Professional Documents
Culture Documents
Edited by
M.L. ROONEY
Principal Research Scientist
CSIRO
Division of Food Science & Technology
North Ryde
New South Wales
Australia
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
McNaIIy 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
Acknowledgements ............................................................ v
Contributors ........................................................................ vi
This page has been reformatted by Knovel to provide easier navigation. viii
Contents ix
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)
packaging is used to distinguish the situation where the choice of the
permeability ratio of oxygen/carbon dioxide determines whether respiring
horticultural produce generates a viable gas atmosphere or not (Gill, 1990).
Thus where modified atmosphere packaging (MAP) is used with processed
foods and involves merely flushing with an initial gas mixture the packaging
is not active. EMA packaging is one of the borders between active and
passive packaging. Some aspects of EMA packaging are discussed in this
book because the limitations of conventional packaging films are being
increasingly addressed using active materials.
If the physical interactions of a package with the food are removed we are
left only with the chemical (and increasingly, biochemical) effects. Such a
restriction is probably unduly strict and in time we should expect to see
further subdivision of active packaging to take account of whether 'activity'
is a property of the packaging material itself or of inserts within the
package.
We are beginning to see reference to the benefits of active packaging in
the popular press with reference to 'packaging that is niftier and cooks your
food' and 'Hi-Tech' packaging (Sprout, 1994). The active packaging so
described includes susceptors and reflectors in microwaveable packs as well
as horticultural smart films that absorb ethylene. These are described
together with temperature sensitive labels that help determine when food is
cooked, i.e. 'doneness indicators'.
There are other areas of packaging developing concurrently and there are
areas of overlap with active packaging as noted with MAP above. Probably
the closest area is Intelligent Packaging, a grouping of technologies defined
in the CEST publication by Summers (1992) as 'an integral component or
inherent property of a pack, product or pack/product configuration which
confers intelligence appropriate to the function and use of the product itself.
This grouping covers the area of product identity, authenticity, traceability,
tamper evidence, theft protection, and quality as indicated by time-
temperature indicators. The latter was originally included by Labuza (1987)
in his seminal review of active packaging. Time-temperature indicators also
fit the definition of active packaging given above; they play a role in
defining the steps that need to be taken to ensure the quality and safety of the
packaged food. A somewhat related field of packaging which so far has
fallen between the two definitions is that of gas composition indicators. To
date they have been used in the form of tablets to indicate when oxygen-
scavenging sachets have achieved their purpose (Anon, undated). There have
been steady efforts made for several years to produce oxygen-indicating
printing inks but thus far, like the pellets, these indicators largely change
colour at oxygen levels below 0.1%.
The description of this field as interactive packaging is also seen. There is
some benefit in such a description as it links desired and undesired
interactions of foods and their packaging, such as flavour scalping (Hirose et
al, 1989). However, this lack of distinction is probably a disadvantage
overall, hence the naming of this book.
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.
Table 1.1 History of iron-based oxygen scavengers
Additional reagents Form Reference Country
Water absorbents powder Tallgren, 1938 Finland
Iron compounds powder Isherwood, 1943 UK
Sodium carbonate powder Buchner, 1968 Germany
Carbon, water powder Nawata el al., 1977 Japan
Alkali metal halides powder Mitsubishi, 1977 Japan
Ammonium chloride powder Kureha, 1982 Japan
Sodium chloride powder Fujishima, 1985 Japan
Un-named film Koyama/Oda, 1992 Japan
rears
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.
Composition Design
Applications
Years
Figure 1.2 Patent applications for oxygen scavengers based on composition or design.
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).
The International Conference on Modified Atmosphere Packaging at
Stratford-upon-Avon (UK) in 1990 organised by the Campden Food and
Drink Research Association included several reviews relating to active
packaging. Louis described several innovative active packages which
generated modified atmospheres. Abe gave the first comprehensive quantita-
tive assessment of the impact of active packaging. He estimated the market
size for each of the broad classes of such packaging systems. His review
reveals that around 6.7 billion oxygen-scavenging sachets and 70 million
ethanol-generating sachets were manufactured in Japan in both 1989 and
1990. The estimated market for films containing mineral powders was only
1000 tonnes in 1989 with 40% of consumption as home use.
The review by Robertson (1991) emphasised the application of active
packaging to processed foods. The emphasis was placed on crown seals for
bottled beer, oxygen-scavenging plastics films and microwave susceptors.
The use of the term active packaging rather than smart films was noted by
that reviewer and by Sacharow (1991) who also noted the use of sachets of
potassium permanganate in silica gel for ethylene removal in produce packs.
By this time the claimed benefits of freshness preservation technologies for
horticultural products were being examined critically, especially in Japan.
Ishitani (1993a,b) surveyed the number of patent applications for this
purpose from 1984 to 1989. Over the first two years the annual rate was
around 35 applications. This increased to a peak rate of 220 per annum in the
second half of 1987 before dropping to around 60 per annum in 1989. It was
noted that initial developments were directed at the needs for low-
temperature maintenance and moisture control. The boom in 1987 was the
consequence of the attention being paid to gas composition control and
ethylene removal. By 1989 gas composition was the main object of
developments but moisture control and coating methods were also impor-
tant. Ishitani (1993a) observed two factors that led to much rethinking.
These were the lack of data on the requirements of produce and doubts about
the capacity of powder-filled plastics to remove enough ethylene. More
recent developments have been focused on ethylene removal at high
humidities and on matching gas composition and temperature to the
requirements of enzymic systems of plants. Several recent books on MAP
have included discussion of the gas-packaging requirements for horticultural
produce as well those for some processed foods (Ooraikul, 1993; Parry,
1993). The environmental aspects of active packaging have not been
considered to any great extent in reviews to date. Rooney (1991) addressed
some issues drawing attention to the need to consider the nature of the
packaging which can be replaced by these new technologies.
The current state of development and commercial application of active
packaging has been reviewed in three papers at the symposium Interaction:
Foods - Food Packaging Material held in Sweden in June 1994. Miltz et al
(1994) reviewed the field in general, Ishitani (1994) concentrated on
Japanese developments, especially antimicrobial films, Day (1994) concen-
trated on fresh produce and Guilbert and Gontard (1994) focused on edible
and biodegradable packaging. Several posters described original research
and that of Paik described photoprocessing of a film surface to generate
antimicrobial properties. Perdue (1993) has briefly reviewed antimicrobial
packaging from the viewpoint of the Cryovac Division of W.R. Grace
Company and presents a somewhat pessimistic picture.
Respiring Produce
Delayed ripening
Temperature abuse
Fungal growth
Aseptic
Oxidation Oxidation Dry
Liquids
Hydration Foods
active
packaging
Prepared Microwave Colour Chilled
Meals cooking Retention Meats
Mould
Growth
Bakery
Products
REQUIREMENT FOODCLASS
Time (hours)
Figure 1.4 Oxygen scavenging from loosely packed biscuits packs () compared to tightly packed
packets (A) (simulating domestic use).
Next Page
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.
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.
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
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.
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-O2 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 al, 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
development. Inserts or films capable of regulating humidity levels are
required, especially where temperature abuse is likely. The use of sealed
plastic bags for equilibrium modified atmosphere generation makes this
requirement more critical.
Current commercial oxygen scavenging sachets are supplied in a wide
variety of forms to suit particular temperature and relative humidity
conditions. These designs place limitations on the shelf-life of the sachets
once the master-packs are opened and before insertion into the food
package. An ideal sachet would be useable under a wide variety of
conditions and activated for a particular application by the food packer.
Some early steps towards overcoming the shelf-life limitation have been
reported in the patent literature. The use of a peelable barrier on a sachet
with a self-adhesive backing has been proposed.
Attempts to include oxygen scavengers in plastics packaging materials
have not yet been successful commercially except in closure liners for
beverage bottles. Compositions which are able to withstand extrusion and
yet be activatable are required.
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 amines, 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.
1.9 Regulatory considerations
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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
combustion of almost any hydrocarbon. It is thus a common air pollutant, its
chief source being automobile engines.
Biological sources of ethylene include higher plant tissues, several species
of bacteria and fungi, some algae, and some liverworts and mosses. The
biosynthetic pathways for ethylene are diverse among these different
organisms. The pathway of synthesis from methionine has been described in
detail for higher plants (Yang and Hoffman, 1984). The pathways for
synthesis in bacteria appear to be diverse since any of several carbon sources
other than methionine will serve as precursors (Sato et al, 1987). Nitrogen-
fixing bacteria can reduce acetylene to ethylene (Dillworth, 1966). Approx-
imately 25-30% of fungal species tested produce ethylene on appropriate
media (Fukuda et al, 1984; Hag and Curtis, 1968). The pathways of plant
and fungal ethylene synthesis appear to be distinct, as the inhibitor
rhizobitoxin blocks synthesis in plants but not in the fungus Penicillium
digitatum (Owens et al, 1971). The pathway of ethylene synthesis in non-
vascular plants may be different from that in vascular plants (Osborne,
1989a).
Because this chapter is primarily concerned with methods of eliminating
ethylene, not producing it, it is not necessary to go into the details of
production by different organisms. This has been reviewed in detail
elsewhere (Abeles et al, 1992). The important point is that environmental
ethylene can be biologically produced by a wide range of organisms, both
visible and invisible, and such sources ought to be considered when devising
strategies to reduce ambient ethylene.
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 paraffinicum, is thought to be an efficient
oxidizer of ethylene (Abeles et al, 1992).
Ethylene reacts with ozone to yield water, carbon dioxide (CO2), carbon
monoxide (CO), and formaldehyde (Scott et al, 1957). Ultraviolet light will
interact with oxygen (O2) 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
including ethylene oxide, ethane, CO, propylene, acetaldehyde, propanol,
butanol, hydrogen and dioxyketone (Leighton, 1961).
The double bond of ethylene makes it very reactive through a number of
reaction pathways. The double bond will undergo hydrogenation, in the
presence of any of several metal catalysts, to yield ethane (Morrison and
Boyd, 1966). Ethylene will react with halogens (chiefly chlorine and
bromine) through halogenation and hydrohalogenation reactions to form
dihaloalkanes. Thus, ethylene can be eliminated from air by passing it over
brominated activated charcoal to form dibromoethane (Talib, 1983). Bromi-
nated charcoal filters are relatively efficient removers of ethylene. Up to
90% of the bromine will react with ethylene. However, bromine also reacts
with water to form HBr and Br2 gas is released from the carbon filter. These
compounds are injurious to plant tissues and corrosive to stainless steel. In
addition, brominated activated charcoal is hygroscopic and will become wet
in humid conditions. Alternatively, ethylene will react with hydrogen halides
to form ethyl halides (Morrison and Boyd, 1966). Ethylene reacts with
concentrated sulfuric acid to form ethyl hydrogen sulfate or with water in the
presence of acids to yield ethanol (Morrison and Boyd, 1966).
