ACTIVE FOOD PACKAGING

Edited by
M.L. ROONEY
Principal Research Scientist
CSIRO
Division of Food Science & Technology
North Ryde
New South Wales
Australia

BLACKIE ACADEMIC & PROFESSIONAL

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Preface

Food packaging materials have traditionally been chosen to avoid unwanted

interactions with the food. During the past two decades a wide variety of
packaging materials have been devised or developed to interact with the
food. These packaging materials, designed to perform some desired role
other than to provide an inert barrier to outside influences, are termed active
packaging. The benefits of active packaging are based on both chemical and
physical effects.
Active packaging concepts have often been presented to the food industry
with few supporting results of background research. This manner of
introduction has led to substantial uncertainty by potential users because
claims have sometimes been based on extrapolation from what little proven
information is available. The forms of active packaging have been chosen to
respond to various food properties which are often unrelated to one another.
For instance, many packaging requirements for postharvest horticultural
produce are quite different from those for most processed foods.
The objective of this book is to introduce and consolidate information
upon which active packaging concepts are based. Scientists, technologists,
students and regulators will find here the basis of those active packaging
materials which are either commercial or proposed. Some types of active
packaging are inevitably omitted but the book should assist the inquirer to
understand how other concepts might be applied or where they should be
rejected.
Chapter 1 is the editor's overview of the field. Here I have sought to
define active packaging and to establish its limits and the background to its
development. The history of oxygen scavenging is used as a case study.
Chapter 2 is contributed by Dr Devon Zagory of Devon Zagory &
Associates Inc., California. Dr Zagory has been a major contributor to
present knowledge of modified atmosphere packaging of horticultural
produce. In this chapter he discusses the background to the use of active
packaging to remove ethylene from the headspace of respiring produce. He
discusses the options currently available and their limitations.
Chapter 3, by Dr Kit Yam of Rutgers University, New Jersey and Dr
Dong Sun Lee of Kyungnam University in South Korea, address the
interface between active packaging and equilibrium modified atmosphere
packaging now in use. They introduce a simple method of modelling gas
atmospheres to show where additional active packaging concepts are
required.

Chapter 4 is the editor's discussion of the field of active packaging based

on polymers. This includes use of thermoplastics for films and more rigid
containers but also provides background useful when consideration is given
to other polymer-based coatings. The aim has been to unify the many
alternative unrelated concepts being offered to packers of both fresh and
processed foods.
Chapter 5 is contributed by Dr Bernard Cuq and Dr St6phane Guilbert
of CIRAD-SAR, and Dr Nathalie Gontard of ENSIA-SIARC, all of
Montpellier, France. Their research into the edible coating of foods needs no
introduction. They describe in this chapter how edible coatings are often
already active packaging and introduce the current and potential use as
delivery systems for food additives.
Chapter 6 is contributed by Dr J.P. Smith of McGiIl University, Montreal,
Canada, Yoshiaki Abe, President of Mitsubishi Gas Chemical Europe
GmbH and Dr Jun Hoshino, Chief Microbiologist of Mitsubishi Gas
Chemical Company, Inc., Tokyo. Jim Smith has published the results of
many of the key investigations of the impact of modified atmosphere and
active packaging on food microbiology. Mr Abe and Dr Hoshino have been
responsible for the introduction of 'Ageless' oxygen scavenging sachets,
particularly outside Japan. In this chapter they consolidate knowledge of
sachet-based technologies.
Chapter 7 is co-authored by Dr John Budny, President of PharmaCal Ltd.,
California and Dr Aaron Brody, who is Managing Director of Rubbright
Brody Inc. Dr Brody was formerly with Schotland Business Research of
Princeton and is a widely respected packaging consultant and author. These
authors provide the background to and opportunities for the use of enzymes
in active packaging. This is still a frontier field and requires the carefully
explained background presented in this chapter.
Chapter 8 is contributed by Dr Fred Teumac of ZapatA Technologies Inc.
of Hazleton, Pennsylvania, USA, who was jointly responsible (with
Advanced Oxygen Technologies Inc.) for developing the first commercially
successful oxygen scavenging closures for bottled beer. In this chapter he
presents this and other systems as case studies in active package development.
Chapter 9, by Stanley Sacharow, President of The Packaging Group Inc.,
New Jersey, is an examination of the role played by active packaging in
current commercial use. Stan Sacharow is a leading international consultant
in packaging and has written several books and many articles on packaging
technology. This chapter provides the necessary understanding of the status
of active packaging in the USA today. Active packaging for microwaveable
foods is a key topic.
Chapter 10 is by Dr Jeremy Selman, Head of the Food Technology
Division of the Campden Food and Drink Research Association in the UK.
Dr Selman is widely respected for his work on food quality monitoring via

time-temperature indicators (TTIs). In this chapter he provides the background to TTIs and summarizes their role with much tabulated information.
He provides substantial unity to the TTI field by discussing their recent
introduction to thermal process validation.
Chapter 11 completes this work by drawing together the implications of
active packaging for food safety. Prof. Joseph Hotchkiss of Cornell
University, New York, has contributed widely to research and discussion of
the role of packaging in food safety. In this chapter he draws together the
safety issues which arise from the use of active packaging and illustrates
how active packaging can itself contribute to food safety in the use of
antimicrobial films.
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

Y, Abe

Mitsubishi Gas Chemical Europe GmbH, Immermannstrasse 45, Deutsch-Japannische Center, 40210
Dusseldorf, Germany

AX. Brody

Rubbright-Brody Inc., 733 Clovelly Lane, Devon, PA

19333-1808, USA

JA. Budny

PharmaCal Ltd., 31308 Via Colinas, Suite 107, Westlake

Village, CA 91362, USA

B. Cuq

CIRD-SAR, 73 rue J.F. Breton, BP 5035, 34032

Montpellier, France

N. Gontard

ENSIA-SIARC, 1101 Avenue Agropolis, BP 5098, 34033

Montpellier, France

S. Guilbert

CIRD-SAR, 73 rue J.F. Breton, BP 5035, 34032

Montpellier, France

J. Hoshino

Mitsubishi Gas Chemical Company, Inc, 1-1, Nijuku

6-Chome, Katsushika-ku, Tokyo 125, Japan

J.H. Hotchkiss Institute of Food Science, Cornell University, 119

Stocking Hall, Ithaca, NY 14853-7201, USA
D.S. Lee

Department of Food Engineering, Kyungnam University,

449 Wolyoung-dong, Masan City 630-701, Korea

M.L. Rooney

Principal Research Scientist, CSIRO Food Research Laboratory, PO Box 52, North Ryde, New South Wales 2113,
Australia

S. Sacharow

The Packaging Group Inc, PO Box 345, Milltown, NJ

08850, USA

J.D. Selman

Director of Food Technology Division, CFDRA, Chipping

Campden, Gloucestershire, GL55 6LD, UK

JLP. Smith

McGiIl University, Department of Food Science and

Agricultural Chemistry, Macdonald Campus 21, 111
Lakeshore, Ste-Anne-de-Bellevue, Quebec, H9X 3V9,
Canada

F.N. Teumac

Vice-President Research and Development, ZapatA

Technologies Inc., PO Box 2278, Forest Road, Humboldt

Industrial Park, Hazleton, PA 18201, USA
K.L. Yam

Assistant Professor, Department of Food Science, Rutgers

University, PO Box 231, New Brunswick, NJ
08903-0231, USA

D. Zagory

Devon Zagory & Associates, Postharvest Technology

Consultants, 759 North Campus Way, Davis, CA 95616,
USA

Contents

Preface ...............................................................................

iii

Acknowledgements ............................................................

Contributors ........................................................................

vi

1.

Overview of Active Food Packaging ........................

1.1

Active, Intelligent and Modified Atmosphere

Packaging .................................................................

Origins of Active Packaging ......................................

1.2.1

Why Active Packaging ................................

1.2.2

Historical Development ..............................

1.3

Literature Review ......................................................

10

1.4

Scope for Application of Active Packaging ................

12

1.4.1

Do-it-yourself Active Packaging ..................

17

1.5

Physical and Chemical Principles Applied ................

20

1.6

Implications for Other Packaging ..............................

27

1.6.1

Whole Packages Designed to Be Active ....

29

1.7

Limitations of Current Approaches ............................

31

1.8

Future Potential .........................................................

32

1.9

Regulatory Considerations ........................................

33

References ..........................................................................

33

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viii

1.2

2.

Contents

ix

Ethylene-removing Packaging ..................................

38

2.1

The Chemistry of Ethylene ........................................

38

2.1.1

Synthesis ....................................................

38

2.1.2

Degradation ................................................

39

2.1.3

Adsorption and Absorption .........................

40

Deleterious Effects of Ethylene .................................

41

2.2.1

Respiration .................................................

42

2.2.2

Fruit Ripening and Softening ......................

42

2.2.3

Flower and Leaf Abscission .......................

42

2.2.4

Chlorophyll Breakdown ..............................

43

2.2.5

Petal Inrolling in Carnations ........................

43

2.2.6

Postharvest Disorders ................................

43

2.2.7

Susceptibility to Plant Pathogens ...............

43

Interactions of Ethylene and Other Gases ................

44

2.3.1

Oxygen .......................................................

44

2.3.2

Carbon Dioxide ...........................................

44

2.3.3

Ozone .........................................................

45

Ethylene Sources in the Environment .......................

45

2.4.1

Combustion ................................................

45

2.4.2

Plant Sources .............................................

45

2.4.3

Ripening Rooms .........................................

46

2.4.4

Fluorescent Ballasts and Rubber

Materials .....................................................

46

Microorganisms ..........................................

46

Commercial Applications in Packaging .....................

46

2.2

2.3

2.4

2.4.5
2.5

2.5.1

Potassium Permanganate-based
Scavengers ................................................

46

2.5.2

Activated Carbon-based Scavengers .........

47

2.5.3

Activated Earth-type Scavengers ...............

48

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Contents
2.5.4

3.

New and Novel Approaches to Ethyleneremoving Packaging ...................................

50

Acknowledgements .............................................................

51

References ..........................................................................

51

Design of Modified Atmosphere Packaging for

Fresh Produce ............................................................

55

3.1

Introduction ...............................................................

55

3.2

Literature Review ......................................................

57

3.3

Feasibility Study ........................................................

59

3.3.1

Optimum Conditions ...................................

60

Respiration Rates ......................................................

61

3.4.1

Temperature Effect .....................................

61

Measurement of Respiration Rates ...........................

62

3.5.1

Flow-through System .................................

62

3.5.2

Closed System Method ..............................

63

Model Equations and Package Requirements ..........

64

3.6.1

Unsteady-state Equations ..........................

65

3.6.2

Steady-state Equations ..............................

66

Polymeric Films for MAP Applications ......................

67

3.7.1

Perforation and Microporous Films .............

68

3.7.2

Temperature Compensating Films .............

70

3.7.3

Ceramic-filled Films ....................................

70

Concluding Remarks .................................................

70

Nomenclature ......................................................................

71

References ..........................................................................

72

Active Packaging in Polymer Films .........................

74

4.1

74

3.4
3.5

3.6

3.7

3.8

4.

Introduction ...............................................................

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xi

Oxygen Scavenging ..................................................

74

4.2.1

Forms of Oxygen-scavenging Packaging ...

76

4.2.2

Plastics Packaging as Media for Oxygen

Scavenging .................................................

77

Brief History of Oxygen-scavenging

Films ...........................................................

80

4.2.4

Chemistry of Oxygen Scavenging ..............

83

4.2.5

Chemical Barrier to Oxygen Permeation ....

92

Moisture Control Films ..............................................

94

4.3.1

Liquid Water Control ...................................

95

4.3.2

Humidity Buffering ......................................

96

4.4

Removal of Taints and Food Constituents ................

99

4.5

Ingredient Release .................................................... 102

4.2

4.2.3

4.3

4.5.1

Antioxidant Release from Plastics .............. 103

4.6

Permeability Modification .......................................... 105

4.7

Current Use Commercially ........................................ 106

4.8

Regulatory and Environmental Impacts .................... 106

References .......................................................................... 107

5.

Edible Films and Coatings as Active Layers ........... 111

5.1

Introduction ............................................................... 111

5.2

Use of Edible Active Layers to Control Water Vapor

Transfer ..................................................................... 114

5.3

Use of Edible Active Layers to Control Gas

Exchange .................................................................. 121

5.4

Modification of Surface Conditions with Edible

Active Layers ............................................................. 126

5.5

Conclusion ................................................................ 134

Acknowledgements ............................................................. 135

References .......................................................................... 135
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xii
6.

Contents
Interactive Packaging Involving Sachet
Technology ................................................................. 143
6.1

Introduction ............................................................... 143

6.2

Oxygen Absorbents ................................................... 144

6.3

6.4

6.2.1

Classification of Oxygen Absorbents .......... 145

6.2.2

Main Types of Oxygen Absorbents ............ 149

6.2.3

Factors Influencing the Choice of Oxygen

Absorbents ................................................. 152

6.2.4

Application of Oxygen Absorbents for

Shelf-life Extension of Food ....................... 153

6.2.5

Advantages and Disadvantages of

Oxygen Absorbents .................................... 161

6.2.6

Effect of Oxygen Absorbents on

Aflatoxigenic Mold Species ........................ 164

Ethanol Vapor ........................................................... 164

6.3.1

Ethanol Vapor Generators .......................... 166

6.3.2

Uses of Ethicap for Shelf-life Extension of

Food ........................................................... 168

6.3.3

Effect of Ethanol Vapor on Food

Spoilage/food Poisoning Bacteria ............... 171

6.3.4

Advantages and Disadvantages of

Ethanol Vapor Generators .......................... 171

Conclusion ................................................................ 172

References .......................................................................... 172

7.

Enzymes as Active Packaging Agents .................... 174

7.1

Enzymes ................................................................... 174

7.2

Potential Roles of Enzymes in Active Packaging ...... 176

7.3

History ....................................................................... 178

7.4

Oxygen Removal ....................................................... 179

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xiii

7.5

Antimicrobial Effects .................................................. 186

7.6

Time-temperature Integrator-indicators ..................... 188

7.7

Lactose Removal ...................................................... 189

7.8

Cholesterol Removal ................................................. 190

References .......................................................................... 191

8.

The History of Oxygen Scavenger Bottle

Closures ..................................................................... 193
8.1

Background ............................................................... 193

8.2

Oxygen Measurements ............................................. 193

8.3

8.2.1

Techniques for Measuring the Oxygen

Content of Bottles ....................................... 193

8.2.2

Results of Measurements ........................... 194

8.2.3

Oxygen Ingress .......................................... 195

8.2.4

Combining the Effect of Initial and Ingress

Oxygen ....................................................... 196

Oxygen Scavenger Liners ......................................... 197

8.3.1

Theoretical .................................................. 197

8.3.2

Commercial Activity .................................... 197

8.3.3

Health and Environmental Concerns .......... 199

8.4

The Effect of Scavenging Closures on Beer Flavor .. 199

8.5

The Advantages of Oxygen Control Bottles .............. 200

8.6

The Future of Oxygen Scavenging Closures ............ 200

References .......................................................................... 201

9.

Commercial Applications in North America ............ 203

9.1

Packaging Overview ................................................. 203

9.2

Marketplace Susceptors ............................................ 203

9.2.1

Susceptor Types ........................................ 204

9.2.2

Field Intensification Devices ....................... 206

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xiv

Contents
9.2.3

Susceptor Applications ............................... 208

9.3

Application of Temperature Indicator to

Microwaveable Packaging ........................................ 209

9.4

Active Packaging Produce ..................................... 209

9.5

9.4.1

Oya Produce Bags ..................................... 209

9.4.2

Oya Test Results ........................................ 210

9.4.3

Modified Atmosphere Produce ................... 211

Oxygen Absorber Food Applications ......................... 211

9.5.1

9.6

Bottle Closures Oxygen Scavengers ....... 213

Other Applications ..................................................... 213

References .......................................................................... 214

10. Time-temperature Indicators .................................... 215

10.1 Introduction ............................................................... 215
10.2 Indicator Systems ...................................................... 217
10.3 Indicator Application Issues and Consumer
Interests .................................................................... 227
10.4 Chemical Indicators for Thermal Process
Validation .................................................................. 230
10.5 Conclusions ............................................................... 234
References .......................................................................... 234

11. Safety Considerations in Active Packaging ............ 238

11.1 Introduction ............................................................... 238
11.2 Packaging and Food Safety ...................................... 238
11.3 Passive Safety Interactions ....................................... 240
11.3.1

Barriers to Contamination ........................... 240

11.3.2

Prevention of Migration .............................. 241

11.4 Active Safety Interactions .......................................... 242

11.4.1

Emitters and Sorbers .................................. 243

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xv

11.4.2

Active Packaging and Migration ................. 243

11.4.3

Barrier to Contamination ............................ 244

11.4.4

Indirect Effects on Safety ........................... 244

11.4.5

Indicators of Safety/spoilage ...................... 245

11.4.6

Direct Inhibition of Microbial Growth ........... 246

11.4.7

Modified Atmosphere Packaging ................ 246

11.4.8

Antimicrobial Films ..................................... 248

11.4.9

Rational Functional Barriers ....................... 250

11.4.10 Combined Systems .................................... 252

11.5 Conclusions ............................................................... 252
References .......................................................................... 253

Index .................................................................................. 256

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Overview of active food packaging

