastics dry.
When the container fabricated from these plastics is retorted at l20°C for 30
min, water vapour permeating the container wall is absorbed and takes part
in the rusting of the iron. Retention of water by the composition allows the
Oxyguard to continue to act as a chemical oxygen barrier when the package
returns to room temperature. This is the opposite situation to that with
conventional passive retort package material based on EVOH where
retention of water in the EVOH lowers the oxygen barrier and increases
oxygen availability to the packaged food for many weeks after retorting
(Tsai and Wachtel, 1990).
The Oxyguard and other oxygen-scavenging plastics compositions can
reduce the cost of the barrier layer by reducing the need for inclusion of
mica platelets in the EVOH or for desiccants in the polypropylene layer of
retortable trays. Another form of active packaging which can also reduce
complexity of oxygen-barrier packaging is ethanol release. Hirata (1992) has
OVERVIEW 29
The ideal active package would sense the requirements of the food and
adjust its properties in order to meet them. At the same time this would be
cost-effective and have minimal environmental impacts. Current commercial
active packages do not meet these criteria although there are some which are
second-generation concepts. The latter include meat packs with inserts
which release carbon dioxide in response to absorption of weep or juice
(Sacharow, 1988).
Horticultural active packaging is not yet based on films with a sufficiently
wide range of CO2 :02 permeability ratios. This ratio would need to be
temperature responsive in the same manner as the enclosed fruit or
vegetable. The Intellimer side-chain-crystallisable polymers from Landec
Corporation (Menlo Park, CA, USA) offer some answers to the temperature
problem (Stewart et at., 1994). There is a lack of convincing evidence that
several of the films designed to scavenge ethylene do in fact work
satisfactorily under actual conditions of use. Industry confidence would be
well served by self-indicating films which change colour on reacting with
ethylene at physiologically important concentrations. The control of humid-
ity in liner bags of fruit and vegetables is still in its early stages of
32 ACTIVE FOOD PACKAGING
The future of any innovation in packaging depends upon the extent to which
it can satisfy the requirements of the product packaged. Commercial
development therefore will be driven by needs as perceived in the food
industry or in other industries with related problems. It is clear from patent
searches that inventors of active packaging frequently see potential applica-
tions for their concepts in several industries. This is evident in claims for use
of oxygen scavengers in the packaging of clothes, pharmaceuticals, fine
chemicals such as arnines, printing inks, electronic components, metals and
many more areas. Some iron-based oxygen scavengers have been suggested
for use in hand-warmers for skiers.
If the potential of active packaging technologies is to be realised there will
need to be a recognition that changes in packaging can open up new methods
of presenting foods. The use of oxygen-scavenging plastics as chemical
barriers to permeation should allow retortable plastics to provide product
shelf-lives closer to those found using metal cans. Horticultural produce,
such as flowers, should be transportable internationally with reduced
losses.
Acceptance of active packaging solutions to food industry problems will
continue to depend upon evidence of effectiveness demonstrated by
independent investigators. The lack of hard evidence supporting many
claimed benefits of some early horticultural produce packages has inhibited
commercial usage. If the majority of patent claims already made prove
useful and economically viable, active packaging has a bright future.
OVERVIEW 33
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2 Ethylene-removing packaging
D. ZAGORY
The ethylene molecule is of the alkene type, being simply two carbons
linked by a double bond with two hydrogen atoms on each carbon. Such a
simple molecule can be synthesized through several different pathways and
is subject to many kinds of chemical reaction.
2.1.1 Synthesis
Ethylene can be synthesized both biologically and non-biologically. It is a
common component of smoke and can be found as a product of aerobic
ETHYLENE-REMOVING PACKAGING 39
2.1.2 Degradation
Ethylene undergoes several types of degradation reactions. Because of its
double bond, ethylene absorbs ultraviolet (UV) radiation at 161, 166 and 175
nm (Roberts and Caserio, 1967). Ultraviolet photodecomposition of atmos-
pheric ethylene is an important environmental ethylene sink (Scott and
Wills, 1973) and yields primarily hydrogen, acetylene, n-butane and ethane
(Noyes et al., 1964). Soil microorganisms can degrade ethylene and at least
one species, Mycobacterium parajJinicum, is thought to be an efficient
oxidizer of ethylene (Abeles et al., 1992).
Ethylene reacts with ozone to yield water, carbon dioxide (C02), carbon
monoxide (CO), and formaldehyde (Scott et al., 1957). Ultraviolet light will
interact with oxygen (02) in air to form ozone which breaks down ethylene,
but UV light will directly degrade ethylene as well. Thus, UV light will
effectively eliminate ethylene even in low O2 atmospheres (Shorter and
Scott, 1986). However, the reaction is inefficient at very low ethylene
concentrations such as those found in fresh produce environments so the
commercial potential of ozone as an ethylene scrubber is limited. Atomic
oxygen will also react with ethylene and can form an array of compounds
40 ACTIVE FOOD PACKAGING
1989), Ohya-ishi (Oya stone) and zeolite (Urushizaki, 1986a). Oya stone is
mined from the Oya cave in Tochigi Prefecture in Japan. The cave has been
used to store fresh produce and is reputed to confer added storage life. The
salutary properties of the cave are thought to reside in the largely zeolitic
stone interior. To improve its ethylene adsorptive capacity, the Oya stone is
first finely ground with a small amount of metal oxide. The mixture is then
kneaded and heated to 200-900°C, then oxidized with ozone or electro-
magnetic radiation (Urushizaki, 1986b).
Some regenerable adsorbents have been shown to have ethylene adsorbing
capacity and have the benefit of being reusable after purging. Examples of
such adsorbents include propylene glycol, hexylene glycol (Rizzolo et ai.,
1987a), squalene, Apiezon M, phenylmethylsilicone, polyethylene and
polystyrene (Rizzolo et ai., 1987b).
Some adsorbents have been combined with catalysts or chemical agents
that modify or destroy the ethylene after adsorption. For example, activated
charcoal has been used to adsorb ethylene. In some cases, the activated
charcoal has been impregnated with bromine or with 15% KBr0 3 and O.5M
H2S04 to eliminate the activity of the ethylene (Osajima et al., 1983). A
number of catalytic oxidizers have been combined with adsorbents to
remove ethylene from air. Examples include potassium dichromate, KMn04'
iodine pentoxide, and silver nitrate, each respectively on silica gel (Eastwell
et al., 1978).
Electron-deficient dienes or trienes, such as benzenes, pyridines, diazines,
triazines and tetrazines, having electron-withdrawing substituents such as
fluorinated alkyl groups, sulphones and esters (especially dicarboxyoctyl,
dicarboxydecyl and dicarboxymethyl ester groups), will react rapidly and
irreversibly with ethylene at room temperature and remove ethylene from
the atmosphere. Such compounds can be embedded in permeable plastic
bags or printing inks to remove ethylene from packages of plant produce
(Holland, 1992).
Metal catalysts immobilized on absorbents, such as platinized asbestos,
cupric oxide-ferric oxide pellets and powdered cupric oxide, will effectively
oxidize ethylene, but in many cases the reactions require high temperatures
(> 180°C). Clearly such systems would be inappropriate for food packaging
applications.
2.2.1 Respiration
Perishability of produce generally is well correlated with respiration rate.
Commodities such as asparagus, broccoli and mushrooms that have very
high respiration rates are very perishable, having postharvest lives measured
in days. Those commodities such as nuts, dates, dried fruits, potatoes and
onions that have very low respiration rates have postharvest lives measured
in months (Kader, 1985). Reduction of respiration rate increases postharvest
life and elevation of respiration rate generally decreases it. This is one of the
reasons why low temperature is so important in postharvest management.
Reducing the temperature rapidly reduces the respiration rate of the
product.
Ethylene accelerates the respiration of fruits, vegetables and ornamental
plants. In the case of climacteric fruit, ethylene can induce a rapid and
irreversible elevation in respiration leading directly to maturity and
senescence. In non-climacteric plant organs, ethylene induces a reversible
increase in respiration. In most cases, exposure to a few parts per million
(ppm) of ethylene leads to increased respiration and increased perish-
ability.
Ethylene has been shown to accelerate abscission for many, though not all,
plants and plant parts (Jankiewicz, 1985; Osborne 1989b; Reid, 1985a).
Ethylene causes flower and leaf abscission of many potted ornamental plants
(Cameron and Reid, 1983).
2.3.1 Oxygen
Ethylene production, biosynthesis and explosiveness are all related to
ambient oxygen concentration. Most pathways of ethylene synthesis,
whether biological or chemical, are oxidative conversions or cleavages.
Although rice and some other aquatic plants have been reported to
synthesize ethylene in the absence of 02 (Ku et al., 1970), most plants
require O2 for ethylene synthesis. However, the oxygen affinity of ethylene-
forming enzyme (EFE) is much less than that for respiratory enzymes. The
I\n for conversion of 1-arninocyclopropane-l-carboxylic acid (ACC) to
ethylene in apple is about 1.4% O2 (Banks et al., 1984; Butler and Streif,
1986) but I\n values for other plants organs are generally 3-10% (Burg and
Thimann, 1959; Lieberman et al., 1966). In some cases, reduced 02 in a
package may more effectively reduce ambient ethylene through reduced
ethylene synthesis than ethylene-adsorbing capacity built into the package.
However, reduced 02 apparently slows the conversion of ACC to ethylene,
resulting in accumulation of ACC (Burg and Thimann, 1959; Hansen, 1942;
Imaseki et al., 1975; Jackson et al., 1978). Upon exposure to higher O2
concentrations, the accumulated ACC will be rapidly converted into
ethylene so low 02 must be maintained continuously to maintain low
ethylene concentrations.
The combustion of organic materials requires O2 and results in ethylene as
one of the combustion products. Ethylene at concentrations between 3.1 and
32% by volume, is explosive in air (Reid, 1985b). Neither of these
conditions occurs in packages.
2.3.3 Ozone
As was mentioned above, ozone oxidizes ethylene to simple breakdown
products and has been used experimentally to remove ethylene from produce
storage areas. However, ozone would not normally be found or introduced
into a food package.
2.4.1 Combustion
Ethylene is a common breakdown product of virtually all aerobic combus-
tion processes. Burning agricultural wastes, wildfires, diesel- or propane-
powered forklifts, cigarette smoke, truck and auto exhaust, and industrial
stack emissions are all common sources of ethylene. In addition, the heat
generated by combustion (from forklifts, for example) can raise the
temperature of the product sufficiently to stimulate production of product-
generated ethylene.
Ambient atmospheric levels of ethylene are normally in the range of
0.001-0.005 ppm (Abeles et al., 1992), however, urban air levels as high as
0.5 ppm have been measured (Scott et al., 1957). Such high levels are
sufficient to have physiological effects on some fresh produce. Removing
agricultural sources of ethylene and insulating storage rooms from ethylene
air pollution can significantly reduce ambient ethylene.
2.4.5 Microorganisms
Although several soilborne microorganisms produce ethylene, others de-
grade it. The net effect appears to be that the soil serves primarily as a sink
for ethylene.
Postharvest plant pathogens growing on stored products in enclosed
holding areas can be important sources of ethylene. All infested foodstuffs
should be immediately discarded.
toxicity. However, sachets could be used inside produce packages and have
been shown to effectively scavenge ethylene from packages of bananas,
persimmons, kiwifruit, avocados (Ben-Arie and Sonego, 1985; Fuchs and
Temkin-Gorodeiski, 1971; Hatton and Reeder, 1972; Krishnamurthy and
Kushalappa, 1985; Liu, 1970; Maotani et al., 1982; Scott et al., 1970).
Typically, such products contain - 4-6% KMn04 on an inert substrate
such as perlite, alumina, silica gel, vermiculite, activated carbon or celite
(Abeles et al., 1992). The performance and useful lives of these scavengers
depends on the substrate surface area and the content of reagent (KMn04).
Formulations differ in density and surface area of substrate and the loading
of reagent.
Some suppliers of KMn04-based ethylene scavengers are listed in Table
2.1. This table is not a complete listing of all companies supplying such
products but only those known to the author at the time of writing.
(Abeles et aI., 1992). Apparently Ethad® has not been used to adsorb
ethylene in packages.
Evert-Fresh Corporation markets Evert-Fresh bags in the USA. The bags
are, presumably, polyethylene with Japanese Oya stone dispersed within the
film matrix. Oya stone has putative ethylene-adsorbing capacity. Evert-Fresh
Corp. offers shelf-life data for several fresh commodities to demonstrate the
benefits of their bags.
A product called BO Film is marketed by the Odja Shoji Co. Ltd. of
Japan. It is a low-density polyethylene film extruded with finely divided
crysburite ceramic which is claimed to confer ethylene-adsorbing capacity
(Joyce, 1988).
There are many other similar bags being sold throughout the world offer-
ing improved postharvest life of fresh commodities due to the adsorption of
ethylene by the minerals dispersed within the film. The evidence offered in
support of this claim is generally based on shelf-life experiments comparing
common polyethylene bags with mineralized bags. Such evidence generally
shows an extension of shelf-life and/or a reduction of headspace ethylene.
Such data are unconvincing. Although the finely divided minerals may
adsorb ethylene, they will also open pores within the plastic bag and alter the
gas-exchange properties of the bag. Because ethylene will diffuse much
more rapidly through open pore spaces within the plastic than through the
plastic itself, one would expect ethylene to diffuse out of these bags faster
than through pure polyethylene bags. In addition, CO 2 will leave these bags
more readily and O2 enter more readily than is the case for a comparable
polyethylene bag. These effects can improve shelf-life and reduce headspace
ethylene concentrations independently of any ethylene adsorption. In fact,
almost any powdered mineral can confer such effects without relying on
expensive Oya stone or other speciality minerals. Hercules Chemical
Company relied on this effect while using calcium carbonate to improve the
gas-transmission properties of their Fresh Hold breathable bags without
making any claims regarding ethylene adsorption (Anderson, 1989).
Although the minerals in question may have ethylene-adsorbing capacity,
the data supporting the commercial products incorporating these minerals
fail to demonstrate such capacity. Even if they do have ethylene-adsorbing
capacity, it is possible that they will lack significant capacity while
embedded in plastic films. The ethylene would have to diffuse through the
plastic matrix before contact with the dispersed mineral, thus greatly slowing
any processes of adsorption. Once the ethylene has diffused part-way
through the plastic film, venting to the outside may be nearly as fast and
effective as adsorption on embedded minerals.
In a study performed in Australia with BO film, the mineral in the bag
took up little ethylene (Joyce, 1988). Furthermore, in studies with pure
mineral granules of Cera-sutora A, the author found that the ethylene
50 ACTIVE FOOD PACKAGING
Acknowledgements
Thanks for literature and helpful discussion are owed to: Linda Dodge,
Cheryl Reeves, Michael Reid, Michael Rooney, Mikal Saltveit and Kit
Yam.
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Reid, M.S., Paul, J.L., Farhoomand, M.B., Kofranek, A.K and Staby, G.L. (1980) Pulse
treatment with the silver thiosulphate complex extends the vase-life of cut carnations. J.
Amer. Soc. Hort. Sci., 105, 25-7.
Rizzolo, A., Polesello, A. and Gorini, F. (1987a) Laboratory screening tests of some suitable
regenerable adsorbents to remove ethylene from cold room atmospheres. 1. Glycols and
polyglycols. In: Third Subproject: Conservation and Processing of Foods - A Research
Report (1982-1986), National Research Council of Italy, Milano. pp. 99-100.
Rizzolo, A., Polesello, A. and Gorini, F. (1987b) Laboratory screening tests of some suitable
regenerable adsorbents to remove ethylene from cold room atmospheres. 1. Apolar phases.
In: Third Subproject: Conservation and Processing of Foods - A Research Report
(1982-1986), National Research Council of Italy, Milano. pp. 101-2.
Roberts, J.D. and Caserio, M.C. (1967) Modem Organic Chemistry, Benjamin, NY.
Sato, M., Urushizaki, S., Nishiyama, K, Sakai, F. and Ota, Y. (1987) Efficient production of
ethylene by Pseudomonas syringae pv. glycinea which causes halo blight of soybeans.
Agric. Bioi. Chem., 51, 1177-8.
Scott, W.E., Stephens, E.R., Hanst, P.C. and Doerr, R.C. (1957) Further developments in the
chemistry of the atmosphere. Proc. Amer. Petrol. Inst., 37, 171-83.
Scott, KJ., McGlasson, W.B. and Roberts, E.A. (1970) Potassium permanganate as an
ethylene absorbent in polyethylen.e bags to delay ripening of bananas during storage. Aust.
1. Expt. Agric. Anim. Husb., 10, 237-40.
Scott, KJ. and Wills, R.B.H. (1973) Atmospheric pollutants destroyed in an ultraviolet
scrubber. Lab. Pract., 22, 103-6.
Shorter, AJ. and Scott, KJ. (1986) Removal of ethylene from air and low oxygen atmospheres
with ultraviolet radiation. Lebensm. Wiss. U. Technol., 19, 176-9.
Someya, N. (1992) Packaging sheet for perishable goods. US Patent No. 5084337.
54 ACTIVE FOOD PACKAGING
Talib, Z. (1983) Ethylene in the storage of fresh produce. In: Developments in Food
Preservation, Vol. 2, S. Thorne, (ed.), Applied Science Publishers, London and New York.
pp. 149-77.
Urushizaki, S. (1987a) On the Effects of Functional Films. Autumn Meeting of Japan Society
Horticultural Science. Symposium: Postharvest Ethylene and Quality of Horticultural Crops.
University of Kyushu, October 8, 1987.
Urushizaki, S. (1987b) Development of Ethylene Absorbable Film and its Application to
Vegetable and Fruit Packaging. Autumn Meeting of Japan Society Horticultural Science.
Symposium: Postharvest Ethylene and Quality of Horticultural Crops. University of
Kyushu, October 8, 1987.
Wittenbach, V.A. and Bukovac, M.J. (1973) Cherry fruit abscission: Effect of growth
substances, metabolic inhibitors and environmental factors. J. Amer. Soc. Hort. Sci., 98,
348-51.
Yang, S.F. and Hoffman, N.E. (1984) Ethylene biosynthesis and its regulation in higher plants.
Ann. Rev. Plant Physiol., 35, 155-89.
Zagory, D., Brecht, B. and Kader, A.A. (1988) Unpublished data.