Certain oxidizing agents react with ethylene to form glycols. The most
common of these oxidizing agents is potassium permanganate (KMnO4)
which oxidizes ethylene to ethylene glycol and thence to CO2 and water
(Morrison and Boyd, 1966). Potassium permanganate is often adsorbed onto
Celite, vermiculite, silica gel or alumina pellets. Permanganate scrubbers are
also effective in adsorbing air pollutants such as O3, H2S, SO2, NO and
NH3.
It is clear that ethylene is a very reactive compound that can be altered or
degraded in many ways. This creates a diversity of opportunities for
commercial methodologies for the removal of ethylene and, in fact, many
different methods have been used. However, many of the common reactions
undergone by ethylene require high concentrations of ethylene and/or high
temperatures and pressures. Therefore, many of the processes most com-
monly used to modify ethylene in the petrochemical industry are not
appropriate for the conditions generally found in a food package environ-
ment.
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.
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 O2 (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
K1n for conversion of 1-aminocyclopropane-l-carboxylic acid (ACC) to
ethylene in apple is about 1.4% O2 (Banks et al., 1984; Bufler and Streif,
1986) but K1n values for other plants organs are generally 3-10% (Burg and
Thimann, 1959; Lieberman et al, 1966). In some cases, reduced O2 in a
package may more effectively reduce ambient ethylene through reduced
ethylene synthesis than ethylene-adsorbing capacity built into the package.
However, reduced O2 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 O2 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.
2.4.1 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. AU infested foodstuffs
should be immediately discarded.
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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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
C6H12O6+ 6 O2 -> 6 CO2 + 6 H2O + heat (3.1)
that involves the oxidation of organic substrates (such as starch, sugars, and
organic acids) to CO2 and H2O along with heat generation. Kinetic theory
and Equation (3.1) suggest that the respiration rate may be reduced by
decreasing the O2 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
allowing the produce to respire inside the package so that an equilibrium is
slowly attained. In both cases, once the modified atmosphere is established,
it is maintained through a dynamic equilibrium of respiration and per-
meation.
Designing MAP for fresh produce is a complicated task, requiring good
understanding of the dynamic interactions among the product, the environ-
ment, and the package. The food technologist who is asked to design MAP
for fresh produce faces many difficult but practical questions, such as
whether the MAP technology is applicable to the product, what is the
optimum gas composition, what kind of packaging material is needed, and
I
Verify model predictions with
experiments
Figure 3.1 Flow chart for designing MAP for fresh produce.
how to protect the product from the potential hazards of a modified
atmosphere.
Prince (1989) has reported that the majority of modified atmosphere
packages are designed by trial-and-error methods, which often lead to poor
designs that are either ineffective or injurious to the product. Although
numerous articles have already been written on the various aspects of MAP,
almost none of them provides an overview of the design process. To fill this
gap, a simple process for designing MAP of fresh produce is presented in
this chapter. The process is necessarily somewhat simplified because many
biological aspects underlying the effects of modified atmosphere on the
shelf-life of plant tissues are still not understood (Solomos, 1994). The steps
involved in the design process are outlined in the flow diagram of Figure
3.1.
Before designing MAP for a product, the first step is to determine whether
CA storage can indeed provide benefits for the product. Reviewing the
Fruits
Apple 0-5 90 2-3 1-2
Apricot 0-5 90 2-3 2-3
Avocado 5-13 85-90 2-5 3-10
Banana 12-15 85-95 2-5 2-5
Blueberry 0-5 90-95 0-10 11-20
Cherry, sweet 0-5 90-95 3-10 10-12
Grapefruit 10-15 85-90 3-10 5-10
Peach 0-5 90 1-2 5
Pear 0-5 90-95 2-3 0-1
Persimmon 0-5 90-95 2 8
Strawberry 0-5 90-95 10 15-20
From Labuza and Breene (1989), Powrie and Skura (1991), and Katzyoshi (1992)
literature data is a good start to gather preliminary information about the
product or similar products. Helpful information that may be available in
the literature is assessment of the potential benefit of CA storage and MAP,
optimum storage conditions (such as gas concentration, temperature, and
relative humidity), O2 and CO2 tolerance limits, respiration rate, temperature
below which chilling injury of the product occurs, whether the product is
climacteric or nonclimacteric, and so on.
The recommended O2 and CO2 concentrations for some fruits and
vegetables are listed in Table 3.1. More data are available elsewhere (Prince,
1989; Labuza and Breene, 1989; Singh and Oliveira, 1994). The data may
also be represented in the form of CO2 versus O2 plots (such as in Figures
3.2 and 3.3), in which the windows represent the boundary of recommended
gas concentrations. The size of a window has a practical implication in that
the smaller it is, the more rigid is the design requirement. However,
literature data should be used only as a reference because discrepancies
sometimes exist among data from different sources (due to possible reasons
Cherry
Banana Grapefruit
Air P = 0.8
Kiwi. Ne< arine, Peach Orange
Apricot
Grape LDPEp = Cy
Cranberry Plum
O2 Concentration (%)
Figure 3.2 Recommended gas concentrations for CA storage of fruits. (Redrawn from Singh and
Oliveira, 1994, with permission.)
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.
Air P = 0.8
CO2 Concentration (%)
Mushrooms
Asparagus
Leeks
Broccoli
Brussels ! >pr< >uts'
Beans Parsley
Cabbage Okra
Spinach
Cauliflower
Tomato LDPE B = 0.8
Pepper
Artichokes
Lettuce Radish
O2 Concentration (%)
Figure 3.3 Recommended gas concentrations for CA storage of vegetables. (Redrawn from Singh
and Oliveira, 1994, with permission.)
(a)
Gas In Gas Out
Gas Sampling Port
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 aL> 1968). As Equation
(3.1) shows, respiration involves the rate of O2 consumption (R0) and the
rate of CO2 evolution (RCo2)- 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 aly 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, C2H4 concentration, O2 and CO2 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.
(3.7)
(3.8)
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
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 O 2 and CO 2 concentrations inside a closed jar containing
the product as a function of time (Haggar et al., 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 O2/low CO 2 concentra-
tions at the beginning to low O2/high CO 2 concentrations toward the end.
The respiration rates at these O 2 and CO 2 concentrations may be calculated
using the equations
(3.9)
(3.10)
The negative sign in Equation (3.9) signifies that the O 2 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)
(3.14)
(3.15)
The model requires two different sets of adjustable coefficients (Vm, Km, and
Kj): one for ROi and the other for Rcc>2. 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 a/., 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 O2 and CO2 concentrations
(Haggar et aL, 1992).
Mathematical models are useful for defining the package requirements for
MAP. Several models (Jurin and Karel, 1963; Veeraju and Karel, 1966;
Table 3.2 Respiration model parameter values and respiration activation engergies for some
products
Respiration model parameters Activation
Temp. Respiration vm energy
Commodity (0C) expression (mg/kgh) (% O2) (% CO2) (kJ/mol)
Blueberry 15 O2 consumption 68.0 0.4 2.9 147.3
"Coville"3 CO2 evolution 51.0 0.2 4.9 163.3
7 O2 consumption 210.3 0.6 2.3 62.7
Broccolib CO2 evolution 235.2 1.7 1.93 66.1
13 O2 consumption 133.7 1.7 3.0 21.2-48.2
Cauliflower0 CO2 evolution 134.4 1.4 3.1 21.2-48.2
10 O2 consumption 54.3 6.0 1.3 48.7-57.3
Green pepperd CO2 evolution 31.8 2.4 4.3 48.7-57.3
a
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 O 2 and CO 2 mass balances to
describe the interactions among the respiration of product, the permeability
of the package, and the environment.
(3.16)
(3.17)
where the subscripts i and o 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 [O2]; = 21 and [CO2]; = O at
t = O. Note that the respiration rates R02 and RCOi are functions of O2 and
CO2 concentrations, which can be expressed using the enzyme-kinetic model
of Equation (3.15).
(3.18)
(3.19)
where [O2]0 and [CO2I0 are assumed to be 21 and 0%, respectively. Further,
if RQ is assumed to be 1 and PCQJPOi is defined as (3, Equation (3.20) may
be rewritten as
(3.19)
between 3 and 6; however, Figures 3.3 and 3.4 show that many fruits and
vegetables require P values outside this narrow range. This problem has also
been recently investigated by Exama et al. (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.
[CO 2 ] % CO 2 concentration
[CO2J1 % CO 2 concentration inside the package at any time
[CO2J1 s % CO 2 concentration inside the package at steady state
[CO 2 ] in Inlet CO 2 concentration in flow-through system (%)
[CO 2 ] out Outlet % CO 2 concentration in flow-through system
[CO 2 ] O CO 2 concentration outside the package (%); 0% for air
[O 2 ] O 2 concentration (%)
[O2J1 O 2 concentration inside the package at any time (%)
[O 2 ] in Inlet O 2 concentration in flow-through system (%)
[C^lout Outlet O 2 concentration in flow-through system (%)
[Cy^s Steady-state O 2 concentration inside the package (%)
[O 2 ] o O 2 concentration outside the package (%); 2 1 % for air
a Conversion factor (1 hr"1)
(S Permeability ratio, PCQJPO2 (dimensionless)
a t , a2 Coefficients (Ir 1 )
bj, b 2 , C1, c 2 Coefficients (dimensionless)
JE1CO2, E02 Activation energies for respiration (J/mole)
EpCO2, EpOi Activation energies for permeability (J/mole)
F G a s flow rate (ml/h)
K1n M i c h a e l i s - M e n t e n constant (% O 2 )
K1 Inhibition constant (% C O 2 )
L Thickness of film ( m m )
MCO2 Molecular weight of C O 2 (0.044 kg/mole)
M02 Molecular weight of O 2 (0.032 kg/mole)
Patm Pressure of 1 atmosphere (atm)
^co2> ^ 2 Pre-exponential factors for permeability ( m g mil/m 2 h atm)
PCO2 Permeability to CO 2 (mg mil/m 2 h atm)
P02 Permeability to O 2 (mg mil/m 2 h atm)
P Pressure in the package or the jar (Pa)
R Gas constant (8.314 J/mol K)
^Co2' R o 2 Pre-exponential factors for respiration (mg/kg h)
RCo2 Rate of CO 2 evolution (mg/kg h)
RQ2 Rate of O 2 consumption (mg/kg h)
S Package surface areas (m 2 )
t Time (h)
T Absolute temperature ( 0 K)
V Free volume in package or in jar (ml)
Vm Maximum respiration rate (mg/kg h)
W Product weight (kg)
References
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Cameron, A.C., Boylan-Pett, W. and Lee, J. (1989) Design of modified atmosphere packaging
systems: modeling oxygen concentrations within sealed packages of tomato fruits. J. Food
ScL, 54, 1413-16, 1421.