M.L. ROONEY

1.1 Active, intelligent and modified atmosphere packaging

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 terminology 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 timetemperature 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 oxygenscavenging 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 Origins of active packaging
1.2.1 Why active packaging
Inherent in the definition is the point that active packaging now plays a role
in the protection of the food which is additional to the classic purposes of
any packaging, viz. containment, protection, convenience and communication (Robertson, 1993). This role can be addressing a single aspect of the
packaging requirements of a food, such as making up for an inadequacy of
a packaging material - which is already a compromise. Thus, for semiaseptic or retort trays of steamed rice, oxygen-scavenging sachets are
bonded to the lid to consume oxygen passing through the trays, especially
when retorted. Ethanol-releasing sachets are used with bakery products of
high aw to suppress mould growth because low oxygen barrier packaging is
used. These examples show that there are opportunities to reduce the cost of
packaging materials or packaging processes by use of active packaging with
cheaper passive packaging. This has been demonstrated by Alarcon and
Hotchkiss (1993), who showed that crusty bread rolls packaged in a medium
barrier plastics laminate had a shelf-life similar to that provided by a more
expensive foil laminate (see Chapter 6). The key to using chemical forms of
active packaging for economic benefit is that the benefit must be achievable
before the chemical is exhausted. This is particularly important in the area of
fresh and extended shelf-life foods as originally described by Labuza and
Breene (1989) but not only in that area. For example, the suppression of
enhanced oxygen permeation of retortable trays (caused by retorting) by
application of a desiccant layer is important while the water is being
absorbed rapidly during retorting, in order to impart multi-year shelf-life at
ambient temperatures.
The key focus of active packaging therefore is the match of the package
properties to those of the food, a target that normally has been considered to
require compromise. The result of this matching is therefore optimisation of
shelf-life and permitting processes, formulations and presentation which
were previously impossible. It is possible to add hurdles to enhance the
safety of food packaging processes. It is in this area that antimicrobial
packaging may make a substantial contribution as it develops from its
current early stage.
It should be emphasised that active packaging is not a generally applied
concept like, for instance, water vapour barrier packaging plastics. It is
rather the application of specific packaging properties to specific situations.
In this way, we see a large number of niche markets, some niches being very

large indeed as with oxygen scavenging crown closures for bottled beer. In
some instances we see the need for application of two forms of active
packaging to achieve a goal. This has been demonstrated by Naito et al
(1991) who showed that use of an oxygen absorber alone suppressed growth
of bacteria and of yeast (Hansenula anomala) in packages of sponge cake
but that the inclusion of an ethanol or carbon dioxide emitter was even more
effective. The use of combined-effect sachets, for instance, is now
commonplace - see Chapter 6.
1.2.2 Historical development
Because it applies to a collection of niche markets, active packaging has a
very uncoordinated history. This aspect can best be examined by seeking to
subdivide it, albeit somewhat artificially, into processed food packaging and
fresh food packaging.
Probably the earliest form of active packaging was the wine skin which,
while causing a variety of unwanted interactions, was intended to collapse as
the wine was consumed without necessarily increasing the quantity of
oxygen within. Just how good a barrier the skin is to oxygen permeation is
not known, so this is a far from perfect example. The most obvious
commencement of active packaging was the use of tinplate for construction
of cans. The tin is sacrificially corroded, protecting the iron base can, while
concurrently saving the food from contamination with large amounts of iron.
The latter, with its two readily accessible oxidation states, can function as an
autoxidation catalyst when residual oxygen is present. The tin also acts as a
reducing agent for food constituents such as pigments. It also contributes to
development of the flavour associated with die 'traditional' canned orange
juice. This became economically significant with the introduction of
aluminium cans when it was observed that the 'traditional' flavour was not
generated in the absence of tin.
A subsequent development was the introduction of sulfur-staining
resistant lacquers (or enamels). The sulfur staining is due to the decomposition of sulfur-containing amino acids in foods to produce compounds which
react with the tinplate, so staining the metal surface. The introduction of zinc
oxide results in a reaction which forms products not observable in the
otherwise white lacquer.
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

Water absorbents
Iron compounds
Sodium carbonate
Carbon, water
Alkali metal halides
Ammonium chloride
Sodium chloride
Un-named

powder
powder
powder
powder
powder
powder
powder
film

Reference

Country

Tallgren, 1938
Isherwood, 1943
Buchner, 1968
Nawata el al., 1977
Mitsubishi, 1977
Kureha, 1982
Fujishima, 1985
Koyama/Oda, 1992

Finland
UK
Germany
Japan
Japan
Japan
Japan
Japan

The development of iron-based oxygen scavengers is summarised in

Table 1.1 which shows movement from Europe to Japan as development of
commercially useable systems occurred.
Concurrent with the development of iron-based scavengers was the
development of other inorganic and organic systems, both based on the use
of sachets. The reaction of sodium dithionite with oxygen can be triggered
by the presence of water from a food headspace. The steps involved in the
scavenging of oxygen by such agents are shown in the following equations
(Nakamura and Hoshino, 1983).
Na2S2O4 + Ca(OH) 2 + O

-*

Na 2 SO 4 + CaSO 3 + H2O

(1.1)

Na 2 S 2 O 4 + O 2

->

Na 2 SO 4 + SO 2

(1.2)

Ca(OH)2 + SO2

->

CaSO 3 + H2O

(1.3)

The reactions involved in the scavenging of oxygen by iron-based

compositions are discussed in Chapter 6.
Additional processes involving organic chemicals have also been developed, commencing with catechols and related substances and resulting in the
widespread claims of use of ascorbic acid in patents in recent years. The
recent growth in the number of patent applications, found via the Derwent
Index, for systems which do not involve iron can be seen in Figure 1.1. The
Derwent Index catalogues patent applications by the earliest national
application. Any applications for coverage of the same matter in other
countries are indexed therewith. These results were generated by taking the
numbers of earliest applications without consideration of the number of
additional countries covered. Not all applications are necessarily granted but
patenting activity is an indication of interest in developing new ideas.
The results in Figure 1.1 show the distribution of such early applications
for composition claims over the 20-year period from 1975 to the first half of
1994. The incremental unit is 2 years and the applications were distinguished by their involvement with or frequent inclusion of zinc, copper or
nickel since non-food applications also constitute a very large potential
market. The interest in systems not involving elemental metals was initially
the strongest although claims for metallic systems peaked around 1980 after

Other

Applications

Metal

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 undergone 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 compounds such as fatty acids, squalene and rubbers.

Applications

Composition

Design

Years
Figure 1.2 Patent applications for oxygen scavengers based on composition or design.

Evidence of the maturity of this field of active packaging is shown by the

trend in patent applications for novel designs aimed at overcoming
deficiencies in either handling or effectiveness found in the early versions.
The ease of triggering an active state in oxygen-scavenging compositions is
more important than with most other forms of active packaging. Design
patents were scarcely considered for the first 8 years of this period until the
products of companies such as Mitsubishi Gas and Chemical Co. and
Toppan Printing Co. made an impact on food packaging in Japan. Since that
time the number of applications for new designs has increased sharply, with
the numbers of design applications over the last 10 years exceeding those for
new compositions. This maturity of the market is seen in the progressive
expansion of use of such products in the USA, Europe and Australasia. The
current production of oxygen-scavenging sachets alone is understood to
exceed 7 billion per annum in Japan, several hundred million in the USA
and some tens of millions in Europe.
Another of the aspects of oxygen-scavenger development is the respective
positions of sachet and film-based technologies. These aspects are considered in detail in Chapter 4.
A recent trend is the incorporation of scavengers into the packaging
material itself, rather than being used in a sachet which hitherto had been the
main commercial application. Chapter 4 deals with development of
scavenging plastics for packages in general, and the specific commercial
application to bottle closures, especially as liners for crown seals for beer
bottles, is discussed in Chapter 8.
Besides the main lines of research and development of oxygen scavengers
referred to above there have been other, less popular, lines of research and

commercial development. The catalytic conversion of hydrogen to water,

initially in tinplate cans then in laminate pouches, was first described by
King (1955) who saw the need for removal of oxygen from spray-dried
canned milk powder.
There has also been continuous research into ways of stabilising enzymic
catalysts for oxygen removal. The oxidation of glucose, catalysed by glucose
oxidase, has been studied intermittently following the work with OxyBan by
Scott and Hammer (1961). This subject is discussed in detail in Chapter
7.
1.2.2.2 Composite systems. An early observation was that in-pack
removal of oxygen from package headspaces creates a corresponding
decrease in pressure which results in either package collapse or development
of a partial vacuum. The latter may be tolerable in rigid packaging where the
seal integrity is good, but in flexible packs pressure decreases of as little as
a few kPa result in package collapse where the headspace is small. The
simultaneous release of carbon dioxide by sachets which consume oxygen
was devised by several companies (see Chapter 6). This concurrent release
of carbon dioxide can be additionally useful in the suppression of microbial
growth (Naito et al9 1991). The concentration of this gas needs to reach
20%, preferably more, and is potentially useful where packages already have
some carbon dioxide in the atmosphere. Such systems are based on either
ferrous carbonate or a mixture of ascorbic acid with sodium bicarbonate.
More effective use of dual-function active packaging inserts has been
foreseen by several companies in this field. The potential for generation of
conditions suitable for growth of anaerobic pathogenic microorganisms
exists if oxygen scavengers are used inappropriately. Accordingly, the
release of ethanol or carbon dioxide concurrent with oxygen removal has
been cited for this purpose by both Toppan Printing KK (1985) and Leon et
ah (1987). This performance of commercial dual-function scavenging
sachets is discussed in Chapter 6.
The historical development of other forms of emitters of ingredients such
as flavours, antioxidants and antimicrobial agents is dealt with in other
chapters. This applies also to packaging for microwaveable foods where
there is the potential for one form of active packaging to interact with
another. Thus there is the need to ensure that oxygen-scavenging sachets do
not interfere with microwave heating of packages of ready-to-eat foods such
as retorted steamed rice. This product is marketed with an organic reagent,
ascorbic acid, in a sachet bonded to the inside of the lid of the tray with a hot
melt adhesive. An additional approach to overcome the same problem, also
by Mitsubishi Gas and Chemical Co., is the patenting of scavengers based
on boron and its compounds.

1.2.2.3 Horticultural active packaging. Active packaging for horticultural produce has evolved via the concept of 'smart films'. It has long been
known that respiring produce will generate its own modified atmosphere, but
in so doing it may reach a stage of ripeness which is not desired. As long ago
as the 1970s choices were made between packaging films in an effort to
achieve a modified atmosphere which suppressed respiration and lengthened
shelf-life (Prince, 1989). Since there was difficulty in achieving satisfactory
performance with many produce-film combinations, highly permeable
porous patches were introduced. This enabled packers to use film of any
commodity while ensuring that there was adequate exchange of oxygen and
carbon dioxide. This is unsuitable for developing equilibrium modified
atmospheres close to the optimum for all produce but is useful both in
preventing injury due to excessively high concentrations of CO2 and in
stopping anaerobic respiration from being initiated. This approach has been
developed progressively in the USA with the patches of microporous film
developed by Hercules Freshold Corp. and with subsequent patches, the gas
permeability of which changes with the degree of hydration.
Concurrently, other workers have approached the same problem by
seeking to make the entire packaging film more permeable or by seeking to
develop some enhancement of selectivity. This field has developed either by
use of patents or merely by use of advertising claims with little or no
scientifically developed results supporting such claims. Thus films have been
made porous by inclusion of porous powders such as zeolites or volcanic
rock, or by inclusion of crushed rocks. More recently, porosity has been
increased by burning or etching controlled diameter holes to prevent both
condensation and oxygen depletion. Recently, again, some considerable
scientific modelling effort has been focused on the use of a single pore in a
package to achieve the necessary rate of gas exchange (Mannapperuma and
Singh, 1994).
During the 1980s, when marketing of films containing inorganic powders
was commenced, widely ranging claims were made for effects such as the
emission of infra-red radiation from ceramics. Claimed benefits include
preservation of the produce and absorption or scavenging of ethylene.
Evidence for removal of ethylene from package headspaces other than by
enhanced permeation through porous solids or porous film does not appear
to be substantial.
Some films containing inorganic powders are claimed to offer multiple
benefits for packaging of horticultural produce. Katsura (1989) reports that
FH film containing Oya stone dispersed on the film surface absorbs ethylene,
is a freshness preservative, and controls levels of water vapour, oxygen and
carbon dioxide in the pack.
Chemical scavenging of ethylene, however, has been the subject of
considerable research since the work of Scott et al. (1970). Their work with
potassium permanganate in porous slabs of vermiculite in bags of bananas

demonstrates the early success of this approach. The detail of the historical
development of research and commercial development of such processes is
described in Chapter 2.
The use of edible or otherwise non-toxic coatings on fruit skins as
vehicles for active chemicals has been known for several years. The
modification of the atmosphere close to the skins of fruit has been achieved
by shrink wrapping. Both these techniques assist in eliminating the build-up
of surface water as a cause of microbial growth on fruit surfaces. The recent
introduction of minimally processed fruits and vegetables in packaged form
has heightened awareness in this area. The importance of hygiene in the
preparation of sliced and diced produce has been discussed by Varoquaux
and Wiley (1994). The potential for antimicrobial edible films is reviewed in
Chapter 5.
1.3 Literature review
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 quantitative 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 lowtemperature 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 important. 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) concentrated 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.
1.4 Scope for application of active packaging
Active packaging is still developing as a collection of niche markets so it is
not surprising that a diverse range of packages active in the physical and
chemical sense are either proposed or commercially available. Early among
these was the use of the reaction of lime with water to generate heat for selfheating cans of sake (Katsura, 1989). The Verifrais process for meat

Respiring Produce

Delayed ripening
Temperature abuse
Fungal growth

Aseptic
Liquids

Oxidation

active
packaging
Prepared
Meals

Microwave
cooking

Oxidation
Hydration

Colour
Retention

Dry
Foods

Chilled
Meats

Mould
Growth

Bakery
Products
REQUIREMENT

FOODCLASS

Figure 1,3 Properties of foods amenable to active packaging.

packaging uses the reaction of organic acid with bicarbonate to produce

carbon dioxide in response to meat drip in foam trays. The carbon dioxide
released helps to suppress microbial growth.
Some properties of foods which can be addressed by active packaging are
summarised in Figure 1.3. These properties are grouped depending upon
whether they are designed to sustain living foods, suppress insect or
microbial life in any foods, prevent oxidative attack on food constituents,
retain flavour, or facilitate serving of the food for consumption. The ways in
which such packaging performs these roles are elaborated in the remainder
of this section.
Active packaging can been seen in one sense as a means of maintaining
the optimum conditions to which a food was exposed at the immediately
preceding step in its handling or processing. Passive packaging has been
used in an effort to minimise the deleterious effects of a limited number of
external variables such as oxygen, water, light, dust microorganisms, rodents
and to some extent, heat. Hence, active packaging has the potential to
continue some aspects of the processing operation or to maintain chosen
variables at particular levels. This aspect of active packaging is a unifying
theme and crosses the border between foods such as plant produce, and
processed foods, including those thermally processed.
A second aspect of active packaging is that it can be involved in the
preparation of the food for consumption. This includes aspects of temperature modification either for organoleptic or food safety purposes. These
properties therefore include heating, cooling and foaming.
Non-processed, respiring food such as agricultural and horticultural
produce, fish, crustaceans and other seafood can be stored and/or shipped
over long distances provided the respiration requirements are satisfied under
controlled temperature conditions. Thus if the packaging can regulate the
supply of oxygen to the animal or produce such that a minimum respiration
rate can be sustained, an enhanced period of prime-quality life can often be
achieved. In plant products the optimum oxygen concentration of the
environment varies with the species, and levels down to 1% may be possible
without inducing anaerobic respiration (Labuza and Breene, 1989). The
generation of elevated levels of carbon dioxide to suppress ethylene
synthesis and to suppress microbial action can be achieved by selection of
plastics films of appropriate permeabilities. However, achievement of the
optimum balance of oxygen and carbon dioxide concentrations by use of
plastics films alone is frequently impossible, particularly as allowance must
be made for temperature abuse.
It is possible to predict the potential packaging requirements for
horticultural produce by modelling the properties of the food and the
packaging film. There have been several reports published on approaches to
modelling such systems, and they have been compared by Solomos (1994),
who has tabulated the characteristics provided for in each of the models.

Some of these are quite complicated and they are set out in Chapter 3 to
provide an easy-to-use model. This form of packaging is commonly termed
modified atmosphere packaging (MAP) or more appropriately equilibrium
modified atmosphere (EMA) packaging.
EMA packaging involving selection of polymer films is, as mentioned
previously, the borderline between active and passive packaging. Chapter 3
shows how modelling can indicate quickly whether available packaging
plastics are going to be suitable for maintaining EMA over the temperature
range chosen. Several approaches to overcoming the limitations of these
films have been reported. One which is still in its infancy is the use of liquidcrystal polymers which undergo a phase change at a characteristic
temperature. The permeability of the polymer to oxygen sharply increases as
this temperature is exceeded, thus providing the oxygen necessary to prevent
packaged horticultural produce from switching from aerobic to anaerobic
respiration. The present state of the art is not sufficiently advanced to cover
EMA films which match produce over a wide temperature range, but
research has opened up this possibility.
An alternative involves pores in portions of a package which open when
the temperature exceeds a precisely set value. This has been achieved by
filling pores in a patch on a package with a wax which melts appropriately
(Cameron and Patterson, 1992). This wax, when liquid, is drawn away by a
wick such as a microporous film to leave the pore open to gas exchange.
This type of high-temperature emergency valve is applicable to packages
over a wide range of sizes. Microporous patches are already used
commercially on retail trays of some fruit.
The use of pores in packaging materials to actually balance the
atmosphere in packages of respiring fruit has been the subject of some
research and a large amount of marketing. Several forms of crushed rock,
coral and synthetic zeolites have been incorporated into extruded film but
there has been very little disinterested scientific evaluation done. Such films
extend the range of gas permeability values of the commodity films in
current use. Some results for P-Plus, a porous film currently manufactured
by Sidlaw Packaging, Bristol (UK), have been presented (Gill, 1990).
Predictive research and some experimental verification of the effects of
single pores in produce packages have been reported (Mannapperuma and
Singh, 1994). The effects of changes in temperature on gas composition
need to be evaluated.
Extension of the post-harvest life of fruits and vegetables requires more
than EMA packaging. The water relations between the horticultural
foodstuff and its atmosphere need to be balanced both to prevent
dehydration and to avoid condensation induced by temperature abuse. Since
the RH of such packages exceeds 95%, a temperature drop from 12C to
110C at the pack surface can cause condensation. The visually unpleasant
appearance in retail packs is frequently overcome by antifogs in the plastic

and innovative forms of active packaging are described in Chapter 4.