3 Design of modified atmosphere packaging for
fresh produce
K. L. YAM and D. S. LEE
3.1 Introduction
Controlled atmosphere (CA) storage and modified atmosphere packaging
(MAP) are two useful technologies to extend the shelf-life of fresh
agricultural and horticultural produce. Simply stated, these technologies
involve storing a fruit or vegetable in a modified atmosphere usually
consisting of reduced O2 and elevated CO2 concentrations compared to air.
The modified atmosphere reduces the rates of respiration and ethylene
production, which are often associated with the benefits of retardation of
physiological, pathological, and physical deteriorative processes occurring in
the product. Aerobic respiration is a complicated process that involves a
series of enzymatic reactions taking place through the metabolic pathways of
glycolysis, the tricarboxylic acid (TCA) cycle, and the associated electron
transport system (Kader, 1987). However, the overall reaction describing the
respiration process may be simply expressed as
C6H 120 6 + 6 02 ~ 6 CO2 + 6 H20 + heat (3.1)
that involves the oxidation of organic substrates (such as starch, sugars, and
organic acids) to CO2 and H 20 along with heat generation. Kinetic theory
and Equation (3.1) suggest that the respiration rate may be reduced by
decreasing the 02 and/or by increasing the CO2 concentration.
There are differences between the ways CA storage and MAP create and
maintain a modified atmosphere. In CA storage, a gas generator is usually
used to create and control the modified atmosphere in a cold warehouse
where the product is kept. In MAP, the product is kept in a carefully
designed permeable package, and the modified atmosphere is created and
maintained through an intricate interplay between the respiration of the
product and the gas permeation of the package. MAP is a more economical
technology because an expensive gas generator is not needed; however, it is
also a more difficult technology to implement because of the rather
complicated interactions between the product and the package. This chapter
is focused on the design of MAP for fresh produce.
The modified atmosphere in MAP can be created by either active or
passive modification. In active modification, the modified atmosphere is
created rapidly by flushing the headspace of the package with a desired gas
mixture. In passive modification, the modified atmosphere is created by
56 ACTIVE FOOD PACKAGING
Yes No
Figure 3.1 Flow chart for designing MAP for fresh produce.
DESIGN OF MAP FOR FRESH PRODUCE 57
Before designing MAP for a product, the first step is to determine whether
CA storage can indeed provide benefits for the product. Reviewing the
20
14
"'"'
~
'-'
12
§
.~
10
U
I
N
8
.riI-=~- Avocado
Persimmon
0
U 6 JIt'o='it- Banana
4 arine, Peach
0
0 2 4 6 8 10 12 14 16 18 20
02 Concentration (%)
Figure 3.2 Recommended gas concentrations for CA storage of fruits. (Redrawn from Singh and
Oliveira, 1994, with permission.)
DESIGN OF MAP FOR FRESH PRODUCE 59
such as maturity and cultivar of the product) and the criteria used in making
recommendations are seldom reported. Therefore conducting a feasibility
study is often required, particularly if no literature data are found for the
product of interest.
Figure 3.3 Recommended gas concentrations for CA storage of vegetables. (Redrawn from Singh
and Oliveira, 1994, with permission.)
60 ACTIVE FOOD PACKAGING
-
(a) (b)
Product
Samples
Respiration rate values are required for mathematical modeling and for
defining the package requirements. Respiration is often a good index for the
storage life of fresh produce: the lower the respiration rate, the longer the
storage life (Powrie and Skura, 1991; Lebermann et at., 1968). As Equation
(3.1) shows, respiration involves the rate of O2 consumption (Ro,) and the
rate of CO 2 evolution (Rco,). The respiratory quotient (RQ) is a convenient
term, which is defined as the ratio of CO2 evolution to O2 consumption. RQs
are reported to range from 0.7 to 1.3, depending upon the metabolic
substrate (Kader, 1987; Kader et at., 1989).
The respiration rates are known to be affected by several internal and
external factors (Robertson, 1992). Internal factors include the type of
product and cultivar, maturity, resistance of plant tissue to gas diffusion, and
whether the product is climacteric or nonclimacteric. The external factors
include temperature, C2H 4 concentration, O2 and CO 2 concentrations and
stress due to physical damage or excessive water loss.
Because respiration rates under modified atmospheres for most fruits and
vegetables are not available in the literature, they must be determined by
experiment. There are three methods for measuring respiration rates: the
flow-through system, the closed system, and the permeable system (Lee,
1987). The flow-through system and the closed system are illustrated in
Figure 3.4.
M PF
R - ([CO] - [CO]) cO2
(3.8)
CO2 - 2 out 2 in 100 W R T
where the subscripts in and out denote the inlet and the outlet concentrations,
respectively. The flow-through system has an advantage of being able to
DESIGN OF MAP FOR FRESH PRODUCE 63
provide more accurate data than the closed system. However, the usefulness
of the flow-through system is limited by the precision of the gas
chromatography measurements, because the differences between the inlet
and outlet concentrations are usually rather small. There are three ways to
increase the concentration differences, as suggested by Equations (3.7) and
(3.8): work only with produce of high respiration; reduce the gas flow rate;
increase the sample weight. Another drawback of the flow-through system is
that each experiment measures only the respiration rate at a single gas
concentration, and thus much time and labor are required if respiration rates
at many gas concentrations are to be measured.
The closed system method (Figure 4b) is more efficient for measuring
respiration rates as a function of gas concentrations. This method involves
monitoring the 0z and COz concentrations inside a closed jar containing
the product as a function of time (Haggar et aI., 1992). The initial
gas concentrations inside the jar are usually those of air, but other gas
concentrations may also be used. As the product respires, the gas con-
centrations in the jar change with time - from high 0zllow COz concentra-
tions at the beginning to low Ozlhigh COz concentrations toward the end.
The respiration rates at these 0z and COz concentrations may be calculated
using the equations
R _ d[Ozl M o, P V
(3.9)
0, - dt 100 W R T
d[CO zl M co, P V
(3.10)
R co, = dt 100 WR T
The negative sign in Equation (3.9) signifies that the 0z concentration in the
jar decreases with time. In order to evaluate the first derivatives, the data of
gas concentration versus time should first be curved fitted. The recom-
mended functions for fitting the data are
(3.11)
(3.12)
d[O]
_ _2_ = act (a t +b )(-1--<:,) - (a t + b )-<0, (3.13)
dt 1 1 1 1 1 1
V rn [02]
R or R = ---------- (3.15)
0, co, ~ + (1 + [C0 2])IK i [02]
The model requires two different sets of adjustable coefficients (Vrn' Krn , and
K): one for R o, and the other for R co,. The model has been verified quite
extensively using experimental data for a wide variety of products. Since the
model is based on the principle of enzyme kinetics, it requires less adjustable
coefficients and is likely to be more predictive than those purely empirical
models (Cameron et at., 1989; Yang and Chinnan, 1988) used in the
literature. However, the applicability of the model to any new set of data
should always be confirmed by comparing the predicted values with the
experimental data. Overextending the model to predict respiration rates at
concentrations very different from those generated from the closed system
experiments should be avoided. Table 3.2 lists the model parameter values
and respiration activation energies for some fruits and vegetables. The
activation energies are not strong functions of 02 and CO2 concentrations
(Haggar et at., 1992).
Mathematical models are useful for defining the package requirements for
MAP. Several models (Jurin and Karel, 1963; Veeraju and Karel, 1966;
DESIGN OF MAP FOR FRESH PRODUCE 65
Table 3.2 Respiration model parameter values and respiration activation engergies for some
products
Respiration model parameters
Activation
Temp. Respiration Vrn K", Ki energy
Commodity (0C) expression (mg/kg h) (% °2) (% CO 2) (kJ/mol)
Blueberry 15 02consumption 68.0 0.4 2.9 147.3
"Coville"a CO2 evolution 51.0 0.2 4.9 163.3
Broccolib 7 O2 consumption 210.3 0.6 2.3 62.7
CO2 evolution 235.2 1.7 1.93 66.1
Cauliflower' 13 02consumption 133.7 1.7 3.0 21.2--48.2
CO2 evolution 134.4 1.4 3.1 21.2--48.2
Green peppe.n 10 02 consumption 54.3 6.0 1.3 48.7-57.3
CO 2 evolution 31.8 2.4 4.3 48.7-57.3
'Song et al. (1992); bHaggar et al. (1992); cYam et al. (1993) and Exama et al. (1993); dExama et
al. (1993).
Hayakawa et al., 1975; Deily and Rizvi, 1981) are available in the literature,
and some of them have been reviewed by Zagory and Kader (1988).
Basically those models use the principles of O2 and CO 2 mass balances to
describe the interactions among the respiration of product, the permeability
of the package, and the environment.
M0,P V _d[O 1
_2_1 = _s0P_ , ([0] _ [0 ].) Patm - W R (3.16)
100 R T dt L 2 0 2 1 0,
Mco,P V d[C0 21
WORT dt
= (3.17)
where the subscripts i and 0 denote the inside and outside of the package,
respectively. Equations (3.16) and (3.17) are first-order linear differential
equations that can be solved quite easily using a computer. They are useful
for describing the unsteady-state behaviour of the MAP system, such as
during the process of passive modification and during temperature fluctu-
ations. The equations can be tailored to fit a particular physical situation
through the application of initial boundary conditions. For example, the
initial conditions for passive modification are [02]j = 21 and [C021 = 0 at
66 ACTIVE FOOD PACKAGING
t = O. Note that the respiration rates R02 and Reo, are functions of O2 and
CO2 concentrations, which can be expressed using the enzyme-kinetic model
of Equation (3.15).
When the accumulated terms are zero, Equations (3.16) and (3.17) are
reduced to the steady-state equations
(3.18)
(3.19)
experiments; [02ks and [C02ks are assumed to be the optimum 02 and CO2
concentrations; [02]0 and [C02]0 are 21 and 0%, respectively. With six
variables fixed and two equations to satisfy, there are only (11-6-2) = 3
design variables. That is, only three out of the remaining five variables (W,
S, L, Po, and P co,) can be specified arbitrarily. For example, if the food
technologist chooses to specify the dimensions of W, S, and L (within
practical limits), the permeabilities Po, and P co, must then be determined by
Equations (3.18) and (3.19).
The equations also provide a convenient means to reject films not suitable
for a particular application. Dividing Equation (3.19) by Equation (3.18)
yields
DESIGN OF MAP FOR FRESH PRODUCE 67
(3.20)
where [02]0 and [C02]0 are assumed to be 21 and 0%, respectively. Further,
if RQ is assumed to be 1 and Pco/Po, is defined as 13, Equation (3.20) may
be rewritten as
(3.19)
al. (1993).
Table 3.3 Penneabilities at 10°C and permeability activation energies for polymeric film
Permeabilities (ml millm2h peo 2 Activation energies (kJ/mol)
atm)
Polymeric films P0 2 P0 2 P0 2 E p•o, Ep•co,
Polybutadiene 1118 9892 8.8 29.7 21.8
Low-density 110 366 3.3 30.2 31.1
polyethylene
Ceramic-filled LDPE 199 882 4.4 36.8 28.4
Linear low-density 257 1002 3.9
polyethylene
High-density 2.1 9.8 4.6 35.1 30.1
polyethylene
Cast polypropylene 53 151 2.9
Oriented polypropylene 34 105 3.1
Polyethylene 1.8 6.1 3.3 26.8 25.9
terephthalate
Nylon laminated 1.7 6.0 3.5 52.6 50.0
multilayer film
Ethylene vinyl acetate 166 985 5.9 48.4 37.0
Ceramic-filled 116 630 5.4 34.5 26.2
polystyrene
Silicone rubber II 170 71300 6.4 8.4 0.0
Perforation (air) 2.44 X 109 1.89 X 109 0.8 3.6 3.6
Microporous film 3.81 X 107 3.81 X 107 1.0 13.0 3.7
From Exama et al. (1993); Lee et al. (1992); Lee et al. (1994); Ohta et al. (1991); Mannapperuma
and Singh (1990); Anderson (1989); and Shelekshin et al. (1992).
between 3 and 6; however, Figures 3.3 and 3.4 show that many fruits and
vegetables require f3 values outside this narrow range. This problem has also
been recently investigated by Exama et at. (1933), who conclude most films
do not satisfy both the gas flow and selectivity requirements for many fruits
and vegetables packaged in typical MAP configurations.
There are at least two possible solutions for this problem. The first
solution is to compensate the inadequacy of the films with techniques such
as placing oxygen absorbers in the package or using two different films to
selectively control the permeability. The second solution is to look for new
and better films - some recent advances in the development of polymeric
films suitable for fresh produce are discussed below.
Nomenclature
References
Powrie, W.D. and Skura, BJ. (1991) Modified atmosphere packaging of fruits and vegetables.
In: Modified Atmosphere Packaging of Food, B. Ooraiku1 and M.E. Stiles (eds), Ellis
Horwood, New York.
Prince, T.A. (1989) Modified atmosphere packaging of horticultural commodities. In:
Controlled/Modified AtmospherelVacuum Packaging of Foods, A.L. Brody (ed.), Food &
Nutrition Press, Trumbull, Connecticut, 67-100.
Robertson, G.L. (1992) Packaging of horticultural products. In: Food Packaging: Principles
and Practice, Marcel Dekker, New York, 470-506.
Shelekhin, A.B., Dixon, A.G. and Ma, Y.H. (1992) Adsorption, permeation, and diffusion of
gases in microporous membranes. II. Permeation of gases in microporous glass membranes.
1. Membrane Sci., 75, 233-44.
Singh, R.P. and Oliveira, F. (1994) Minimal Processing of Foods and Process Optimization.
CRC Press, Boca Raton, Florida, 438-9.
Solomos, T. (1994) Some biological and physical principles underlying modified atmosphere
packaging. In: Minimally Processed Refrigerated Fruits and Vegetables, R.c. Wiley (ed.),
Chapman & Hall, New York, 183-225.
Song, Y.S., Kim, H.K. and Yam, K.L. (1992) Respiration of blueberry in modified atmosphere
at various temperatures. 1. Amer. Soc. Hort. Sci., 117(6), 925-9.
Veeraju, M. and Karel, M. (1966) Controlling atmosphere in fresh-fruit package. Modern
Packaging, 40, 168, 170, 172, 174, 254.
Weichmann, J. (1986) The effect of controlled-atmosphere storage on the sensory and
nutritional quality of fruits and vegetables. Hort. Rev., 8, 101-27.
Yam, K.L., Haggar, P.E. and Lee, D.S. (1993) Modeling respiration of low CO2 tolerance
produce using a closed system experiment. Foods Biotechnol., 2(1), 22-5.
Yang, c.c. and Chinnan, M.S. (1988) Modeling the effect of O2 and CO2 on respiration and
quality of stored tomatoes. Trans. ASAE, 31, 920-5.
Zagory, D. and Kader, A.A. (1988) Modified atmosphere packaging of fresh produce. Food
Technology, 42(9), 70-7.
4 Active packaging in polymer films
M.L. ROONEY
4.1 Introduction
Polymers constitute either all or part of most primary packages for foods and
beverages and a great deal of research has been devoted to the introduction
of active packaging processes into plastics. Plastics are thermoplastic
polymers containing additional components such as antioxidants and
processing aids. Most forms of active packaging involve an intimate
interaction between the food and its package so it is the layer closest to the
food that is often chosen to be active. Thus polymer films potentially
constitute the position of choice for incorporation of ingredients that are
active chemically or physically. These polymer films might be used as
closure wads, lacquers or enamels in cans and as the waterproof layer in
liquid cartonboard, or as packages in their own right.
The commercial development of active packaging plastics has not
occurred evenly across the range of possible applications. Physical processes
such as microwave heating by use of susceptor films and the generation of
an equilibrium modified atmosphere (EMA) by modification of plastics
films have been available for several years. Research continues to be popular
in both these areas. Chemical processes such as oxygen scavenging have
been adopted more rapidly in sachet form rather than in plastics. Oxygen
scavenging sachets were introduced to the Japanese market in 1978 (Abe
and Kondoh, 1989) whereas the first oxygen-scavenging beer bottle closures
were used in 1989 (see Chapter 8). The development of plastics active
packaging systems has been more closely tied to the requirements of
particular food types or food processes than has sachet development.
This chapter surveys the range of polymer-based active packaging
processes that have been reported, their chemical or physical basis and their
application to foods and beverages. Attention is given to opportunities for,
and obstacles to, either commercialisation or extension of the current range
of application. Some processes which have become economically important
are treated individually in other chapters.
The removal of oxygen from package headspaces and from solution in foods
and beverages has long been a target of the food technologist. Introduction
of vacuum packaging and inert-gas flushing has provided solutions for some
POLYMER FILM 75
manufactured in Japan by Ajinimoto under the Take Out brand name. The
self-adhesive label concept of US company Multiform Desiccants is used in
the Marks & Spencer retail chain's preserved meat packs in the UK.
Beyond the concept of adhesion of sachets to the package lies a wide
range of possibilities and it is to this area that much of the recent research
and development has been directed. Alternatives include package inserts in
the form of cards or sheets, or layers coated onto the inner wall of the
package. An example is the beverage crown seal liner currently used in the
beer industry. This liner was developed by Advanced Oxygen Technologies
Inc. and Zapata Industries Inc. under the name SmartCap and independently
by W.R. Grace and Company and under the name Daraform. Both
companies manufacture in the USA. Alternatively an iron-based system has
been developed under the name Oxyguard by Toyo Seikan Kaisha Ltd in
Japan. The industrial development and history of oxygen-scavenging
closures is discussed in detail in Chapter 8.
Oxygen-scavenging films or other plastics packaging materials are
alternatives to sachets. Low molecular weight ingredients may be dissolved
or dispersed in a packaging plastic or the plastic may be made from a
polymeric scavenger. The scavenger may be incorporated into a solid which
is dispersed in the plastic or may be introduced into various layers of the
package such as in the form of adhesive, printing ink, lacquer or enamel,
such as found in cans.
Sachets can be a highly efficient form of oxygen scavenger but their
nature does not favour contact with liquid foods or where cling of the
package to the film may isolate the sachet from areas of oxygen entrapment
or ingress. In such situations it would be preferable to have the scavenger in
the packaging material. This allows all exposed surfaces of the food to be
deoxygenated or protected from oxygen ingress by permeation.