Deily, K.R. and Rizvi, S.S.H. (1981) Optimization of parameters for packaging of fresh
peaches in polymeric films. /. Food Processing, 5(1), 23-41.
Emond, J.P., Castaigne, F., Toupin, CJ. and Desilets, D. (1991) Mathematical Modeling of
Gas Exchange in Modified Atmosphere Packaging. Transactions of the ASAE, 34(1),
239-45.
Exama, A., Ami, J., Lencki, R.W., Lee, L.Z. and Toupin, C. (1993) Suitability of plastic films
for modified atmosphere packaging of fruits and vegetables. J. Food ScL, 58(6),
1365-70.
Haggar, P.E., Lee, D.S. and Yam, K.L. (1992) Application of an enzyme kinetics based
respiration model to closed system experiments for fresh produce. J. Food Process
Engineering, 15, 143-57.
Hayakawa, K., Henig, Y.S. and Gilbert, S.G. (1975) Formulae for predicting gas exchange of
fresh produce in polymeric film package. J. Food ScL, 40, 186-91.
Isaka, T. (1988) Recent trends in use of far IR radiations: use on packaging films. Food lnd.
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Jurin, V. and Karel, M. (1963) Studies on control of respiration of Mclntosh apples by
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Joyce, D.C. (1988) Evaluation of a ceramic-impregnated Plastic Film as a Postharvest Wrap.
HortScience, 23, 1088.
Kader, A. A. (1987) Respiration of gas exchange in vegetables. In: Post Harvest Physiology of
Vegetables, J. Weichmann (ed.), Marcel Dekker, New York, Chapter 3.
Kader, A.A., Zagory, D. and Kerbel, E.L. (1989) Modified atmosphere packaging of fruits and
vegetables. CRC CHt. Rev. Food ScL Nut., 28(1), 1.
Katzyoshi, T. (1992) Freshness keeping packaging. In: Handbook of Food Preservation. K.
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365-74.
Labuza, T.P. and Breene, W.M. (1989) Application of 'active packaging' for improvement of
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Lebermann, K.W., Nelson, A.I. and Steinberg, M.P. (1968) Post-harvest changes of broccoli
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Lee, D.S., Haggar, P.E. and Yam, K.L. (1992) Application of ceramic-filled polymeric films
for packaging fresh produce. Packaging Technology and Science, 5, 27-30.
Lee, D.S., Haggar, P.E., Lee, J. and Yam, K.L. (1991) Model for fresh produce respiration in
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In: Modified Atmosphere Packaging of Food, B. Ooraikul and M.E. Stiles (eds), Ellis
Horwood, New York.
Prince, T.A. (1989) Modified atmosphere packaging of horticultural commodities. In:
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at various temperatures. J. Amer. Soc. Hort. Sci., 117(6), 925-9.
Veeraju, M. and Karel, M. (1966) Controlling atmosphere in fresh-fruit package. Modern
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Yam, K.L., Haggar, P.E. and Lee, D.S. (1993) Modeling respiration of low CO2 tolerance
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quality of stored tomatoes. Trans. ASAE, 31, 920-5.
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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
Table 4.1 Food characteristics influenced by oxygen scavengers
Characteristic Targets
Microbiological status Moulds, aerobic bacteria
Infestation Insects, larvae, eggs
Chemical degradation Rancidity, pigment/nutrient loss, browning
Physiological changes Respiration
Sachet Plastics
Applications
Years
Figure 4.1 Patent applications for oxygen scavengers involving sachets and plastics.
to overcoming previous deficiencies. This is particularly evident in patent
applications for systems involving oxidation of carbon-carbon double bonds
in small molecules like squalene and fatty acids or in polymers like rubbers.
In each case the transition-metal catalysed oxidation results in development
of odorous compounds such as low molecular weight aldehydes which are
adsorbed by zeolites, carbon or other adsorbents. In one example linseed oil,
iron oleate, calcium carbonate and active clay are mixed with activated
carbon to give a solid oxygen scavenger (Toppan, 1992). The advantage of
this system is that water is not needed as a reagent. Some compositions, such
as that of W.R. Grace and Co. for oxidation of squalene with a transition
metal catalyst (Ebner et al9 1992), appear not to include an adsorbent for
odorous products. Some patents involve claims of conventional antioxidants
as oxygen scavengers. The use of bifunctional antioxidants at up to 2% in
rigid poly(vinyl chloride) was claimed to reduce the permeability of that
polymer 20-fold although the period of effectiveness was not reported
(Wijbrief, 1971). These antioxidants are normally associated with reactions
of primary products of reaction of molecular oxygen with polymers, so the
mode of action of this process is still uncertain.
W. R. Grace and Co. has applied for patents for the use of ascorbic acid
dispersed into plastics such as the common heat-seal plastics or closure
liners (Hofeldt and White, 1989). This process relies on the presence of
water from the food or beverage as well as the presence of isoascorbic acid
or a metallic sulfite such as sodium sulfite. The process is now commercial
and follows the patent of Farrell and Tsai (1985) who patented the
sandwiching of either a sulfite alone, or one mixed with potassium acetate,
between the layers of a retortable pouch structure. Several other applications
for oxygen-scavenging plastics containing ascorbic acid have subsequently
been lodged. One combines oxygen scavenging with the antimicrobial action
of a silver zeolite (Shimagawa Nenryo KK, 1992).
CMB Foodcan pic has developed a novel system for use in blow-moulded
bottles made from PET into which up to 7% MXD-6 nylon had been
blended (Cochran et ai, 1991). An additional catalyst in the form of a
polymer-soluble cobalt salt such as cobalt stearate was necessary to cause
the nylon to react with oxygen.
An example of the performance of a bottle made from the Ox-Bar
(Trademark of CMB Technologies pic) has been given by Folland (1990).
The results suggest that beer held in such a bottle would be saved from
oxygen ingress via the bottle wall for at least 12 months thus providing
oxygen-barrier performance functionally equivalent to that of glass. As with
any form of active packaging, oxygen-scavenging plastics are designed to
achieve a specific effect - in this case protection of a packaged food from
oxygen. As it turns out, the shelf-life of carbonated beverages like beer is
limited by the loss of carbon dioxide by permeation. Thus the effect of the
oxygen-scavenging bottle would be to change the nature of the limiting
variable if used in those countries where beer has a high level of
carbonation.
This process has not reached the market place since the reaction products
need to be defined in greater detail. What is particularly interesting in this
case is that the use of a cobalt salt catalyst in PET appears to have satisfied
some national regulatory authorities.
2NaOH
HOHC HOHC
CH2OH
BROWNPRODUCTS
(4.2)
(4.3)
(4.4)
(4.5)
(4.6)
(4.7)
Time (min)
Figure 4.3 Oxygen scavenging by natural rubber , and PEF 0.5M in ethyl cellulose a, both dyed
with tetraphenylporphine, 103M. Volume of air, 20ml, pouch area 100cm2. (Reprinted from
Rooney, 1982b, with permission.)
oxygen (%)
time (minutes)
in darkness
illuminated
% Oxygen
Time (days)
in darkness
illuminated
% Oxygen
Time (days)
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
24C, 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 C26H30O8 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 mg/kg (Chandler et al, 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 1-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 mg/kg 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
(Johnson, R.L., private communication). On the other hand, the sorption of
limonene oil from packaged juices by heat-seal layers has been the subject
of several studies (Mannheim et al, 1989; Hirose et al, 1989). Thus
opportunities for active packaging can be closely related to problems of
food-package interactions.
A closely related goal had long been achievable commercially in the
tinplate canning of foods in which protein degradation resulted in the release
of sulfur compounds from the food. These sulfur compounds cause the
phenomenon of 'sulfur staining' on the tinplate and so it has been the
practice to disperse zinc oxide in tinplate lacquers to intercept such
compounds reacting with them before they can diffuse to the tinplate
surface.
The remaining methods described in the literature to date for removal of
taints or off-flavours have largely involved incorporation of ingredients with
a specific interaction or reaction with a functional group known to be present
in the taint or undesirable food component. Two types of taints amenable to
removal by active packaging have been identified by researchers responsible
for current commercial products. These are amines resulting from protein
breakdown in fish muscle and aldehydes formed from the breakdown of
peroxides which result from the initial stages of autoxidation of fats and oils.
The formation of aldehydes can make a wide variety of oil-containing foods
organoleptically unacceptable well before there is significant damage to the
nutritional or functional properties of the food. Examples of such products
would be fried snackfoods such as potato crisps, biscuits and cereal
products. Early developments occurred in Japan where there was seen to be
a need to remove amine smells from fish which was stored in domestic
refrigerators. The amines formed in fish muscle degradation include strongly
basic compounds and thus are potentially strong in their interaction with
acidic compounds such as citric or other food acids. Hence the earliest work
involved incorporation of such acids in heat-seal polymers such as
polyethylene and extruding them as layers in packaging (Hoshino and
Osanai, 1986).
A later approach to removal of amines odours has been provided by the
ANICO Company Ltd in Japan under the trade name ANICO BAG. Bags
made from film containing ferrous salt and an organic acid such as citric or
ascorbic acid are claimed to oxidise the amine or other oxidisable compound
as it is absorbed by the polymer.
If these materials can be shown to be effective there is an opportunity to
determine which variables optimise their rate and extent of reaction.
Questions which would need to be answered are What is the nature of the
products of such reaction and What is their fate. Questions such as these are
of particular interest to regulatory authorities, and the potential for several
active packaging systems to generate mobile reaction products is considered
in Chapter 11.