Microporous pads containing inorganic salts have been shown to buffer the
water vapour pressure (Shirazi and Cameron, 1992). Some of these are used
commercially in the USA and Japan but others are close to commercial
development.
There have been some patents directed towards use of combination effects
in active packaging for horticultural produce. Thus there have been patents
of combination CO2 emitter/water vapour absorbers and otherwise similar
compositions but including an oxygen scavenger as well. Yet another is
Neupalon, which is described in Chapter 2. This would bring the advantages
of reducing the time the packaged horticultural product is subjected to high
oxygen levels and inhibiting the onset of ripening, particularly with
climacteric fruit. The rapid oxygen scavenger films of Rooney (1982) and
Maloba (1994) could be suitable for this purpose if they met with regulatory
requirements.
Other approaches to enhancing the storage life of horticultural produce
have been directed towards removing ethylene produced by ripening fruits
and vegetables. Since ethylene is both produced by ripening fruits and
triggers their ripening it is essential to prevent those fruits which are further
along the ripening process from triggering ripening of others in the same
enclosed space. Injured fruits are a particular problem in this regard and this
emphasises the need for strict quality control in EMA packaging. The
isolation of packages containing fruit rapidly generating ethylene may be the
appropriate target of technologies for ethylene removal. Chapter 2 includes
the approaches taken both commercially and in research reports. The
challenge appears to be to provide independently verifiable chemical
processes which function satisfactorily to remove ethylene at physiologically
significant concentrations in packages under conditions of high humidity and
possibly in the presence of condensation. Since the quantities of ethylene are
tiny, the cost should not be the major obstacle to commercial development.
Produce packages normally have large headspaces so both sachet and
packaging film scavengers should prove acceptable.
Several other 'freshness enhancing' properties have been claimed for
some commercial films but the processes occurring therein have not been
clarified. This matter is dealt with in more detail in Chapter 2.
Besides horticultural produce and living seafood which are meant to be
kept alive during transportation, there is the very important field of chilled
meats which retain muscular respiration for some hours or days postslaughter. While beef, for instance, is capable of oxygen scavenging by
muscle respiration for a few days at meatworks chiller temperatures of-1C
to 1C, it is no longer capable of doing so for the remainder of the desired
storage period, usually 4-8 weeks. Lactic acid bacteria lower the pH and
suppress the growth of Bronchothrix thermosphacta and Pseudomonas spp.
and other species. There is scope for oxygen scavenging films in bag

construction to prevent oxygen permeation and for lactic-acid-releasing

films to enhance this effect in some cases.
The removal of residual oxygen from MAP meat packs by oxygen
scavengers would increase security and decrease the need for slow,
sophisticated packaging processes in this case. The carbon dioxide levels are
normally very high (> 99%), as in the Captech process (Gill, 1989), so
oxygen scavengers would need to operate wet in this environment.
An additional definition of active packaging specific to horticultural
produce distinguishes between passive and active modified atmosphere
packaging (Zagory and Kader, 1988). The passive form which we are
considering as EMA involves choice of the packaging material for its ratio
of permeabilities to O2 and CO2 as well as for their absolute values. Active
MAP has been defined as gas atmosphere replacement by flushing or
evacuation-back flushing, although the option of adding other active agents
has also been considered (Kader, Zagory and Kerbel, 1989).
Modified atmosphere packaging of non-living foods is now a mature area
of research and has resulted in filling significant niche markets, particularly
in the bakery, cheese and fresh pasta areas. Fresh pasta, which has been a
recent success internationally, is dependent on MAP (Castelvetri, 1990).
The growth of moulds, while suppressed by elevated carbon dioxide
concentrations, is not uniformly affected across the range of species. Low
levels of oxygen can in some cases support some species of mould,
particularly as carbon dioxide is lost by permeation of packaging films.
There is a need to remove most residual oxygen which may reach more than
1% when flushing is used without prior evacuation. Oxygen concentrations
below 0.1% are desirable especially when cut surfaces are exposed, as in
pizza-type cheeses and some MAP meats.
Besides mould growth, chemical effects such as oxidative attack on
colours in preserved meats (Andersen and Rasmussen, 1992), nutrient
degradation such as vitamin C loss which can result in browning products
(Waletzko and Labuza, 1976), and rancidity generation in fats and oils
(Nakamura and Hoshino, 1983) can be prevented or minimised by use of
oxygen scavengers. The substantial development work aimed at overcoming
these problems is demonstrated by the results shown in the Historical
Development section of this chapter. One benefit to researchers of oxygenabsorbers is allowing ultimate effects of near-zero oxygen content atmospheres to be evaluated so that prediction of shelf-lives under other less
perfect conditions can be more firmly based. Although initial development,
and current commercial practice, is based on sachets of scavengers inserted
into packs, much recent research and development has been directed towards
scavenging polymers which can address problems with oxidisable liquids
such as beer, wines, fruit juices and other beverages. Polymers, because of
their ease of melt formation, can take the scavenging capacity to localised

areas such as closures and to areas of close contact of product and package
as found with meats, cheeses and wet foods generally.
The ability of polymers to act where there is close contact opens the way
to provide a variety of food additives via a diffusive mechanism. This
includes antimicrobial action (Halek and Garg, 1988) or antioxidant (Han et
aL, 1987) effects. To date, the use of such packaging has been restricted to
controlled release of antioxidant into cereal products (Miltz et aL, 1989).
The benefit of slow release of antimicrobial agents and antioxidants is the
potential for maintenance of the requisite high concentration at wet food
surfaces. This applies especially to high-water-content foods in which
diffusion from the surface into the bulk can deplete surface concentrations
(Torres et aL, 1985). This effect has been noted by Smith et aL (1990) who
investigated the effectiveness of ethanol-emitting sachets on the growth of
Sacchawmyces cerevisiae on apple turnovers. For active packaging to fulfil
a useful role in this field it will be necessary for it to provide controllable,
slow release matched to the needs of the food. Water-triggered sachets of
silica containing ethanol are very much a first generation approach to this
form of packaging. The role of edible food coatings in release of food
additives is discussed in Chapter 5.
Besides antimicrobials and antioxidants there is a wide variety of other agents
that can be added to foods or which can act on them. Thus flavours can be
added to offset degradation on storage, enzymes can remove oxygen or other
undesirable food components, and insecticides can repel insects or kill them
with permitted fumigants. There is a potential ethical dilemma which may arise
from the application of such approaches to food packaging. There is also the
potential for foods to be self-promoting via the aroma of their packaging. Thus a
desirable flavour might be generated by an outer layer of a package to attract
customers rather than being released from an inner layer to offset scalping or
processing losses. In an extreme case, supermarkets might become a confusing
garden of unbalanced aromas competing for the organoleptic senses of the
customer in much the same way as package print attracts the customer visually.
At this point the packaging ceases to be active in the sense of the present
definition and can be described as intelligent in the definition of the CEST
report (Summers, 1992). Introduction of many of these forms of active or related
packaging technologies will necessitate serious consideration of explanatory
labelling. In some cases this may require regulation, as with oxygen-scavenging
sachets in Japan, the USA and Australia where the "Do not eat label" is required.
In Australia at least, minimum sizes are specified to reduce risk of
ingestion.
1.4.1

Do-it-yourself active packaging

Shelf-life extension of foods in the home, particularly following opening of

the original package, can be seen as a natural extension of the systems used

in previous centuries. For instance the modern bag-in-box systems such as

Intasept (Southcorp Flexible Packaging, Australia) is an extension of the
Spanish wine-skin concept. Various evaporative coolers for bottled wine or
butter etc. were the predecessors of self-cooling cans frequently invented but
less frequently manufactured (Katsura, 1989).
Following the successful introduction of cling-wraps as short-term
moisture barriers in the home, there has been a steady progression of
developments in active packaging for in-home use. Typical applications are
the short-term packaging of unused food portions such as chicken or fish
pieces or freshness retention in vegetables. Most of these forms of packaging
are directed towards refrigerated items. An exception to this would be a
desiccant pack for cookies or biscuits replacing the early canisters with
regenerable silica gel desiccant in the twist cap insert in the lid. Such
desiccant could be regenerated in the oven with gentle heating. It is
surprising that such a packaging adjunct is not widely available since biscuit
packs made from oriented polypropylene readily tear and generally are not
resealable.
Examples of do-it-yourself active packaging already available are listed in
Table 1.2. The potential for the reduction of the surface aw of food pieces by
Pichit multilayer film is described in more detail in Chapter 4. The sale of
such film in domestic packs of 10 sheets, 19 cm x 27 cm, or on a perforated
roll (as with polyethylene bags for plant produce in supermarkets) is
particularly effective. Different approaches to modification of water vapour
transfer from foods such as produce are found in the various perforated bags
available in many countries. Perforations in the Ziploc recloseable bags of
Dowbrands (USA), are a clear example. Less quantifiable are the effects of
mineral-loaded bags such as are supplied as Natural Radiation Bag
(Mitsubishi, Japan). The latter contains zeolite particles with large pores and
is available for meat packaging or produce packaging in retail sizes. Such
bags as are made by Mitsubishi and Asahi are claimed to have 'natural
radiation' or 'infra-red radiation' effects, which are discussed in as much
detail as is possible in Chapters 2 and 3.
ANICO bags have a different type of inclusion in the polymer, consisting
of iron and ascorbic acid (Anico, undated). Freshness may be enhanced by
release of superoxide, although the mechanism has not been demonstrated in
detail. Evidence is presented for reduced microbial growth on four foods
Table 1.2 'Do-it-yourself active packaging
Process

Example

RH Modification
Freshness
Freshness
Natural radiation
Oxygen scavenger

Pichit - humectants
Asahi - zeolite
Anico - iron sulfate + ascorbate
Ceramic particles
Mitsubishi - iron powder

Oxygen (%)

when wrapped in paper impregnated with ANICO. Results presented

demonstrate the removal of ammonia, hydrogen sulfide and methyl
mereaptan by the reactive ingredients in solution. The quantity of powdered
inclusions is insufficient to cause substantial change in the water vapour
transmission rate.
An entirely different approach has been developed by Mitsubishi in the
form of bags with a 'roll-over and clamp' style of removable pressure seal
in kit form for use with cookies. The cookies are placed in the oxygenbarrier laminate bag and an oxygen-scavenger sachet is removed from a
protective metallised film sachet and inserted before the pressure seal is
applied. This is particularly effective in removing the oxygen from the
headspace within 10 h as shown in Figure 1.4. This type of domestic active
packaging is very suitable for foods unlikely to be affected by anaerobic
pathogens. The regulatory dilemma arises in assessing the likelihood of
domestic purchasers using such a scavenger system with raw fish or
vegetables prone to pathogen infestation.
A partially regenerable system involving use of haemoglobin analogues to
buffer the oxygen concentration at low levels might be useful in some
instances. This might take advantage of the high equilibrium constant for
reversible binding of oxygen to a cobalt complex. Some such complexes
reversibly bind oxygen until its partial pressure becomes so low that the rate
of dissociation equals that of association. The result is buffer action. By

Time (hours)
Figure 1.4 Oxygen scavenging from loosely packed biscuits packs () compared to tightly packed
packets (A) (simulating domestic use).

Next Page

careful choice of the equilibrium constant for binding, an oxygen concentration which is a compromise between protection against oxidation and
suppression of anaerobic organisms could be achieved. It should be noted
that oxygen levels needed for anaerobe suppression are higher than has often
been claimed (Smith et al., 1990).
A metal complex would require a high binding constant for oxygen at 4C
and a much lower one at 1000C. Accordingly, the oxygen can be desorbed
by immersion of the device in boiling water before reuse. This process
could, in principle, be repeated until the accumulation of products of side
reactions resulting in cobalt (3) formation reduced oxygen uptake unacceptably. Aquanautics Inc. (USA) investigated the use of such complexes for
extraction of oxygen from seawater for submarine use. Other military
applications were provision of oxygen for welding on warships and for
provision of life-support oxygen in high-altitude aircraft.
Retail sales of microwave susceptor films have been limited, presumably
as a result of the US FDA concerns about the effect of high temperatures on
the adhesives which bind the polyester layer to any backing. However,
susceptor films consisting of paper/adhesive/metallised polyester have been
marketed in Australia since the mid 1980s.
1.5 Physical and chemical principles applied
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.
1.5.1.1 Porosity control. Researchers in modified atmosphere packaging
of respiring horticultural produce have long sought to generate equilibrium
modified atmospheres (EMAs) by use of the permselectivity towards carbon
dioxide over oxygen of plastics films. Although the ratio of permeability to
carbon dioxide to that of oxygen commonly varies from 3.3 to 8.3 (see Table
4.4), this range is insufficient when considered in conjunction with the
absolute values of these properties. Hence research became directed more at
methods of controlling the size and distribution of pores in packaging
materials. This research has ranged from the modelling of the size of single
pores in a package (Mannapperuma and Singh, 1994) to the incorporation of
coral sand (Abe, 1990).
The temperature-controlled opening of pores in polymer films is a
substantially more difficult concept to apply in practice. Cameron and
Patterson (1992) devised a system that allows sufficient oxygen to prevent
anaerobic respiration to enter a package if the temperature is raised too high

Previous Page

careful choice of the equilibrium constant for binding, an oxygen concentration which is a compromise between protection against oxidation and
suppression of anaerobic organisms could be achieved. It should be noted
that oxygen levels needed for anaerobe suppression are higher than has often
been claimed (Smith et al., 1990).
A metal complex would require a high binding constant for oxygen at 4C
and a much lower one at 1000C. Accordingly, the oxygen can be desorbed
by immersion of the device in boiling water before reuse. This process
could, in principle, be repeated until the accumulation of products of side
reactions resulting in cobalt (3) formation reduced oxygen uptake unacceptably. Aquanautics Inc. (USA) investigated the use of such complexes for
extraction of oxygen from seawater for submarine use. Other military
applications were provision of oxygen for welding on warships and for
provision of life-support oxygen in high-altitude aircraft.
Retail sales of microwave susceptor films have been limited, presumably
as a result of the US FDA concerns about the effect of high temperatures on
the adhesives which bind the polyester layer to any backing. However,
susceptor films consisting of paper/adhesive/metallised polyester have been
marketed in Australia since the mid 1980s.
1.5 Physical and chemical principles applied
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.
1.5.1.1 Porosity control. Researchers in modified atmosphere packaging
of respiring horticultural produce have long sought to generate equilibrium
modified atmospheres (EMAs) by use of the permselectivity towards carbon
dioxide over oxygen of plastics films. Although the ratio of permeability to
carbon dioxide to that of oxygen commonly varies from 3.3 to 8.3 (see Table
4.4), this range is insufficient when considered in conjunction with the
absolute values of these properties. Hence research became directed more at
methods of controlling the size and distribution of pores in packaging
materials. This research has ranged from the modelling of the size of single
pores in a package (Mannapperuma and Singh, 1994) to the incorporation of
coral sand (Abe, 1990).
The temperature-controlled opening of pores in polymer films is a
substantially more difficult concept to apply in practice. Cameron and
Patterson (1992) devised a system that allows sufficient oxygen to prevent
anaerobic respiration to enter a package if the temperature is raised too high

Table 1.3 Physical and chemical principles applied in active packaging

Principle

Application

Porosity Control

Gas pressure release

Gas composition balance

Polymer Permeability

Gas composition balance

Temperature compensation

Melting of Waxes

Time-Temperature indicators
Temperature compensation

Thermal Expansion

Doneness indicators

Energy Shielding

Microwave shielding
Thermal insulation
Shock absorption

Energy Transfer

Microwave crisping
UV absorption

Inorganic-Organic Oxidation

Oxygen scavenging
Oxygen permeation barrier
Oxygen indicator
Carbon dioxide generation
Ethylene scavenging
Taint removal

Enzyme Catalysis

Oxygen scavenging
Time-Temperature indication
Lactose removal
Cholesterol removal

Acid-Base Reaction

CO2 absorption
CO2 generation
Odour absorption

Adsorption

Taint removal
Oxygen scavenging
Ethylene scavenging
Water removal

Absorption

Humidity buffering
Condensation control
Drip collection

Hydrolysis

Sulfur dioxide release

Benomyl release

Desorption

Ethanol release
Hinokitiol release
Water release

Organic Reactions

Ethylene removal
Oxveen barrier

during distribution. Their approach was to block a pore in a package with a

wax which melted at the chosen upper temperature limit. When molten, the
wax was drawn away by an absorbent wicking material.
The use of sophisticated pore control is not limited to respiring produce
packaging. DRG Flexible Packaging pic introduced the Ventflex tray in
which long capillaries formed horizontally in the lid to regulate gas

exchange. Yet another approach is to weld a plastic pressure-release valve

into the wall of packs for freshly roasted coffee beans to release the carbon
dioxide held in the beans under pressure for some days. This valve has gone
through at least two designs with the early protrusion from the package
surface being replaced by a design with the valve flush with the outer
surface.
1. 5.1.2 Polymer permeability. Equilibrium modified atmosphere generation is still the major goal of polymer permeability modification. Modelling
produce requirements with film properties is becoming increasingly popular
(Chapter 3). A review of this area is also found in Solomos (1994).
However, with temperature abuse in produce distribution, the temperature
dependence of film permeability to oxygen and carbon dioxide is quite
different from that of the respiration rate. Hence a film which allows
generation of a satisfactory EMA at one temperature may cause anaerobic
respiration at another. Use of liquid crystal polymers is an approach to
solving this problem but those currently available do not offer large enough
changes in permeability to be very significant at present.
Polymer blending has been used to develop sufficiently high permeability
to water vapour and smoke flavours at 400C while retaining a substantial
oxygen barrier at 23C. The accrued knowledge of polymer permeability
properties is already very great and other applications in active packaging
may be expected.
1.5.1.3 Melting of waxes. Use of wax melting for porosity controlled
temperature compensation has been mentioned above. This property was
used for indicating temperature abuse, especially in chilled and frozen foods
(see Chapter 10).
1.5.1.4 Thermal expansion. As the package is being used more extensively as the vessel in which foods are reheated or cooked, the opportunities
for indicating completion of the heating of the food are expanding. To date
the so-called 'doneness' indicators for turkeys are an initial example. These
plastic inserts in the food expand when the temperature at a predetermined
depth reaches a chosen value. Other forms of time-temperature indication
may replace these devices but a considerable amount of modelling of
thermal processing may need to be done first.
It is perhaps surprising that thermal expansion has not yet been used in
temperature compensating devices for balancing gas compositions in EMA
packs of horticultural produce.
1.5.1.5 Energy shielding. The insulation of foods by corrugated fibreboard cartons or polystyrene foam cartons scarcely satisfies the definition of
active packaging. However, insulation has been brought into retail units in

such novel ways that they deserve attention. Labuza and Breene (1989)
reviewed novel two-layer packages both with and without an intermediate
layer such as a chillable gel which imparts an increased thermal load. The
use of labels which expand to give an insulating foam when plastics lunchcups are retorted is a novel example.
A higher level of sophistication is found in the inclusion of selective
shielding of portions of microwaveable meals by appropriate placement of
metallised strips in the top dome of packs. This makes possible the
engineering of food products with mixtures of components with very
different heating requirements (see Chapter 9).
The concept of shielding the food from energy applied externally can also
be applied to shock absorption by layers of foam. One such laminate is
described by Yoshizaki (1976). This approach is not substantially different
from the application of shrinkable foamed sleeves to glass soft-drink
bottles.
1.5.1.6 Energy conversion. The ease with which energy is converted
from one form to another has led to the development of microwave
susceptors (Robertson, 1993). Although the regulation of susceptors is
complicated by concerns about migration, their potential in the crisping of
pastries and other foods has been widely accepted (Sacharow and Schiffman,
1992).
Energy transfer has long been used in protection of plastics for use in
exposed conditions (Brydson, 1982). Absorption of this energy has normally
been followed by energy conversion to heat, either by the process of internal
conversion or by energising chemical reactions. Such processes have been
proposed increasingly for food packaging, in the patent literature. This
follows the demonstration of the effects of light, both in the near UV and
visible regions, on foods (Andersen and Rasmussen, 1992).
1.5.1.7 Adsorption. The introduction of adsorbents into food packages,
both in sachets and dispersed in plastics, has been one of the main
approaches to active packaging. The major advantage such materials have
over chemical reagents is their absence of migration into the food, or their
inertness. Adsorbents used or described in the literature include activated
carbon, zeolites, silica gel, wood fibres and other forms of cellulose as well
as various clays and crushed rocks (Labuza and Breene, 1989). A
disadvantage of adsorbents is the often-reversible nature of the bonding and
the limited capacity. They have been used, or proposed for use, for
intercepting taints permeating plastics packages (Kiru Kogyo KK, 1994),
adsorbing water vapour (Wagner, 1990), releasing water as a reagent in
oxygen scavenging (see Chapter 6), adsorbing ethylene to some extent
(Louis and de Leiris, 1991), and binding odorous products of some oxygen-