Table 4.4 Penneability coefficients P X 10 10 (cm 3 mm cm-2 sec- l cm- l Hg) @ 30°C
Film material N2 02
Polyvinylidene chloride 0.0094 0.053 0.29
Polyester (Mylar A) 0.05 0.22 1.53
Polyamide (Nylon 6) 0.10 0.38 1.6
Polyethylene (d = 0.960) 2.7 10.6 35
Polyethylene (d = 0.922) 19 55 352
Polystyrene 2.9 11.0 88
Polyvinylchloride 0.40 1.2 10
(Reproduced from Paine, 1962, with permission.)
into the barrier layer as in the Ox-bar bottle of CMB Technologies plc
(Folland, 1990) that portion closer to the outside becomes exposed to
relatively large amounts of oxygen.
The permeability of the polymer medium in which the scavenging
reaction occurs need not be the limiting variable determining scavenging
rate. Depending upon the chemistry involved, the oxidation reaction can be
inherently slow, as with crystalline sulfites at room temperature or the
reaction can require the presence of an additional species as with the rusting
of iron. The permeability of the heat-seal layer to both oxygen and water
vapour can be limiting as in the mixed sulfite/acetate layer in retort pouches
patented by Farrell and Tsai (1985). In this case the water is needed in
substantially larger quantity than the oxygen in order to dissolve the
deliquescent potassium acetate in which solution the potassium sulfite
dissolves and reacts with oxygen.
An approach to overcoming any limitation on scavenging rate by the heat-
seal layer' s permeability has been to use microporous polymers such as non-
woven polyolefins. Several recent patent applications describe claims of
enhanced availability to the package atmosphere of granular reagents, as in
that of Mitsubishi Gas Chemical Industry Co. Various sulfites can be held in
a fibrous layer sandwiched between, for example, one layer of foil, and a
second of a plastic or paper with an oxygen permeability greater than 7000
rnlIm2/day atm. A second patent describes a package consisting of three
layers. The outer layer is a plastics film, the middle is a perforated or non-
woven layer containing an oxygen scavenger and the inner layer of the
package is a microporous film which resists the flow of liquids through its
pores. This is claimed to be useful for packaging liquid foods (Ohtsuka et
al., 1984). Such films cannot be used where transparency is required but may
have application in many forms of packaging.
Traditionally, poly(vinylidene chloride) copolymers have provided a
water-insensitive oxygen barrier when used as a layer in laminates, coated
films or coextrusions. The introduction of ethylene-vinyl alcohol copoly-
mers (EVOH) and poly(vinyl alcohol) means that, together with traditional
nylons, most oxygen barriers are now water sensitive. The permeability to
oxygen of EVOH copolymers increases approximately 1O-fold when
exposed to a relative humidity change from about 40-100%. Such a change
may render a material which is suitable for packaging an oxygen-sensitive
food at low relative humidity into one which is most unsuitable at high
relative humidity.
The plasticising effect of water on the barrier properties of EVOH (or
other hydrophilic barriers) is time dependent, especially if the hydrophilic
layer is protected by a water-barrier layer such as polypropylene as in the
case of retortable lunch-cups. When such retortable packs containing a wet
food such as an entree are subjected to steam retorting, water is absorbed by
the EVOH in such large quantities that the barrier layer becomes quite
80 ACTIVE FOOD PACKAGING
70~---------------------------------------'
60 ........................................ .
I_ Sachet D Plastics I
50 ............................... .
(/)
c:
N
li30
40
Co
«
20
10
o 75n6 77n8 79/80 81/82 83/84 85/86 87/88 89/90 91/92 93/94
Years
Figure 4.1 Patent applications for oxygen scavengers involving sachets and plastics.
82 ACTIVE FOOD PACKAGING
(4.1)
HO
HOH~J:::(O
OH
+ 2NaOH
- N··X",' HOHC 0 0
I
CH20H CH20H
l
l
l
BROWN PRODUCTS - fJ--.
o CHO
oxidation of sodium sulfite to the sulfate. Whether this occurs in the ambient
or low-temperature storage of beer has not been described in the literature.
Given the heterogeneous nature of the reaction mixture it is doubtful
whether this desirable regeneration occurs to a very great extent in
commercial practice without the formation of an aqueous solution as
described by Farrell and Tsai (1985).
As can be seen from the summary in Figure 4.2 one of the reaction
products of oxidation of ascorbic acid to dehydroascorbic acid is hydrogen
peroxide or initially the hydroperoxy free radical. Further hydrogen
abstraction by this radical forms hydrogen peroxide. The use of sodium
sulfite, or another reducing agent, would therefore seem to be desirable if the
ultimate re-introduction of an oxidising agent is to be avoided. The role of
ascorbic acid as a promoter of browning when oxidised in foods is already
known (Tannenbaum, 1976).
The use of ascorbic acid or its isomers or salts is the basis of the W.R.
Grace and Co. and Zapata Inc oxygen-scavenging closures in common use
in some beer bottles.
D -..?hU *D (4.2)
*D -..? 3D (4.3)
3D + O2 -..? D + 102 (4.4)
A + 102 -..? A02 (4.5)
102 -..? O2 (4.6)
*D -..?D (4.7)
triplet energy transfer (Equation 4.4). The oxygen diffusing into the polymer
from the package headspace (for instance) needs to come very close to the
excited, immobile dye molecules during the triplet lifetime of the latter. This
is of the order of 10-1000 microseconds. Thus, for such a process to be
useful the polymer matrix (such as an inner layer of a laminate) would need
to be very permeable to oxygen.
Once excited to its singlet state the oxygen can react with any e1ectron-
rich acceptors, A, present in the polymer matrix (Equation 4.5) provided
they are within the distance the singlet oxygen can diffuse before it is
quenched back to the ground state (Equation 4.6). The process occurs only
within the lifetimes of the excited sensitiser (Equation 4.7) and singlet
oxygen and so requires continuous illumination. The distance singlet oxygen
can diffuse before quenching in a polymer matrix is of the order of 100A
depending on the polymer permeability and other factors (Turro et al.,
1981).
This chemistry has been used in the laboratory as an oxygen-scavenging
process where the polymer matrix is, for instance, cellulose acetate or ethyl
cellulose (Rooney et al., 1981; Rooney, 1982). The sensitisers include
erythrosine or meso-tetraphenylporphine and the acceptors are bis(fur-
furylidene)pentaerythritol and ascorbic acid. It was found that the permeabil-
ity of the polymer film is an important determinant of scavenging rate, with
the ethyl cellulose being a better matrix for rapid scavenging than cellulose
acetate. Ethyl cellulose has an oxygen permeability coefficient at 25°C of 7
Barrers (cm3 (STP) cmlcm-2 S-I cm- I Hg x 10-10) compared with that of 0.7
Barrers for cellulose acetate (Bixler, 1971). It was also found that the rate of
scavenging of oxygen from a pouch by the film is limited by light intensity
initially but becomes diffusion limited when the oxygen partial pressure
reaches low values (Rooney et al., 1981). The light intensity used was 2 x
105-7 X 105 Lux. It was subsequently shown that the rate of oxygen
scavenging reaches a maximum at a concentration of tetraphenylporphine
above 10-3 M but less than 10-2 M. When the scavenger film was used as a
roll it was found that the rate was dependent upon the length of film in the
roll consistent with increased access of oxygen to the film.
The singlet oxygen acceptor does not need to be a small molecule
dissolved in the polymer. It has been shown the double bond of natural
rubber can be photo-oxidised at a rate sufficient to bring about rapid oxygen
scavenging from the headspace of a package. Figure 4.3 shows the rate of
scavenging of oxygen from air, 20 mI, in a 10 cm x 10 cm pouch coated on
the inside with either natural rubber dyed with tetraphenylporphine, 10-3 M,
or ethyl cellulose 0.6 M with respect to PEF and 10-3 M with respect to
tetraphenylporphine. The rubber scavenged oxygen substantially faster than
the PEF in the ethyl cellulose. This was interpreted as being due to the
higher concentration of double bond (13.5 equivalentsllitre) in the rubber
than the concentration of furan rings (1.2 equivalents/litre of film) in the
POLYMER FILM 89
25 r--------------------------------------------------,
20
c 15
Q)
Cl
~
0
;fi. 10
5 •
oL-------~------~==~====~==~~
o 10 20 30 40
Time (min)
Figure 4.3 Oxygen scavenging by natural rubber e, and PEP 0.5M in ethyl cellulose ., both dyed
with tetraphenylporphine, 1O-3M. Volume of air, 20 mI, pouch area 100 cm2 . (Reprinted from
Rooney, 1982b, with permission.)
90 ACTIVE FOOD PACKAGING
21
18
15
.......
;:,R
0 12
c
CD
0)
>-
>< 9
0
3 0
o
o 5 10 15 20 25 30
time (minutes)
0.09
0.08
,in darkness
0.07
I
I
c:
Q)
0> I
~0.06
0 I
?f.
•
0.05
0.04
allow the water absorbent to be held in place rather than aggregating towards
one edge of the sheet when tilted towards one edge.
Such sheets are then used either as pads under whole chickens or chicken
pieces to absorb drip, thereby preventing discoloration of either the meat or
the white foam tray. Given the interest in reducing the volume of solid waste
by decreasing foam polystyrene usage, the use of drip-absorbers may
become even more necessary to prevent water damage to the more
hydrophilic alternatives.
Large sheets are used for absorption of melted ice in the packaging of
seafood for air transportation. The superabsorbent polymer used in the
Thermarite® Pty Ltd sheet manufactured in Australia is capable of
absorbing at least 100 times and possibly as much as 500 times its own
weight of liquid water depending dramatically upon salinity (Malouthi et al.,
1994). Another product of this type is Toppan Sheet manufactured in Japan.
A recent patent application in Japan describes a water-absorbent sheet which
has a high barrier to oxygen for use with fresh meat (Showa Denko KK,
1990). This would necessitate use of a sealed outer pack.
The preferred polymers used to absorb the water are polyacrylate salts,
although graft copolymers of starch can also be used. Such copolymers
consist of a polysaccharide backbone with synthetic polymer chains
radiating from the starch backbone. The strong association of the poly-
saccharide chains is disrupted allowing the starch to exercise its affinity for
water by hydrogen bonding. Such polymers tend to become slimy when
swollen with large amounts of water.
The swelling of the polymer on hydration results in substantial distortion
of the duplex sheet, an effect that is controlled somewhat by the quilted seal
pattern. This effect can be controlled by choice of the amount and the
capacity of the superabsorbent polymer.
The significance of such active packaging in seafood shipment by air lies
in the removal of the potential for spillage of salt water from cartons in
aircraft holds. The aluminium construction of aircraft makes them easily
susceptible to corrosion damage, at great cost.
The interaction of packaging plastics with food aroma has long been
recognised, especially through the flavour 'scalping' which is of consider-
able commercial interest. Hirose et al. (1989) demonstrated the impact of the
nature of the metal ion in SUrlyn film layers in aseptic brick-packs on the
scalping of limonene from orange juice. In periods as short as 2 weeks at
24°C, almost 30% of the limonene was found in the Surlyn-1601 and 20%
in the polyethylene layer in brick packs. Commercially, plastics packaging
has not been used to remove selectively components of the flavour or aroma
of foods which are considered undesirable, but a potential opportunity has
been available for over a decade.
Some varieties of orange, such as the Navel, contain a tetraterpenoid of
the formula C26H300g which is initially present in the albedo but which is
extracted into the juice on standing or heating. Thus the juice of such
oranges becomes bitter on pasteurisation when this compound, limonin,
reaches concentrations exceeding 8-12 mglkg (Chandler et ai., 1968).
Processes have been developed for debittering such juices by passing them
through columns packed with cellulose triacetate or nylon beads (Chandler
and Johnson, 1979).
A simple active packaging process was suggested by the same authors,
who proposed that since the juice extracts the bitter principle on standing for
24 h, inclusion of the absorbent in the packaging might remove it as it is
extracted. To this end they proposed using their absorbents in film form such
as cellulose triacetate or as acetylated paper. They showed that a I-litre
plastic bottle coated internally with cellulose acetate-butyrate reduced the
limonin content of 500 ml of juice from 42 to 11 mg/kg after 3 days'
refrigeration. Similarly, when cans lined with acetylated filter paper
containing juice with 14.9 mglkg limonin were spin cooked and allowed to
stand, the juice was only slightly bitter after 4-13 days.
It appears that this process has not been taken up commercially although
it offers considerable potential for freshly squeezed Navel juice marketing
100 ACTIVE FOOD PACKAGING
Active packaging materials considered so far have exerted their action on the
packaged food by removing unwanted components of either the food or of
the headspace enclosed with the food. Another form of interaction is by
release of desirable ingredients into the food from the packaging materials or
from inserts packaged with the food. Some substances released commer-
cially or which have been the subject of investigation are listed in Table 4.8.
Most are used for their antimicrobial activity, although sulfur dioxide also
serves as a chemical stabiliser of colour and flavour by preventing progress
of the Maillard reaction which causes non-enzymic browning of products
such as dried fruit and wines (Davis, 1975; Davis et at., 1978). Hinokitiol,
also known as (3-thujapricin (Hirata, 1992), derived from cypress bark, is an
additional antimicrobial compound specific to the Japan market.
Processing of foods often results in loss of flavour by degradation or
evaporation. Another mechanism of flavour loss is the scalping of some
flavour components by plastics used in packaging (Mannheim et at., 1989).
There is therefore the opportunity to replace these lost food constituents by
diffusion from the packaging, especially where scalping or flavour degrada-
tion occurs after packaging. There is, however, the question of whether a
food is being sold as fresh when this is not so. This is more a legal matter
of consumer protection than a technical one as the question arises of when
Two factors acting concurrently are likely to influence the use of packaging
materials as sources of antioxidants in some foods. The first of these is the
need of the industry to respond to pressure by some consumer advocates for
reduced use of food additives (Smith, 1993). The second is the renewed
interest of plastics resin manufacturers in using natural, or other approved
food antioxidants in polymer stabilisation replacing some of those developed
specifically for plastics. Dilaurylthiodipropionate and its base acid, thiodi-
propionic acid, are approved food additives in some countries and are used
as stabilisers in food-grade polyethylene (Anon., 1992).
The potential for evaporative migration of antioxidants into foods from
their packaging plastics has been studied by Calvert and Billingham (1979)
who developed a theoretical model. This work has been taken further by Han
et al. (1987) who determined the effect of temperature on both the diffusion
coefficient of butylated hydroxytoluene (BHT) in HDPE and the rate of its
evaporation into the package of oat flakes. It was found that at 39°C only
55% of the original BHT remained in the film after 1 week. The loss by
outward migration was 70%, and 25% of the BHT was found in the cereal.
After 6 weeks the HDPE film was free of antioxidant and 19% of that
originally in the film remained in the cereal. The workers compared the
impact of two starting levels in the film on oxidation of the cereal oil and
found that with an initial 0.32% BHT there was less oxidation than with
0.02%.
These results of Han et al. (1987) demonstrate the potential for release of
antioxidant into foods provided the rate of diffusion can be matched to the
food's needs. The outward loss can be controlled by use of a layer of film
with low permeability to the antioxidant or by use in a closure. In the case
of liquid foods or solids with close-fitting packaging the process could be
based on diffusion alone and not require the antioxidant to be able to
evaporate.
Commercial use of this approach to antioxidant release has been reported
by Labuza and Breene (1989) who noted that waxed paper has sometimes
104 ACTIVE FOOD PACKAGING
ene film and worst, polypropylene film. This work might be developed to
provide a low-cost answer to some of the major problems of fumigation,
including the cost of repeated fumigations with methyl bromide approx-
imately bi-monthly, as well as reducing the exposure of staff to fumigant
application conditions. The permethrin or alternative treatments would need
to be submitted for regulatory approval.
It has been suggested recently that enzymes might be released into foods
from packaging materials, probably to achieve effects such as antimicrobial
action. Labuza and Breene (1989) have reviewed the potential for release of
bound enzymes into foods. Enzyme inhibitors might also be bound to a film
surface. An example would be the binding of the inhibitor of methyl esterase
to the package surface to bind methyl esterase. The result might be
prevention of cloud drop in fresh orange juice (R.L. Johnson, private
communication). The subject of enzymes in active packaging is discussed in
Chapter 7. The use of enzymes in edible coatings is discussed in Chapter
5.
References
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Abe, Y. and Kondoh, Y. (1989) Oxygen absorbers. In: Controlled/Modified Atmosphere!
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Alarcon, B. and Hotchkiss, J.H. (1993) The effect of Fresh-Pax oxygen-absorbing packets on
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Anese, M., Pittia, P. and Nicoli, M.C. (1993) Oxygen consuming properties of heated glucose/
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Brody, AL. (1989) Modified atmosphere packaging of seafoods. In: Controlled/Modified
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Chandler, B.V. and Johnson, R.L. (1979) New Sorbent gel forms of cellulose esters for
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108 ACTIVE FOOD PACKAGING
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of untreated polyester or permethrin-treated polypropylene film. J. Econ. Entomol., 79,
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Australia Workshop on Food Processing. National Food Res. Inst., Tsukuba, Japan, pp.
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155283.
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POLYMER FILM 109
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5 Edible films and coatings as active layers
B. CUQ, N. GONTARD and S. GUILBERT
5.1 Introduction
Edible films and coatings are traditionally used to improve food appearance
and conservation. The most common examples are wax coatings for fruit
(used in China since the 12th century), chocolate coatings for confectionery,
lipid films to protect meat products, and soy milk-based lipoprotein films to
improve the appearance and preservation of certain foods in Asia.
Formulations for edible films or coatings must include at least one
component able to form a suitably cohesive and continuous matrix. The
basic materials can be classified in three categories: polysaccharides,
proteins and lipidic compounds. Polysaccharides (vegetable and microbial
gums, starches, celluloses and derivatives, etc.) have good film-forming
properties. Films formed from these hydrophilic compounds provide
efficient barriers against oils and lipids (Murray et al., 1972), but their
moisture barrier properties are poor. Although not as extensively studied,
protein-based films have highly interesting properties. Many protein materi-
als have been tested: collagen, zein, wheat gluten, ovalbumin, soybean,
casein, etc. (Guilbert and Biquet, 1989). The mechanical and barrier
properties of these films are generally better than those of polysaccharide-
based films; this is due to the fact that, contrary to polysaccharides which are
monotonous polymers, proteins have a specific structure which confers
larger potential functional properties (Guilbert and Graille, 1994). Many
lipidic compounds, such as animal and vegetable fats (natural waxes and
derivatives, acetoglycerides, surface-active agents, etc.), have been used to
make edible films and coatings (Guilbert and Biquet, 1989; Kester and
Fennema, 1986). They are generally used for their excellent moisture barrier
properties, but there can be problems concerning stability (particularly
oxidation), texture and organoleptic quality (opacity, waxy taste).