Removal of aldehydes such as hexanal and heptanal from package
headspaces is claimed by Dupont Polymers, Packaging Division, for their
recently introduced tie layer Bynel IXPlOl which is a high-density
polyethylene (HDPE) resin masterbatch. This masterbatch is blended
(2.5-12%) with unmodified HDPE or other linear polyethylenes to form an
intermediate layer in coextrusions. It is specified that the heat-seal layer
should not be a 'good to excellent gas barrier' (Dupont, 1993). It is
interesting to note that the use of a form of active packaging can place
restrictions on other components of the packaging. The restriction in this
case, and many others, is that the extrusion temperature should not exceed
2200C to avoid fuming. The chemistry of the process is not described but
such a process would require the reaction with the aldehyde to be effectively
irreversible at least over the temperature range the package is likely to
encounter. One such reaction would be the formation of a Schiff base by
reaction of the aldehyde with an amino group. The amino group would need
to be rather stable to heat and oxygen in order to remain unaffected after the
extrusion at temperatures up to 2200C in an air atmosphere.
There may well be a wide range of food constituents which can be
removed by making use of specific interactions with selected packaging
components or by chemical reaction with them. A fertile research field
would seem to be open especially with liquid foods since solubility and
diffusion of food constituents in the packaging can be utilised so that the
removal process is not limited to compounds with a significant vapour
pressure at distribution temperatures. It will be necessary for industry and
regulators to ensure that such processes are not used to conceal the
marketing of sub-standard or even dangerous products if for instance
microbial odours were to be scavenged.
The tainting of foods by compounds originating either in the packaging
material itself (e.g. monomers) or outside but permeating the packaging
material continues to be a source of problems for the food industry. The
approaches described above may contribute to their solution but additional
approaches have been described in the patent literature. These are formation
of chemical barriers as distinct from physical barriers like aluminium foil or
crystalline polymers.
Myrcene (7-methyl-3-methylene-l,6-octadiene) has been found to react
with traces of styrene or acrylonitrile when the latter are present in
acrylonitrile-butadiene-styrene copolymers or blends being extruded
(Tokas, 1979). Addition of myrcene is claimed to introduce no new taint
while reducing residual levels of the monomers. In another patent, foods
packaged in plastics consisting of more than one layer are claimed to be
protected against taints from the outside by inclusion of the appropriate
adsorbent in the outer layer (Kiru Kogyo KK, 1994). The adsorbent is
chosen for expected taints and is kneaded onto the outer layer, apparently
retaining the taints there. The period of this type of equilibrium adsorption
needs to be established, especially when a package is subjected to
temperature changes. This may have application in areas where products are
to be stored or shipped together with odorous products which are
inadequately packaged.
A compound which while not a taint is often found undesirable in
packages of respiring horticultural produce is the gaseous auxin ethylene.
The potential benefits resulting from such removal are particularly great and
are discussed separately in Chapter 2.
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 aL9 1978). Hinokitiol,
also known as p-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 aL, 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 CaIvert 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 39C 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
been used as a reservoir for antioxidant release by the US cereal
industry.
Other antioxidants might also be used in this way. Lignert and Eriksson
(1980) found that Maillard reaction products have a strong antioxidant
function. This work has been extended by Anese et al (1993). The potential
for applying such antioxidants to foods via packaging materials has been
suggested (Eriksson, private communication).
The patent of Goyo Shiko KK (1993) describes application of amino acids
and saccharides which produce reducing sugars on decomposition and
perform as oxygen scavengers when used in coating or lamination of
packaging films. These compositions would be expected to undergo the
Maillard reactions but their rate would depend upon the thermal conditions
used in preparing the packaging and any thermal processing of the packaged
product. The inventors nominate liquid foods in cans as a target product area
and, given the hydrophilic nature of the polymers involved, it appears likely
that Maillard reaction products could be extracted into the food to act as
antioxidants as well as scavengers.
It has recently been shown that polyethylene bottles stabilised with
vitamin E cause less noticeable flavour in distilled water than bottles
stabilised with either BHT or Irganox (a hindered amine antioxidant for
polymers). There is an opportunity to investigate whether oils can be
stabilised by diffusive addition of antioxidant at sustained low levels from
the packaging.
The observation of Han et al (1987) that BHT was lost outwards from
HDPE film packs points to an otherwise unrelated opportunity for active
packaging. There has been constant pressure from importers of grains and
other agricultural products for reduced levels of pesticide residues in these
products at the time of delivery. Packages such as sacks and lined cartons
containing these products are often attacked by insects during warehousing
and transport. The inclusion of low-toxicity fumigants such as pyrethrins in
an outer layer of packaging material offers the opportunity to achieve
sustained insecticidal activity without substantial addition of fumigant to the
food. Highland and Cline (1986) found that polypropylene containing
203 mg m~2 of permethrin provided rather similar resistance to attack by
burrowing insects to that provided by polyester which has a harder, slippery
surface. Their work involved exposing: polyethylene; polypropylene/poly-
propylene/polyethylene laminate, the latter containing permethrin in the
outer layer; and polyester/polyethylene pouches of many foods, to four
insect populations. The permethrin-treated pouches were resistant to two
insect species for 24 months. The effect was not entirely consistent since the
treated pouches failed at 24 months with one insect species and were better
than polyester with one of the remaining species and worse than polyester
with the other. The authors concluded that the order of descending resistance
of films to the insects was permethrin-treated film, polyester film, polyethyl-
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.
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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.9 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
can be applied by different methods: with a paint brush or by spraying,
dipping-dripping, fluidizing, etc. Films are preformed separately from the
food product. They can be produced, for instance, by drying a film-forming
solution on a drum-drier, by cooling a molten compound, or through
standard techniques used to form synthetic packagings, e.g. thermoforming
or extrusion techniques for thermoplastic materials (Guilbert and Biquet,
1989; Kester and Fennema, 1986).
The production process from a film-forming solution generally includes a
first step with macromolecule solubilization in a solvent medium (often
water-, ethanol- or acetic acid-based) which can contain several additives
(plasticizers, crosslinking agents, solutes, etc.). The film-forming solution is
spread in a thin layer, usually followed by a drying treatment. The functional
properties of the film are dependent on a number of parameters (Gontard,
1991; Gontard et al.9 1992): formulation (characteristics and concentration
of the basic and secondary components, pH, denaturing conditions, etc.),
film-forming conditions (type of surface upon which the film-forming
solution is spread, drying conditions) and conditions in which the film is
used (temperature, relative humidity).
The degree of cohesiveness of the matrix is a critical parameter affecting
the functional properties of edible films (Banker, 1966). It is sometimes
difficult to obtain adequate adhesion of the film to the food product, for
instance when a hydrophobic film-forming material is used to protect a
hydrophilic food product. In such cases, surface-active agents can be coated
on the food or added to the film-forming solution, or a material capable of
adhering to both components can be applied as an intermediate precoating
(e.g. precoating with cocoa before sugar-coating peanuts).
An edible film is an integral part of the food product it encloses and
therefore must have neutral sensorial properties (or compatible with product
nature) so as not to be detected during consumption. Application of an edible
barrier layer is an easy means to structurally strengthen certain foods, to
reduce particle clustering and to improve the visual and tactile features on
the surface of the product. For example, Allen et al. (1963b) used alginate
and cornstarch coatings to improve texture juiciness, general appearance,
surface texture and color of beef steaks and pork chops. Edible films can
also be used to package components or additives that are to be dissolved in
hot water or food mixes (Daniels, 1973; Kroger and Igoe, 1971).
Edible films or coatings act as an additional parameter for improving
overall food quality and stability. They represent one way to apply hurdle
technology to solid foods without affecting their structural integrity
(Guilbert, 1994; Guilbert et aL, 1995). Many functions of edible films are
the same as those of synthetic packaging (water, gas and solute barriers,
mechanical properties, opacity, etc.). However, they must be chosen
according to their specific application (i.e. type of food product and main
deterioration mechanisms).
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 ai9 1994; Guilbert, 1988; Torres et aL, 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
Water Transfer
Storage
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).
properties, on modification of surface conditions and on their own
antimicrobial properties.
Table 5.2 Effect of coating operation on water vapor permeance 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
permeance T Thickness RH %
Film (X 108 mol m~2 s'1 Pa'1) (0C) (X 103 m) conditions
_ _ _ _ _ _ 84_22
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 35C) (after Torres and Karel, 1985).
increase in film moisture content (rise in the sorption isotherm) and so
induces an increase in water vapor permeability. At high aw, extensive
swelling of the protein network with water probably enhances water
molecule diffusion and such films would clearly not be efficient water vapor
barriers (Figure 5.3).
Many authors have studied the effect of temperature on water vapor
transfer using synthetic, simple edible films (protein or cellulose-based) or
composite edible films (cellulose derivatives and lipids). A rise in tem-
perature causes an increase in water vapor permeability (Figure 5.4). This is
often characterized by Arrhenius-type representations (Donhowe and
Fennema, 1993b; Higuchi and Aguiar, 1959; Kester and Fennema, 1989a, c).
In films formed with hydrophilic materials, temperature-dependent varia-
tions in barrier properties are affected by the moisture level (see Figure 5.3
for gluten films). However, it was difficult to interpret the temperature
dependence of the effect of hydration on water vapor permeability of gluten
film in terms of disruptive water-polymer hydrogen bonding in a polymer
hydrogen-bonded network. The critical role of water as plasticizer of gluten
film appeared to be highly temperature dependent. According to Levine and
Slade (1987) and Slade et al (1989), the structure/property relationships of
hydrated proteins, and particularly of gluten, could be better understood
through the theories of glass transition used in polymer science, in terms of
critical variables of time, temperature and moisture content. Glass transition
Water activity
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 mg/cm2) at 25C and 32% RH
gradient (according to Kamper and Fennema, 1984a), and of edible wheat gluten films at 5, 30 and
500C, and 10% RH gradient (according to Gontard et al., 1993). , MC and C 1 8 -C 1 6 at 25C
(WVT x 0.1); D, gluten at 500C; D, gluten at 300C; D, gluten at 5C
hydrated proteins, and particularly of gluten, could be better understood
through the theories of glass transition used in polymer science, in terms of
critical variables of time, temperature and moisture content. Glass transition
is typically described as a transition from a brittle glass to a highly viscous
or rubbery solid. It is well established that plasticization by water affects the
glass transition temperature of amorphous or partially crystalline proteins
such as gluten (Gontard et al., 1993; Hoseney et al., 1986), gelatin (Marshall
and Petrie, 1980; Yannas, 1972), collagen (Batzer and Kreibich, 1981) and
elastin (Kakivaya and Hoeve, 1975; Scandola et al., 1981), thus resulting in
a drop in the glass transition temperature. The anomalous diffusion behavior
of glassy polymers may be directly related to the influence of the changing
polymer structure on solubility of the penetrant and diffusional mobility of
the penetrant (Crank, 1975).