scavenging reactions (Inoue and Komatsu, 1988; Toppan Printing Co.,

1992).
1.5.1.8 Absorption. Absorption processes in active packaging have
largely involved control of the availability of water in packages. The
simplest form of absorption has been removal of weep from meats orfishby
microporous pads containing superabsorbent polymers. This absorption
process has been coupled with carbon dioxide release in the case of the
Verifrais process (Sacharow, 1988) and in oxygen or ethylene scavenging in
the TM Corrugated case (Louis and de Leiris, 1991). More complicated, but
meeting a complex need, are the humidity-buffering and condensationcontrol systems for cartoned horticultural produce described by Patterson,
Jobling and Moradi (1993). The humidity-buffering action can also be seen
in the carbohydrate and glycol mixture used in Pichit sheet for food-surface
de watering in the home (Labuza and Breene, 1989).
1.5.1.9 Desorption. The use of paniculate solids as vehicles for delivery
of active ingredients has been a commonly used process commercially. The
use of a variety of porous solids such as vermiculite to hold water for
oxygen scavenging has already been mentioned and is described in Chapter
6. The desorption of ethanol from dry silica gel is the basis of Ethicap
sachets (Freund Co.) which consist of 55% silica gel and 35% ethanol.
When these are exposed to water vapour in the headspace of a food pack,
they desorb ethanol and a masking flavour. An extension of this is the
concurrent ethanol release and oxygen scavenging by Negamold (Freund
Co.). These processes rely on the stronger binding of water to silica gel
displacing the more weakly held ethanol.
Carbohydrates such as dextrins have been the subject of substantial
research as vehicles for carrying ingredients in the pharmaceutical and
flavour industries because of the range of binding forces which can be found.
Cyclodextrins in particular are attractive because of their cyclic structure and
owing to their favourable regulatory status in some countries. Cyclodextrins
exist in three forms, a, (3 and 7, which consist of ring-shaped molecules with
6, 7 and 8 anhydroglucose units joined, respectively. To date they have been
used to release hinokithiol antimicrobial agent from non-woven fabrics and
plastics films under the Hosenshi trade name of Seiwa Chemical (Katsura,
1989).
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 carboxylicacid-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.
1.5.1.11 Acid/base reactions. The abundance of food constituents and
permitted additives which are mildly acidic or basic has facilitated the
introduction of acid/base reactions for altering packaged food environments.
The reaction of ascorbic acid with sodium bicarbonate is commonplace in
oxygen scavengers which replace oxygen consumption with carbon dioxide
generation. Conversely, the removal of unwanted carbon dioxide from packs
by reaction with lime in coffee packs has also been introduced commercially
(Russo, 1986).
The use of food acids dispersed in polymer films for removal of
malodorous amines from fish has been patented by Hoshino and Osanai
(1986). The interest in deodorising food packaging in Japan should result in
more research and development in this area. Katsura (1989) noted that
Nippon Unicar has introduced a flavonoid-based compound in low-density
polyethylene for this purpose also.
Combinations of many of these principles are found in commercial
packages and in proposed systems. The Verifrais system and related systems
which have followed involve a superabsorbent polymer to absorb water, the
latter dissolving an acid and bicarbonate to release carbon dioxide in a
controlled manner.
1.5.1.12 Inorganic/organic oxidation. Since oxygen scavenging was one
of the earliest forms of active packaging to be introduced the use of
oxidation reactions for several other purposes readily followed. The
oxidation of metals had been limited to headspace oxygen scavenging but
recent developments in bringing water, oxygen and iron together in plastics
films has made an oxygen permeation barrier possible by this method (anon.,
1994). Oxidation of organic substrates such as polyamides, rubbers, fatty
acids and ascorbic acid has been developed for oxygen permeation barriers
in plastics films (Chapter 4). Dyes which can be reversibly oxidised have
been developed as indicators of oxygen concentration by formulation with
reducing agents (Nippon Soda KK, 1993).
Carbon dioxide generation is possible as ferrous carbonate is oxidised by
molecular oxygen. This has been patented for applications where package
collapse on oxygen scavenging cannot be accepted.

Following the early work of Scott et al (1970) on oxidation of ethylene

by potassium permanganate, a variety of these rather non-specific oxidant
sachets have become available. Their regulatory status should be examined
before they are used. Whereas such non-specific oxidising systems have the
possibility of generating taints, the reaction of ferrous iron with organic
acids has been developed in plastics films for oxidative removal of taints
(Anico, undated).
7.5.7.75 Organic reactions. Otherwise unclassified organic reactions
have also been proposed in several patent applications. Ethylene removal by
reaction with tetrazines has been demonstrated to occur efficiently at
physiologically important concentrations (Holland, 1992). The Maillard
reaction seems to be the basis of a patent in which reducing sugars and
amino acids are brought together under moist conditions in a plastic film
(Goyo Shiko KK, 1993). The products are claimed to reduce oxygen
permeation but may also migrate into packaged liquid food to act as
antioxidants.
1.5. L14 Enzymic catalysis. One of the earliest attempts at producing a
sachet-based oxygen-scavenging system was based on the reaction of
glucose with oxygen, catalysed by glucose oxidase in the presence of
catalase (Scott and Hammer, 1961). Several systems involving both sachet
and in-film chemistry have been developed but have not yet been proven in
commercial practice. Kuhn and Kuhn (1991) have claimed spreading either
the enzyme or glucose on the packaging material and adding the other
component immediately before sealing. Ernst and Vonraffay (1991) and
Ernst and Ernst (1992) described compositions of silica gel, glucose oxidase,
glucose and water. The water can be supplied absorbed in microcrystalline
cellulose. Carbon dioxide can be formed as oxygen is removed if an alkaline
earth carbonate is included in the composition. The compositions can be
pellets, in sachets or between two layers of an oxygen-barrier laminate.
Glucose oxidase has been given GRAS status in the USA (Labuza and
Breene, 1989) so there is considerable interest in making such systems
function efficiently. A range of other applications of enzymes in active
packaging are discussed in Chapter 7.
The enzymatic hydrolysis of a lipid has been introduced as a timetemperature indicator by I-Point Biotechnology in the USA. The resulting
change in pH was detected by means of a dye following mixing of the
substrate and enzyme.
This listing of principles and applications is not intended to be exhaustive
but rather is aimed at indicating the basis and diversity of active packaging
approaches.

1.6 Implications for other packaging

The decision to address at least one attribute of a food by means of active
packaging can have a significant impact on the choice of the total package.
The impact can vary from the choice of resin into which to blend zeolites or
ceramics for permeability modification to the temperature stability of outer
packaging of microwave-reheatable packs for pastries. Impacts may be such
as to allow the use of cheaper packaging, as with the use of oxygen
scavengers in packaging relatively short shelf-life foods. Alternately it might
be necessary to use more expensive materials in order to gain the benefits of
the active agents.
Several forms of active packaging require direct contact between the food
and the active components of the package. When multilayer structures are
used this implies that the heat-seal layer contains the active components, as
with Zeopac antimicrobial trays offered commercially by Mitsubishi in
Japan. In this laminate the cast polypropylene layer containing Zeomic
zeolite is closest to the food. Zeomic is a zeolite in which silver ion is
bonded in the surface layer of the pores. It is manufactured by Shinanen
New Ceramic Company in association with Mitsubishi (Abe, 1990). The
zeolite particles have a larger diameter than the thickness of this foodcontact layer and are thus exposed to any liquid at the food-package
interface. Other silver zeolites are available, such as Bactekiller manufactured by Kanebo Zeolite Co. (Louis and de Leiris, 1991).
Hirata (1992) has found that silver zeolite, used at 1% concentration in the
heat-seal polyethylene layer of a laminate, can reduce the surface bacterial
count on the plastic from 105-106 cells/ml to 10 cells/ml in 24 hours. The
cells are spread on the surface in aqueous suspension. While there is still
discussion as to whether the microorganisms need to come in contact with
the silver surface, it seems far more probable that the silver ion is dissolved
in the liquid by leaching (Ishitani, 1994). This form of packaging has been
used for fresh oysters (Abe, 1990) and oolong tea (Ishitani, 1994).
Halek and Garg (1988) demonstrated the antifungal effect of Benomyl
bound to the ionomer film Surlyn (Dupont) by coupling with dicyclohexyl
carbodiimide. The aim of this work was to determine whether a surfacebound antifungal agent would be effective, thus reducing the chance of the
residues remaining in the food. It was therefore essential that the heat-seal
layer should be the Surlyn. In fact, it was demonstrated that some of the
Benomyl probably broke free of the ionomer and diffused into the agar test
medium.
Where it is intended that the active agent is to be released into, or onto,
the food there may be less restriction on the location of the film layer. Thus
there are opportunities to use slow-release binding agents such as cyclodextrins (Katsura, 1989) or microencapsulation agents either within the heatseal or other layers. The only requirement therefore is that the layer(s)

between the active one and the food is sufficiently permeable. This is the
basis of the ethanol-releasing sachets Ethicap and Negamold (both from
Freund Ltd., Tokyo) and of the CO2-releasing sachets manufactured by
Mitsubishi Gas and Chemical Co., Toppan Printing Co. (both of Tokyo) and
Multiform Desiccants Inc. of Buffalo, NY. The permeability of the sachet
material to water vapour or ethanol is of critical importance in the
application of these sachets. Most frequently, microporosity of a hydrophobic film material has been made use of to achieve this.
Similar considerations to the above apply when active packaging is
chosen to remove a food/headspace component such as oxygen, carbon
dioxide or odours. The need to separate the scavengers from the food by a
layer impermeable to the scavenger has thus far been relatively simple, as
inorganic substances such as iron powder have been used both commercially
(Koyama and Oda, 1992) and in proposed systems (Teijin, 1981; Toyobo,
1981). The choice of film materials permeable to oxygen, carbon dioxide or
organic off-flavours has been relatively simple as polyolefins serve this
purpose well. Where concurrent permeation of the barrier layer to water is
also required, problems are encountered with the polyolefins which are
highly permeable to non-polar gases and vapours but are not sufficiently
permeable to water vapour. This problem is overcome in sachet manufacture
by use of microporous films which are hydrophobic and resist liquid water
penetration (Mitsubishi, 1983). Substantial numbers of patents describe
methods of achieving the requisite permeabilities to water and oxygen using
this approach. The careful choice of food contact layer plastics for retortable
packages by Toyo Seikan (Koyama and Oda, 1992) and American Can
Company has resulted in the development of heat-triggered oxygen
scavengers which function when the water vapour transmission rate of the
laminate reaches the necessary value. The premature oxidation of the
reduced iron scavenger in the Toyo Seikan Oxyguard process at extrusion
temperatures of around 220 0 C is minimised by keeping the plastics dry.
When the container fabricated from these plastics is retorted at 12O0C for 30
min, water vapour permeating the container wall is absorbed and takes part
in the rusting of the iron. Retention of water by the composition allows the
Oxyguard to continue to act as a chemical oxygen barrier when the package
returns to room temperature. This is the opposite situation to that with
conventional passive retort package material based on EVOH where
retention of water in the EVOH lowers the oxygen barrier and increases
oxygen availability to the packaged food for many weeks after retorting
(Tsai and Wachtel, 1990).
The Oxyguard and other oxygen-scavenging plastics compositions can
reduce the cost of the barrier layer by reducing the need for inclusion of
mica platelets in the EVOH or for desiccants in the polypropylene layer of
retortable trays. Another form of active packaging which can also reduce
complexity of oxygen-barrier packaging is ethanol release. Hirata (1992) has

shown that common commodity polymers such as oriented polypropylene

form a sufficient barrier to ethanol permeation to retain this sterilant in the
package for extended periods of time. Thus in those applications where
suppression of mould by ethanol is possible, simple packaging materials can
be considered since oxygen control may not be necessary. Currently ethanol
use in this way is not widely permitted, with the result that present
opportunities are limited. Smith et ah (1987) have suggested that the use of
ethanol could reach approval status in North America for 'brown and serve'
products such as pastries.
1.6.1 Whole packages designed to be active
Some forms of active packaging do not require changes in design of the
package in order to achieve their effects. Examples of these include the
insertion of the various sachets which modify the gas atmosphere, as
described in Chapter 6. Other examples are the various forms of porous or
mineral-filled plastics which can be used with respiring horticultural
produce. In some instances the consumer may not be aware that the package
is different from its passive counterpart as with the oxygen-scavenging
closures for bottled beverages, described in Chapter 8.
Redesign of packages is necessary for some effects to be achieved,
particularly when some of the physical principles listed in Table 1.3 are
involved. This is particularly important where shielding of components in
microwaveable meal packs is desired, because the location of the shields is
critical (Sacharow and Schiffman, 1992; Robertson, 1993). The use of
susceptors to achieve surface crisping of foods means that the distance
between the food surface and the susceptor must be carefully controlled.
Amcor Fibre Packaging in Australia has developed a susceptor-coated
corrugated inner layer of packs for pastries. The exposed corrugating
medium provides a heating surface claimed to be ideal for such crisping. A
corrugated fibreboard base for a susceptor film is also used to drain fat
coining from foods like fish on heating.
Wagner (1989) reported that in 1988 Japan exported over 30 million selfheating cans for sake alone. Aluminium cans for sake are heated when lime
and water in the base are mixed. Steel cans for coffee are also heated using
the same chemistry. This process also has been used to heat lunch boxes
(Katsura, 1989).
Self-cooling cans have also been marketed in Japan for raw sake. The
endothermic dissolution of ammonium nitrate and chloride in water is used
to cool the product. It is necessary to shake the can to ensure the mixing of
the salts with water.
Packages for chilled foods have also been redesigned to allow for the
presence of an active component. Control of carbon dioxide concentration in
packs for meat or fish under modified atmospheres is the aim of a French

package designed to be active (Louis and de Leiris, 1991). The Verifrais

package manufactured by Codimer consists of a heat sealable lid with a tray
with a false bottom which is perforated to allow juice from the product to
drain into the base of the tray. A porous sachet containing sodium
bicarbonate and ascorbic acid is in the base. The delay in access of the liquid
to the sachet is controlled by an absorbent paper pad located between the
sachet and the porous tray. The commencement of dissolution of the acid
and bicarbonate can be delayed for up to 24 hours, by which time the carbon
dioxide concentration can be decreasing due to dissolution in the meat and
permeation of the tray and lid. Release of carbon dioxide from the sachet
serves to offset this loss. Meats can have a shelf-life of up to 21 days at
2-4C in this pack compared with the 10-15 days under normal MAP
(Louis, 1990). The shelf-life of fish can be extended similarly to 10 days
versus 4-5 days under MAP. A more recent variant on this design has the
carbon-dioxide-generating components concealed in a foam tray with
channels for juice drainage (Leon et ai, 1987). The preferred chemicals are
sodium chloride (50%), citric acid (25%), and sodium carbonate (25%). The
chemicals can be in aggregate form rather than held in sachets as with
Verifrais. These chemicals help to reduce package collapse owing to
outward permeation of carbon dioxide by generation on a continuous basis.
The aim is to prevent growth of anaerobic pathogens on meats and seafood
packed in low-oxygen-content modified atmospheres. An alternative to these
active packaging processes is the Valle Spluga process which involves
insertion of a pellet of solid carbon dioxide into the pack before sealing to
provide sufficient additional gas to retain package shape (Louis, 1990). The
carbon dioxide is pelletised in-line to a predetermined dosage. The
packaging material needs to have a strong heat-seal if leakage is to be
avoided within the first day of packing.
Although the mineral-filled and other porous horticultural-produce carton
liners differ very little from conventional liners, not all horticultural active
packaging is so simple. The Ventflex laminate pack introduced by DRG
Packaging in the UK relies on channels between the layers lidding the film
to allow some regulation of evolution of carbon dioxide by the packaged
produce. Oxygen can enter through the same channels or more slowly
through the polyester barrier film forming the lid.
The condensation control carton design of Patterson et al (1993) reduces
substantially the chance of produce damage by water condensation caused
by temperature abuse. The carton is lined with three additional layers which
provide in-pack buffering of the water vapour in the carton headspace. Louis
and de Leiris (1991) describe the TM corrugated case of the Mantsune Co.
which, while superficially similar to the above, has no microporous food
contact polymer but does contain a ceramic claimed to absorb ethylene. This
carton lining is designed to act as a humidity buffer.
Redesign of packages has also been used to address the problems of

packaging of freshly roasted coffee. Taylors of Harrogate, Tea and Coffee

Ltd. (UK) pack the beans in foil laminate pouches which resist the pressure
of carbon dioxide evolved by the beans. This gas evolution usually occurs
for at least the first day after roasting. The Taylors' bag contains a one-way
plastic release valve welded into the face of the bag and this prevents seal
rupture. The original valve design had a protruding component and so was
welded into the side gusset. An alternative approach was adopted by General
Foods in the USA. A Mitsubishi Ageless sachet which absorbs carbon
dioxide and oxygen was included with the coffee in their packs (Russo,
1986). The General Foods pack did not require redesign to accommodate the
sachet. Both active packaging approaches were designed to retain the easily
oxidised fresh coffee flavours normally lost when coffee is allowed to stand
for 24 hours to desorb carbon dioxide.
The forms of active packaging which involve minimal changes to the preexisting package design have been most readily adopted commercially so
far. The widespread use of sachets for headspace atmosphere modification
demonstrates this point. The number of oxygen-scavenging sachets manufactured in Japan in 1989 was estimated at 6.7 billion (Abe, 1990). The
expansion of this market appears to have been limited by the preference of
food manufacturers not to include sachets in the packages with the foods.
Recent introduction of sachets bonded to the package walls should facilitate
greater market penetration (see Chapter 6).
1.7 Limitations of current approaches
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 humidity 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.
1.8 Future potential
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 applications 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