Edible films and coatings formed with several compounds (composite
films) have been developed to take advantage of the complementary
functional properties of these different constitutive materials and to
overcome their respective drawbacks. Most composite films studied to date
combine a lipidic compound and a hydrocolloid-based structural matrix
(Cole, 1969; Daniels, 1973; Gontard et al., 1994a; Guilbert, 1986; Kamper
and Fennema, 1984a, b).
Coatings are formed directly on the food product using either liquid film-
forming solutions (or dispersions) or molten compounds (e.g. lipids). They
112 ACTIVE FOOD PACKAGING
Films with substantial gas and moisture barrier properties are required for
many applications: to control gas exchange for fresh foods and oxygen
exchange for oxidizable foods and to reduce moisture exchange with the
external atmosphere (Guilbert and Biquet, 1989). Retention of specific
additives in edible films can lead to a functional response generally confined
to the surface of the product (modification and control of surface
conditions), (De Savoye et at., 1994; Guilbert, 1988; Torres et ai., 1985a, b;
Torres and Karel, 1985). Oil and solute penetration into foods during
processing can also be limited by edible coatings (Daniels, 1973; Guilbert
and Biquet, 1989).
In this chapter, we will expand on the use of edible films and coatings as
active layers, i.e when the edible film contributes by itself to the
preservation. Figure 5.1 gives a schematic representation of food preserva-
tion with edible films and coatings as active layers when the first mode of
deterioration results from respiration, from dehydration or moisture uptake,
or from surface microbial development or oxidation. The protective features
of edible films and coatings are dependent on gas and water vapor barrier
•
Storage
Food additives in
•
Storage FIlM
CONTROL
of Water Transfer
Figure 5.1 Schematic representation of food preservation with (top) or without (bottom) edible
films and coatings as active layers, when the first mode of deterioration results from respiration (a),
from dehydration or moisture uptake (b), or from microbial development or oxidation (c).
114 ACTIVE FOOD PACKAGING
i1Wx
P=---
i1t A i1p
where i1W is the permeant weight that passes through a film of thickness x
and area A; where L1t is the time and i1p is the differential partial pressure
across the film. The diffusion coefficient can be obtained by taking
EDIBLE ACTIVE LAYERS 115
Table 5.2 Effect of coating operation on water vapor perrneance of edible multicomponent films
composed of MC and paraffin wax (weight ratio 1:1); gluten and beeswax (at 2.4 mg/cm2); and
HPMC and stearic-palmitic acids (at 9 mg/cm2)
Water vapor
perrneance T Thickness RH%
Film (X 108 mol m-2 S-l Pa- 1) CC) (X 103 m) conditions
MC(I) 30.0 25 0.020 84-22
MC and paraffin wax (emulsion)(1) 7.39 25 0.090 84-22
MC and paraffin wax (bilayer)(l) 0.251 25 0.130 84-22
Glutten(2) 10.1 30 0.050 100-00
Gluten and beeswax (emulsionj12) 0.727 30 0.120 100-00
Gluten and beeswax (bilayer)(2) 0.0257 30 0.090 100-00
HPMC(3) 8.02 25 0.040 85-00
HPMC and fatty acids (emulsion)(3) 0.00643 25 0.040 85-00
HPMC and fatty acids (bilayerj13) 1.07 25 0.125 85-00
(According to Debeaufort et al .• 1993(1); Gontard et al., 1994a(2); Kamper and Fennema,
1984b(3).)
(HPMC = hydroxypropylmethy1cellulose; MC = methy1cellulose; RH = relative humidity; T =
temperature. )
118 ACTIVE FOOD PACKAGING
20
15
10
o 25 50 75 o 20 40 60
Lipid Materials Content (%wlw)
Figure 5.10 Effect of reduced surface pH on the microbiological quality of an intermediate moisture
cheese analog coated with a carrageenan and agarose film; challenged with Staphylococcus aureus
S-6 (aw = 0.88 and 35°C) (after Torres and Karel, \985).
EDIBLE ACTIVE LAYERS 119
Figure 5.3 Effect of average water activity on water vapor transmission rate of edible films
composed of methylcellulose and palmitic-stearic acids (at 0.76 mglcm2) at 25°C and 32% RH
gradient (according to Kamper and Fennema, 1984a), and of edible wheat gluten films at S, 30 and
50°C, and 10% RH gradient (according to Gontard et aI., 1993). e, MC and C'S-C'6 at 2SoC
(WVT x 0.1); D, gluten at 50°C; 0, gluten at 30°C; 0, gluten at soc.
120 ACTIVE FOOD PACKAGING
25
20
15
10
o 10 20 30 40 50 60
Temperature (OC)
Figure 5.4 Effect of temperature on water vapor permeance of edible wheat gluten films, at RH
conditions 90--80% (according to Gontard et al., 1993); of edible glycerol monostearate films, at RH
conditions 100-0% (according to Higuchi and Aguiar, 1959); and of edible films composed of
methylcellulose and beeswax, at RH conditions 97-0% (according to Kester and Fennema, 1989b).
0, Gluten (WVP X 0.1); A, Me and beeswax; e, monostearate.
EDIBLE ACTIVE LAYERS 121
The gas barrier properties of edible films and coatings are potentially of
great interest. For instance, edible oxygen barrier films can be used to
protect foods that are susceptible to oxidation (rancidity, loss of oxidizable
vitamins, etc.). In contrast, a relatively high gas permeability is necessary for
fresh fruit and vegetable coatings (especially carbon dioxide permeability).
The development of edible films with selective gas permeability (oxygen,
carbon dioxide, ethylene) allows the control of respiration exchange and
microbial development and seems very promising for achieving a 'modified
122 ACTIVE FOOD PACKAGING
atmosphere' effect in fresh fruit and for improving the storage potential of
these products (Smith et at., 1987; Trout et at., 1953), as schematized in
Figure 5.1.
Gas permeability can be measured using air porosimeters and specific
permeability cells. As in the case with moisture barrier properties, the
formulation, manufacturing and environmental parameters have an impact
on a film's response to gases. The oxygen and carbon dioxide permeability
values of various edible films and synthetic films are given in Table 5.3.
Films formed with hydrocolloids (proteins, polysaccharides) generally
have good oxygen barrier properties, particularly under low-moisture
conditions. The oxygen permeability of hydrocolloid-based films (at 0%
relative humidity) is often lower than that of common synthetic films such as
polyethylene and non-plasticized PVCs. For example, the oxygen permeabil-
ity of wheat gluten film was 800 times lower than that of low-density
polyethylene and twice as low as that of polyamide 6, a well-known high
oxygen barrier polymer.
Films formed with lipid derivatives have suitable oxygen barrier proper-
ties. For example, the oxygen permeability value for beeswax film lies
between those of low-density and high-density polyethylene (Table 5.3).
According to Blank (1962 and 1972), lipids with the best oxygen barrier
properties are those formed with straight-chain and saturated fatty acids.
Increased un saturation (or branching) and a reduction in the length of the
carbon chain result in decreased oxygen permeability. The following barrier
efficiency order was observed by Kester and Fennema (1989c): stearic
alcohol > tristearine > beeswax > acetylated monoglycerides > stearic
acid > alkanes. These differences can be explained by the presence of pores
or cracks, and by the homogeneity of the composition density of the network
(Kester and Fennema, 1989b, c). The network density is dependent on the
polymorphic shape and orientation of the chains and morphological
differences in the lipid layers.
As previously mentioned for water vapor permeability, formulation of
composite films allows advantage to be taken of the complementary barrier
properties of each component. At high aw ' where hydrophilic materials are
not effective as gas barriers (see below), the addition of lipidic compounds
results in a decrease in the gas permeability of the film. For example, at aw
= 0.91, the oxygen permeability is reduced by about 30% for a composite
gluten and beeswax film (Table 5.3).
The effect of temperature on gas permeability is similar to that reported
for water vapor permeability (Donhowe and Fennema, 1993b; Gennadios et
al., 1993). These variations can be characterized by Arrhenius-type
representations. But, as far as gas solubility decreases with temperature
increase, the increase of gas permeability with temperature is lower than for
water vapor permeability (Gontard et al., 1994b).
High aw conditions cause an increase in gas permeability in hydrophilic
EDIBLE ACTIVE LAYERS 123
films but generally not in synthetic hydrophobic films which are not water
sensitive (Figure 5.5). In these hydrophilic films, increased aw promotes both
gas diffusivity (due to the increased mobility of hydrophobic macromolecule
chains) and gas solubility (due to the water swelling of the matrix), leading
to a sharp increase in gas permeability (Kumins, 1965). The effects of aw on
gas barrier properties of composite films (methylcellulose and palmitic acid)
and of gluten protein-based films was studied by Rico-Pena and Torres
(1990) and by Gontard et al. (1994b) respectively, and are compared in
Figure 5.5 with oxygen permeabilities of synthetic hydrophilic films.
Carbon dioxide permeability in hydrocolloid-based films is often much
1000
100
10
0.1 ...------6-------....-
0.01 +--....---r--..----,,-----..r----,---...---r--...---j
0.0 0.2 0.4 0.6 0.8 1.0
Water activity
Figure 5.5 Effect of water activity on oxygen permeability of edible and synthetic films at 25°C
(according to Gontard et al., 1994b (0, gluten); Poyet, 1993 C.. , EVOH; ., Nylon 6); Rico-Pena and
Torres, 1990 (0, MC and palmitic acids, at weight ratio 3:1); Rigg, 1979 (e, cellophane». (MC is
methylcellulose; EVOH is ethylene-vinyl alcohol).
EDIBLE ACTIVE LAYERS 125
higher than oxygen permeability (Table 5.3). The effect of film aw on carbon
dioxide permeability is similar to that on oxygen permeability, but the sharp
increase of permeability is more important. This could be explained by the
differences in water solubility of these gases (Schwartzberg, 1985), i.e.
carbon dioxide is very soluble (carbon dioxide solubility in water =
34.5mmol/l at 25°C and 105 Pa; oxygen solubility = 1.25mmol/l at 25°C
and 105 Pa).
At high aw ' the addition of lipidic components to gluten film results in a
high decrease of carbon dioxide permeability. For example, at aw = 0.91,
the carbon dioxide permeability is reduced by about 75% for a composite
gluten and beeswax film (Table 5.3). This could be related to the
hydrophobic characteristics of these components which for the same aw
reduce the amount of water available for solubilisation of carbon dioxide.
The selectivity coefficient between carbon dioxide and oxygen is defined
as the ratio of the respective permeabilities of both gases. In hydrophilic
materials, the effect of an aw increase on permeability is greater for carbon
dioxide than for oxygen. The selectivity of these materials is thus sensitive
to moisture variations (for example, the selective coefficient of edible gluten
films varies from 4.0 at aw = 0.30, to 25 at aw = 0.95), (Gontard et at.,
1994b), whereas the selectivity coefficient for synthetic polymers remains
relatively constant, at 4 to 5 (Table 5.4).
Edible films with selective gas permeability can be applied to reduce
degradation of some fresh fruits and vegetables. In fact, the diffusion of
oxygen and carbon dioxide between fruit or vegetables and the environment
is a basic element in the post-harvest physiology of fruit (Burton, 1974,
1978; Cameron and Reid, 1982). The type of coating material applied alters
the relative effects on the skin permeability to oxygen and carbon dioxide
(Trout et al., 1953). For example, waxing increased the carbon dioxide
content and decreased the oxygen content of the orange's internal atmos-
phere (Eaks and Ludi, 1960). The coating of peach surfaces with beeswax-
coconut oil emulsion decreased oxygen gas transfer (Erbil and Muftugil,
1986). Chitosan coatings retarded ripening and prolonged storage life of
tomatoes, cucumber and bell pepper fruit without affecting their ripening
characteristics (EI Ghaouth et al., 1990, 1991). Lowings and Cutts (1982)
reported that an edible composite coating (carboxymethylcellulose, sucrose
fatty acid esters and mono- and diglycerides) would produce a semi-
permeable modified atmosphere within fresh fruit after application. The
post-storage uses of these coatings were investigated on apples (Chu, 1985;
Drake et al., 1987; Elson et al., 1985; Smith and Stow, 1984), on pears
(Elson et al., 1985), on bananas (Banks, 1983, 1984; Lowings and Cutts,
1982), on limes (Motlagh and Quantick, 1988) and on mangoes (Dhalla and
Hanson, 1988). For example, the selective gas permeability properties of
these films applied on bananas can reduce oxygen flux fivefold, while carbon
dioxide flux is only decreased by about half (Banks, 1984). Other examples
of gas permeability control by edible active layers are gelatin films used to
protect frozen meats from rancidity (Klose et al., 1952), to coat candies
and dried products (Grouber, 1983) and to microencapsulate flavors
(Anandaraman and Reineccius, 1980).
The development of edible active films with selective gas permeability
seems have considerable potential applications for achieving a modified
atmosphere effect for fruits and vegetables.
Edible active films and coatings can be applied on foods to modify and
control surface conditions. They can be used as surface retention agents to
limit food additive diffusion in the food core. The improvement of food
microbial stability can also be obtained by using edible active layers which
have specific antimicrobial and pH lowering properties.
Surface microbial growth is a main cause of spoilage for many food
products (Gill, 1979; Maxci, 1981; Olson et al., 1981; Vitkov, 1973, 1974).
Edible films and coatings can be used in combination with treatments such
as refrigeration and controlled atmosphere to improve the microbiological
quality of certain foods. For example, calcium alginate-based films were
tested to limit microorganism contamination on the surface of beef pieces
(Williams et al., 1978). These films were found to have a significant effect
EDIBLE ACTIVE LAYERS 127
" Retention
100
80
60
40
20
0
0 10 20 30 40 50
Time (days)
Figure 5.6 Tocopherol retention at 25°C in gelatin layers and in gelatin layers treated with tannic
acid in contact with aqueous model food (aw = 0.95) or in contact with margarine (according to
Guilbert, 1988). 0, Gelatin layer - aqueous model food; ., gelatin layer treated - aqueous model
food; 0, gelatin layer - margarine; ., gelatin layer treated - margarine.
moisture agar model system, Guilbert et at. (1985) reported a value of 2.0 x
1O- lOm2/sec. Torres et at. (1985b) found with an intermediate moisture
cheese analog a value of 1.0 x 1O- lOm2/sec (Table 5.5). The sorbic acid
diffusivity values in edible films were found to be 150- to 300-fold lower
than those determined for model intermediate moisture foods (Table 5.5).
These few examples indicate that edible films could be used for additive
retention on the surface of food products.
Preservative diffusion through edible films is influenced by various
parameters: film characteristics (type, manufacturing procedure), food
characteristics (pH, ~), storage conditions (temperature, duration, etc.) and
solute characteristics (hydrophilic properties, molar mass).
The effect of the film-forming material on sorbic acid permeability has
been studied for various edible films (Table 5.6). It appears that film
composition (type of film forming agent, presence of lipids) affects even the
sorbic acid permeability. For example, a 65% reduction of the sorbic acid
permeability of a methylcellulose edible film is observed when palmitic acid
is added to the hydrocolloid matrix, there is a 75% reduction for a
hydroxypropyl methylcellulose edible film.
Table 5.6 Sorbic acid permeability of various edible films at 24°C and a w =
0.77
Sorbic acid permeability
Film (x 108 g mm m-2 S-I (glltl)
Chitosan 0.865
MC 0.334
HPMC 0.830
MC and palmitic acid (weight ratio 3: 1) 0.120
HPMC and palmitic acid (weight ratio 3:1) 0.205
Zein Similar values
(According to Torres et al., 1985b; Vojdani and Torres, 1989a, b.)
(HPMC = hydroxypropylmethyIcellulose; MC = methyIcellulose.)
130 ACTIVE FOOD PACKAGING
0.10
0.05
0.00 ~--1Jo-..,L..---.--"T""""___.4__+-.__..,....___._-.___-r-~-..,...__;
Figure 5.7 Effect of water activity on sorbic acid permeability of edible multicomponent films
composed of methylcellulose and palmitic acid (weight ratio 3:1), at 24°C (0), (according to Rico-
Pena and Torres, 1991); and on sorbic acid diffusivity in agar gels with sucrose (_) or glycerol (0)
at 25°C (according to Giannakopoulos and Guilbert, 1986b).
EDIBLE ACTIVE LAYERS 131
1.2
0.8
0.4
o 10 20 30 40 50
Figure 5.8 Effect of temperature on sorbic acid permeability of edible multi component films
composed of methylcellulose (MC) or hydroxypropylmethylcellulose (HPMC) and palmitic acid
(weight ratio 3:1); of edible chitosan films, at aw = 0.77 (according to Vojdani and Torres, 1989b
and 1990); and of edible pectin films, at aw = l.0 (according to De Savoye et al., 1994).0, MC; .,
MC and palmitic acid; D, HPMC; ., HPMC and palmitic acid; ... , chitosan; 6, pectin (SAP X
0.005).
0.3
0.2
0.1
0.0 ;-~--.__-,-__,r_-.-__r--~_r--.--....---,.--..,._~__l
2 3 4 5 6 7 8 9
pH
Figure 5.9 Effect of pH on sorbic acid permeability of edible mUlticomponent films (.) composed
of methylcellulose and palmitic acid (weight ratio 3: 1), at a w = 0.77 and 24°e (according to Rico-
Pena and Torres, 1991) and of edible pectin (Psa X 0.01) films (D) at aw = l.0 and 20 0e (according
to De Savoye et at., 1994).
barrier layers double the shelf-life of the food product before the appearance
of microorganisms. Torres et aZ. (1985b) have assessed the potential sorbic
acid retention efficiencies of edible films according to utilization conditions.
For example, a composite film (methylcellulose-palmitic acid) applied to a
food item (at pH = 5.0 and aw = 0.8) stored at 24°C reduces the amount of
sorbic acid diffused in the food mass by more than 50%. The effect that
edible active film (according to sorbic acid permeability) has on increased
surface microbial stability has been estimated by Torres (1987). For
example, with the use of a methYlcellulose and palmitic acid (weight ratio =
3:1) edible film on food stored at 24°C, then the permeability = 0.042 g mm
m-2 24 h- l (g/l)-l; the surface protection can be predicted to last 30 and 120
days for a 0.1 mm film and 0.2 mm film respectively. If the item is stored
under refrigeration (at 5°C), these values increase to 82 and 328 days
respectively (Torres, 1987; Vojdani and Torres, 1989a). According to these
authors, these estimations need to be confirmed using a specific food system
and challenging microorganism.