The water vapor barrier properties of edible active films and coatings have
been used in several food systems. For example, meat coatings composed of
corn starch and alginate were used by Allen et al. (1963a) to reduce moisture
loss by 40-48%. Avena-Bustillos et al. (1993) found that sodium caseinate
and stearic acid emulsion coatings improved the storage stability and
reduced water loss of peeled carrots. The use of sucrose esters of fatty acids,
mono- and diglycerides, and the sodium salt of carboxymethylcellulose
coatings allowed the increase of water vapor resistance (up to 75%) in
zucchini fruit (Avena-Bustillos et al., 1994). Wax is commercially applied to
Temperature (0C)
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).
a, Gluten (WVP X 0.1); A, MC and beeswax; , monostearate.
many fruits and vegetables to reduce dehydration and improve consumer
appeal (Hall, 1981), e.g. to oranges (Albrigo and Brown, 1970; Bursewitz
and Singh, 1985; Eaks and Ludi, 1970), to apples (Hall, 1966; Trout et al,
1953), to prune plums (Bain and McBean, 1967), and to sweet cherries
(Drake et aL, 1988; Lidster, 1981). Ukai et al (1976) used hydrophobic
emulsions to coat fruits and vegetables such as orange, peas, apples, green
beans, tomatoes, pears, and peaches. Lidster (1981) suggested the use of
xanthan gum applied to cherries as a postharvest dip to prevent water loss.
El Ghaouth et al. (1991) used edible chitosan coating to reduce water loss of
cucumber and bell pepper fruits.
The use of edible films to lessen internal migration of moisture in foods
has been studied by several investigators, and some of these films appear
promising for commercial use (Fennema et al, 1993; Greener and Fennema,
1989b; Kamper and Fennema, 1985; Kester and Fennema, 1989d; Rico-Pena
and Torres, 1990). One standard example of moisture transfer control in
heterogeneous food is the wafer-ice cream system of ice cream cones. In
standard conditions, the wafer loses its crispness after three months' storage
at -23C. This qualitative degradation is due to moisture transfer between
the ice cream and the wafer. Rico-Pena and Torres (1990) tested composite
films (methylcellulose and chocolate and methylcellulose, chocolate and
palmitic acid) to separate the two components. Films can limit moisture
transfer during ice cream cone storage at -23 0 C or -12C and preserve wafer
crispness. Films based on methylcellulose, chocolate and palmitic acid are
the most efficient. In addition, several studies have confirmed the efficiency
of chocolate and cocoa butter coatings as moisture barriers (Biquet and
Labuza, 1988; Kempf, 1967; Landman et al, 1960; Neidiek, 1981; Soboleva
and Chizhikova, 1978; Tiemstra and Tiemstra, 1974).
These examples show that water vapor transfer in food products can be
controlled using edible films and coatings. The knowledge of the influence
of parameters such as structure and composition of film-forming materials,
allows modulation of the water barrier properties of these edible active
layers either on the food surface or in multicomponent foods.
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
atmosphere' effect in fresh fruit and for improving the storage potential of
these products (Smith et a/., 1987; Trout et al., 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 unsaturation (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.9 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 a/., 1994b).
High aw conditions cause an increase in gas permeability in hydrophilic
Table 5.3 Oxygen and carbon dioxide permeabilities of various films
O2 Permeability CO2 Permeability T
Film (X 1O18HIoImIn-2S-1Pa-1) (X 1018 mol m m 2 s 1 Pa 1 ) (0C) aw
_ _ _ __ _ _ __ 0 0
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
Water activity
Figure 5.5 Effect of water activity on oxygen permeability of edible and synthetic films at 25C
(according to Gontard et al, 1994b (o, gluten); Poyet, 1993 (A, EVOH; , Nylon 6); Rico-Pena and
Torres, 1990 (D, MC and palmitic acids, at weight ratio 3:1); Rigg, 1979 (, cellophane)). (MC is
methylcellulose; EVOH is ethylene-vinyl alcohol).
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 25C and 105 Pa; oxygen solubility = 1.25mmol/l at 25C
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 aL,
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
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
on microbial growth (natural microflora and coliform inocula). The specific
antimicrobial activity of calcium alginate coatings has not yet been
explained, but could be partially due to the presence of calcium chloride. El
Ghaouth et aL (1990, 1991) used chitosan-based coatings to protect fresh
vegetables (cucumbers, peppers). These coatings improved fruit appearance
and reduced microbial degradation. This effect, which has also been
obtained on strawberries, can be attributed to the specific antifungal
properties of chitosan molecules (Allan and Hadwiger, 1979; Hirano and
Nagao, 1989; Stossel and Leuba, 1984). Zein-based films have been found to
successfully reduce microorganism penetration into chicken egg shells after
surface inoculation (Tryhnew et aL, 1973).
Development of processes that specifically enhance surface microbial
stability is required; food processors have used preservative dips and sprays.
Potassium sorbate (or sorbic acid), which has a wide range of bacteriostatic
and mycostatic properties, can be used by dipping to reduce the total number
of viable bacteria at both refrigeration and elevated temperatures
(Cunningham, 1979; D'Aubert et aL, 1980; Lueck, 1984; Robach, 1979,
Robach and Ivey, 1978; Robach and Sofos, 1982; To and Robach, 1980;
Torres et aL, 1985b; Zamora and Zaritzky, 1987a, b). However, the shelf-life
extension achieved by these surface treatments is limited by problems
related to potassium sorbate (or sorbic acid) stability and diffusion. The
stability of sorbic acid (in its active non-dissociated form) is dependent on
application conditions; e.g. a lowered pH improves stability (Eklund, 1983).
The diffusion into the core of the food results in a reduction in preservative
concentration on the surface which allows microorganisms to overcome the
sorbate-induced bacteriostasis (Greer, 1981; Torres, 1987).
It is important to be able to predict and control surface preservative
migration between phases during food treatments (e.g. absorption of sorbic
acid during the processing of dried prunes, or its loss during cooking of
fabricated foods), storage of composite foods (e.g. dairy products or cakes
containing pretreated fruits), storage of foods in contact with wrapping
materials or films containing sorbic acid (absorption by dairy products
covered with paper saturated with sorbic acid) and storage of foods coated
with an external edible layer highly concentrated in sorbic acid (Guilbert,
1988).
Edible films and coatings can be used as food preservative media
(particularly as antioxygen and antifungal agents) and as surface retention
agents to limit preservative diffusion in the food core (Guilbert, 1986, 1988;
Kester and Fennema, 1986; Torres et aL, 1985b; Vojdani and Torres, 1989a,
b, 1990). Maintaining a local high and effective concentration of pre-
servative may allow, to a considerable extent, a reduction of its total amount
in the food for the same effect (as schematized in Figure 5.1), i.e. at the
surface of the food to reduce aerobic contamination and/or oxygen
influence.
% Retention
Time (days)
Figure 5.6 Tocopherol retention at 25C 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). D, Gelatin layer - aqueous model food; , gelatin layer treated - aqueous model
food; o, gelatin layer - margarine; , gelatin layer treated - margarine.
moisture agar model system, Guilbert et al. (1985) reported a value of 2.0 x
10~10m2/sec. Torres et al. (1985b) found with an intermediate moisture
cheese analog a value of 1.0 x 10"10m2/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, aw), 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 24C and aw =
0.77
Sorbic acid permeability
Film (x 108 g mm m"2 s'1 (g/1)"1)
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 = hydroxypropylmethylcellulose; MC = methylcellulose.)
According to Vojdani and Torres (1990), sorbic acid permeability
decreases in composite films (hydroxypropyl methylcellulose or methylcel-
lulose and fatty acids) as the lipid derivative concentration increases; it also
decreases as the length of the carbon chain in fatty acids increases and with
the presence of double bonds. This is consistent with published data on the
solute permeability of synthetic lecithin liposomes. De Gier, et al. (1968)
found that increasing the lecithin fatty acid chain length decreased the
permeability of glycerol and erythritol through these artificial membranes.
McElhaney et al. (1970) showed that the permeability of liposomes was
altered by the geometrical configuration and the number of double bonds in
the fatty acid component.
The composite film-forming technique used to form composite films or
coatings (emulsions or multilayers) also affects the sorbic acid barrier
properties. According to Vojdani and Torres (1989a) the lowest permeability
values are found with bilayer composite films. For example, the sorbic acid
permeability for an emulsion composite film of methylcellulose and palmitic
acid was 3 times lower than for bilayer composite film.
As noted for water vapor and gas permeability, temperature and relative
humidity affect the permeability of edible film to sorbic acid (Figure 5.7). At
constant temperature, the sorbate permeation rate decreased as aw decreased
(Vojdani and Torres, 1989a; Rico-Pena and Torres, 1991). This is consistent
with studies in food model systems (Giannakopoulos and Guilbert, 1986a)
where sorbic acid diffusivity rises at high aw.
Water activity
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 24C (), (according to Rico-
Pena and Torres, 1991); and on sorbic acid diffusivity in agar gels with sucrose () or glycerol (o)
at 25C (according to Giannakopoulos and Guilbert, 1986b).
Sorbic Add Permeability (SAP), (x 108 g . m . nr*. s ! . (g /1)')
Temperature (0C)
Figure 5.8 Effect of temperature on sorbic acid permeability of edible multicomponent 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 = 1.0 (according to De Savoye et al., 1994). o, MC; ,
MC and palmitic acid; a, HPMC; , HPMC and palmitic acid; A, chitosan; A, pectin (SAP X
0.005).