At least three types of regulation have an impact on the use of active
packaging in foods. First, any need for food-contact approval should be
established before any form of active packaging is used. Second, environmental regulations of packaging material usage can be expected to increase
in the coming years. Third, there may be a need for labelling in cases where
active packaging can give rise to consumer confusion.
Food-contact approval will often be required because active packaging
may affect foods in two ways. A substance may migrate into the food or may
be removed from it. Migrants may be intended or unintended. The intended
migrants include food additives which would require regulatory approval in
terms of their identity and concentration. Unintended additives include
active substances which achieve their purpose inside the packaging material
and do not need to enter the food. Food additive regulations require
identification and quantitation of any such migration. The likely introduction
of the 'Threshold of Regulation' concept by the US FDA early in 1995, and
the chance of the European Union adopting similar concepts later, may
facilitate the approval procedures for active packaging. Removal of oxygen
from packages may lead to the growth of anaerobic pathogens in some cases.
The manner in which oxygen scavengers are used may be subject to
regulation. Developments in active packaging discussed in this book are not
necessarily commercial and care should be taken in using any of them.
Environmental regulations for packaging materials often refer to recyclability or identification to assist in recycling. The effect of active packaging
materials on recycling may need to be determined on a case-by-case basis.
Active packaging is often used currently to allow foods to be packaged with
simpler materials than would otherwise be possible. The environmental
impact of the food-package combination should be considered.
Labelling is currently required to reduce the risk of ingestion of sachets of
oxygen scavengers, ethanol emitters, etc. Some form of external labelling
may be required when various forms of indicator come into use. Such
indicators would show gas composition, thermal history, or 'done-ness' in
the case of microwaved foods. Some active packages may be expected to
look different from their passive counterparts. It may be advisable to use
labelling to explain this even in the absence of regulation.
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Ethylene-removing packaging
D. ZAGORY

Ethylene is a chemically simple, ubiquitous chemical that has diverse and

profound effects on the physiology of plants. Ethylene has so many different
effects on plants, is effective in such low concentrations, and its effects are
so dose-dependent, that it has been identified as a plant hormone. Though
many of the effects of ethylene on plants are economically positive, such as
induction of flowering in pineapples, de-greening of citrus and ripening of
tomatoes, often ethylene has been seen to be detrimental to the quality and
longevity of many horticultural products. For this reason, there has long
been interest in removing ethylene from the horticultural environment and in
suppressing its effects.
Some of the diverse ways in which to absorb, adsorb, counteract or
chemically alter ethylene have led to products designed to reduce its
deleterious effects. This chapter will briefly review the chemistry, physiology and agricultural effects of ethylene preparatory to describing the
research and commercial effort undertaken to incorporate ethylene control
agents in packages for horticultural products. Some of this effort has met
with commercial success, but much has not. However, with the rapid growth
of packaging of fresh fruits and vegetables, particularly fresh cut salads and
fruits, opportunities for such products are bound to increase. Therefore, it is
timely to review the basis and activities relating to these products to better
elucidate the possible forms that they can and will take and to point out
some of the advantages and disadvantages of the various approaches likely
to emerge.
2.1 The chemistry of ethylene
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). Nitrogenfixing bacteria can reduce acetylene to ethylene (Dillworth, 1966). Approximately 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 nonvascular 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 atmospheric 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). Brominated 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 commonly used to modify ethylene in the petrochemical industry are not
appropriate for the conditions generally found in a food package environment.
2.13

Adsorption and absorption

In addition to chemical cleavage and modification, ethylene can be absorbed

or adsorbed by a number of substances including activated charcoal,
molecular sieves of crystalline aluminosilicates, Kieselguhr, bentonite,
Fuller's earth, brick dust, silica gel (Kays and Beaudry, 1987) and
aluminium oxide (Goodburn and Halligan, 1987). A number of clay
materials have been reported to have ethylene adsorbing capacity. Examples
include cristobalite (> 87% SO2, > 5% AlO 2 , > 1% Fe2O3) (Kader et ai,

1989), Ohya-ishi (Oya stone) and zeolite (Urushizaki, 1986a). Oya stone is
mined from the Oya cave in Tochigi Prefecture in Japan. The cave has been
used to store fresh produce and is reputed to confer added storage life. The
salutary properties of the cave are thought to reside in the largely zeolitic
stone interior. To improve its ethylene adsorptive capacity, the Oya stone is
first finely ground with a small amount of metal oxide. The mixture is then
kneaded and heated to 200-9000C, then oxidized with ozone or electromagnetic radiation (Urushizaki, 1986b).
Some regenerable adsorbents have been shown to have ethylene adsorbing
capacity and have the benefit of being reusable after purging. Examples of
such adsorbents include propylene glycol, hexylene glycol (Rizzolo et al,
1987a), squalene, Apiezon M, phenylmethylsilicone, polyethylene and
polystyrene (Rizzolo et a/., 1987b).
Some adsorbents have been combined with catalysts or chemical agents
that modify or destroy the ethylene after adsorption. For example, activated
charcoal has been used to adsorb ethylene. In some cases, the activated
charcoal has been impregnated with bromine or with 15% KBrO3 and 0.5M
H2SO4 to eliminate the activity of the ethylene (Osajima et a/., 1983). A
number of catalytic oxidizers have been combined with adsorbents to
remove ethylene from air. Examples include potassium dichromate, KMnO4,
iodine pentoxide, and silver nitrate, each respectively on silica gel (Eastwell
et al, 1978).
Electron-deficient dienes or trienes, such as benzenes, pyridines, diazines,
triazines and tetrazines, having electron-withdrawing substituents such as
fluorinated alkyl groups, sulphones and esters (especially dicarboxyoctyl,
dicarboxydecyl and dicarboxymethyl ester groups), will react rapidly and
irreversibly with ethylene at room temperature and remove ethylene from
the atmosphere. Such compounds can be embedded in permeable plastic
bags or printing inks to remove ethylene from packages of plant produce
(Holland, 1992).
Metal catalysts immobilized on absorbents, such as platinized asbestos,
cupric oxide-ferric oxide pellets and powdered cupric oxide, will effectively
oxidize ethylene, but in many cases the reactions require high temperatures
( > 1800C). Clearly such systems would be inappropriate for food packaging
applications.
2.2 Deleterious effects of ethylene
Ethylene has long been recognized as a problem in postharvest handling of
horticultural products. Since the discovery in 1924 that ethylene can
accelerate ripening in fruits (Denny, 1924) it has become clear that ethylene
can be the cause of undesirable ripening of fruits and vegetables. It is now
recognized that ethylene, in very low amounts, can be responsible for a wide

array of undesirable effects in plants and plant parts. The physiological

effects of ethylene are so important, so diverse, and are induced by such
small amounts of ethylene that it is considered a plant hormone. The diverse
physiological effects of ethylene have been extensively reviewed elsewhere
(Abeles et ai, 1992) so only those effects that are deleterious to packaged
plant produce will be discussed here.
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 perishability.
2.2.2 Fruit ripening and softening
Ethylene has been referred to as a 'ripening' hormone because it can
accelerate softening and ripening of many kinds of fruit. Exposure of mature
fruit to ethylene leads to increased respiration, increased production of
endogenous ethylene, and softening of fruit tissues (Abeles et aiy 1992).
This is achieved through the direct or indirect stimulation of synthesis and
activity of many ripening enzymes by ethylene.
Some fruits, such as bananas and tomatoes, are often deliberately exposed
to high concentrations of ethylene (~ 100 ppm) to induce rapid ripening. In
most cases, for packaged fruits it would be desirable to prevent exposure to
ethylene and thereby prevent rapid ripening.
2.2.3 Flower and leaf abscission
Cell wall hydrolysis of specific cells at the base of leaves, petioles, petals,
pedicels and fruit leads to abscission of the distal organ (Abeles et al., 1992).

Ethylene has been shown to accelerate abscission for many, though not all,
plants and plant parts (Jankiewicz, 1985; Osborne 1989b; Reid, 1985a).
Ethylene causes flower and leaf abscission of many potted ornamental plants
(Cameron and Reid, 1983).
2.2.4 Chlorophyll breakdown
Ethylene increases the rate of chlorophyll degradation in leaf, fruit and
flower tissues (Aharoni, 1989; Knee, 1990; Kusunose and Sawamura, 1980;
Makhlouf et al, 1989). This can be of particular concern in the case of leafy
green vegetables such as spinach, immature fruits such as cucumbers and
squash, and flowers such as broccoli (Reid, 1985b). The presence of low
levels of ethylene can cause yellowing and reduced quality.
2.2.5 Petal inrolling in carnations
Low concentrations of ethylene (< 1 ppm) cause inrolling (or sleepiness)
of the flower petals of sensitive carnation varieties accompanied by a loss of
turgor in the petal tissues (Halevy, 1986). Some carnations are so sensitive
to ethylene that they have been used as ethylene bioassays. Such sensitive
varieties are often subjected to a pulse treatment with silver thiosulphate to
render them insensitive to the effects of ethylene (Cameron and Reid,
1983).
2.2.6 Postharvest disorders
Ethylene can be responsible for a number of specific postharvest disorders of
fruits and vegetables. Examples include russet spot (small oval brown spots,
primarily on the midrib) of crisphead lettuce, formation of bitter-tasting
isocoumarins in carrots, sprouting of potatoes, and toughening of asparagus
(Reid, 1985b).
2.2.7 Susceptibility to plant pathogens
Many postharvest plant pathogens are opportunistic microorganisms that
thrive on injured or senescent tissues. To the degree that ethylene accelerates
senescence and causes specific physiological disorders, it also enhances the
opportunities for pathogenesis. The growth of a number of postharvest
pathogens is directly stimulated by ethylene (Barkai-Golan, 1990; BarkaiGolan and Lavy-Meir, 1989; Kepczynska, 1993). In addition, several
postharvest plant pathogens produce ethylene (Barkai-Golan, 1990) and this
ethylene may compromise the natural defences of the plant tissues.

2.3 Interactions of ethylene and other gases

The activity and reactivity of ethylene depends, in part, on the presence of
other atmospheric gases. The user of packaging materials for the removal or
inactivation of ethylene should consider the presence and concentrations of
oxygen, carbon dioxide, ozone and ethylene and their interactions with each
other and with plant tissues.
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 ethyleneforming 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.
232

Carbon dioxide

Carbon dioxide may stimulate, inhibit or have no effect on ethylene

synthesis, depending on the plant tissue (Abeles et al, 1992) and the
concentration of CO2. More importantly, CO2 renders normally sensitive
plant tissues insensitive to the effects of ethylene, thereby preventing
abscission (Wittenbach and Bukovac, 1973), floral senescence (Nichols,
1968), chlorophyll loss (Aharoni and Lieberman, 1979) and growth
(Chadwick and Burg, 1967).

2.3.3 Ozone
As was mentioned above, ozone oxidizes ethylene to simple breakdown
products and has been used experimentally to remove ethylene from produce
storage areas. However, ozone would not normally be found or introduced
into a food package.
2.4 Ethylene sources in the environment
Ethylene is ubiquitous at low levels in the environment. It is a common
pollutant that can be detected with sensitive instruments. As most methods
of adsorbing or decomposing ethylene have finite capacities for activity, it
seems prudent to reduce environmental ethylene to avoid saturating the
environment of the package with ethylene. Ethylene can come from many
sources both within and outside the package.
Although there are no national standards for environmental ethylene,
California, USA standards recommend human exposures to no more than
0.5 ppm for 1 h or 0.1 ppm for 8 h (Anon., 1962). Such levels are below
damage thresholds for all but the most sensitive horticultural commodities.
2.4.1 Combustion
Ethylene is a common breakdown product of virtually all aerobic combustion processes. Burning agricultural wastes, wildfires, diesel- or propanepowered 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 productgenerated 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.
2.4.2 Plant sources
Growing plants do not normally produce enough ethylene to alter ambient
atmospheric levels of the chemical. In closed areas, such as storage rooms,
packing houses, shipping containers, greenhouses and warehouses, plantgenerated ethylene can be significant (Abeles et al., 1992). Sensitive
products should not be held or stored in proximity to ethylene-generating
products or product-ripening rooms.

2.4.3 Ripening rooms

Bananas and tomatoes are routinely ripened by exposure to 50-100 ppm
ethylene in large sealed rooms. When such rooms are vented, the dispersal
of ethylene can be significant. When ripening rooms are built into produce
storage or distribution warehouses, the ethylene can come in contact with
other products being held in the warehouse. If that produce were packed in
ethylene-adsorbing packaging, the ethylene at such levels might saturate the
packaging and render it ineffective.
2.4.4 Fluorescent ballasts and rubber materials
The ballasts that hold fluorescent lights are sources of ethylene. In addition,
rubber materials exposed to heat or UV light can release ethylene (Reid,
1985b).
2.4.5 Microorganisms
Although several soilborne microorganisms produce ethylene, others degrade 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.
2.5

Commercial applications in packaging

Several of the technologies described above have been incorporated into

packaging materials that are either commercially available or are likely to
become available in the near future. As is common in the commercial sector,
some of the claims for ethylene ad-/absorbing capacity for these packaging
materials have been poorly documented and thus the efficacy of the
materials is difficult to substantiate.
Most substances designed to remove ethylene from packages are delivered
either as sachets that go inside the package or are integrated into the
packaging material, usually a plastic polymer film or the ink used to print on
the package.
2.5.1 Potassium permanganate-based scavengers
Many vendors offer ethylene adsorbers based on KMnO4 immobilized on
any of several minerals. These products are available in sachets for packages
and on blankets that can be placed in produce-holding rooms. Potassium
permanganate is not integrated into food-contact packaging because of its

toxicity. However, sachets could be used inside produce packages and have
been shown to effectively scavenge ethylene from packages of bananas,
persimmons, kiwifruit, avocados (Ben-Arie and Sonego, 1985; Fuchs and
Temkin-Gorodeiski, 1971; Hatton and Reeder, 1972; Krishnamurthy and
Kushalappa, 1985; Liu, 1970; Maotani et al.9 1982; Scott et al9 1970).
Typically, such products contain ~ 4-6% KMnO4 on an inert substrate
such as perlite, alumina, silica gel, vermiculite, activated carbon or celite
(Abeles et al, 1992). The performance and useful lives of these scavengers
depends on the substrate surface area and the content of reagent (KMnO4).
Formulations differ in density and surface area of substrate and the loading
of reagent.
Some suppliers of KMnO4-based ethylene scavengers are listed in Table
2.1. This table is not a complete listing of all companies supplying such
products but only those known to the author at the time of writing.
2.5.2 Activated carbon-based scavengers
Various metal catalysts on activated carbon will effectively remove ethylene
from air passing over the bed of carbon. Commercial units, known as
swingtherm ethylene converters, are based on such a system. However, they
require heat and movement of gases and so are not applicable to packaged
produce. Activated charcoal impregnated with a palladium catalyst placed in
paper sachets effectively removed ethylene in an experiment on maintaining
quality of lightly processed kiwifruit, banana, broccoli and spinach (Abe and
Watada, 1991).
The Japanese company Sekisui Jushi has developed a product, Neupalon,
that is a sachet containing activated carbon and a water absorbent capable of
Table 2.1 Suppliers (USA) of potassium permanganate ethylene scavengers
Air Repair Products, Inc.
PO Box 1006
Stafford, TX 77477
Cams Chemical Company, Inc.
1001 Boyce Memorial Drive
Ottawa, IL 61350
Complete Control
PO Box 1006
Stafford, TX 77477
DeltaTrak, Inc.
PO Box 398
Pleasonton, CA 94566
Ethylene Control, Inc.
PO Box 571
Selma, CA 93662

ExtendaLife Systems
PO Box 55044
Hayward, CA 94545-0044
Loomix, Inc.
405 E. Branch Street
PO Box 490
Arroyo Grande, CA 93420
Purafil, Inc.
PO Box 80434
Chamblee, Georgia 30366
Purity Corporation
9539 Town Park
Houston, TX 77036

Note: Nippon Greener Co. is reported to use potassium permanganate by Abe

(1990) in his listing of ethylene absorbers.

absorbing up to 500-1000 times its weight of water. The company provides

data showing that Neupalon adsorbs 40 ml ethylene per m2.
Honshu Paper, also in Japan, has a product called the Hatofresh System
that is based on activated carbon impregnated with bromine-type inorganic
chemicals. They do not specify which bromine compounds are used. The
carbon-bromine substance is embedded within a paper bag or corrugated
box, which is used to hold fresh produce. They claim that the bag will
adsorb 20 ml ethylene per g of adsorbent. It is unlikely such bags could be
used in most developed countries due to the reaction of bromine compounds
with water, which can release toxic bromine gas.
Mitsubishi Chemical Company of Japan produces a product called SendoMate which is based on palladium catalyst on activated carbon which
adsorbs ethylene and then catalytically breaks it down. The product comes in
woven sachets that can be placed in packages of produce.
2.5.3 Activated earth-type scavengers
In the past several years a number of packaging products have appeared
based on the putative ability of certain finely dispersed minerals to adsorb
ethylene. Typically these minerals are local kinds of clay that are embedded
in polyethylene bags which are then used to package fresh produce. Many,
though not all, of the bags are marketed by Japanese or Korean companies,
though some are also sold in the United States and Australia.
The Cho Yang Heung San Co. Ltd. of Korea markets a film bag called the
Orega bag, based on the US patent of Dr Mitsuo Matsui (Matsui, 1989). Fine
porous material derived from pumice, zeolite, active carbon, cristobalite or
clinoptilolite is sintered together with a small amount of metal oxide before
being dispersed in a plastic film. Neither plastics containing chlorine such as
polyvinyl chloride or polyvinylidene chloride, nor plasticizers, are apparently suitable for these applications (Choi, 1991). The inorganic materials
have pores ranging from 2000 to 2800A and the resulting film is reported to
have the capacity to adsorb at least 0.005 ppm ethylene per hour per m2
(Choi, 1991). Adsorption of this small amount of ethylene may not be
helpful for some situations.
Another such film is described in a US Patent assigned to Nissho and Co.
Ltd. of Japan (Someya, 1992). This film incorporates finely ground coral
(primarily calcium carbonate), having pore sizes in the range of
100,000-500,000A. After incorporation in a polyethylene film, the coral is
claimed to absorb ethylene. However, no data have been presented to
support this claim.
A product called Ethad has been developed by the Rubber Research
Institute of Malaysia; it releases ethylene in order to stimulate the production
of latex by rubber trees. The product is based on powdered zeolite in viscous
oil or grease. The zeolite is reported to adsorb 8% ethylene by weight