Guilbert (1988) conducted microbiological tests on intermediate moisture
fruit pieces (Table 5.7). Significant improvement of the microbial stability
was observed with coatings containing sorbic acid and no spoilage could be
detected after 40 days' storage in the case of papaya cubes coated with
carnauba wax containing sorbic acid. The coating efficiencies were in the
following order: carnauba wax + sorbic acid > carnauba wax > casein +
sorbic acid > casein > no coating. The fact that casein film with sorbic acid
was less effective than the carnauba wax with sorbic acid may be explained
EDIBLE ACTIVE LAYERS 133
Table 5.7 Stability of coated intennediate moisture papaya cubes (as a function of aw) at 30°C
inoculated with A,pergillus niger(a) or Staphylococcus rouxii(b)
Delay for first apparent spoilage aw aw aw aw
(days) 0.71 0.75 0.84 0.90
Control (non coated) (a) >40 >40 13 4
(b) >40 >40 3 I
Coated with casein (a) >40 >40 12 4
(b) >40 >40 2 2
Coated with casein and sorbic acid (a) >40 >40 22 10
(b) >40 >40 >40 17
Coated with camauba wax (a) >40 >40 >28 10
(b) >40 >40 >40 14
Coated with camauba wax and (a) >40 >40 32 10
sorbic acid (b) >40 >40 >40 >40
(According to Guilbert, 1988.)
by the poor retention properties and the high initial pH of the casein film
(Guilbert, 1988).
The improvement of food microbial stability can also be obtained by
reducing surface pH. This can be achieved by using films or coatings that
immobilize either specific acids or charged macromolecules. Torres and
Karel (1985) succeeded in obtaining a temporary pH difference between the
surface and the core of intermediate moisture foods by adding lactic acid to
zein-based edible films. The development of edible films that immobilize
(reduced pH swface)
2.0
o 2 4 6 8 10 12
Time (days)
Figure 5.10 Effect of reduced surface pH on the microbiological quality of an intennediate moisture
cheese analog coated with a carrageenan and agarose film; challenged with Staphylococcus aureus
S-6 (aw = 0.88 and 35°C) (after Torres and Karel, 1985).
134 ACTIVE FOOD PACKAGING
5.5 Conclusion
Edible films and coatings can be used to control gas exchange (water vapor,
oxygen, carbon dioxide, etc.) between the food product and the ambient
atmosphere, or between components in a mixed food product, and to modify
and control food surface conditions (pH, level of specific functional agents,
etc.). It should be stressed that the characteristics of the film or coating and
the application technique must be adapted to each specific utilization.
Edible superficial layers provide supplementary and sometimes essential
means to control physiological, microbiological and physicochemical chan-
ges in food products. The active edible layers concept can thus be extended
to new fully adapted superficial or internal applications for food products.
Among these new potential applications, layers enriched with susceptors for
microwave treatments or with catalyst for specific reactions on the one hand,
or with flavor, preservative, ethanol, etc., for slow-release systems on the
other hand, can be mentioned. The development of an active edible layer is
mainly limited by formulation constraints, i.e. the layer composition must be
compatible with the product characteristics and regulation, and by industrial
EDIBLE ACTIVE LAYERS 135
Acknowledgements
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6 Interactive packaging involving sachet
technology
J.P. SMITH, J. HOSHINO and Y. ABE
6.1 Introduction
Over the past decade, there has been a tremendous growth in interactive
packaging for shelf-life extension of food. Packaging can be defined as
'interactive' when it 'performs some role in the preservation of the food
other than providing an inert barrier to outside influences' (Rooney, 1992).
There are many examples of interactive packaging technologies including
antimicrobial and antioxidant films, ethylene absorbing sachets and tem-
perature control indicators, some of which have been discussed in previous
chapters of this text. However, perhaps one of the best examples of
interactive packaging, and one which fulfils the above definition in all
aspects, is modified atmosphere packaging (MAP). MAP has been defined as
'the enclosure of food products in a high gas barrier film in which the
gaseous environment has been changed or modified to slow respiration rates,
reduce microbiological growth and retard enzymatic spoilage with the intent
of extending shelf-life' (Young et ai., 1988). The growth in MAP
technology has resulted from advances in packaging technology, the food
industry's need for less energy-intensive forms of food preservation than
drying, freezing or thermal processing, and consumer needs for convenience
foods with extended shelf-life yet retaining their fresh characteristics. The
atmosphere in MAP foods has traditionally been modified by vacuum or gas
packaging, the latter involving various mixtures of CO 2, either alone or in
conjunction with nitrogen and sometimes oxygen depending on the product
gas packaged, e.g., meat or fruits and vegetables (Smith et ai., 1990).
Although this form of interactive packaging can be used to extend the shelf
life and keeping quality of food, aerobic spoilage can still occur in these
packaged products depending on the level of residual oxygen in the package
headspace. The level of residual oxygen in vacuum/gas packaged products
could be due to a number of factors such as oxygen permeability of the
packaging material; ability of the food to trap air; leakage of air through
poor sealing; and inadequate evacuation and/or gas flushing (Smith et ai.,
1986).
In recent years, novel methods of oxygen control and atmosphere
modification have been developed, primarily by the Japanese. These include
144 ACTIVE FOOD PACKAGING
North America and Europe has been slow, although several major
companies in both continents are now using this technology.
Oxygen absorbents comprise of easily oxidizable substances usually
contained in sachets made of air-permeable material. These sachets come in
a variety of sizes capable of absorbing 20-2000ml of headspace oxygen.
When placed inside the packaged food, they actively modify the package
headspace and reduce the oxygen levels to < 0.01% within 1-4 days at
room temperature. However, some are designed to scavenge oxygen at
refrigerated or frozen storage temperatures and are used to further extend the
shelf-life and keeping quality of muscle foods. This oxygen-free environ-
ment protects the food from microbiological and chemical spoilage and is
also effective in preventing damage by insects. A combination of some or all
of these factors helps maintain the quality and freshness of food, which
facilitates the marketing of oxygen absorbents. The classification and the
main types of oxygen absorbents will now be briefly reviewed.
absorption reaction only takes place after moisture has been absorbed from
the food; these type of absorbents are easier to handle as they do not react
immediately upon exposure to air. However, they absorb oxygen quickly
after sealing and oxygen can be absorbed within 0.5-1 day in certain
products. Examples of self-reacting and moisture dependent types of oxygen
absorbents are shown in Table 6.2.
20
~
c:
0
+'
....
«I
.....
c:
Q)
Col 10
c:
0
Col
....
(:)
o 1 2 3
Time (day)
Figure 6.1 Effect of storage temperature on oxygen absorbing speed of Ageless S-lOO, a self
working type (fast working type) of oxygen absorber.
.-.
~
-
c
CI
...
:;:::l
C'CI
c
II)
c
u 10
CI
u
....
CI
Time (day)
Figure 6.2 Effect of storage temperature on oxygen absorbing speed of Ageless Z-IOO, a self
working type (medium working type) of oxygen absorber.
148 ACTIVE FOOD PACKAGING
20
~
-
c:
0
:j:j
15
....
~
cQ):
u
c: 10
0
u
0'"
5
Time (day>
Figure 6.3 Effect of frozen temperature (-2S°C) on oxygen absorbing speed of three types of
oxygen absorbents.
SACHET TECHNOLOGY 149
Type Z is designed for food products with water activities of less than
0.65 and reduces residual headspace oxygen to 100 ppm in 1-3 days. It is
available in sizes that can scavenge 20-2000 ml of oxygen (an air volume of
100-10 000 ml).
Two other types of Ageless (FX and S) work best at higher water
activities and have a faster reaction rate (0.5-2 days). They have the same
oxygen scavenging capacity as above. Type FX is moisture dependent and
does not absorb oxygen until it is exposed to an aw greater than 0.85. Thus,
it can be easily handled if kept dry. Type S, on the other hand, contains
moisture in the sachet and is a self-working type. This type of absorbent
requires careful handling since it begins to react immediately on exposure to
oxygen. Absorbent type SS is similar to type S. However, it has the ability
to rapidly scavenge oxygen under refrigerated and frozen storage conditions.
These absorbents (Ageless type SS) are widely used to extend the
refrigerated shelf-life of muscle foods such as fresh meat, fish and poultry.
Yet another new absorbent is type FM which can be used with micro-
waveable products (Table 6.3).
A commonly used absorbent is type E which also contains Ca(OH)2 in
addition to iron powder. Type E scavenges CO2 as well as 02' It is used for
ground coffee, where CO2 removal reduces the chance of the package
bursting. Marketed under the brand name Fresh Lock, it is used in Maxwell
House ground coffee cans (Table 6.3).
Two other types commonly used in the Japanese market are type G and
type SE. Type G is a self-working type and absorbs oxygen and generates an
equal volume of CO2, It is used mainly with snack food products, such as
nuts, to maintain the package volume and hence appearance of the product.
Another new innovation is Ageless type SE. This absorbent is moisture
dependent and absorbs oxygen and generates ethanol vapor. It is used to
extend the mold-free shelf-life of bakery products in Japan. The various
types of Ageless and their characteristics are summarized in Table 6.3.
SACHET TECHNOLOGY 151
bD
C
C
~
.........
bD 300 AGELESS
E
280 " ,
(.)
:>
240
220
--------------------
.....
«i
I-
Q
200
T
2 3 4 5 6 7
(MONTHS)
Figure 6.4 Effect of an oxygen absorbent on the vitamin C content of Green tea. Bag made from
oriented nylon/polyethylene/foil/polyethylene. Conditions: Material. 100 g; air, 200 ml; storage
temperature, 25°C; absorber, Ageless Z-50.
S N 2 gas
-
b Il
~
120 F
C'
Q)
E 100
80
Q)
:::I
"i6
>
Q)
"0 60
...c.
')(
Q
Q)
40
::-
AGELESS
c
c..
20
~~~-===~==~===~
0 30 60 90 120 150
Time (day)
Figure 6.5 Effect of oxygen absorbents on the peroxide value (POV) of packaged fried rice cakes
by comparison under photo-irradiation. S, Sunlight; F, fluorescent light.
SACHET TECHNOLOGY 155
absorbents for shelf life extension of food can be found in the excellent
articles referenced at the beginning of this section.
6.2.4.2 In the USA. While oxygen absorbents are used extensively in Japan,
their use in North America is still in its infancy. Examples of the known US
companies currently using oxygen absorbents for shelf-life extension of
products are shown in Table 6.12. The earliest use of this technology was with
Maxwell House coffee which used a dual function absorbent (Ageless E). This
absorbent, marketed under the trade name Fresh Lock, contains iron powder
for absorption of oxygen and calcium hydroxide which scavenges carbon
dioxide. The use of this absorbent in coffee delays oxidative flavor changes
and absorbs the occluded carbon dioxide produced in the roasting process and,
which if not removed, would cause the packages to burst. More recently, a
mold-free shelf-life of 1 year has been achieved for a specialty therapeutic
gluten-free bread, Ener-Getic. The bread is packaged in a copolymer film of
Mylar/EVOH/Surlyn film with 100% carbon dioxide and a Freshilizer oxygen
absorbent/carbon dioxide generator (type CW) supplied by the Toppan Printing
Company, Japan. The bread remained mold-free for 1 year at room temperature
and physico-chemical changes, i.e., staling, were minimal at the end of storage
in the gluten-free bread (Anon., 1988).
Studies by Powers and Berkowitz (1990) at the US Army Natick Research,
showed that a FreshPax oxygen scavenger enclosed in a high gas barrier pouch
made of polyester/aluminium foil/HDPE with baked, meal ready-to-eat (MRE)
bread prevented mold growth on bread for 13 months at ambient storage
temperature. Based on the results of this study, two companies, Sterling Foods
U\
0\
-
VI
-..l
-
......
U\
00
Table 6.10 Use of Ageless for shelf-life extension of meat and deli products
Water activity of Type and size of
Type of food food Packaging materials Ageless Prevents Shelf-life @ RT
Pizza crust - 0.94--0.95 KON FX200 Mold growth 2 months at 5°C
Pizza 0.99 KON S200 Mold growthlDiscoloration 2 weeks at 5°C
Fresh carved sausage 0.99 KON FX50 Discoloration/Rancidity 3 weeks at 0-4°C
Pre-cooked hamburgers 0.99 PS Tray/KON SIOO DiscolorationlRancidity 3 weeks at 0-4°C
Pre-cooked chicken nuggets 0.99 KON FXlOO DiscolorationlRancidity 3 weeks at 0-4°C
Salami sticks 0.8---D.85 KON Z50 Discoloration 1-2 months
:>
Sliced salami 0.8---D.85 KON SIOO Discoloration I month
9<
tIl
Table 6.11 Use of Ageless for shelf-life extension of miscellaneous products
Water activity of Type and size of 8
tl
Type of food food Packaging materials Ageless Prevents Shelf-life @ RT
~
('J
Rice crackers/fried bean < 0.3 TinIPlastic/Aluminium lid ZIOO OxidationlRancidity I year
Peanuts < 0.3 KON GlOO OxidationlRancidity 6 months
Peanut butter/chocolate coated 0.5---D.6 KONIPaper box Z200 OxidationlRancidity 9 months z~
Cl
Chocolate peanuts 0.5---D.6 KON Z30-IOO OxidationlRancidity 9 months
Candy-type cheese 0.9---D.95 KON FX50 + lOO%N2 OxidationlRancidity I month at 0-4°C
Smoked cheese 0.9 KON S30-50 OxidationIMold growth I month at 0-4°C
Soy bean paste 0.8---D.85 Paper/ACIEVA FX20 Discoloration 3 months
Bakery food (milk powder) < 0.3 Tin can ZIOO OxidationlRancidity 6-12 months
Green tea < 0.3 Tin can Z50 Oxidation I year
Flavored tea 0.5-0.6 KON Z50 Oxidation I year
EVA = ethylene vinyl acetate.
RT = Room Temperature.
SACHET TECHNOLOGY 159
expensive film lif an oxygen absorber pack was included in the package
(Alarcon and Hotchkiss, 1993).
Oxygen absorbents have several advantages for the food processor, both
from a marketing and food quality viewpoint (Harima, 1990; Smith et ai.,
1990; Smith, 1992). These are:
labels cover only one third of the lid surface, providing consumers with a
clearer view of the product yet absorb oxygen and protect products from the
adverse oxidizing effect of light and oxygen on meat pigments (Multiform
Desiccants, personal communication).
package headspace was not significant in affecting the time until toxin
production (Lambert et at., 1991b,c).
In more recent agar plate studies with Listeria monocytogenes, high CO2
levels (> 60%) promoted the growth of this pathogen at 1O-15°C (Morris et
aI., 1994). However, when an oxygen-free environment was achieved using
Ageless SS, growth of L. monocytogenes was completely inhibited even at
mild temperature abuse storage conditions. Further studies are now
underway to determine the antimicrobial efficacy of Ageless SS and gas
packaging on L. monocytogenes in packaged pork.
8.0~-----------------------------------------------.
".2o
"0
CI
o
~ 6.0-
:;;
Co for long term
®
Co
«
to)
~
:i: for short term
tu 4.0 --
~
.
N
0;
/
Gi
J:
~
In
2.0
"~
..
"5
--- --'
cr
II:
O.O--~----~~~~-~'-~-c-~-~-~-~'----~~~~--~~~--L-~~~
0.6 0.7 0.8 0.9 1.0
Water activity of food
Figure 6.6 Relationship between aw of food and required size of Ethicap sachet. Short term, 1-2
weeks; long term, 8-13 weeks. (Reproduced with permission from the Freund Technical Co., Ltd.,
Japan.)
168 ACTIVE FOOD PACKAGING
2.0
1.5
>
...
~
..J
0
Z
C
...
w
:J:
1.0
w
(.J
----~----.-----.
...c
'"C
Q
w
:J:
0.5
o L-__~----~--------~----~----~--~
3 5 10 12 14 16
Figure 6.7 Effect of water activity Caw) on generation and absorption of ethanol vapor. ., 0.85 + E4 ;
6 0.95 + E4 ; . , 0.99 + E4 ; 0, 0.85 + E\; ... , 0.95 + E\; 0, 0.99 + E\.
inhibit mold growth, indicating that the ethanol vapor also exerts an anti-
staling effect (Freund Technical Information, 1985). Ethicap is also widely
used in Japan to extend the shelf-life of semi-moist and dry fish products.
Examples of bakery and fish products preserved by Ethicap in the Japanese
market are shown in Table 6.17.
Pafumi and Durham (1987) also found that the mold-free shelf-life of 200
g Madeira cake could be extended for about 6 weeks at room temperature
using a 3 G sachet of Ethicap. However, there was a significant change in
Table 6.17 Use of Ethicap for shelf-life extension of food (adapted from Freund Technical
Information, 1985)
Size of Packaging
Food aw of food Ethicap material Shelf-life @ RT
Bakery products
Bread 0.92 IG OPP 1 week
Cupcake 0.85 3G OPP/pP 2 months
Jam doughnut 0.83 3G OPP 20 days
American cake 0.80 2G OPP/pP 6 months
Rice cake 0.76 4G OPP/pP 2 months
Chocolate sponge cake 0.72 2G OPP/pP 6 months
Fish products
Smoked squid 0.85 IG OPP 3 months
Boiled squid 0.68 0.6G OPP 3 months
Boiled & dried squid 0.69 0.6G OPP/pE 2 months
Boiled & dried small fish 0.63 IG OPP 3 months
170 ACTIVE FOOD PACKAGING
6.4 Conclusion
In conclusion, the use of gas absorbents and ethanol vapor generators is,
without doubt, one of the most exciting interactive packaging technologies
available to the food industry. While both oxygen absorbent technology and
ethanol vapor generators are used extensively in Japan to extend the shelf-
life and keeping quality of a variety of products, their use to date in the
North American market is limited due to the cost of the sachets, consumer
resistance to the inclusion of sachets in packaged products and lack of
regulatory approval for Ethicap. Nevertheless, the use of gas absorbents/
ethanol vapor generator sachets or labels offers the food industry a more
viable alternative method of interactive packaging than vacuum/gas flushing
for shelf-life extension of its products.