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 aw = 0.77 and 24C (according to Rico-
Pena and Torres, 1991) and of edible pectin (Psa X 0.01) films (D) at aw = 1.0 and 200C (according
to De Savoye et ah, 1994).
barrier layers double the shelf-life of the food product before the appearance
of microorganisms. Torres et al. (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 24C 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 24C, then the permeability = 0.042 g mm
m"2 24 h"1 (g/1)"1; 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 5C), 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
Table 5.7 Stability of coated intermediate moisture papaya cubes (as a function of a w ) at 30 0 C
inoculated with Aspergillus niger(a) or Staphylococcus rouxii{h)
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 1
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 carnauba wax (a) > 40 > 40 > 28 10
(b) >40 >40 >40 14
Coated with carnauba 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
(uncoated control)
(reduced pH surface)
Time (days)
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 35C) (after Torres and Karel, 1985).
charged macromolecules has made it possible to obtain a pH difference
between the surface and core of enveloped intermediate moisture food
products. A Donnan equilibrium model for semipermeable membranes
containing charged macromolecules can be used to assess the possibility of
obtaining a permanent pH difference between two components separated by
a membrane. The use of agarose- and carrageenan-based edible films (with
charged macromolecules) decreases the surface pH by about 0.5. In addition
to carrageenans, slightly esterified pectins could probably be used for similar
applications (Guilbert and Biquet, 1989). A decrease in surface pH can also
improve the stability and efficiency of antimicrobial agents such as sorbic
acid.
Microbiological analyses have confirmed the antimicrobial efficiency of
this type of surface treatment (Torres and Karel, 1985). Studies of bacterial
growth (Staphylococcus aureus) on intermediate moisture foods revealed
improved microbiological stability with the use of carrageenan-based edible
films (Figure 5.10).
Edible films and coatings are a useful mean to reduce the rate of some
deteriorative reactions such as surface microbial development or oxidation.
They could also be used to achieve the slow release of flavor compounds
during food storage or consumption. Initial choices of film-forming
materials and of fabrication conditions allow modification of solute retention
properties of these edible active layers, and allow selection of the efficient
functional properties in relation to each specific application, according to
specific needs.
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
production constraints, i.e. coatings or preformed films applications proce-
dure must be realizable on the industrial scale and be easily integratable in
the food processing line.
Acknowledgements
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chitosan, methylcellulose and hydroxypropyl methylcellulose. Journal of Food Process
Engineering, 12, 33-48.
Vojdani, F. and Torres, J.A. (1990) Potassium sorbate permeability of methylcellulose and
hydroxypropyl methylcellulose coatings: effect of fatty acids. Journal of Food Science,
55(3), 841-6.
Watters, G.G. and Brekke, J.E. (1961) Stabilized raisins for dry cereal products. Food
Technology, 5, 236-8.
Williams, S.K., Oblinger, J.L. and West, R.L. (1978) Evaluation of a calcium alginate film for
use on beef cuts. Journal of Food Science, 43, 292-6.
Yannas, LV. (1972) Collagen and gelatin in the solid state. / . Macromol. Sci. - Revs.
Macromol. Chem., 7, 49.
Zamora, M.C. and Zaritzky, N.E. (1987a) Antimicrobial activity of undissociated sorbic acid
in vacuum packaged beef. Journal of Food Science, 52(6), 1449-53.
Zamora, M.C. and Zaritzky, N.E. (1987b) Potassium sorbate inhibition of microorganisms
growing on refrigerated packaged beef. Journal of Food Science, 52(2), 257-62.
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 aL, 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 CO2, 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 al., 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
oxygen/carbon dioxide absorbents, oxygen absorbents/carbon dioxide gen-
erators, and ethanol vapor generators. This technology involves the use of
sachets which can be placed alongside the food and actively modify the
package headspace thereby extending product shelf-life. This chapter will
review the various types of absorbent/generator sachets available in the
marketplace, the methods by which these sachets actively modify the gas
atmosphere in the packaged product, and their uses, advantages and
disadvantages for shelf-life extension of food.
Time (day)
Figure 6.1 Effect of storage temperature on oxygen absorbing speed of Ageless S-IOO, a self
working type (fast working type) of oxygen absorber.
Time (day)
Figure 6.2 Effect of storage temperature on oxygen absorbing speed of Ageless Z-100, a self
working type (medium working type) of oxygen absorber.
However, if used with refrigerated or frozen products these absorbents react
very slowly. To overcome this problem, some absorbents can now scavenge
oxygen rapidly from the package headspace of food stored under low-
temperature conditions. A comparison of the oxygen absorbing speed of one
such type of oxygen absorbent (Ageless SS) with absorbents which function
mainly at ambient storage temperatures, is shown in Figure 6.3.
AGELESS FX-100
Time (day)
Figure 6.3 Effect of frozen temperature (-250C) on oxygen absorbing speed of three types of
oxygen absorbents.
bents-carbon dioxide generators. The latter type of sachets absorb O2 and
generate the same amount of CO2 as that of absorbed oxygen. They are
mainly used in products where package volume and package appearance is
critical, e.g., packaged peanuts. These sachets contain iron carbonate and
ascorbic acid as the reactants. Another dual functional absorbent scavenges
oxygen and releases alcohol vapor. These absorbents could be used to
control the growth of facultative bacteria and yeasts which grow under
reduced oxygen tensions. However, this type of dual functional absorber is
not widely used by the Japanese food industry (Harima, 1990). Examples
of single function and dual function oxygen absorbents are shown in
Table 6.2.
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 O2. 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.
Table 6.4 Types and properties of Freshilizer oxygen absorbents
Absorption speed
Type Function Moisture status Water activity (day)
F Series (ferrous metal)
FD Decreases O2 Self-reacting <0.8 1-3
FH Decreases O2 Self-reacting 0.6-0.9 0.5-1.0
FT Decreases O2 Moisture dependent > 0.8 0.5-1.0
C Series (Non-ferrous metal)
C Decreases O2 Self-reacting < 0.8 3-5
Increases CO2
CW Decreases O2 Self-reacting 0.8-0.9 2-3
Increases CO2
CV Decreases O2 Self-reacting < 0.3 3-8
Decreases CO2
Courtesy of Toppan Printing Co., Tokyo, Japan.
AGELESS
AIR
(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, 25C; absorber, Ageless Z-50.
AIR N 2 gas
POV (peroxide value : meq/kg)
AGELESS
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,fluorescentlight.
Table 6.7 Effect of an oxygen absorbent on the shelf life quality of
chocolate-coated almonds.
40 days 3 months 6 months
Ageless O2(%) 0.01 0.01 0.01
POV almond 2.3 1.2 1.5
POV chocolate 1.1 1.0 1.0
Flavor score 5 5 4
Air O2(%) 18.2 13.3 9.5
POV almond 7.8 16.4 23.5
POV chocolate 0.9 1.2 2.1
Flavor score 4 3 2
(Almond without chocolate coating)
Air O2(%) 14.3 6.7 1.7
POV almond 14.0 21.1 28.8
Flavor score 2 1 1
Material: 20Og in an ON/PVDC/PE bag; Water activity: 0.31;
Moisture content: 2.1% (almond), 0.8% (chocolate); Stored: 25C;
Ageless: Z-50PK. Flavor score: 5 = no rancid smell, good aroma and
good flavor; 4 = aroma slightly lost but good flavor; 3 = little rancid
smell but good flavor; 2 = rancid smell and flavor weakened;
1 = obvious rancid smell and flavor loss.
absorbents for shelf life extension of food can be found in the excellent
articles referenced at the beginning of this section.
62.42 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
Table 6.8 Use of Ageless for shelf-life extension of bakery products
Water activity of Type and size of
Type of food food Packaging materials Ageless Prevents Shelf-life @ RT*
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:
Inexpensive and simple to use.
Approved by the US Food and Drug Administration as non-toxic and
safe to use.
Prevent aerobic microbial growth and extend shelf-life of product.
Arrest the development of rancid off-flavor in fats and oils.
Maintain flavor quality by preventing oxidation of the flavor com-
pounds.
Maintain product quality without additives.
Increase product shelf-life and distribution radius.
Allow a long time between deliveries and allow fewer, longer deliv-
eries.
Increase length of time product can stay in the distribution pipeline.
Reduce distribution losses.
Replace chemical pesticides to prevent insect damage of foods.
Reduce evacuation/gas flushing times in gas packaged products thereby
increasing product throughput.
Reduce costs required for gas flushing equipment.
A few of the disadvantages of oxygen absorbents are (Harima, 1990; Smith
et aL, 1990; Smith, 1992):
There needs to be a free flow of air surrounding the sachet in order to
scavenge headspace oxygen if an O2 absorbent is used alone.
May cause package collapse; this can be overcome by using an O2
absorbent/CO2 generator.
O2 absorbents/CO2 generators may cause flavor changes in high
moisture/fat foods due to the dissolution of CO2 in the aqueous/fat phase
of product.
Cost - approximately 2.5-10 cents per sachet depending on size of
sachet and volume ordered. Many processors regard oxygen absorbent
sachets too expensive.
Consumer concerns about sachets inside the packages and possible
consumer misuse of sachets.
May promote growth of potentially harmful anaerobic bacteria.
The two latter concerns will be briefly discussed.
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.)
-I*
O
Z
<
Z
Ul
Ul
O
(0
S
Ul
X
DAYS STORAGE 25 *C
Figure 6.7 Effect of water activity (aw) on generation and absorption of ethanol vapor. , 0.85 + E4;
A 0.95 + E4; , 0.99 + E4; o, 0.85 + E1;*, 0.95 + E1; o, 0.99 + E1.
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
quality after 3 weeks, characterized by a loss of moistness and firmness of
the texture and development of soapy and rancid flavors. Therefore, while
Ethicap could be used to extend the mold-free shelf-life of the product, the
sensory quality of the product was not significantly extended (Pafumi and
Durham, 1987).
Black et al (1993) examined the combined effect of gas packaging and
Ethicap (size unknown) to extend the shelf-life of pita bread. They reported
a 14 day mold-free shelf-life for pita bread packaged in 40% CO2 (balance
N2) or 100% CO2. However, the shelf-life was doubled when an Ethicap
sachet was incorporated into the gas packaged products (Black et al, 1993).
However, these authors reported that ethanol vapor had little anti-staling
effect on pita bread. While the effect of increased firmness due to staling
was reversed by microwave heating, it failed to eliminate the stale flavors in
the pita bread (Black et al, 1993). The authors also observed a slight
increase in headspace oxygen in all gas packaged products stored with
Ethicap. They hypothesized that the ethanol vapor may have dissolved in the
film and acted as a plasticizer, thereby affecting the permeability of the film
to both oxygen and carbon dioxide (Black et al, 1993).