(Abeles et ah, 1992). Apparently Ethad has not been used to adsorb
ethylene in packages.
Evert-Fresh Corporation markets Evert-Fresh bags in the USA. The bags
are, presumably, polyethylene with Japanese Oya stone dispersed within the
film matrix. Oya stone has putative ethylene-adsorbing capacity. Evert-Fresh
Corp. offers shelf-life data for several fresh commodities to demonstrate the
benefits of their bags.
A product called BO Film is marketed by the Odja Shoji Co. Ltd. of
Japan. It is a low-density polyethylene film extruded with finely divided
crysburite ceramic which is claimed to confer ethylene-adsorbing capacity
(Joyce, 1988).
There are many other similar bags being sold throughout the world offering improved postharvest life of fresh commodities due to the adsorption of
ethylene by the minerals dispersed within the film. The evidence offered in
support of this claim is generally based on shelf-life experiments comparing
common polyethylene bags with mineralized bags. Such evidence generally
shows an extension of shelf-life and/or a reduction of headspace ethylene.
Such data are unconvincing. Although the finely divided minerals may
adsorb ethylene, they will also open pores within the plastic bag and alter the
gas-exchange properties of the bag. Because ethylene will diffuse much
more rapidly through open pore spaces within the plastic than through the
plastic itself, one would expect ethylene to diffuse out of these bags faster
than through pure polyethylene bags. In addition, CO2 will leave these bags
more readily and O2 enter more readily than is the case for a comparable
polyethylene bag. These effects can improve shelf-life and reduce headspace
ethylene concentrations independently of any ethylene adsorption. In fact,
almost any powdered mineral can confer such effects without relying on
expensive Oya stone or other speciality minerals. Hercules Chemical
Company relied on this effect while using calcium carbonate to improve the
gas-transmission properties of their Fresh Hold breathable bags without
making any claims regarding ethylene adsorption (Anderson, 1989).
Although the minerals in question may have ethylene-adsorbing capacity,
the data supporting the commercial products incorporating these minerals
fail to demonstrate such capacity. Even if they do have ethylene-adsorbing
capacity, it is possible that they will lack significant capacity while
embedded in plastic films. The ethylene would have to diffuse through the
plastic matrix before contact with the dispersed mineral, thus greatly slowing
any processes of adsorption. Once the ethylene has diffused part-way
through the plastic film, venting to the outside may be nearly as fast and
effective as adsorption on embedded minerals.
In a study performed in Australia with BO film, the mineral in the bag
took up little ethylene (Joyce, 1988). Furthermore, in studies with pure
mineral granules of Cera-sutora A, the author found that the ethylene

sorption capacity of the material was only - 170 nmol/g after 15 h at 200C
(Joyce, 1988). This amount of ethylene sorption is insignificant.
In studies in the USA, the author tested four proprietary bags from Japan,
all containing dispersed minerals and all claiming ethylene-adsorbing
capacity. Weighed samples of each bag were placed in sealed jars with
sampling ports attached. A second set of jars were left empty. We injected
a known quantity of ethylene into each jar. Each day for seven days we
sampled the ethylene concentrations in each jar. We could detect no
differences in ethylene concentrations between the jars with film and those
without film. Our conclusion was that none of the four films adsorbed
measurable amounts of ethylene (Zagory et al.9 1988).
In the future, it would be useful if companies claiming ethylene-adsorbing
capacity for their products presented direct evidence for these claims. Shelflife studies and headspace analysis of ethylene concentrations do not support
claims of ethylene-adsorbing capacity. Direct measurement of ethylene
depletion in closed systems containing samples of the bags without any
produce to confound the results would be much more instructive. Furthermore, such studies should be done at low temperature and high relative
humidity to mimic the conditions under which they will be expected to
perform.
2.5 A

New and novel approaches to ethylene-removing packaging

There are some new and unusual approaches to developing ethyleneremoving packaging that deserve mention.
Perhaps the most promising new development in ethylene-removing
packaging is the use of electron-deficient dienes or trienes incorporated in
ethylene-permeable packaging. The preferred diene or triene is a tetrazine.
However, since tetrazine is unstable in the presence of water, it must be
embedded in a hydrophobic, ethylene-permeable plastic film that does not
contain hydroxyl groups (Holland, 1992). Appropriate films would include
silicone polycarbonates, polystyrenes, polyethylenes and polypropylenes.
Approximately 0.01-1.0 M dicarboxyoctyl ester of tetrazine incorporated in
such a film was able to effect a ten-fold reduction in ethylene in sealed jars
within 24 h and a 100-fold reduction within 48 h (Holland, 1992). The
tetrazine film has a characteristic pink color when it is new and turns brown
when it becomes saturated with ethylene so it is possible to know when it
needs replacing.
A new product called Frisspack has been developed in Hungary for use in
storage of fresh fruits and vegetables. The product consists of a chemisorbent of small particle size dispersed among the fibers in the early phase
of paper production. The result is a paper sheet with putative ethyleneadsorbing capacity. The nature of the chemisorbent and data supporting the

claim of ethylene adsorption are not available. No response was received

from the vendor following the author's request for information.
Although there are many packaging products claiming ethylene-removing
capabilities, few of the claims are backed up with reliable data. Standardized
procedures for demonstrating efficacy would aid the development of this
growing industry. In addition, a thorough understanding of the physiological
effects of ethylene and its importance in sealed permeable packages should
precede any use of these products. In many cases, the elevated carbon
dioxide levels common in modified atmosphere packages may obviate the
need for ethylene removal. In other cases, with very sensitive commodities
such as kiwifruit and carnations, ethylene-adsorbing capability may be
crucial in the maintenance of shelf-life and commercial quality.
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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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 permeation.
Designing MAP for fresh produce is a complicated task, requiring good
understanding of the dynamic interactions among the product, the environment, 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

Conduct literature review

Conduct feasibility study

Could CA storage provide"

benefits?

Determine optimum conditions and

tolerant limits

Neither CA storage nor

MAP is suitable for the
product

Determine respiration rates

Use mathematical model to

determine package requirments

I
Verify model predictions with
experiments

Is suitable permeable film

available?

Design of MAP possible

Only CA storage is suitable

for the product

Need to develop new

permeable films for MAP

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.
3.2 Literature review
Before designing MAP for a product, the first step is to determine whether
CA storage can indeed provide benefits for the product. Reviewing the
Table 3.1 Recommended optimal modified atmosphere conditions for produce
Commodity

Temperature
range (0C)

Relative
humidity (%)

0-5
0-5
0-5
0-5
0-5
0-5
8-12
0-5
0-5
8-12
0-5
8-12

0-5
0-5
5-13
12-15
0-5
0-5
10-15
0-5
0-5
0-5
0-5

Modified atmosphere
O2

CO2

95
95
95
90-95
95
95
90-95
95
90
90-95
95
85-90

air
1-2
1-2
3-5
2-5
2-4
3-5
2-5
air
3-5
air
3-5

5-10
5-10
5-7
5-7
2-5
10-20
0
0
10-15
2-8
10-20
0

90
90
85-90
85-95
90-95
90-95
85-90
90
90-95
90-95
90-95

2-3
2-3
2-5
2-5
0-10
3-10
3-10
1-2
2-3
2
10

1-2
2-3
3-10
2-5
11-20
10-12
5-10
5
0-1
8
15-20

Vegetables
Asparagus
Broccoli
Brussels sprouts
Cabbage
Cauliflower
Corn, sweet
Cucumber
Lettuce
Mushroom
Pepper
Spinach
Tomato, partly ripe
Fruits
Apple
Apricot
Avocado
Banana
Blueberry
Cherry, sweet
Grapefruit
Peach
Pear
Persimmon
Strawberry

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

CO2 Concentration (%)

Blackberry, Blueberry, Fig,

Raspberry, Strawberry

Cherry

Mango, Papaya, Pineapple

Avocado
Persimmon
Banana

Grapefruit
Air P = 0.8

Kiwi. Ne< arine, Peach

Orange

Apricot

Grape
Cranberry Plum

LDPEp = Cy

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.
3.3 Feasibility study
A simple feasibility study consists in conducting experiments to monitor the
quality of the product as a function of time under various modified
atmospheres. To define quality, a set of instrumental and sensory quality
attributes must be selected. Although the selection procedure is different for
each product, it generally includes assessment of texture, flavor, odor, color,
nutritional quality, and microbial growth. The effects of CA storage on the
sensory and nutritional quality of fruits and vegetables have been reviewed
by Weichmann (1986).

CO2 Concentration (%)

Air P = 0.8

Mushrooms
Asparagus
Leeks
Broccoli
Brussels ! >pr< >uts'
Beans
Cabbage

Parsley

Okra

Spinach

Cauliflower

Lettuce

Tomato
Pepper
Artichokes
Radish

LDPE B = 0.8

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

Figure 3.4 Flow-through system (a) and closed system (b).

The modified atmosphere can be created using the flow-through system

(Figure 3.4a) that involves storing the product in a glass jar that has an inlet
port and an outlet port through which a pre-mixed gas (consisting of lowered
O2 and elevated CO2) passes. For this feasibility study, the authors suggest
the use of a 3-level factorial experimental design with O2 and CO2
concentrations as independent variables, while keeping temperature and
relative humidity constant. The response or dependable variables are two or
three relevant quality attributes for the product. The O2 and CO2 ranges are
to be selected between 2 and 10% and O and 20%, respectively. The
suggested temperature and relative humidity are 5C and 90%, respectively.
Air (21% O2 and 0% CO2) should always be used as a control.
The purpose of the feasibility study is to determine if CA storage can
provide better storage quality than air storage. If the results are not
favorable, it is likely that MAP is not a suitable technology, and the food
technologist should avoid spending more time on designing MAP for this
particular product.
33.1

Optimum conditions

Further work is justified if the feasibility study confirms the benefit of CA

storage for the product. The question then is whether the same benefit can be
achieved by MAP without the use of an expensive gas generator. Since the
feasibility study provides only preliminary data, more experiments are
needed to more closely define the optimum conditions. This should be done
by extending the experimental design to include additional O2 and CO2
concentrations that are expected to give good results. The effects of
additional temperatures (O and 10C) and relative humidities (85 and 95%)
on storage quality should also be examined.
There are three major design constraints: O2 tolerance limit, CO2 tolerance

limit, and temperature below which chilling injury occurs. Keeping O2

concentration above the O2 tolerance limit is necessary for maintaining
aerobic respiration; otherwise, anaerobic respiration will lead to the
formation of off-flavor and off-odor inducing compounds such as alcohols
and aldehydes. Keeping CO2 concentration below the CO2 tolerance limit is
necessary for protection of the product from unfavorable physiological
disorder such as breakdown of internal tissues. Keeping the product above a
certain temperature is necessary for avoiding cell damage leading to loss of
flavor and invasion of spoilage organism. Usually the O2 tolerance limit
varies between 1 and 3%, the CO2 tolerance limit varies between 10 and
20%, and the chilling temperature varies between O and 15C, depending on
the product - the actual values can be determined experimentally using the
flow-through system illustrated in Figure 3.4a. The O2 tolerance limit may
be determined by monitoring the increase in ethanol content of the tissue.
3.4 Respiration rates
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.
34.1

Temperature effect

Temperature is the most important factor because it affects both the

respiration rate and the permeability of the package. In practice, most
products experience some temperature fluctuations during storage and
distribution. The Arrhenius model is often used to describe the temperature
dependence of respiration, and the equations for rate of O2 consumption and
rate of CO2 evolution are
/?O2 = R2exp(-O2/R7^

(3.2)

#co2 = Rco2 exp(-CO2/R 7^

(3.3)

Another common way to express the temperature dependence is Q10, defined

as
10

Respiration rate at (T + 10)C

"~
Respiration rate at rC

which is applicable to either O2 consumption rate or CO2 evolution rate.

Typical Q10 values for vegetables are 2.5-4.0 at 0-1O0C, 2.0-2.5 at
10-200C, 1.5-2.0 at 20-300C, and 1.5-2.0 at 30-400C (Robertson, 1992).
Mathematically, the activation energy is approximately linearly proportional
to Q10 if the temperature range of interest is small (less than 400C
difference), a condition satisfied by most practical circumstances. Similarly,
Arrhenius-type equations can also be used to describe the temperature
dependence of gas permeabilities.
(3.5)
(3.6)

3.5 Measurement of respiration rates

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.
5.5.7

Flow-through system

The experimental setup of the flow-through system is shown in Figure

3.4(a). It is important to position the inlet and the outlet tubes sufficiently far
apart to ensure thorough mixing of the gas in the jar. The steady-state inlet
and outlet concentrations are measured with an instrument such as a gas
chromatograph. The equations for calculating the respiration rates are
(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.

3.5.2

Closed system method

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 concentrations in the jar change with time - from high O2/low CO 2 concentrations 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 recommended functions for fitting the data are
(3.11)
(3.12)
and their first derivatives are

(3.13)
(3.14)
The validity of Equations (3.11) and (3.12) should be confirmed by
comparing the fitted values with the experiment data. If the comparison is
poor, other forms of functions should be attempted. For convenience, the
conversion factor a is omitted in Equations (3.13) and (3.14).
The respiration rates calculated from Equations (3.9) and (3.10) are at O2
and CO2 concentrations unique to a particular closed system experiment. It
is usually difficult to design a priori a closed system experiment to generate
certain desired gas concentrations. The question is how the respiration rates
obtained from closed system experiments can be useful to estimate the
respiration rates at other gas concentrations. An answer is to first fit the
respiration rate data with a model and then use the model to estimate
the respiration rates at the desired gas concentrations.
The best model presently available for this purpose is the enzyme-kinetic
type respiration model proposed by Lee et al. (1991).
(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).
3.6 Model equations and package requirements
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
Commodity
Blueberry
"Coville"3
Broccolib
Cauliflower0
Green pepperd

vm

Activation
energy
(kJ/mol)

Temp.
(0C)

Respiration
expression
O2 consumption
CO2 evolution

(mg/kgh)
68.0
51.0

(% O2)

15

0.4
0.2

2.9
4.9

147.3
163.3

O2 consumption
CO2 evolution

210.3
235.2

0.6
1.7

2.3
1.93

62.7
66.1

13

O2 consumption
CO2 evolution

133.7
134.4

1.7
1.4

3.0
3.1

21.2-48.2
21.2-48.2

10

O2 consumption
CO2 evolution

54.3
31.8

6.0
2.4

1.3
4.3

48.7-57.3
48.7-57.3

(% CO2)

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.
3.6.1

Unsteady-state equations

A simple model based on the principle of mass balance requires that

Rate of O2 or CO2
accumulated in package

Rate of O2 or CO2

Rate of O2 or CO2

permeated into package

generated by respiration

and the mass balance equations for O 2 and CO 2 are

(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 fluctuations. 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).
3.6.2 State-state equations
When the accumulated terms are zero, Equations (3.16) and (3.17) are
reduced to the steady-state equations
(3.18)

(3.19)
where the subscript s denotes steady-state condition. Equations (3.18) and
(3.19) describe the dynamic equilibrium behaviour of the MAP system,
when the CO2 evolution rate equals the efflux rate of CO2 through the
package and the O2 consumption rate equals the influx rate of O2 through the
package. In most situations, steady-state or dynamic equilibrium is approached within two days. For long storage of the product, the dynamic
equilibrium behavior is more important than the unsteady-state behavior.
To use Equations (3.18) and (3.19) as design equations, it is necessary to
keep track of how many independent or design variables are available. There
are a total of 11 variables: R02, RCOi, and W are associated with the product;
P02, PCQ2, S, and L are associated with the package; [O2]o, [O2J1 s, [CO2]O, and
[CO2I1 s are associated with the environment. (Although temperature is not
explicitly shown, it is an implicit variable that affects both the respiration
rates and the permeabilities to O2 and CO2.) Once the product and the
temperature are selected, six out of the 11 variables are already decided: R02
and RCOi are determined by the flow-through system or the closed system
experiments; [O2J1 s and [CO2], s are assumed to be the optimum O2 and CO2
concentrations; [O2]o and [CO2J0 are 21 and 0%, respectively. With six
variables fixed and two equations to satisfy, there are only (11-6-2) = 3
design variables. That is, only three out of the remaining five variables (W,
5, L, P 02 and PCO2) can be specified arbitrarily. For example, if the food
technologist chooses to specify the dimensions of W, S, and L (within
practical limits), the permeabilities P 02 and PCO2 must then be determined by
Equations (3.18) and (3.19).
The equations also provide a convenient means to reject films not suitable
for a particular application. Dividing Equation (3.19) by Equation (3.18)
yields

(3.20)

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)
Equation (3.19) may be represented as a straight line with slope P on a plot
of [CO2I1 s versus (21 - [O2]; s). Two such lines (P = 0.8 and (3 = 5) are
shown in Figures 3.3 and 3.4. As an example of application, cauliflower
requires a P = 5 (Figure 3.3), and thus a film with (3 varying considerably
from 5 (such as 2) should be rejected for packaging cauliflower. However,
there is no guarantee that a film with (3 = 5 will work well for cauliflower
because, in addition to (3, the individual F 02 and PCOi must be also
determined by solving Equations (3.17) and (3.18) simultaneously. Satisfying Equation (3.19) is a necessary but non-sufficient requirement for
selecting a suitable polymeric film.
There are on-going research efforts being made to develop more
sophisticated models for more accurate prediction, since none of the existing
models considers every factor of the MAP system. A more complete model
should include the generation of H2O and heat and the effects of N2 and
C2H4 in addition to balancing the O2 consumption rate and CO2 evolution
rate. In the meantime, the simple model described above can be used to
provide helpful information for preliminary design of MAP.
3.7 Polymeric films for MAP applications
Since there are many varieties of produce, a wide range of permeabilities is
required. High permeabilities are needed for rapidly respiring produce, low
permeabilities for slowly respiring produce. Table 3.3 lists the permeabilities, (3 values, and permeability activation energies of some common
food packaging polymeric films. Among them, low-density polyethylene and
polyvinyl chloride are most widely used for packaging fruits and vegetables
(Zagory and Kader, 1988).
A fortunate situation occurs when the desired P 02 and PCOl requirements
are met by one or more existing commercial films. If this is the case, a good
chance exists for a successful design. Unfortunately, this is not often the
case because the choices of suitable commercial polymeric films are rather
limited. The problem can be appreciated by examining Table 3.3, which
reveals that the (3 values for most films fall within a rather narrow range

al (1993).
Table 3.3 Permeabilities at 100C and permeability activation energies for polymeric film
Permeabilities (ml mil/m2h
atm)
Polymeric
films
Polybutadiene
Low-density
polyethylene
Ceramic-filled LDPE
Linear low-density
polyethylene
High-density
polyethylene
Cast polypropylene
Oriented polypropylene
Polyethylene
terephthalate
Nylon laminated
multilayer film
Ethylene vinyl acetate
Ceramic-filled
polystyrene
Silicone rubber
Perforation (air)
Microporous
film

PCO2

Activation energies (kJ/mol)

E

PQ2
1118
110

PQ2
9892
366

PQ2
8.8
3.3

Ep.o2
29.7
30.2

P,co;
21.8
31.1

199
257

882
1002

4.4
3.9

36.8

28.4

2.1

9.8

4.6

35.1

30.1

53
34
1.8

151
105
6.1

2.9
3.1
3.3

26.8

25.9

1.7

6.0

3.5

52.6

50.0

166
116

985
630

5.9
5.4

48.4
34.5

37.0
26.2

11170
2.44 X 109
3.81 X 107

71300
1.89 X 109
3.81 X 107

6.4
0.8
1.0

8.4
3.6
13.0

0.0
3.6
3.7

From Exama et al (1993); Lee et al. (1992); Lee et al. (1994); Ohta et al (1991); Mannapperuma
and Singh (1990); Anderson (1989); and Shelekshin et al (1992).