References
Morris, J., Smith, J.P., Tarte, I. and Farber, J. (1994) Combined effect of chitosan and MAP
on the growth of Listeria monocytogenes. Food Microbiology; (Submitted for publica-
tion).
Nakamura, H. and Hoshino, J. (1983) Techniques for the preservation of food by the
employment of an oxygen absorber. Mitsubishi Gas Chemical Co., Tokyo, Japan, 1-45.
Ooraikul, B. (ed.) (1993) Modified Atmosphere Packaging of Food, Ellis Horwood PubL, New
York, NY, pp. 49-117.
Pafumi, J. and Durham, R. (1987) Cake shelf life extension. Food Technology in Australia, 39,
286-7.
Palumbo, S.A. (1986) Is refrigeration enough to restrain food borne pathogens? 1. Food
Protection, 49, 1003-9.
Plemons, R.F., Staff, C.H. and Cameron, F.R. (1976) Process for retarding mold growth in
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Powers, E.M. and Berkowitz, D. (1990) Efficacy of an oxygen scavenger to modify the
atmosphere and prevent mold growth in meal, ready-to-eat pouched bread. 1. Food
Protection, 53, 767-71.
Rooney, M. (1992) Reactive Packaging Materials for Food Preservation. In: Proceedings of
the First Japan-Australia Workshop on Food Processing, Tsukuba, Japan, pp. 78-82.
Seiler, D.A.L. (1978) The microbiology of cake and its ingredients. Food Trade Review, 48,
339-44.
Seiler, D.A.L. (1988) Microbiological problems associated with cereal based foods. Food
Science and Technology Today, 2, 37-41.
Seiler, D.A.L. and Russell, N.J. (1993) Food Preservatives, Blackie Academic & Professional,
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Shapero, M., Nelson, D.A. and Labuza, T.P. (1978) Ethanol inhibition of Staphylococcus
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Smith, J.P., Ooraikul, B., Koersen, W.J. and Jackson, E.D. (1986) Novel approach to oxygen
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Smith, J.P., Ooraiku1, B., Koersen, W.J., van de Voort, F.R., Jackson, E.D. and Lawrence,
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7 Enzymes as active packaging agents
A.L. BRODY and J.A. BUDNY
7.1 Enzymes
Enzymes are biological catalysts which are found in all living cells, whether
plant or animal. These macromolecular proteins exhibit two outstanding
characteristics in addition to the fact that they occur naturally and are found
in living systems.
The first characteristic is their catalytic power. Enzymes accelerate
chemical reactions that occur in biological systems by factors that exceed a
million over their uncatalyzed rate. In essence, enzymes allow living
systems to carry out reactions that would not ordinarily occur or occur so
slowly that the rates would not be of any practical significance. A simple
reaction of the formation of carbonic acid from carbon dioxide and water
occurs 107 times faster with the enzyme carbonic anhydrase than the non-
enzymatic or chemical reaction.
ENZYMES 175
7.3 History
Although many enzymes and their roles have been known for several
decades, the notion of incorporating them into package materials to achieve
a desirable result dates back only to the 1940s. Almost simultaneously with
the idea of protecting against browning of dry foods such as eggs by
removing residual oxygen, the notion of in-package glucose oxidase/catalase
reactions was born. In reality, the initial action of glucose oxidase is with
residual quantities of glucose, a reducing sugar active in the non-enzymatic,
non-oxidative Maillard browning reactions. Highly reactive hydrogen
peroxide is produced by glucose oxidase, and is removed by catalase which
breaks it into water and oxygen. This concept was put into practice by
employing porous packets of the enzyme mix in which the enzymes slowly
reacted with minute quantities of residual oxygen, an analogue of the
commercial incorporation of sachets of desiccants to reduce the in-package
relative humidity. The applications during the 1940s and 1950s appear to
have been largely confined to very long term storage of military foods.
The concern for the adverse effects of temperature abuse on frozen foods
led to numerous ventures into development of time-temperature indicators,
among which have been enzymatically actuated versions, beginning in the
1970s.
The exponential growth of modified atmosphere packaging in the 1980s
led to the notions of oxygen and carbon dioxide and moisture control using
in-package sachets of chemicals. Some enzymatic agents were included in
these chemicals.
Towards the end of the 1980s, interest increased with the formation of
PharmaCal, Ltd. whose objective was to develop the application of enzymes
in unit size situations. This company and its principal, the co-author of this
article, suggested and, in some instances, physically evaluated three areas in
which immobilized enzymes within package structures would catalyze
reactions of products contained within packages.
• Lactase to remove lactose.
• Cholesterol reductase to remove cholesterol.
• Glucose oxidaselcatalase to remove oxygen.
Whether or not the communications emanating from PharmaCal were
ENZYMES 179
the product. Expressed differently, this patent does not indicate that the
enzymes are either part of the package structure or in an independent packet
within the primary package. Thus, although the 1949 patent described
perhaps for the first time the employment of enzymes to eliminate in-
package oxygen, it did not indicate that the enzymes were part of the
package material or structure.
This concept of enzyme incorporation into a package material was first
overtly described in a 1956 patent (Sarett, 1956). (Sarett, incidentally, was
the assignee for the Baker patent.) In this patent, the same basic enzymatic
reactions as in the Baker patent were reiterated as a reference, but the
enzymes glucose oxidase and catalase in a solution were impregnated into or
on a moistureproof or fabric sheet. The enzyme was bound to the sheet with
a water-dispersible adhesive such as polyvinyl alcohol, starch, casein or
carboxymethyl cellulose. The enzyme-coating face must contact the moist
product to ensure that the requisite oxygen reduction reactions take place.
The enzyme system was indicated to serve as a barrier to oxygen which
would otherwise be transmitted through the sheet. Products described as
being benefited by this system of oxygen reduction include cheese, butter,
frozen foods subject to browning, etc.
Although during the period of the patent a Kraft packaging paper called
moistureproof (which, as it happens, was not actually moistureproof) was
often used to package butter and cheese, the patent does not indicate the use
of this material. Rather, the package material is described as having ' ... an
exposed surface covered with a gas-permeable packaging material and
having an inter layer between and in contact with packaging material and ...
food ... inter layer providing an oxygen barrier. ... ' The specific package
materials identified were moistureproof cellophane, paper, rubber hydrochlo-
ride with impregnation employed for the papers and coating for the plastic
and cellulose films. Also cited as being suitable substrates were wax paper,
styrene, polyethylene and vinyls.
Experiments discussed in the body of the patent indicated results in which
oxidation of cheese surfaces was retarded by the presence of the enzyme-
containing package material.
In 1958, Scott (co-inventor on the 1956 Sarett patent) of Fermco
Laboratories, published a paper on Enzymatic Oxygen Removal from
Packaged Foods in which enzymes were incorporated into packaging
materials or introduced into packets. Fermco Laboratories was a manu-
facturer of enzymes, one category of which was labeled Fermcozyme
antioxidants, and of the packets which were named Oxyban. This paper
marked the first publication to our knowledge on the use of packets of
chemicals in packages.
The glucose oxidaselcatalase systems were derived from mold mycelia
which were disrupted, filtered and further purified. To be effective in
ENZYMES 181
The inventors noted that with increasing temperature, the gas permeability
of package materials increases and so also does the ability of the enzyme
system to reduce the oxygen content from the 20.9% of air to about 1% at
ambient temperature within 24 hours.
From technological and potential commercial perspectives, this Finnish
work is so precise as to imply a major advance in the ability to implement
the principles of enzymes as active package components.
Co-author Budny and his company PharmaCal, Ltd. have been actively
researching enzymes for active packaging since the 1980s. The contribution
of PharmaCal, Ltd. to enzymes in active packaging was to expand the
concept of packaging beyond the two long-regarded functions of packaging:
containment of the product; and protection of the contents. These require-
ments originally were embodied in wine skins that ancient goat- and sheep-
herders used for their sustenance beverages. Throughout history, while there
have been advancements in materials and approaches, there have not been
any fundamental changes or additions to the necessary requirements for
containers or packages. Whether they are animal skins, a lid or a multi-layer
stock, they should protect the contents and not leak.
PharmaCal, Ltd. added a third dimension to packaging by allowing an
individual package to become a processing unit or to perform a process step
or function that previously was limited to in-plant operations. With a
combination of patent applications and proprietary technology, PharmaCal,
Ltd. has been able to expand the concept of packaging to include processing
steps, value-addition to packaged products and increased processing effi-
ciencies.
PharmaCal, Ltd. has developed a two-enzyme system involving glucose
oxidase and catalase to intercept oxygen and has applied the technology for
enzymes in active packaging to improve the proven concept of oxygen
removal with the dual enzyme system of glucose oxidase and catalase. The
use of the enzymes to remove oxygen has been acknowledged as not new,
but their role in enzyme-based active packaging has been regarded as a more
advanced application. Figure 7.1 illustrates the mechanism in which
packaged liquid reacts enzymatically with glucose in the package wall to
form gluconate. The resulting hydrogen peroxide is enzymatically reacted
with catalase to produce oxygen and water that re-enter the contained
product liquid.
A container with an internal reactor, in reality an integral section of the
package wall through which the liquid contents may flow, permits the
enzymes to be retained for a reaction described in a 1989 patent application
(Budny, 1989).
A 1991 patent (Ernst, 1991), described a glucose/glucose oxidase enzyme
mixture in a porous precipitated silica acid carrier. Calcium carbonate,
calcium hydrogen phosphate, magnesium carbonate or disodium hydrogen
184 ACTIVE FOOD PACKAGING
Head
space
Packaged
liquid
°2
-+-- H2 0
Outside
of
container Inside of container
Container wall
Labuza and Breen (1989) have analyzed the issues involved in the
incorporation of glucose oxidase into package materials.
To counteract the quantity of oxygen passing through an aluminum foil
lamination an enzyme surface will have to react with oxygen in the
following manner:
Rate = permeability X area X oxygen pressure difference
between the outside and inside
Rate = 0.1 X 1 [0.21 - 0.01] = 0.2 m1 per day per m2
= 20 ILl/day
The calculation above assumes air outside and < 1% oxygen inside. For the
worst case and with a pinhole or cracked score, there would be the need to
scavenge 1 rnl/day. A film could be made equivalent to a barrier by binding
the oxygen scavenging enzyme to the inside surface of the film to react with
the excess oxygen.
Glucose oxidase transfers two hydrogens from the -CHOH group of
glucose to oxygen with the formation of glucono-delta-lactone and hydrogen
peroxide. The lactone then spontaneously reacts with water to form gluconic
acid. One mole of glucose will consume one mole of oxygen and so a
package with 500 m1 heads pace is required, to reach zero oxygen, with only
0.0043 mole of glucose needed as a substrate. The major factors are the
speed at which the enzyme works, the amount of glucose available, and the
rate at which oxygen permeates into the package. In the presence of catalase,
a normal contaminant of commercial glucose oxidase, the hydrogen
peroxide is broken down, and so with catalase one mole of glucose will react
with only a half mole of oxygen, decreasing the overall effectiveness of the
system. Pure glucose oxidase without catalase is reportedly expensive.
If no surface exists for the peroxide for diffusion, the glucose oxidase will
be inactivated, precluding this application. Since many foods may have
minimal contact with the package surface, except on the sides and bottom,
this may not be the best approach for oxygen scavenging.
At 30-40°C, pure glucose oxidase has a rate of oxygen consumption of
about 150000 fllIh/mg. Based on this, and spreading 1 mg per m2 on a film,
this would be equivalent to reacting with all the oxygen passing through a
film with an oxygen permeability of about 18000 rnl/day m2 atm.
Thus at room temperature, aIm square surface with 1 mg of enzyme
spread out on it should be able to handle all the oxygen passing through any
package film. One advantage is that both polypropylene and polyethylene
are good substrates for immobilizing enzymes. One factor to take into
account is the stability of the enzyme when bound to the film. An unknown
factor is how stable the enzyme will be on the film over time. Glucose
oxidase bound to a plastic surface has been shown to undergo a 50% drop in
activity in 2-3 weeks followed by little loss over the next four weeks.
186 ACTIVE FOOD PACKAGING
during the early 1980s) demonstrated that the enzyme treatments retarded
the onset and magnitude of adverse microbiologically triggered spoilage
odors. The researchers explained the result as due to reductions in surface
pH under the refrigerated conditions of the test. These changes influenced
the metabolism of putrefactive microorganisms. They also suggested that the
generation of hydrogen peroxide might inhibit the growth of psychrotropic
microorganisms which are reported to be sensitive to the chemicals used.
Other possible microbistatic agents include gluconic acid, reportedly a metal
complexing agent, and gluconolactone, reported to be a binding agent for
water and metal ions. Another factor reported by the group was an altered
gaseous microenvironment in which oxygen in the muscle interstices was
depleted by the enzymatic action thus retarding the growth of aerobic
psychrophiles. This last, of course, is synergistic with the oxygen removal
aspects of the enzyme system.
The authors cited a Japanese patent in which catalase-free glucose oxidase
was demonstrated to be effective in preserving other proteinaceous foods
such as ground chicken and tofu (Fukazawa, 1980).
Although the Rand et al. work did not specifically state the incorporation
of enzymes into package materials, the implications were sufficiently clear
in the examples of the enzyme-containing ice and the enzyme-containing
algin blanket. Either of these could have been relatively easily substituted
with a skin package material which had been surface tested with the enzyme
system. The notion of hydrogen peroxide as an intentional active anti-
microbial agent is somewhat of a contradiction since this chemical is quite
reactive with many food constituents, especially lipids, and residual free
hydrogen peroxide is not readily accepted by regulatory officials. If the
hydrogen peroxide is fully reacted with microorganisms as in aseptic
packaging, however, perhaps the proposed system may warrant further
consideration. Unfortunately, work at the University of Rhode Island on this
topic has been discontinued.
A German patent assigned to Continental Group (Anon. 1977) describes
incorporation of biologically active enzymes into polymers on the interiors
of package structures to destroy microorganisms of contained products. The
enzymes were intended to destroy microorganisms by breaking cell walls
and also to consume oxygen, thus increasing shelf-life without heat. The
applicable products were beer and fruit juices.
Enzymes such as muramidase for cell wall destruction and glucose
oxidase for oxygen interception were attached to the internal polymer by
covalent bonds. 'Non-essential' functional groups such as NH2 , COOH, OH
phenol, imidazole and sulfhydryl were cited as examples.
The polymer was described as a terpolymer of monomer alkyl acrylate
and vinyl aromatic applied to the interior of a glass container from a solvent
and dried by heat. The enzyme was subsequently applied as a coating from
an aqueous dispersion.
188 ACTIVE FOOD PACKAGING
For many years, efforts have been underway to develop a practical, accurate,
reliable and economic indicator of total temperature-time exposure of food
products. Among the routes has been the application of the principles of
temperature sensitivities of enzymes. Although the original objectives were
aimed at frozen food defrosting devices, more recent interest has been
focused on chilled foods. Among the issues are activation only when
actually at the beginning of shelf-life, accuracy over the entire range, how
reflective the integrator-indicator is of the actual temperature-time experi-
ence, and another basic question, how well the measurement represents the
effect of the temperature-time integral on the food itself.
Kramer and Farquhar (1976) listed a number of the problems in their
evaluation of five commercial, time-temperature indicating and defrosting
devices. No descriptions were given the mechanisms for sensing, integrating
or measuring time-temperature.
On the other hand, Blixt and Tim (1976) described a commercial
enzymatic time-temperature monitor, called I-point® TTM. The authors, of
Kockums Chemicals of Malmo, Sweden, stated that their device met all the
requirements of reliability, accuracy, size, cost, understandable message and
ability to integrate '... both length and degree of all temperature
exposures.'
The reaction was based on enzymatic degradation to colored end points.
The device was a two-part system, one containing an enzyme and pH
indicator since the system was based on pH change caused by enzymatic
activity plus a substrate. Because of the enzymatic core of the pH change,
the temperature response was exponential with increasing temperature, and
so evidently indicative of actual biochemical changes arising due to the
temperature-time experience. Although the indicators reportedly functioned
very effectively, no reference was made to the type of enzyme used. One
might speculate on the simple glucose oxidase-catalase system producing
gluconic acid as the reaction proceeded.
This product was another manifestation of the application of enzymes in
package systems to an inactive mode.
A 1989 US patent (Klibanov and Dordich, 1989) claimed a temperature-
change indicator composed of an enzyme and substrate, a colorimetric
ENZYMES 189
o Glucose
--+_----t~ V Galactose
Q) Lactose
Outside
Container Inside of container
of
container wall
Cholesterol
reductase
~Oo/
enzyme
~ &
Coprosterol
~O Cholesterol
References
Anon. (1977) Packaged foods and drinks in containers coated internally with polymer carrying
enzyme with sterilising action. German Patent DE2817854A.
Anon. (1990) Packaged milk containing lactose enzyme-giving milk with reduced lactose
content. UK Patent Application.
Baker. D.L. (1949) Deoxygenation Process. 20 September. US Patent 2482724.
Best. D. (1990) Fermentation opportunities ripen. Prepared Foods, 159, 5.
Blixt, K. and Tim, M. (1977) An Enzymatic Timenemperature Device for Monitoring the
Handling of Perishable Commodities. International Symposium on Freeze-Drying Biolog-
ical Products, 36, 237.
Budny, J. (1989) A transporting storage or dispensing container with enzymatic reactor.
International Patent Application W089/06273.
Budny, J. (1990) Presentation at Pack Alimentaire, San Francisco, California, May.
192 ACTIVE FOOD PACKAGING
Copeland, J.e., Adler, H.I. and Crow, W.D. (1991) Method and composition for removing
oxygen from solutions containing alcohols and/or acids. US Patent 4996073.
Copeland, RA. (1994) Enzymes, the catalysts of life. Today's Chemist at Work, March.
Courtland, S.B., McGrew, G.N. and Richey, L. (1992) Food packaging improvements, 30 June.
US Patent 5126174.
Ernst, R. (1991) Oxygen absorbent and use thereof, 2 July. US Patent 5028578.
Field, C., Pivarnik, L.F., Barnett, S.M. and Rand, A.G. (1986) Utilization of glucose oxidase
for extending the shelf-life of fish. J. Food Science, 51.
Fukazawa, R. (1980) Methods of preveJ1ting spoilage of foods. Japanese Patent 23071180.
Hopkins, T.R, Smith, V.J. and Banasiak, D.S. (1991) Process utilizing alcohol oxidase, 10
December. DS Patent 5071660.