Ethicap has also been used as a means of further extending the shelf-life
of gas packaged apple turnovers (Smith et al., 1987). Apple turnovers, with
a water activity of 0.93, had a shelf-life of 14 days when packaged in a CO2:
N2 (60:40) gas mixture at ambient temperature due to growth of and CO2
production by Saccharomyces cerevisiae. However, when Ethicap (E4) was
incorporated into the packaged product either alone or in conjunction with
gas packaging, yeast growth was completely suppressed and all packages
appeared normal at the end of the 21-day storage period (Smith et al,
1987).
Ethicap has also proved effective in controlling secondary spoilage
problems by 5. cerevisiae in gas packaged strawberry and vanilla layer cakes
and cherry cream cheese cake. Ooraikul (1993) reported that 5 G sachets of
Ethicap inhibited growth of, and CO2 production by, 5. cerevisiae in both
strawberry and vanilla layer cakes. This size of the Ethicap sachet had no
adverse effect on the organoleptic quality of cakes. Indeed, Ooraikul (1993)
reported that the aroma of the cake packaged with Ethicap was more
pleasant than that of the fresh cake and that the taste also remained excellent.
However, a 6 G Sachet of Ethicap failed to inhibit yeast spoilage in cherry
cream cheese cake (Ooraikul, 1993). He recommended a 7-8 G sachet of
Ethicap in conjunction with a preservative, such as ethyl paraben, to control
secondary yeast fermentation problems in cherry cream cheese cake
(Ooraikul, 1993). These studies show that larger sizes of Ethicap, and hence
higher levels of ethanol vapor, are required to inhibit yeast growth compared
to mold growth. Indeed, agar model studies have shown that yeasts can
grow in media containing 8% (v/v) ethanol while most molds were inhibited
by 4% ethanol (Freund Technical Information, 1985).
633 Effect of ethanol vapor on food spoilage/food poisoning bacteria
While most studies to date have focused on the use of Ethicap as an
antimycotic agent, few studies have evaluated its potential to control food
spoilage and food poisoning bacteria. Ethanol, when incorporated into agar
media, has proved to be effective against several spoilage and pathogenic
bacteria (Freund Technical Information, 1985; Shapero et al., 1978). Seiler
and Russell (1993) also reported that ethanol at a level of 1% by product wt.,
delayed the onset of 'rope' caused by the growth of Bacillus subtilis. They
also reported that low concentrations of ethanol (0.5-1% by product wt.)
inhibited bacterial growth in both whipping cream and custard, two well-
known vectors of food poisoning bacteria in filled bakery products. These
studies clearly illustrate the antibacterial properties of ethanol when
incorporated directly into media or a food product. More recently, Morris et
al. (1994) examined the effect of Ethicap on the growth of Listeria
monocytogenes, a psychrotrophic food-borne pathogen of public health
significance. They observed that a 4 G sachet of Ethicap could control the
growth of L. monocytogenes (Scott A) on agar media at 5, 10 and 15C, the
latter storage conditions representing mild temperature abuse. Further
studies are now underway to determine the volume of ethanol vapor
generated at these storage temperatures and the effect of these concentra-
tions on the microbiological and chemical shelf-life of fresh packaged
pork.
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.
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Ellis, W.O., Smith, J.P., Simpson, B.K., Khanizadeh, S. and Oldham, J.H. (1993) Control of
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(MAP) conditions. Food Microbiology, 10, 9-21.
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transmission rates on aflatoxin production by Aspergillus flavus in peanuts packaged under
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Harima, Y. (1990) Food Packaging, Academic Press PubL, London, UK, pp. 229-52.
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Lambert, A.D., Smith, J.P. and Dodds, K.L. (1991c) Effect of initial O 2 and CO2 and low-dose
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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.
The second important characteristic of enzymes is their specificity.
Enzymatic specificity takes on two distinct forms: the type of chemical
reaction; and for any type of chemical reaction, a specificity for the reactant
or substrate. Consequently, for each chemical reaction that occurs in a
biological system, there is a unique enzyme required for the optimal
production of reaction products. With so many different biological reactions,
it follows that there are many different enzymes.
As with all catalysts, enzymes do not alter equilibrium conditions. An
enzyme increases a forward reaction in the same way and to the same extent
that it increases the reverse reaction, i.e., enzymes accelerate the rate at
which a chemical equilibrium is reached but an enzyme does not distort the
ratio of the equilibrium concentrations of the products to reactants.
The catalytic potential of enzymes and the speed at which they facilitate
chemical reactions lies in their ability to reduce the Gibbs Free Energy of
Activation (Ea). Enzymes accomplish their catalytic objectives, not by
reducing the Ea of the uncatalyzed reaction but by creating a new and
different transition state and hence a different reaction path or mechanism.
This new or different transition state is the enzyme-substrate complex (ESC)
where the reactant becomes associated or bound to the free enzyme at the
reactive center or site, followed by the release of the product which
generates the free enzyme again. The now free enzyme is once again
available to combine with another molecule of reactant to repeat the process.
The net effect of this sequence is that reactant or substrate becomes product
and the enzyme is unchanged.
The active site is an area or region of an enzyme where the bond-breaking
and bond-forming of the reactants and products occur. The participation, and
hence the reactivity, of an enzyme for a particular substrate-product pair is
determined by the amino acid sequence and the geometric or spatial
arrangement of the enzyme. Because enzymes are high molecular weight
polymers which are made up of amino acids, it is not surprising that the
active site represents only a small percentage of the total enzyme. It is also
not surprising that the polymeric catalysts are three dimensional, and
consequently the active site has a size (volume) shape to it. This spatial
characteristic of the active site defines the size, shape and type of substrates
or reactants which can be catalyzed by the enzyme.
The kinetics of enzyme reactions are obviously of great importance in
considering their potential commercial applications. At the outset, enzymatic
reaction rates are linear with time until all of the free enzyme is used to form
the ESC. When all of the enzyme exists as ESC, or as soon as the product
is formed, the enzyme reacts with another reactant or substrate molecule,
and the rate of conversion of reactant to product plateaus at the maximal
reaction rate or velocity. Once the initial velocity has been achieved, all of
the enzyme exists as the ESC.
Although enzymes may be classified according to the substrates they
affect, as, for example, proteases for proteins, lipases for lipids, etc., in
reality, these are designations for broad families to break proteins of entities
that are specific to a single protein or lipid under a particular set of
circumstances. An enzyme suitable for a single 16 carbon fatty acid
oxidation reaction will not catalyze an 18 carbon fatty acid oxidation even
though the actual reactions at the sites may be identical. This characteristic
may be viewed as beneficial in that only the specific reaction and no other
is catalyzed by the enzyme. On the other hand, this attribute may be
regarded as undesirable since a specific enzyme is required for a specific
reaction, and no single enzyme can effect a series of related reactions.
Enzymes are proteins whose reactivity is quite sensitive to temperature.
At temperatures as low as 1400F (680C), the catalytic reactivity of the
enzymes may be temporarily or permanently disrupted, thus rendering
enzymes among the most vulnerable of all biological matter. This tem-
perature sensitivity is an important consideration in the commercial
application of enzymes in processing operations.
Among the many enzymes functioning in reactions that have been and are
being used commercially are rennin (chymosin) to precipitate the casein of
milk in cheese making; proteases in laundry detergents to assist in protein
stain removal; amylase to convert starch to sugar for brewing; lactase to
break down lactose in milk; various oxidases to accelerate oxidative
reactions; and catalase to remove hydrogen peroxide that might be formed
during prior oxidative reactions. Other, more generic applications of
enzymes include stereospecific amino acid production, high fructose sugar
production, beer and wine fermentation, tenderizing meats, milling and
baking, juice and wine clarification, juice extraction from fruits and
production of flavor enhancers, to cite a few.
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 oxidase/catalase to remove oxygen.
Whether or not the communications emanating from PharmaCal were
directly responsible, several other enzymatically based active packaging
oxygen control devices have been proposed since that time.
Glucose
oxidase
Gluconate enzyme Glucose
Packaged
liquid
Catalase
Outside enzyme
of Inside of container
container
Container wall
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 Tiru (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
indicator and a trigger mechanism of a solid organic solvent system that
melted when a specific temperature range was reached to permit the enzyme
system to respond to temperature stimulus over time. The enzyme and
substrate cited in the reduction process was peroxidase and peroxide with a
/7-anisdine colorimetric indicator. Another enzyme cited as being effective
was polyphenol oxidase. The organic solvents claimed were basically
paraffins. Applications were as monitors on the exterior of distribution
packages of pharmaceutical and food products.
No further reference to the use of this enzymatic temperature indicator has
been found in the literature.
Milk
Lactase
enzyme Glucose
Galactose
Lactose
Outside
Container Inside of container
of
container wall
Cholesterol
reductase
enzyme
Coprosterol
Cholesterol
References
Anon. (1977) Packagedfoods 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 Tiru, M. (1977) An Enzymatic Time/Temperature 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 WO89/06273.
Budny, J. (1990) Presentation at Pack Alimentaire, San Francisco, California, May.
Copeland, J . C , Adler, H.I. and Crow, W.D. (1991) Method and composition for removing
oxygen from solutions containing alcohols and/or acids. XJS Patent 4996073.
Copeland, R.A. (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 preventing spoilage of foods. Japanese Patent 23071180.
Hopkins, T.R., Smith, VJ. and Banasiak, D.S. (1991) Process utilizing alcohol oxidase, 10
December. US Patent 5071660.
Klibanov, A.M. and Dordich, J.S. (1989) Enzymatic temperature change indicator, 2 May. US
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, U., Jaakkola R. and Kymolainen, 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.
US 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. UK Patent Application 2143544A.
Wiseman, A. (1975) Enzyme utilization in industrial processes, Handbook of Enzyme
Biotechnology, Ellis Horwood, UK.
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.
(A X p)
PERMEABILITY = 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 Modern 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
crowned bottle, the measurements on a closure are best made by modifying
the Mocon to measure the transmission directly for a closed bottle. The
bottle is closed with the test closure and then cut and sealed to a metal block
containing a sealed inlet and outlet. Figure 8.1 is a schematic of the
apparatus. Oxygen-free nitrogen is flushed into the bottle carrying any
oxygen in the bottle out to the detector. By keeping the nitrogen flow rate
constant, a steady state is reached where the oxygen in the stream is a
measure of diffusion of oxygen through or around the closure.