between 3 and 6; however, Figures 3.3 and 3.4 show that many fruits and
vegetables require 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.
3.7.1 Perforation and microporous films
A major challenge is to develop films that have greater permeability and
have a wider range of p values than existing types. Films of enhanced
permeability are necessary for packaging high respiration rate products and
for preventing the development of anaerobiosis. A wider range of (3 values,
especially those below 3, is necessary to better match the respiration
behavior of many products.
The use of either perforation systems or microporous films is a possible
solution to meet these two requirements. These systems and films have

permeabilities many orders of magnitude higher than those of non-perforated

polymeric films, as well as (3 values between 0.8 and 1 (Anderson, 1989).
The uses of perforation systems or microporous films in MAP are currently
being studied in several laboratories.
Emond et al (1991) have studied gas exchange through perforation
systems. They developed empirical equations to predict the effective
permeabilities to O 2 and CO 2 for various diameters, thicknesses, and
temperatures. Their computer simulations showed that neither a silicone
membrane alone nor a perforation system alone could provide a satisfactory
gas concentration for broccoli. However, a combined system, consisting of
silicone membrane with area of 0.0061 m2 and perforations of 0.006 m
diameter and 0.0127 m thickness, could provide favorable conditions for
broccoli. Their other computer simulations also showed that while no
polymeric film or silicone membrane could provide satisfactory conditions
for strawberries, a perforation system (with perforations 0.008 m in diameter
and 0.00159 m thick) could provide an effective solution. However,
experiments are required to confirm these computer predictions.
Meyers (1985) described the use of perforations in MAP of fruits. The
technique involved placing the product in a bag (or on a tray) constructed of
a high-barrier film such as polyvinylidene chloride. The bag was flushed
with N 2 or CO 2 as a preservative gas before sealing. After sealing, the film
was perforated to assure gas outflow from the bag, to prevent distortion and
to provide a gas pressure within the bag sufficient to inhibit air inflow into
the container. The packaging of strawberries and nectarines using this
technique was described.
Mizutani et al (1993) reported that microporous polypropylene sheets
could be prepared by biaxially stretching filler-containing polypropylene
sheets. Examples of fillers were CaCO 3 and SiO2. The gas permeabilities of
those sheets were controllable by adjusting filler content, particle size of
filler, and degree of stretching. The average pore size ranged between 0.14
and 1.4 juum.
Anderson (1989) has described the use of microporous films for MAP of
fruits and vegetables. The package was constructed of a gas-impermeable
material having a microporous membrane panel to provide controlled flows
of O 2 and CO 2 through its walls. The microporous membrane was a biaxially
oriented film composed of a blend of propylene homopolymer and a
propylene-ethylene copoylmer having an ethylene-moiety concentration of
2-5% by weight. The film was filled with 40-60% CaCO 3 based on the total
weight of the film. Depending on the loading of CaCO 3 , the permeance
(defined as permeability per unit thickness) of the film ranged between
77,500 and 465,000,000 ml/m2 day atm. Good results were reported for
strawberries, mushrooms, and broccoli florets with the proper selection of
permeance.

3.7.2 Temperature compensating films

Another challenge is to develop films that can tolerate temperature
fluctuation during storage and distribution. The problem of developing such
films is the mismatch of the activation energies for respiration and
permeation: respiration rates of produce are strongly affected by temperature, but the permeabilities of existing packaging films are only slightly
affected by temperature. In some cases, even a small temperature increase
will cause rapid accumulation of CO2 and depletion of O2 in the package, a
situation that may damage the product. Presently, research is being done on
developing a new class of polymeric films with permeation activation
energies more closely matching the respiration active energies of fresh
produce. This class of polymeric films exhibits dramatic changes in
permeability by transforming the polymer matrix reversibly from a crystalline state to an amorphous state as temperature is increased above a switch
temperature. This switch temperature can be controlled within 2C by
changing the polymer side-chains.
3.7.3 Ceramic-filled films
In recent years, commercial ceramic-filled polymer films have been
introduced in Japan and Korea for packaging fruits. The films usually
contain about 5% of very fine ceramic powder, and the manufacturers claim
that these films emit far-infrared radiation or absorb C2H4 that can help to
extend the shelf-life of the fruits. Although some workers (Isaka, 1988;
Joyce, 1988) have reported that these films seem to improve the storage
quality (especially color) of fresh produce, the benefit of using such films
has not been reported in other laboratories. Lee et al (1992) have reported
that the O2, CO2, and C2H4 permeabilities of ceramic-filled LDPE films are
higher than those of plain LDPE film, and that the temperature dependence
of the permeabilities follows the Arrhenius relationship. The higher
permeabilities make these films more suitable for packaging high respiration
rate products. Since ceramic is a filler, it is expected that higher loadings of
ceramic filler should yield higher permeabilities.
3.8 Concluding remarks
This chapter provides some practical suggestions for designing MAP of
fresh produce. The model equations are a time-saving tool to reduce the
number of experiments and to answer many 'what-if questions. As
mentioned before, the model equations are oversimplified because they do
not include many factors such as transpiration of the product, diffusivity of
skin and flesh to O2 and CO2, effect of C2H4, etc. Thus the model predictions
should be used with an understanding of their limitations, and must always
be verified with experimental data.

Nomenclature

[CO 2 ]
[CO2J1
[CO2J1 s
[CO 2 ] in
[CO 2 ] out
[CO 2 ] O
[O 2 ]
[O2J1
[O 2 ] in
[C^lout
[Cy^s
[O 2 ] o
a
(S
a t , a2
bj, b 2 , C1, c 2
JE1CO2, E02
EpCO2, EpOi
F
K1n
K1
L
MCO2
M02
Patm
^co2> ^ 2
PCO2
P02
P
R
^Co2' R o 2
RCo2
RQ2
S
t
T
V
Vm
W

% CO 2 concentration
% CO 2 concentration inside the package at any time
% CO 2 concentration inside the package at steady state
Inlet CO 2 concentration in flow-through system (%)
Outlet % CO 2 concentration in flow-through system
CO 2 concentration outside the package (%); 0% for air
O 2 concentration (%)
O 2 concentration inside the package at any time (%)
Inlet O 2 concentration in flow-through system (%)
Outlet O 2 concentration in flow-through system (%)
Steady-state O 2 concentration inside the package (%)
O 2 concentration outside the package (%); 2 1 % for air
Conversion factor (1 hr"1)
Permeability ratio, PCQJPO2 (dimensionless)
Coefficients (Ir 1 )
Coefficients (dimensionless)
Activation energies for respiration (J/mole)
Activation energies for permeability (J/mole)
G a s flow rate (ml/h)
M i c h a e l i s - M e n t e n constant (% O 2 )
Inhibition constant (% C O 2 )
Thickness of film ( m m )
Molecular weight of C O 2 (0.044 kg/mole)
Molecular weight of O 2 (0.032 kg/mole)
Pressure of 1 atmosphere (atm)
Pre-exponential factors for permeability ( m g mil/m 2 h atm)
Permeability to CO 2 (mg mil/m 2 h atm)
Permeability to O 2 (mg mil/m 2 h atm)
Pressure in the package or the jar (Pa)
Gas constant (8.314 J/mol K)
Pre-exponential factors for respiration (mg/kg h)
Rate of CO 2 evolution (mg/kg h)
Rate of O 2 consumption (mg/kg h)
Package surface areas (m 2 )
Time (h)
Absolute temperature ( 0 K)
Free volume in package or in jar (ml)
Maximum respiration rate (mg/kg h)
Product weight (kg)

References
Anderson, H.S. (1989) Controlled atmosphere package. US Patent 4842875.
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.
(Shokuhin Kogyo, Jpn.), 31(24), 27.
Jurin, V. and Karel, M. (1963) Studies on control of respiration of Mclntosh apples by
packaging method. Food Technol. Xl, 104-8.
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.
Umeda, K. Yasmoto, K. Utagawa, T. Yokoyama and T. Yamaguchi (eds), Creative, Tokyo,
365-74.
Labuza, T.P. and Breene, W.M. (1989) Application of 'active packaging' for improvement of
shelf-life and nutritional quality of fresh and extended shelf-life foods. / Food Proc. and
Pres., 13, 1-69.
Lebermann, K.W., Nelson, A.I. and Steinberg, M.P. (1968) Post-harvest changes of broccoli
stored in modified atmosphere: I. Respiration of shoots and color of flower head. Food
Technol., 22(4), 143-6.
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
modified atmosphere based on principles of enzyme kinetics. J. Food ScL, 56(6), 1580.
Lee, J. (1987) The design of controlled or modified packaging systems for fresh produce. In:
Food Product-Package Compatibility, Proceedings, J.I. Gray, B.R. Harte and J. Miltz (eds),
Technomic Publishing, Lancaster, PA, USA.
Mannapperuma, J.D. and Singh, R.P. (1990) Micromodel optimization of modified atmosphere
vegetable/fruit packaging. In: Proceedings of the Fifth International Conference on
Controlled/Modified Atmosphere/Vacuum Packaging-CAP90, San Jose, Calif., January
17-19.
Mannapperuma, J.D. and Singh, R.P. (1994) Design of Perforated Polymeric Packages for the
Modified Atmosphere Storage of Fresh Fruits and Vegetables. 1991 IFT Annual Meeting,
Paper 21-8.
Mizutani, Y. et al. (1993) Microporous polypropylene sheets. Ind. Eng. Chem. Res., 32,
221-7.
Meyers, R.A. (1985) Modified Atmosphere Package and Process. US Patent 4515266.
Ohta, H., Nakatani, A., Saio, T., Nagota, Y., Yoza, K. and Ishitani, T. (1991) Gas Permeability
of Commercial Plastic Films. Report of Ginki Chogoku National Agricultural Experimentation Station, 82, 43-6.

Powrie, W.D. and Skura, BJ. (1991) Modified atmosphere packaging of fruits and vegetables.
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:
Controlled/Modified Atmosphere/Vacuum Packaging of Foods, A.L. Brody (ed.), Food &
Nutrition Press, Trumbull, Connecticut, 67-100.
Robertson, G.L. (1992) Packaging of horticultural products. In: Food Packaging: Principles
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Shelekhin, A.B., Dixon, A.G. and Ma, Y.H. (1992) Adsorption, permeation, and diffusion of
gases in microporous membranes. II. Permeation of gases in microporous glass membranes.
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Veeraju, M. and Karel, M. (1966) Controlling atmosphere in fresh-fruit package. Modern
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Weichmann, J. (1986) The effect of controlled-atmosphere storage on the sensory and
nutritional quality of fruits and vegetables. Hort. Rev., 8, 101-27.
Yam, K.L., Haggar, P.E. and Lee, D.S. (1993) Modeling respiration of low CO2 tolerance
produce using a closed system experiment. Foods Biotechnol., 2(1), 22-5.
Yang, CC. and Chinnan, M.S. (1988) Modeling the effect of O2 and CO2 on respiration and
quality of stored tomatoes. Trans. ASAE, 31, 920-5.
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Technology, 42(9), 70-7.

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.
4.2 Oxygen scavenging
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
Infestation
Chemical degradation
Physiological changes

Moulds, aerobic bacteria

Insects, larvae, eggs
Rancidity, pigment/nutrient loss, browning
Respiration

of the problems of distribution of oxygen-sensitive foods as described by

Brody (1989). However, the opportunity to improve on the benefits gained
by application of those technologies, as well as the chance to treat the
problems of distribution of foods individually, has led to the current interest
in oxygen-scavenging plastics.
The properties of foods that can be influenced by the presence of oxygen
scavengers are shown in Table 4.1. The growth of moulds is particularly
important in dairy products such as cheese and in bakery products. Oxygen
levels of 0.1% or lower are required to prevent the growth of many moulds.
Bacterial growth and the growth of yeasts can be a problem in high wateractivity foods including meats and prepared dishes, as well as in juices.
Oxygen scavengers can prevent oxidative damage to flavour and colour in a
wide range of foods. Likewise, they can maintain atmospheres with oxygen
concentrations too low for insect survival in agricultural and horticultural
products. The list in Table 4.2 is indicative of the range of foods which
could benefit from oxygen scavenging, their type of packaging and the forms
in which the scavenger might be applied. The package converter can decide
the nature and quantity of active components used in plastics packaging.
This allows the opportunity for tailoring the packaging to the requirements
of the product.
Table 4.2 Potential applications of oxygen scavenging plastics
Product

Packaging

Aseptic liquids
Bakery products
Beverages
Beer
Cheese
Coffee, tea
Cereals
Dried Fruit
Dried Foods/Nuts
Fried snacks
Fruit/Vegetables
Milk powder
Meat - fresh
- processed

Cartonboard, bag-in-box
film,
coating, adhesive, ink
Flexibles
film,
etc.
Flexibles, bag-in-box
film,
etc.
Crown seal liners
Resin, organosol
Flexibles
film,
etc.
Closures,
flexibles
film,
etc., resin
Flexibles
film,
etc.
Flexibles
film,
etc.
Flexibles, closures
film,
etc., resin
Flexibles
film,
etc.
Flexibles
film,
etc.
Flexibles
film,
etc.
Flexibles
film,
etc.
Flexibles
film,
etc.

Component

Pasteurised liquids

Closures, bottles

resin

Retorted foods

Can lacquers, trays, lidding

resin, film, etc.

Wagner (1990) lists a wide range of oxygen-sensitive prepared foods

which are of increasing importance in consumer societies. Some are suitably
packaged using existing processes. However, quality can often be retained
longer if residual oxygen is removed. This would allow use of different
packaging materials and distribution systems. Some foods, and particularly
beverages, cannot be stabilised adequately with existing packaging technologies in order to allow use of the full range of desired distribution systems.
This is particularly important when reduced levels of additives have been
chosen for regulatory or marketing reasons.
Koros (1990) has set out the maximum quantity of oxygen which a
generalised range of foods can take up and still have a shelf-life of one year.
These quantities are generally in the 1-200 mg/kg range. Abe and Kondoh
(1989) have shown the need for oxygen removal by in-pack systems when
the economic limit of around 0.5% is reached in the general case. This figure
can vary in practice as residue levels of around 2% are often encountered
when form-fill-seal (ffs) gas flushing is used commercially. Alternatively,
less than 0.1% oxygen can be found in vacuum packs of beef primals where
muscule respiration and bacterial action scavenge oxygen.
The most appropriate method of removal of oxygen from a food package
depends on the nature of the food, its prior processing and the packaging
machinery and the way it is distributed. The factors which may need to be
considered, and estimates of efficiency when sachets are used, are
summarised in Table 4.3 which is based on a similar table devised by Hirata
(1992), who compared sachet technologies with vacuum and gas-flush
packaging systems. The expected benefits of use of oxygen-scavenging
plastics are to minimise the materials cost by matching the quantity of
scavenger to the need, and to keep the filling speed high.
4.2,1 Forms of oxygen-scavenging packaging
In-pack oxygen scavenging involves use of a variety of forms of scavenger.
Sachets merely inserted into the food package constitute most of the present
systems in commerce. Alternatively, the scavenger can be hot-melt bonded
to the inner wall of the package. This is done using the Mitsubishi Ageless
scavenger sachet attached to the lid of the steamed rice packages
Table 4.3 Comparison of headspace oxygen removal systems

a
b
c
d
e

System

Residual
O2 kPa

Capital
investment

Film
cost

Filling
speed

Vacuum
N2 Flush
a+b
Scavenger
b+d

< 1.5
1-2
< 1.0
<0.1
<0.1

High
Medium
High
Low
Medium

High
High
High
Medium
Medium

Low
Medium
Low
High
Medium

manufactured in Japan by Ajinimoto under the Take Out brand name. The
self-adhesive label concept of US company Multiform Desiccants is used in
the Marks & Spencer retail chain's preserved meat packs in the UK.
Beyond the concept of adhesion of sachets to the package lies a wide
range of possibilities and it is to this area that much of the recent research
and development has been directed. Alternatives include package inserts in
the form of cards or sheets, or layers coated onto the inner wall of the
package. An example is the beverage crown seal liner currently used in the
beer industry. This liner was developed by Advanced Oxygen Technologies
Inc. and Zapata Industries Inc. under the name SmartCap and independently
by W.R. Grace and Company and under the name Daraform. Both
companies manufacture in the USA. Alternatively an iron-based system has
been developed under the name Oxyguard by Toyo Seikan Kaisha Ltd in
Japan. The industrial development and history of oxygen-scavenging
closures is discussed in detail in Chapter 8.
Oxygen-scavenging films or other plastics packaging materials are
alternatives to sachets. Low molecular weight ingredients may be dissolved
or dispersed in a packaging plastic or the plastic may be made from a
polymeric scavenger. The scavenger may be incorporated into a solid which
is dispersed in the plastic or may be introduced into various layers of the
package such as in the form of adhesive, printing ink, lacquer or enamel,
such as found in cans.
Sachets can be a highly efficient form of oxygen scavenger but their
nature does not favour contact with liquid foods or where cling of the
package to the film may isolate the sachet from areas of oxygen entrapment
or ingress. In such situations it would be preferable to have the scavenger in
the packaging material. This allows all exposed surfaces of the food to be
deoxygenated or protected from oxygen ingress by permeation.
4.2.2 Plastics packaging as media for oxygen scavenging
Oxygen-scavenging packaging has to date been applied only in packs which
have inherently a substantial barrier to oxygen ingress by permeation or
leakage. Abe and Kondoh (1989) recommend that Ageless sachets should be
used in packages with an oxygen transmission rate less than 20 ml/m2/atm/
day. Such requirements therefore rule out the common heat-seal polymers
and thin layers of the more mediocre barriers like polyester (PET) and nylon
6. However, there can be situations such as in transportation of beef primal
cuts in which a shorter period of absolute barrier to oxygen is desirable and
these plastics might be used as the barrier. The patent of Speer and Roberts
(1993) describes a system involving oxidation of poly(l,2-butadiene) and
appears to be directed at that market.
The commonly found oxygen barriers may be in the form of a single-layer
package, as in the case of the PET or PVC bottle, or jar or cup, but are more

Table 4.4 Permeability coefficients P X 1010 (cm3 mm cm"2 sec"1 c m 1 Hg) @ 30 0 C

Film material
Polyvinylidene chloride
Polyester (Mylar A)
Polyamide (Nylon 6)
Polyethylene (d = 0.960)
Polyethylene (d = 0.922)
Polystyrene
Polyvinylchloride