Klibanov, A.M. and Dordich, J.S. (1989) Enzymatic temperature change indicator, 2 May. DS
Patent 4826762.
Kramer, A. and Farquhar, J.W. (1976) Testing of time-temperature indicating and defrost
devices. Food Technology, 30, 56.
Labuza, T. and Breen, W. (1989) Active Packaging. J. Food Processing and Preservation, 13,
1.
Lehtonen, P., Karilainen, D., Jaakkola Rand KymoHiinen, S. (1991) A packaging material
which removes oxygen from a package and a method of producing the material. International
Patent Application WO 91/13556.
Sarett, B.L. and Scott, D. (1956) Enzyme treated sheet product and article wrapped therewith.
DS Patent 2765233.
Scott, D. (1958) Enzymatic oxygen removal from packaged foods. Food Technology, 12(7),
7.
Scott, Don and Hammer, F. (1961) Oxygen scavenging packet for in-packet deoxygenation.
Food Technology, 15(12), 99.
Scott, D. (1965) Oxidoreductase. Enzymes in Food Processing, Academic Press, NY.
Thomas, K. and Harrison, RJ. (1985) Method and apparatus for secondary fermentation of
beverages. DK Patent Application 2143544A.
Wiseman, A. (1975) Enzyme utilization in industrial processes, Handbook of Enzyme
Biotechnology, Ellis Horwood, DK.
8 The history of oxygen scavenger bottle closures
F.N. TEUMAC
8.1 Background
The early history of the use of scavenger chemicals with beer has played an
important part in the development of oxygen scavenger closures.
Gray, Stone, and Atkin (1948) measured oxygen content of bottled beer
and correlated oxygen presence with off-flavor development. The report
made to the American Society of Brewing Chemists concluded that the
addition of anti-oxidants to beer should be studied. The prime candidates
were sulfites and ascorbic acid.
Thomson (1952) reported extensions of the earlier work in the Brewers'
Guild Journal. He found that the use of reductones made from sugar reduces
oxygen, but increases the level of calcium to a level that forms hazes. The
reactions with sulfur dioxide, sodium formate, and phosphites were too
slow. He recommended adding ascorbic acid just prior to bottle filling.
Reinke, Hoag, and Kincaid (1963) reported that the inclusion of oxygen
scavengers in the lining of cans improves the storage stability of canned
beer. Glucose oxidase-catalase was preferred to sulfur dioxide and iso-
ascorbic acid.
Klimovitz and Kindraka (1989) published in the Master Brewers
Association of the Americas Technical Quarterly that a combination of
sodium isoascorbate and potassium metasulfite when added to the silica
hydrogel mixing tanks significantly improved product flavor stability.
argon is detected directly. Because nitrogen and argon do not react with the
bottle contents, other data can be gained by comparing the ratios of the three
gases. The total oxygen and nitrogen can be calculated from the measured
headspace, the temperature, and the oxygen and nitrogen concentration in
the head-space.
Liquid samples can be withdrawn and measured with polarographic
techniques. Again, the bottle should first be equilibrated. The total oxygen of
the bottle can be calculated.
Since the Zahm-Nagel device pierces the closure, each bottle can only be
sampled once. In order to follow the changes in the bottles, it must be
assumed that all the bottles were the same at bottling. This requires the most
reproducible conditions possible.
Depending upon the equipment capability of the brewer, the oxygen content
of bottled beer can be seen to correspond to three categories of brewer:
• Brewers incapable of performing a final blow down with purified carbon
dioxide and without new high technology fillers. The initial oxygen in
the package is about 1700 ppb. This decreases by 30% during
pasteurization, 42% the first day, 54% the second day, and 95% in a
week. The reaction of oxygen with the bottle contents is rapid. These
brewers usually compensate by adding 10 ppm or more of sulfur dioxide
to the beer.
• Brewers capable of good oxygen control up to the last step, but do not
have new high technology fillers. These brewers provide an initial
oxygen content of about 900 ppb. The oxygen depletion in the bottle
proceeds at the same percentage rate as in the first category.
• Brewers that use the best equipment available. The initial values vary
because maintaining the lower value requires the filler to be in top
condition. An initial value of 400 ppb is common. Brewers using 10 ppm
or more of sulfur dioxide obtain values of 200 ppb oxygen; brewers with
8 or less ppm sulfur dioxide experience values of 350-800 ppb of
oxygen depending on the maintenance of the equipment. The oxygen
depletion in the bottle proceeds at the same percentage rate as for the
other two classes.
The effect on flavor deterioration of bottling under different conditions is
difficult to gauge. Each beer is different, so comparisons must be made on
different crowns under the exact same bottling conditions on the same batch
of beer. The few valid comparisons made prior to the introduction of
scavenging crowns indicated that beer bottled with less oxygen had better
shelf-life.
HISTORY OF OXYGEN SCAVENGER BOTTLE CLOSURES 195
Closure of the bottle does not mean that the battle with oxygen is over. For
years a crown or closure was defined as a hermetic seal. Wisk and Siebert
(1987) at Stroh and Heyningen et al. (1987) at Heineken separately
challenged this assumption and came to the same conclusion: crowns allow
oxygen ingress. ZapatA Industries studied oxygen ingress in crowns;
Teumac, Ross and Rassouli (1990) confirmed the earlier conclusions, and
recommended some improvements to eliminate oxygen ingress. This work
was extended to include both plastic and aluminum closures (1991). The
concept of oxygen ingress into the bottle gained slow acceptance because it
is difficult to envision how oxygen will penetrate a bottle with 3
atmospheres of pressure within from an ambient pressure of 1 atmosphere.
The phenomenon has, however, been proven using several techniques by
several workers in the references cited above. It is based on a well
established equation that describes permeability through a permeable
polymer (the liner or gasket).
PERMEABILITY =P (A X p)
L
Permeability as used here means the flow of any gas per unit of time. For a
container, it is the flow of a specific gas through the portion of the container
in question. P is the permeability coefficient; this is determined empirically
for a specific polymer or polymer compound and is specific to the gas and
the conditions of the test. A is the area of the compound surface involved in
the transfer. As metal has no permeability, A for a crown is the area of the
liner compound between the metal and the glass. An aluminum closure
provides a very small area. A plastic closure is totally made up of permeable
material, so the area is quite large. L is the length of the route followed by
the gas. p is the driving force of each gas. It is the difference in the partial
pressure between the respective sides of the liner. It should be emphasized
that it is not the total pressure; it is the partial pressure of the particular gas.
A pressure of three atmospheres in a bottle does not mean that all gases will
move outward from a bottle. If there were a physical leak, that would be the
case. For a polymeric material like PVc, EVA, or polypropylene, gas will
flow from the higher partial pressure to the lower.
Oxygen ingress can be measured by placing a closure on a bottle
containing a known amount of oxygen and periodically measuring the
oxygen in the bottle. The bottle must contain nothing that can react with
oxygen. A simpler method uses an instrument sold by Modem Controls, Inc.
There are several models of an instrument commonly called the Mocon. The
instrument is used primarily to measure transmission through a permeable
membrane. Because of uncertainties of the dimensions of L and A in a
196 ACTIVE FOOD PACKAGING
Hot melt
glue or
5 min. epoxy
8.3.1 Theoretical
Removal of oxygen from a bottle by a closure requires that the reaction
occurs with gaseous oxygen in the headspace of the bottle. About two-thirds
of the oxygen in a bottle is in the headspace. Scavengers can be incorporated
into the closure by two different means.
(i) A compartment is placed in the closure that separates the scavenger via
a membrane that allows oxygen and water vapor to permeate the liner, but
prevents the scavenger from leaching back into the bottle. This approach
lessens the concern of product contamination by the scavenger; thus, it
increases the choices of potential scavengers. There are many patents
describing this approach. In order to be practical, the design and placement
of the compartment must allow normal closure handling and bottling
procedures. The fabrication of such a closure would add significant cost and
require process changes by the brewer. This approach has not been
commercially tested.
(ii) The scavenger is included in the liner compound. The scavenger must
be effective at levels that do not interfere with compound processing, closure
lining, or the closure performance on the bottle. To be effective, the
compound must be permeable to water vapor and oxygen. The rate of
oxygen removal will be determined by the concentration and reactivity of
the scavenger, the permeability of the compound, and the surface area of
liner exposed.
The scavenger should not become degraded during processing thereby
losing activity and should be immune to activity loss during normal
handling. For example, enzymes such as glucose oxidase-catalase are very
reactive, but are destroyed by plastics processing conditions and are much
too reactive for normal filling procedures. Because of close contact with the
product the scavenger should not be noxious from a health or organoleptic
standpoint. It is not surprising then that the most successful scavengers are
the materials tested earlier as direct beer additives.
There are several large brewers, and they can afford and use excellent
oxygen control. With one exception, they have been evaluating PureSeal
oxygen control crowns for about 2 years. Extensive research and large trials
are resolving their concerns and demonstrating the value of oxygen
scavenging crowns. Working with these brewers has resulted in a better
understanding of the role of oxygen in beer flavor chemistry. The original
goal of the project was to remove as much oxygen as quickly as possible.
For bottles containing more than 600 ppb oxygen, rapid removal is
beneficial. As the initial oxygen approaches 250-350 ppb, rapid oxygen
reduction is not always beneficial. The reason for this is that all beers
contain trace amounts of organic compounds, actually hundreds of them.
Some of the sulfide-containing organic compounds included in this number
have a low flavor threshold. Oxygen participates in the reactions that reduce
these flavors. 'Sulfury' beers bottled with low initial oxygen require a lower
200 ACTIVE FOOD PACKAGING
rate of oxygen depletion to allow some of the oxygen to react with the
sulfury components. PureSeal liner compounds are readily adjusted to
achieve both goals. A summary of the results was reported at Pack
Alimentaire (1993).
employed by the beer industry. Oxygen control liners have been introduced
for aluminum roll-on closures to complete the closure requirements for
beer.
The use of oxygen control for other beverage products is a new frontier.
It is a relatively new industry involved in this field, differing in many
respects from the beer ind\lstry. Until recently, refined constituents such as
sugar, com syrup, artificial flavors, and citric acid have been used. There
were relatively few substances that had the potential of becoming oxidized
to off-flavors. As beverage makers begin to use more natural materials such
as fruit juice, the potential for organoleptic problems increases. These
problems can be off-set with additives, but additives must be listed on the
label.
Wines and coolers also contain hundreds of organic compounds that can
react with oxygen. Wine chemistry has dealt with oxygen for centuries.
Wine makers understand the role of oxygen in maturation and/or spoilage in
wine; it is a matter of how much oxygen at what stage. Oxygen scavenging
closures can be part of the oxygen control procedure of a winery.
Many food products are damaged by oxygen. Damage might be in the
form of discoloration, change in texture, loss of flavor, or the generation of
off-flavors. The effect is obvious and well understood by food processors.
Sacrificial reduction of metal and use of preservatives are becoming less
acceptable. Package oxygen control affords a different means of protecting
food from oxygen damage.
Measuring techniques and equipment are now available for evaluation of
the control of oxygen in any package. Nonetheless, 'quick and dirty'
methods are commonly found. This lack of precision will lead to faulty
conclusions or indicate no significant difference. Control of the initial
oxygen content and a valid means of measuring a change in properties are
essential features. The food scientist should become familiar with the latest
developments and only then very carefully plan and execute experiments.
References
Gray, P., Stone, 1. and Atkin, L. (1948) Systematic study of the influence of oxidation on beer
flavor. A S B C Proc., 101-12.
Heyningen, D. et al. (1987) Permeation of gases through crown cork inlays. EBC Congress,
679-86.
Klimovitz, R. and Kindraka, J. (1989) The impact of various antioxidants on flavor stability.
MBAA Technical Quarterly, (30), 70-4.
Reinke, H., Hoag, L. and Kincaid, C. (1963) Effect of antioxidants and oxygen scavengers on
the shelf-life of canned beer. A S B C Proc., 175-80.
Teumac, F., Ross, B. and Rassouli, M. (1990) Air ingress through bottle crowns. MBAA
Technical Quarterly, (27), 122-6.
Teumac, F., Ross, B. and Rassouli, M. (1991) Oxygen Ingress Into Soft Drink Bottles.
Proceedings of the 38th Annual Meeting, Society Of Soft Drink Technologists,
pp. 201-10.
202 ACTIVE FOOD PACKAGING
Teumac, F. (1993) Case Studies of Oxygen Control in Beer. Proceedings of Pack Alimentaire
'93.
Thomson, R. (1952) Practical control of air in beer. Brewers' Guild Journal, 38(451),
167-84.
Wisk, T. and Siebert, K. (1987) Air ingress in packages sealed with crowns lined with
polyvinyl chloride. J. Arner. Soc. Brew. Chern., 45, 14-18.
9 Commercial applications in North America
S. SACHAROW
Packaging exists because it performs four basic functions which may vary in
importance depending on the nature of the products and their modes of
distribution.
The classic functions are:
1. Protection
2. Containment
3. Information
4. Utility of use
In recent years, these properties have been expanded to include both the
environmental disposability of the package material as well as the ability of
the package to perform far beyond the inherent property of the package
media. This may include characteristics such as enhanced shelf-life, the
ability to 'cook' the product or other changes in the product caused by the
packaging material.
Active packaging is the term used for a package that changes the
characteristics of the product packaged. Examples of active packaging
existing in the North American marketplace will be discussed in this
chapter.
• thick films are deposits onto a substrate from dispersions of the material
as, for example, from a paste
Thin films may be only a few angstroms up to a thousand or more angstroms
(l angstrom = 10-8 cm = c. 4 X 10-9 inch) in thickness; as deposition
continues, thickness increases.
The most interesting and potentially most useful effects pertaining to
aluminium in microwave packaging are those which occur at thicknesses
corresponding to Macbeth optical densities (aD) between 18 and 28. These
coatings are largely transparent to visible light (% transmission c. 50%) and
in fact overlap the lower end of the range of thicknesses used in window
films. In this range, particles form a discontinuous film of non-uniform
thickness - an array of electrical resistances - which responds to micro-
waves by becoming increasingly hot, through ohmic heating. At thickness
yielding aD = 35, arcing occurs.
Thickness is a misleading term to apply to these extremely thin coatings because
their surfaces are quite irregular; perhaps the root mean square thickness might be
more apropos.
Early susceptors (c. 1986 - 1987) yielded promising heating results which
produced the desired cripsing and browning, but they also produced
problems in some cases, which since that time have been largely corrected
or eliminated entirely. Two examples are:
(i) A strong unpleasant odour, emitting from the oven or on opening the
door after heating, emanated from the paperboard substrate, the
adhesive, the film base or metal or combinations;
(ii) Uneven crisping, or lack of crisping in some areas of the food when
other areas were done, detracted from the favourable impression this
new technology offered.
In addition, the rapid growth in use of compact ovens, typically less than
500 Wand 201 capacity (0.7 cf) sharply increased demand for convenience
foods most likely to require crisping and browning. The accompanying rush
to formulate suitable foods and packages led to some sub-optimal results.
Most of the recent offerings of susceptor-crisped foods seem to overcome
the early problems, though some remain, especially in the frozen category
where uniform temperature attainment is difficult at best. In tests of oval
cross-section frozen dough-encased pasties (meat pies), centre line tem-
peratures from middle to ends after the recommended heating time varied
from 71-27°C (l60-800P) and were not improved with additional heating up
to the maximum recommended using the sleeve susceptors provided.
Moreover, the susceptor efficiency was noticeably better at the base of the
pies than at the upper surfaces. Standing time of 5 min narrowed the
difference between highest and lowest temperatures from 44 to 33°C (80 to
60 0 P).
206 ACTIVE FOOD PACKAGING
Figure 9.1 Fresh Pax oxygen absorbers introduced by Multiform Desiccants. Inc. for use in a wide
variety of food packs.
212 ACTIVE FOOD PACKAGING
Figure 9.2 MultifotID Desiccants, Inc. introduces FreshMax oxygen absorbers for processed,
smoked and cured meats.
COMMERCIAL APPLICATIONS IN N. AMERICA 213
References
Evert-Fresh (1994) pers. commun. with Evert-Fresh (Houston, TX), August, 1994.
Mitsubishi (1994) pers. commun. with Mitsubishi Chemical (New York City., NY) September,
1994.
Multiform (1994) pers. commun. with Multiform Dessicants (Buffalo, NY), September,
1994.
Packaging Gp. (1987) Microwave Packaging. A multi-client study published by the Packaging
Group, Inc. (Milltown, NJ).
ZapatA (1994) pers. commun. with ZapatA Industries, October, 1994.
10 Time-temperature indicators
J.D. SELMAN
10.1 Introduction
combines the security of a barrier pouch with the ease of a recloseable zipper
seal. Secondary tamper evident features rely on subtle devices based on
chemical reactions, biological markers, and concealing techniques. Some
that are now commercially available utilise pattern adhesive labels and tapes,
solvent soluble dyes and encapsulated dyes, optically variable films and
holographic tear tapes.
A number of other developments are on the horizon, including the
application of smart cards within caps, magnetically coded closures and
electrochemical devices. However, gas sensing dyes are the most advanced,
especially for modified atmosphere packs. For example, a CO2 sensing dye
could be incorporated into the laminated top web film of a modified
atmosphere pack, and this could be designed to change colour when the CO 2
level falls below a set concentration. In the area of product authenticity and
counterfeiting, there is a large range of intelligent package devices which are
being developed for use in various industrial sectors. Some of these will be
applicable to the food industry and include the use of holograms,
thermochromic and photochromic inks, IR and UV bar codes, biotags,
optically variable films, computer scrambled imaging, electromagnetic ink
scattering, and so on.
There is continuing interest in the monitoring of temperature in the food
distribution chain from factory to the consumer, and temperature monitoring
and measurement, particularly of chilled foods, have been discussed by
others (Woolfe, 1992). As part of the approach to assuring product quality
through temperature monitoring and control, attention has focused on the
potential use of indicators. Temperature indicators may either display the
current temperature or respond to some predefined threshold temperature
such as a freezing point or a chill temperature such as 8°C. TTIs usually
utilise a physico-chemical mechanism that responds to the integration of the
temperature history to which the device has been exposed. Many different
types of indicator have been devised over the years and general reviews have
been presented by several authors, including Schoen and Byrne (1972)
covering patent literature from 1933 to 1971, Cook and Goodenough (1975),
Kramer and Farquhar (1976), Olley (1976, 1978), Farquhar (1977), Schoen
(1983), Ulrich (1984), Selman and Ballantyne (1988), Bhattacharjee (1988),
and Selman (1990).