Hot melt
lueor
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
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).
References
Gray, P., Stone, I. and Atkin, L. (1948) Systematic study of the influence of oxidation on beer
flavor. ASBC 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. ASBC 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.
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
poly vinyl chloride. /. Amer. Soc. Brew. Chem., 45, 14-18.
9 Commercial applications in North America
S. SACHAROW
Figure 9.1 Fresh Pax oxygen absorbers introduced by Multiform Desiccants, Inc. for use in a wide
variety of food packs.
situations where carbon dioxide is present, or to control oxygen removal rate
at a wide range of temperature conditions. In 1992 Multiform introduced
FreshMax oxygen absorbing labels (Figure 9.2) designed to meet a market
desire to make the absorber an integral part of the package system.
Formulations are being adapted from FreshPax development, and a wide
variety of substrates, adhesives and custom print are available. Fresh Max
can be automatically applied within packages using conventional labelling
equipment.
Outside the Orient, the most common uses for oxygen absorbers are in
protecting processed and cured meats, peanuts, and other nut varieties, high
value baked goods, refrigerated pasta, snack foods, and dehydrated foods. In
addition to human foods, oxygen absorbers can be found in medical devices,
artemia, pet foods, treats, vitamins and in protecting valuable collectibles.
Some common items containing the absorbers manufactured by Multiform
Desiccants Inc., are as follows:
Hormel Foods corp. - FreshPax 3 oz bottled bacon bits, 8 oz refrigerated
sliced peperoni
Marks & Spencer - St Michael's sliced meat products (UK)
Kraft - DiGiorno refrigerated pasta
Goodmark - beef jerky
Melody Foods - Pioneer beef jerky
Figure 9.2 Multiform Desiccants, Inc. introduces FreshMax oxygen absorbers for processed,
smoked and cured meats.
US Military - shelf stable bread, cake, hamburger buns, chow mein
noodles, potato sticks
John B. Sanfillipo - bulk peanuts and almonds
NASA - shelf stable tortillas
Dietary specialties - shelf stable bread
In addition to this list, the institutional and food service markets have used
oxygen absorbers to protect such products as processed meats, nuts, potato
chips, and whole fat powdered milk. New applications are evolving almost
weekly.
Mitsubishi Gas Chemical Americas' 'Ageless' absorbers (Mitsubishi,
1994) are used as follows:
Hormel Foods Co. - sliced peperoni, bacon bits
Kraft General Foods - fresh pasta (DiGiorgio brand)
Penge Foods - beef jerky
Goodmark Foods - beef jerky
Victor coffee - coffee beans
Advanced Development Corp - powdered drink
Tyson Foods - poultry
Dokosil Foods - sliced ham and poultry
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
Unspecified (two models) Response to isothermal conditions Arnold and Cook (1977)
Imago Industries (La Ciotat, France) have launched their re-usable
thermomarker. This is solid and relatively large (88 x 53 mm), and the
principal element in its makeup is a shape memory alloy. The alloy
effectively 'memorises' two distinct shapes associated with predefined
temperatures. In the device itself, a spring made of shape memory alloy
changes size according to predetermined temperatures within a programmed
range. This in turn activates a system which ejects different coloured balls
that signal the reaching of the various temperature thresholds.
A patent from Microtechnic (Germany) apparently uses the alignment of
two magnets as an indication of the thawing of a frozen food. At the point
of freezing, two magnets are held unaligned in a small liquid container.
However, if the liquid thaws, then the attraction by the opposite poles of the
magnets will promote movement and the two magnets come together,
indicating that thawing has occurred.
Albert Browne (Leicester, UK) make cold chain indicators which can
produce either an abrupt change of colour (yellow to blue) at its end point,
or a more gradual change depending on its application. They have
specialised in thermal indicators for many years and are now promoting their
time-temperature cold chain indicators in both the food and pharmaceutical
industries. Food Guardian (Blandford, UK) have begun to promote their
label which has a thermometer profile. The label indicates the time on the
scale for which the temperature has been above the designated temperature.
Senders (London) have developed a threshold label for application to large
boxes and pallets, and this consists of both a warning indicator that the
temperature is getting too high, and a second indicator showing the need for
rejection. Courtaulds Research (Coventry, UK) have considered developing
a temperature-sensitive colour in acetate film. This could be used to detect
when a product is fully defrosted and ready for cooking, assuming no
storage abuse. Bowater Labels (Altrincham, UK) have recently launched
their Reactt TTI self-adhesive label for monitoring freezing and chilling
distribution temperatures (Pidgeon, 1994). The labels remain inert until
activated, then change from blue to red to reveal underlying graphics when
preset time/temperature limits are exceeded. Trigon Industries Ltd. (Telford,
UK) has also just launched its Smartpak label, which is self-activating
before use and shows an irreversible colour change to reveal an underlying
symbol warning. For example, the Smartpak 1812 label self-activates when
it is frozen below -18C, and subsequently indicates the temperature rising
above -12C.
In the case of microwaveable products, research has shown that for
microbiological and other quality criteria, all points within the food should
be reheated to an equivalent of 700C for 2 min. To date only two doneness
indicators are available. That from 3M (Bracknell, UK) uses a thermo-
chromic ink which undergoes an irreversible colour change (Summers,
1992). The Reactt doneness indicator from Bowater Labels is a modification
of the TTI self-adhesive label and works on the same colour-change
principle described earlier. Other devices are being developed at this time,
although the challenge of measuring and correlating cold point temperatures
with overall pack temperatures remains considerable. Risman (1993) refers
to the gel indicator technique developed at the Swedish Food Research
Institute for assessing the reheating performance of domestic microwave
ovens for ready meals.
Figure 10.1 General classification of time-temperature indicators (after Hendrickx et al, 1993).
application of the TTI 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 TTI, the TTI 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.
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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 180Os 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. Modern 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).
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.
11.4.1 Emitters and sorbers
One the earliest and most successful active packaging concepts was to
incorporate a material which either absorbed or emitted vapors or gases
inside a package after closure. This might be as simple as water vapor
absorbers which are designed to control relative humidity, or more complex
substances which absorb ethylene from produce, absorb undesirable odors
from foods, or emit ethanol to control molds in bakery products. Particularly
desirable types of sorbers are those that remove both residual and ingress
oxygen after the package has been sealed (Rooney, 1994). Oxygen absorbers
which remove oxygen from the headspace of bottled beer, for example, have
been successfully tested commercially. Initially, absorbers/emitters were
contained inside packets which were added to the package along with the
product. More recent technologies have incorporated the sorber/emitter into
the film or container wall. This reduces the likelihood of accidental
ingestion. These absorbers are a form of modified atmosphere packaging and
can change the microbiology of foods. The safety implications of such
changes are the same as those for conventional MAP, as discussed below.
There is also the concern that the components making up the absorber/
emitter will migrate to the food.
11.5 Conclusions
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Index
A
absorbers
food constituents 99 100
free oxygen see oxygen absorbents
odours and taints 100 213
activation energy
permeation 68
respiration model 65
active packaging
chemical 21 24
composite 8
definition 1 2 143 203
do-it-yourself 17
economic benefit 76
future potential 32
history 4
horticultural 9
limitations 31
literature 10
multiple effects 9 252
origins 3
physical 20
reasons for 3
regulatory considerations 33 252
reviews 10
This page has been reformatted by Knovel to provide easier navigation. 256
257
Index terms Links
active packaging (Continued)
scope 12
terminology 1 10
whole packages 29
active packaging plastics
and safety 243
combined effect 82 106
commercial use 106
effects on foods 74
environmental considerations 107
migration from 243
regulations 106
Ageless
and aw 150
capacity 150
chemistry 149
types 149
aldehydes 100
almonds rancidity
and oxygen absorbent 155
amines 100
anaerobic respiration 68
antimicrobials 243 244 248
enzymic 250
silver zeolite 248
antimycotics 249
ascorbic acid
and oxygen absorbent 154
Aspergillus spp 159
C
calcium carbonate
as filler 69
cans
tinplate 238
carbon dioxide
permeability 123
carnauba wax 132
carrots packaging
condensation control 98
cauliflower 65
casein films
sorbic acid in 128
D
deoxidisers see oxygen scavengers
desiccant
retorting 75 79
G
gelatin films
sorbic acid retention 128
tannic acid crosslinked 128
tocopherol retention 128
glucose oxidase 181
gluten films
with beeswax 124
green pepper 65
H
hydrogen oxidation 84
hydrogen peroxide 86
hydroxypropyl methylcellulose 130
I
IMF
and Staphylococcus aureus 134
casein-coated 132
microbiological stability 132
papaya cubes 132
with sorbic acid 132
indicator
bacterial toxins 245
oxygen concentration 2
safety 245
spoilage 245
temperature 209
L
lettuce
gas atmosphere for 251
limonin 99
Listeria monocytogenes 163
ethanol vapour effect 171
M
mathematical modelling 251
limitations 64 70
parameters 71
steady state 66
unsteady state 65
variables 66
meat colour
and oxygen absorbents 160
meat packaging
oxygen scavenging 158
methylcellulose 130
with palmitic acid 132
microbiological stability
carrageenan effect 134
lactic acid effect 133
surface pH effect 133
microencapsulation 85
O
odours
from oxygen scavengers 82 91
organic acids 243
Ox-Bar 82
oxygen
concentration measurement 193 194
permeability of closure liners 195
oxygen absorbents see also oxygen scavengers
advantages 161
and aflatoxins 164
and mould growth 159
applications 148
choice of 152
classification 145
CO2 producing 146
definition 144
disadvantages 161
dual effect 146 150 151
P
package integrity 240
packaging
active constituent impact on 27
antimicrobial 243 244 246
intelligent 2 215 216
interactive 2
modelling 64
modified atmosphere 2 246
safety problems 239
tamper evident 246
with oxygen scavengers 92 153
Q
Q10 62
R
radiation
far infra-red 70 250
regulation 106 242 243 252
release
antimicrobial agents 102
antioxidants 103
butylated hydroxytoluene 104
enzymes 105 179 181
ethanol vapour 165
S
Saccharomyces cerevisiae
ethanol vapour effect 170
sachets
combined effect 146 150 151 152
consumer resistance 162
V
vegetables
gas atmospheres for 59
vitamin C see ascorbic acid
Y
yeast growth
ethanol effect 4 170
oxygen absorber 4
Z
zein films 128
lactic acid retention 134