In general terms, indicators must be able to function in order to monitor
one or more of the following.
useful for determining shelf-life expiry when products are held under proper
refrigerated conditions. However, use is still limited by the lack of response
to short periods of temperature abuse, and the polymerisation reaction is
influenced to some extent by light. The latest types are light-protected by a
red filter. There is at present considerable interest in these indicators, for
example for fresh eggs where short time-temperature rises may not directly
affect quality. Lifelines Inc. also claim good correlation with the quality life
of cooked ready meals, fresh chicken and yoghurt. During 1991, Lifelines
continued to evaluate their polymer-based indicators used in both the food
and pharmaceutical industries, and their Fresh-Check label has been trialled
in some of the department stores of the French company Monoprix, where
they have been applied to over a dozen types of chilled retail products
(Monoprix, 1990). The most prominent of the indicators to date have been
the three referred to above, i.e., 3M Monitormark, the I Point type, and the
Lifelines Fresh-Scan and Fresh-Check. These have been the subject of a
number of independent validation tests, and the test systems and references
are given in Table 10.2.
Marupfroid (Paris, France) has developed a partial history freezer label
based on the melting point of ice. The part of the tag containing the red-
coloured ice is located inside the pack next to the frozen food, with a hazard
warning area visible externally. If thawing has occurred, the red dye moves
along the label and exposes a warning printed in hydrophobic white ink. One
very important point must be highlighted here, and that is that all other
indicators are placed on the outside of a pack and therefore respond to the
environmental temperature. The packaging itself may provide the food with
some insulation from the environment and the food temperature will
therefore lag behind any changes in outside temperature. In the case of this
label, the indicator system is placed inside the pack but with its response
change visible externally.
Johnson Matthey has patented a system based on the corrosion of an
indicator strip (US Patent, 1989). It consists of a film of electrochromic
material (in this case tungsten trioxide), with a metal overprint at one end,
printed onto a card. The dissolution of the metal anode in acid is temperature
sensitive and results in a colour boundary which moves down the strip at a
rate governed by the temperature. The indicator can be engineered to
respond to short total times and shows some promise in this respect, and the
potential exists for miniaturisation of such indicators.
Oscar Mayer Foods Corp. (Madison, USA) have developed a quality
freshness indicator. This is based on pH-sensitive dyes in contact with a dual
reaction system which simultaneously produces acid and alkali to maintain
a constant pH. When one of the substrates becomes depleted, a rapid pH
change occurs, resulting in a sharp visual colour change (green to pink). A
rise in temperature causes a shift in the equilibrium and the colour
changes.
tv
tv
.j>.
Table 10.2 Validation tests on time-temperature indicators
Model System test Reference
Pasteurised whole milk (O°C, 5°C and 10°C) Grisius et al. (1987)
Hamburger rancidity (frozen) Wells et al. (1987)
Hamburger rancidity Singh and Wells (1985a)
Strawberries (- 12 to + 35°C) Singh and Wells (1987)
Seafood salad (pallets) (- 20 to - 10°C) Singh and Wells (1985b)
Cod fish (frozen) (pallets) Olsson (1984)
Steak, beef patties, macaroni cheese (pallets) (- 20 to + 30°C) Olsson (1984)
~
Pizza (- 20 to + 30°C) Kramer and Farquhar (1977) ~
Milk (4.4-1O°C) Mistry and Kosikowski (1983) ~
Response to isothennal conditions (4-30°C) Taoukis and Labuza (l989a) tll
;>:I
Response to non-isothennal conditions (4-30°C) Taoukis and Labuza (1989b) ..,;t>
c::
Response to isothennal conditions Wells and Singh (l988c) ;>:I
ttl
Response to isothennal conditions (- 18 to + 5°C) Wells and Singh (1985)
Z
Response to isothennal conditions (+ 2C, + 10°C, - J2°C, -10°C) Ballantyne (1988) 0
Pi
;t>
3M Monitonnark Hamburger rancidity (> - 17°C) Wells et al. (1987) ..,
0
Singh and Wells (1986) ;>:I
en
Wells and Singh (1985)
Steak, beef patties and macaroni cheese (pallet loads) (- 23.4 to - 15°C) Kramer and Farquhar (1977)
Milk (4.4-JOOC) Mistry and Kosikowski (1983)
Response to isothennal conditions (4-30°C) Taoukis and Labuza (l989a)
Response to non-isothennal conditions (4-30°C) Taoukis and Labuza (1989b)
Response to isothennal conditions (4 - 10°C) Ballantyne (1988)
Unspecified (two models) Response to isothennal conditions Arnold and Cook (1977)
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Vl
226 ACTIVE FOOD PACKAGING
deciding whether a food was safe to eat, with at least 25% putting some of
the blame on the food suppliers. However, the value of TTIs was recognised
for raising confidence in retail handling, and improving hygiene practices
when food is taken home and stored in refrigerators. It is clear that there is
a future for TTIs in monitoring the chill chain. Development of different
indicators is still in progress and technical difficulties have to be overcome
by carrying out the appropriate tests (George and Shaw, 1992). However, the
consumer can appreciate the concept, and the advantages and benefits of
increased food safety for the higher-risk foods that would result.
exhibit heat-induced changes. For example, Kim and Taub (1993) have been
studying the thermally produced marker compounds 2,3-dihydro-3,5-dihy~
droxy-6-methyl-(4H)-pyran-4-one and 5-hydroxymethylfurfural. Both these
compounds are produced when D-fructose is heated, and glucose yields only
the latter compound. Hence, where a food contains either of these sugars,
there is some basis for assessing heat treatment received as the kinetic
characteristics make them suitable as markers for bacterial destruction. As
before, the kinetic response requirement which a TTl should fulfil can be
derived theoretically and should match the response of the target index, such
as a spore or a nutrient, when subjected to the same thermal process.
Potential exists for multicomponent TTls in the evaluation of thermal
processes (Maesmans et aI., 1994).
Regarding the origin of the TTl, an extrinsic TTl is a system added to the
food, while intrinsic TTls are intrinsically present in the food. In terms of the
~ C_h_em~ic_al ~
Working principle
_____________ ________
Response
Origin
Application
Figure 10.1 General classification of time-temperature indicators (after Hendrickx et aI., 1993).
234 ACTIVE FOOD PACKAGING
application of the TTl in the food product, dispersed systems allow the
evaluation of the volume average impact, whilst all three approaches (see
Figure 10.1) can be used as the basis for single point evaluations. When
using intrinsic components as the TTl, the TTl will be more or less evenly
distributed throughout the food, and this also eliminates heat transfer
limitations. This whole field is currently the subject of a major European
collaborative research study co-ordinated by the Centre for Food Science
and Technology at the University of Leuven in Belgium.
10.5 Conclusions
The interest in this subject has generated numerous research studies and
practical evaluations of indicator systems. It is clear that the food industry,
and indeed other sectors such as the medical and pharmaceutical industries,
as well as the consumer, recognise a variety of benefits that can stem from
the application of indicators in aiding the monitoring and assurance of
distribution chains. This, in turn, is leading to the development of new
indicators that are much more precisely designed to meet the needs of the
food industry. In the broader context of time-temperature integration,
applications for thermal process assessment are receiving further attention
and novel approaches are actively being researched. Such developments will
assist in the assurance in and broader introduction of new heat processes
such as microwave sterilisation. Overall, it is likely that there will continue
to be exciting developments during the next five years.
References
Anon. (1989) Is it time for time-temperature indicators? Prepared Foods, 158(12), 219-30.
Arnold, G. and Cook, DJ. (1977) An evaluation of the performance claimed for a chemical
timeltemperature integrating device. Journal of Food Technology, 12, 333-7.
Ballantyne, A. (1988) An Evaluation of Time-Temperature Indicators, Technical Memoran-
dum No. 473, Campden Food and Drink Research Association, Chipping Campden, O1os.,
UK.
Bhattacharjee, H.R. (1988) Photoactivatable time-temperature indicators for low-temperature
applications. Journal of Agricultural and Food Chemistry, 36(3), 525-29.
Blixt, K. (1984) The I-Point TIM - a versatile biochemical time-temperature integrator. In:
Thermal Processing and Quality of Foods, P. Zeuthen, I.C. Cheftel and C. Eriksson (eds),
Elsevier Applied Science Publishers, London.
Blixt, K. and Tiru, M. (1977) An enzymatic time/temperature device for monitoring the
handling of perishable commodities. Developments in Biological Standards, 36, 237.
Boeriu, C.G., Dordick, I.S. and Klibanov, A.M. (1986) Enzymatic reactions in liquid and solid
paraffins: application for enzyme-based temperature abuse sensors. BiolTechnology, 4,
997-9.
Brown, H.M. (1991) The Use of Chemical and Biochemical Markers in the Retrospective
Examination of Thermally Processed Formulated Meals, Technical Memorandum No. 625,
Campden Food and Drink Research Association, Chipping Campden, O1os., UK.
Byrne, C.H. (1976) Temperature indicators - the state of the art. Food Technology, 30(6),
66-8.
TIME-TEMPERATURE INDICATORS 235
Maesmans, G., Hendrickx, M., De Cordt, S. and Tobback, P. (1994) Theoretical considerations
on design of mUlti-component time-temperature integrators in evaluation of thermal
processes. Journal of Food Processing and Preservation, 17, 369-89.
Makata, FX. (1990) The effect of internal thermal gradients on the reliability of surface
mounted full-history time-temperature indicators. Journal of Food Processing and Preserva-
tion, 14, 481-97.
Manske, W.J. (1983) The Application of Controlled Fluid Migration to Temperature Limit and
Time-Temperature Integrators. In: Proceedings of IIR XVIth International Congress of
Refrigeration, Paris, France, pp. 797-804.
Manske, W.J. (1985) Experience with Monitormark product temperature exposure indicators.
In: IIR Annex Bulletin 85-5, pp. 311-17.
Marin, M.L., Casas, C., Cambcro, M.1. and Sanz, B. (1992) Study of the effect of heat
(treatments) on meat protein denaturation as determined by ELISA. Food Chemistry, 43,
147-50.
Ministry of Agriculture, Fisheries and Food (1991) Time-temperature Indicators: Research
into Consumer Attitudes and Behaviour, National Consumer Council, London.
Mistry, V.V. and Kosikowski, F.V. (1983) Use of time-temperature indicators as quality
control devices for market milk. Journal of Food Protection, 46(1), 52-7.
Monoprix (1990) La Plaisir du Frais: Monoprix Lance la Puce Frafcheur, Monoprix, Paris,
France.
Morris, C.E. (1988) Monitoring fresh food shelf-life with TfT labels. Food Engineering, 60(4),
52-7.
Olley, J. (1976) Temperature indicators, temperature integrators, temperature function
integrators and the food spoilage chain. In: IIR Annex Bulletin 76-1, pp. 15-l31.
Olley, J. (1978) Current status of the theory of the application of temperature indicators,
temperature integrators, and temperature function generators to the food spoilage chain.
International Journal of Refrigeration, 1(2), 81-6.
Olsson, P. (1984) TT integrators - some experiments in the freezer chain. In: Thermal
Processing and Quality of Foods, P. Zeuthen, I.C. Cheftel and C. Eriksson (eds), Elsevier
Applied Science, London, pp. 782-8.
Pidgeon, R. (1994) High-tech labels help colour your judgement. Packaging Week, 9(38),
18.
Risman, P.O. (1993) Microwave oven loads for power measurements. Microwave World,
14(1), 14-19.
Schoen, H.M. (1983) Thermal Indicators for Frozen Foods. In: Proceedings of IIR XVIth
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Schoen, H.M. and Byrne, C.H. (1972) Defrost indicators. Food Technology, 26(10), 46-50.
Schubert, H. (1977) Criteria for the application of T -T indicators to quality control of deep
frozen food products. In: IIR Commissions C11C2 77-1, Ettlingen, Germany, pp.
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Selman, J.D. (1990) Time-temperature indicators - how they work. Food Manufacture, 65(8),
30-4.
Selman, I.D. and Ballantyne, A. (1988) Time-temperature indicators: do they work? Food
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25(5), 41-2, 46-7.
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TIME-TEMPERATURE INDICATORS 237
Taoukis, P.S. and Labuza, T.P. (1989a) Applicability of time-temperature indicators as shelf-
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11 Safety considerations in active packaging
J.H. HOTCHKISS
11.1 Introduction
Ever since Appert discovered that heating food in sealed glass jars produced
a stable product, a major goal of packaging has been to safely preserve foods
for extended periods. A scientific understanding of the relationship between
shelf-life, safety, processing/storage conditions, and packaging began to
evolve in the late 1800s as the theoretical basis for the thermal inactivation
of pathogenic spores was developed (Goldblith, 1989). This understanding is
still evolving.
The use of packaging to safely protect and preserve foods has remained a
central focus of packaging development. The primary roles of packaging in
food safety have traditionally been to withstand thermal processing
conditions and to act as a barrier to contamination. It would be of little
benefit to process food if there was no way to prevent recontamination. The
success of the metal can over the last 150 years is due to its ability to
withstand thermal processing and provide a barrier against chemical and
biological contamination. Modem food packaging can also influence the
nutritional and quality attributes of foods and ensure the year-round
availability of many foods. These factors are important in the health and
nutritional aspects of foods.
The major advances in food packaging over the last two decades have
been the development of new materials, combinations of materials, and
containers with specific technical and economic benefits (Downes, 1989).
Most of these new materials and containers are inactive technologies in that
they act primarily as passive barriers which separate the product from its
environment. However, current research is shifting to the development of
packaging which actively contributes to the preservation and safety of foods
(Labuza and Breene, 1989). Such packaging interacts directly with the food
and the environment to extend shelf-life and/or improve quality.
Packaging has often been thought of as a source of risk for foods and seldom
as a technology which could be used to enhance food safety (Wolf, 1992).
SAFETY CONSIDERATIONS 239
Certainly, when packaging fails to preform its protective functions the result
is an unsafe product (Downes, 1993). For example, safety may be
compromised when package components migrate to a food or when there is
a loss of integrity resulting in contamination by pathogenic microorganisms.
Table 11.1 lists several general ways in which packaging can detract from
safety.
However, active packaging can directly enhance food safety. Active
packaging can not only prevent contamination but it can also improve food
safety in several other ways. Examples of 'active' packaging which
improves food safety include antimicrobial polymers and films which inhibit
the growth of pathogenic and spoilage microorganisms, packages which
react with toxins and indicate their presence, packaging materials which
prevent the migration of contaminant, and packages which indicate if
packages are leaking. These and other types of active packaging which
improve safety and quality are areas of current research and commercial
interest (Ishitani, 1994).
Active packaging systems face similar barrier and migration safety issues as
conventional packaging, as well as some additional issues. While there is
concern that some active packaging systems will detract from safety there
also is the possibility that new active systems can enhance safety. Materials
and containers are being developed specifically to reduce food safety
risks.
SAFETY CONSIDERATIONS 243
into food packaging systems for which the risk of toxin formation exists.
Reportedly, methods to quantify the presence of microorganisms on fresh
meats are near commercialization (Bsat et ai., 1994). Such systems could
eventually be incorporated directly into food packaging.
It may likewise be possible to detect the presence of toxic chemicals using
similar technologies. The presence of specific pesticides or other environ-
mental contaminants could be detected with immunological-based systems
(Deshpande, 1994). Lastly, packaging should provide a margin of safety
against tampering. Tamper-indicating packaging has been discussed in detail
since several malicious incidents of tampering with drugs and foods have
occurred (Hotchkiss, 1983). Several simple and complex tamper-evident
packaging systems have been developed and a few implemented for
foods.
a!., 1984; Hale et al., 1986). We have demonstrated that the same compound
is effective at preventing mold growth on cheese surfaces when incorporated
into LDPE films (Weng and Hotchkiss, 1992). Although imazalil is not
approved for cheese, this work established that antimycotic films could be
effective for control of surface molds in foods. Halek and Garg (1989)
chemically coupled the antifungal agent benomyl, which is commonly used
as a fungicide, to ionomer film and demonstrated inhibition of microbial
growth in defined media. While not directly addressed by the authors, the
method used to determine inhibition of growth indicated that the benomyl
migrated from the film to the growth media. It is unlikely that benomyl
would be approved for food use for toxicological reasons.
Reports have appeared which demonstrate the effectiveness of adding
common food-grade antimycotic agents to cellulose-based edible films
(Vojdani and Torres, 1990). Films were constructed of cellose derivatives
and fatty acids in order to control the release of sorbic acid and potassium
sorbate. These films would seem to have the greatest application as fruit and
vegetable coatings. Cellulose films are not heat sealable are not good
barriers in high humidity situations.
We have spectroscopically demonstrated that propionic acid, which is a
common approved food antimycotic agent, could be coupled to ionomeric
films but that antimycotic activity could not be demonstrated on rigorous
testing (Weng, 1992). Direct addition of simple antimycotic acids such as
propionic, benzoic, and sorbic acids to polymers such as LDPE was
unsuccessful because of lack of compatibility between the acid and the non-
polar film. This incompatibility is likely to be due to differences in polarity.
We have solved this problem by first forming the anhydride of the acid
which removes the ionized acid function and decreases polarity (Weng and
Hotchkiss, 1993). Anhydrides are stable when dry and relatively thermally
stable yet become hydrolysed in aqueous environments such as foods.
Hydrolysis leads to formation of the free acid which in tum leads to
migration from the surface of the polymer to the food where the free acids
can be effective antimycotics. This is an example of 'switched on'
packaging; the active ingredient remains in the film until the film comes into
contact with a food. The activity is initiated by the moisture in the food.
Future work in antimicrobial films may focus on the use of biologically
derived antimicrobial materials that are bound or incorporated into films and
do not need to migrate to the food to be effective. For example, a group of
substances known as bacteriocins, which are proteins derived from micro-
organisms in much the same way as penicillin is derived from mold, have
been described in the literature (Hoover and Steenson, 1993). Bacteriocins
are effective against organisms such as Clostridium botulinum and one such
compound, nisin, has been approved for food use. These peptides could,
theoretically, be attached to the surface of food-contact films. Whether or not
such bound bacteriocins would be effective remains unclear.
250 ACTIVE FOOD PACKAGING
11.5 Conclusious
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Index