N2

O2

CO 2

0.0094
0.05
0.10
2.7
19
2.9
0.40

O053
0.22
0.38
10.6
55
11.0
1.2

029
1.53
1.6
35
352
88
10

(Reproduced from Paine, 1962, with permission.)

likely be part of a multilayer package. Table 4.4 shows the oxygen

permeability of a range of polymers. A more extensive tabulation of film
permeability values can be found in the review by Bixler (1971).
Oxygen-scavenging compounds can be dispersed or blended in highpermeability films such as plasticised PVC and polyethylene. Where the
oxygen scavenger is molecularly dispersed in the polymer it is available to
oxygen in its entirety, unlike there case where solid particles are used. The
particular advantage of such polymers is that they allow rapid diffusion of
oxygen and water (at elevated temperatures) from the headspace or food in
to the reactive ingredients. Such a characteristic of the polymer helps offset
the disadvantage of plastics-film-based compositions in comparison with
sachets where the scavenging powder has a large reactive surface area
exposed. Polyethylene and polyvinyl chloride (plasticised) are nominated as
the reaction medium in crown closure liners for beverage bottles such as for
beer, as described in detail in Chapter 8.
The use of plastics as media in which to disperse or dissolve oxygen
scavengers places a severe limitation on the number of reactions which can
be involved in the scavenging process. Whereas molecules of the size of
oxygen or water can diffuse at an adequate rate, larger molecules behave as
if they were immobilised. The fact that a molecule can migrate fast enough
to fail food-contact regulatory tests does not indicate that it can be used in
an oxygen-scavenging system. Thus the use of iron oxidation in polymers
has been a challenge for some years requiring all reagents to be intimately
mixed. A further challenge is to establish whether the breakdown of iron
particles on oxidation occurs as freely in a polymer matrix as it does in
powder form in sachets. Labuza and Breene (1989) note that virtually all of
the iron in commercial sachets is available for oxygen removal.
The high gas and vapour permeability of the common heat-seal polymers
allows them to be used as reaction media for oxygen scavenging in
laminates. Indeed this has been proposed in a large number of patents such
as those of Hofeldt and White (1989) and Farrell and Tsai (1985). The
presence of the oxygen scavenger in the heat-seal layer allows maximum
advantage to be taken of the full thickness of the physical barrier to oxygen
permeation of the barrier layer. However, if the scavenger is incorporated

into the barrier layer as in the Ox-bar bottle of CMB Technologies pic
(Folland, 1990) that portion closer to the outside becomes exposed to
relatively large amounts of oxygen.
The permeability of the polymer medium in which the scavenging
reaction occurs need not be the limiting variable determining scavenging
rate. Depending upon the chemistry involved, the oxidation reaction can be
inherently slow, as with crystalline sulfites at room temperature or the
reaction can require the presence of an additional species as with the rusting
of iron. The permeability of the heat-seal layer to both oxygen and water
vapour can be limiting as in the mixed sulfite/acetate layer in retort pouches
patented by Farrell and Tsai (1985). In this case the water is needed in
substantially larger quantity than the oxygen in order to dissolve the
deliquescent potassium acetate in which solution the potassium sulfite
dissolves and reacts with oxygen.
An approach to overcoming any limitation on scavenging rate by the heatseal layer's permeability has been to use microporous polymers such as nonwoven polyolefins. Several recent patent applications describe claims of
enhanced availability to the package atmosphere of granular reagents, as in
that of Mitsubishi Gas Chemical Industry Co. Various sulfites can be held in
a fibrous layer sandwiched between, for example, one layer of foil, and a
second of a plastic or paper with an oxygen permeability greater than 7000
ml/m2/day atm. A second patent describes a package consisting of three
layers. The outer layer is a plastics film, the middle is a perforated or nonwoven layer containing an oxygen scavenger and the inner layer of the
package is a microporous film which resists the flow of liquids through its
pores. This is claimed to be useful for packaging liquid foods (Ohtsuka et
al, 1984). Such films cannot be used where transparency is required but may
have application in many forms of packaging.
Traditionally, poly(vinylidene chloride) copolymers have provided a
water-insensitive oxygen barrier when used as a layer in laminates, coated
films or coextrusions. The introduction of ethylene-vinyl alcohol copolymers (EVOH) and poly(vinyl alcohol) means that, together with traditional
nylons, most oxygen barriers are now water sensitive. The permeability to
oxygen of EVOH copolymers increases approximately 10-fold when
exposed to a relative humidity change from about 40-100%. Such a change
may render a material which is suitable for packaging an oxygen-sensitive
food at low relative humidity into one which is most unsuitable at high
relative humidity.
The plasticising effect of water on the barrier properties of EVOH (or
other hydrophilic barriers) is time dependent, especially if the hydrophilic
layer is protected by a water-barrier layer such as polypropylene as in the
case of retortable lunch-cups. When such retortable packs containing a wet
food such as an entree are subjected to steam retorting, water is absorbed by
the EVOH in such large quantities that the barrier layer becomes quite

permeable to oxygen. The rate of water release through the outer

polypropylene layer becomes very slow on cooling, so the oxygen
permeability can remain elevated for many weeks (Tsai and Wachtel, 1990).
Although addition of desiccants to the polypropylene (Tsai and Wachtel,
1990) and mica platelets to the EVOH (Bissot, 1990) is used to reduce this
impact there is an opportunity here to include an oxygen-scavenger layer in
the coextrusion to absorb the oxygen, particularly during the period of
enhanced permeability. In fact there has been a recent news report of the
introduction of an oxygen scavenger into such packages by Toyo Seikan
Kaisha Ltd. Thus active packaging has the potential to contribute to solving
the permeability problem in two ways, providing: desiccants which absorb
water in polypropylene; and oxygen scavengers which remove oxygen when
it does pass through the hydrated barrier layer.
Whereas elevated temperatures and high humidity have been used to
advantage in the research of Farrell and Tsai (1985), the effect of
temperature on the performance of oxygen scavengers in polymer-based
films has been reported in only rare cases. W.R. Grace (1994) have
investigated the effect of low temperatures on their (optionally photosensitised) metal-catalysed oxidation of syndiotactic poly(l, 2-butadiene).
They have foumd that this polymer, and certain other low crystallinity
polymers with glass transition temperatures below -15C, scavenge at least
10 ml/m2/day O2 at 100C or lower. The photoinitiated system described by
Rooney (1994) has been shown to function at 00C.
4.2.3 Brief history of oxygen-scavenging films
The initial oxygen-scavenging packaging film was a multilayer described by
Kuhn et al (1970) and by Warmbier and Wolf (1976). These systems were
based on the earlier work of King (1955) and Abbott et al (1961) who
applied palladium metal to the inside surface of can lids. The cans were
flushed with mixtures of hydrogen (8%) in nitrogen to give a mixture in
which the residual oxygen could react with hydrogen to form water on the
palladium surface.
The reaction of hydrogen with residual oxygen on palladium has been
taken further by Hayashi et al (1986) who vacuum-metallised polyester film
at 2.5 x 10"^ moles of Pd/m2 and laminated this to high density polyethylene.
When a bag made from this laminate was filled with 500 ml of a mixture of
hydrogen-nitrogen 8:92% by volume, this layer was found to be effective in
catalysing the conversion of oxygen to water, reducing the oxygen content
from 3-4 to 0.4% in 1 day. Due to the expense of this process it would be
suitable for packaging high-valued items such as probes for an oxygen
analyser, although production of a thinner metal layer may change future
economics.
The earliest investigation involving reaction of oxygen in homogeneous

polymer films was described by Rooney and Holland (1979), Rooney,

Holland and Shorter (1981) and by Rooney (1981, 1982). This technique
takes advantage of the ease of excitation of oxygen from its ground state to
its first singlet excited state and has shown that use of polymers as
scavengers or reaction media need not inhibit rapid oxygen removal.
Very little investigation of the chemistry of oxygen-scavenging films has
been published in peer-reviewed journals. However, numerous patents and
some conference proceedings give sufficient detail to allow a comparison of
the systems reported. The most evident trend in oxygen-scavenging system
development during the past 20 years has been the increasing importance of
patent applications for compositions and designs based on plastics. Very few
of these have involved actual polymer oxidation but rather have required the
reactive ingredients to be dispersed within the polymer matrix or to be
sandwiched between film layers. An examination of patent applications
worldwide gives the results shown in Figure 4.1 which shows the numbers
of initial applications for new compositions or designs without consideration
of whether additional applications for the same idea have been lodged in
other countries. The histogram shows that whereas initially only sachet
technologies were considered, there was a slow growth in the number of
plastics-based systems devised until the numbers were equal for both types
of system in 1993-94.
The increasing number of plastics-based systems results from a substantial
overall increase in the interest in oxygen-scavenging systems, not from a
decrease in the numbers of sachet technology applications. This has resulted
from a more lateral approach to potential reactions coupled with approaches

Plastics

Applications

Sachet

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.
42.4

Chemistry of oxygen scavenging

Unlike most other forms of active packaging, oxygen-scavenging films must

be stable in the oxygen-rich environment of air prior to use. This has
presented a problem to chemists formulating such systems and surprisingly
few methods of activation appear either in the patent literature or in
commercial practice.
In some instances activation might not be a necessary consideration if the
package is prepared from all constituents immediately before filling. Such
packaging systems would include blow-moulding of beverage bottles which
often occurs on the premises of the beverage filler. Thus the catalyst and the
oxidisable substrate can be kept apart until the bottle is blown, as in the OxBar process developed by CMB Technologies pic.
A further factor is the nature of the packaging material carrying the
oxygen scavenger. In the case of the PET bottle, containing MXD-6 nylon
blended into the PET for instance, the oxygen permeability of the bottle is so
low that a delay between blowing and closure is quite reasonable. A general
guide to such circumstances is that if the plastic material actually carrying
the oxygen scavenger is exposed to the outside air during its life as a
package the system can probably be chosen not to have an additional
activation step.
The systems which have been developed for use (or prospective use) in
coatings, laminations or other plastics layers with high oxygen permeability
are normally activated by one of the following mechanisms.

Supplying a reagent on package filling, viz. hydrogen or water

Supplying water as a solvent or swelling agent on filling.
Continuous exposure to light as energy source.
Brief exposure to light for activation of
o chain reactions, e.g. autoxidation
o rapid photoreduction of scavenger precursor

In each of the above processes several variants exist. For instance, the water
can come from the food itself as described in the Oxyguard process of Toyo
Seikan Kaisha Ltd, or in the variety of patents referred to in Chapter 1. This
requirement is elaborated in the discussion on sachet technologies in Chapter
6.

Water needed as a reaction solvent or to burst micro-capsules can be

supplied from the retorting steam in the case of retortable plastics packages
which are processed at around 1200C. In this case water vapour permeation
can be sufficient from the outside of the pack as well as from the food itself
and here heat is also a trigger for commencement of the process. Tsai and
Wachtel (1990) have shown that EVOH trays can take up as much as 2.8%
extra water on retorting, and this diffuses out slowly over a period of some
weeks.
4.2.4.1 Supplying a reagent. The oxidation of hydrogen by molecular
oxygen requires metal catalysis at room temperature. Indeed such a process
has long been used by microbiologists to generate low-oxygen-content
environments for cultivation of anaerobic microorganisms. Conventionally a
mixture of hydrogen (8%) in nitrogen is either flushed into the cultivation
chamber or hydrogen is generated in a sealed anaerobic jar in the presence
of an air headspace. The surface of palladium metal either as mesh or
deposited on porous alumina catalyses the reaction to form water.
The application of this process to packaging by King (1955) and Abbott
et al. (1961) was particularly successful for removing oxygen which desorbs
from canned spray-dried milk powder. The hydrogen content of the flushing
gas is limited to 7% or less to avoid the risk of explosion. It should be noted
that an explosion limit of 6.5% hydrogen is specified in plants for production
of chlorine by electrolysis.
The laminate bag described by Warmbier and Wolf (1976) consists of a
polyester outer layer bonded to aluminium foil then Surlyn. Between this
Surlyn and the heat-seal layer, also of Surlyn, is sandwiched a layer of
powdered alumina upon which palladium metal has been deposited. The bag
was flushed with the above-mentioned H2ZN2 mixture before heat sealing.
On storage the milk desorbed oxygen which diffused, together with the
hydrogen, through the Surlyn to react on the catalyst surface. The quantity of
water which was formed was calculated by the authors to be insufficient to
affect the food. There appears to have been very little use of this system,
marketed as Maraflex 7F by American Can Company, with foods although
it was used in the US space programme.
The oxidation of iron in the presence of electrolytes has been well
established in the sachet technologies reviewed in Chapter 6. Where patents
describe incorporation of treated iron powder into plastics, water ingress is
generally needed. Some specify the need for such materials to be used under
retorting conditions. This is probably for the purpose of introducing
sufficient water on to the iron surface to carry out the reactions described in
Chapter 6. It is doubtful whether an adequate rate of oxygen scavenging can
be achieved when the polyolefin heat-seal plastics are used as the reaction
medium at room temperature.

4.2.4.2 Supplying water as a solvent or swelling agent. Some packaging

applications potentially permit the use of scavenging components as
heterogeneous additives to the packaging material. Particularly where
reagents are in the crystalline form or coated with a low-permeability
substance, the rate of reaction with atmospheric oxygen can be acceptably
low for incorporation into packaging. When the package is exposed to high
humidity and elevated temperatures the rate of transmission of water from
either the food or the outside (e.g. as steam) can be sufficient to dissolve the
reagent thus enabling oxidation to proceed rapidly.
An early example of the dissolution of a salt was patented by Farrell and
Tsai (1985). They incorporated a mixture of potassium acetate and sodium
sulfite crystals (or potassium sulfite alone) between the barrier and heat-seal
layers of a retort pouch laminate which had five layers overall. The
potassium acetate is deliquescent and absorbs sufficient water to dissolve
when the food-filled pouch is retorted. The sodium sulfite dissolves in the
potassium acetate solution and reacts with oxygen diffusing into this
solution from the food and especially from the retort atmosphere. The water
vapour permeability of the laminate can increase 1000-fold from 210C to
121C. The sulphite reacts with oxygen as in Equation 4.1.
2Na2SO3 + O2 -> 2Na2SO4

(4.1)

Although this process can result in the presence of an aqueous solution in

the laminate, it should be possible to consider use of some form of binder for
the solution after retorting. A process such as this which requires both heat
and high humidity is really limited to applications which involve retorting or
substantial heat-treatment of the packaged food.
A recent patent describes the incorporation of a metallic salt and a
complexation agent in separate microcapsules within a polymer film (Zenner
et al.9 1992). On exposure of the film to an atmosphere of high relative
humidity, as in the headspace of some food packs, the microcapsules absorb
water and swell. This results in bursting of the microcapsules and mixing of
the complexing agent and the salt under moist conditions. The resultant
metal chelate forms an oxygen adduct with a binding constant greater than
105M'1. The presence of such a strong adduct is effectively equivalent to
oxygen removal by means of an irreversible reaction.
The reaction of oxygen with a metal complex can also involve a weak
coordinate bond without converting the metal ion to a higher oxidation state.
This type of reaction is the basis of blood oxygenation and can frequently be
reversed, at least to some extent (see Chapter 1). This type of oxygen
absorber was the subject of extensive research by Aquanautics Inc in the
USA, the predecessor of Advanced Oxygen Technologies Inc.
Ascorbic acid and isoascorbic acid react readily with oxygen, more
rapidly at high pH. The use of metallic salts of these acids is described in

patents from many sources. The chemistry of oxidation of ascorbic acid is

complex, consisting of a series of consecutive and concurrent reactions,
depending upon the conditions. The steps involved in the commercially
accepted scavenging compositions have not been described in the scientific
literature. It has been observed in the author's laboratory that cellulose
acetate films containing dissolved ascorbic acid turn light-brown in colour
after standing in darkness under ambient temperature and humidity conditions for one to two years.
The steps involved in ascorbic acid oxidation in solution have been
reviewed by Tannenbaum (1976) who summarised the reactions involved in
the oxidation of ascorbic acid. A simpler summary is shown in Figure 4.2.
The initial step is the formation of dehydroascorbic acid and this step is
strongly dependent upon pH. Ascorbic acid can be regenerated by reaction
with mild reducing agents such as metallic sulfites. It is particularly
interesting that the patent of Hofeldt and White (1989) describes the optional
use of sodium sulfite in combination with ascorbic acid (and its isomers) in
their oxygen-scavenging closure liner for use with beverages such as beer.
There is thus the potential for use of ascorbic acid as an intermediate in the

2NaOH
HOHC

HOHC

CH2OH

BROWNPRODUCTS

Figure 4.2 Oxidation of ascorbic acid.

oxidation of sodium sulfite to the sulfate. Whether this occurs in the ambient
or low-temperature storage of beer has not been described in the literature.
Given the heterogeneous nature of the reaction mixture it is doubtful
whether this desirable regeneration occurs to a very great extent in
commercial practice without the formation of an aqueous solution as
described by Farrell and Tsai (1985).
As can be seen from the summary in Figure 4.2 one of the reaction
products of oxidation of ascorbic acid to dehydroascorbic acid is hydrogen
peroxide or initially the hydroperoxy free radical. Further hydrogen
abstraction by this radical forms hydrogen peroxide. The use of sodium
sulfite, or another reducing agent, would therefore seem to be desirable if the
ultimate re-introduction of an oxidising agent is to be avoided. The role of
ascorbic acid as a promoter of browning when oxidised in foods is already
known (Tannenbaum, 1976).
The use of ascorbic acid or its isomers or salts is the basis of the W.R.
Grace and Co. and Zapata Inc oxygen-scavenging closures in common use
in some beer bottles.
4.2.4.3 Continuous exposure to light as an energy source. Some oxidation reactions which do not occur when oxygen is in its unexcited (ground)
state can be brought about by the process of photosensitisation, which
involves transfer of visible light energy to oxygen via the intermediacy of a
dye. A polymer film can be the medium for these photosensitised oxygenscavenging reactions. Such a film must contain a photosensitising dye and an
electron-rich oxidisable compound termed a singlet oxygen acceptor. The
oxygen-scavenging process occurs when the film is illuminated with UV,
visible or near infra-red irradiation of appropriate wavelengths. The steps in
the process are shown below, and these occur within the matrix of the
polymer film.
(4.2)
(4.3)
(4.4)
(4.5)
(4.6)
(4.7)
When a suitable photosensitiser, D, absorbs light (hx>) it is excited to a
short-lived higher energy singlet state, *D, (Equation 4.2) which largely
converts to the longer-lived triplet excited state, 3D, (Equation 4.3). In this
form the dye can pass the excitation to oxygen by the process of triplet-

triplet energy transfer (Equation 4.4). The oxygen diffusing into the polymer
from the package headspace (for instance) needs to come very close to the
excited, immobile dye molecules during the triplet lifetime of the latter. This
is of the order of 10-1000 microseconds. Thus, for such a process to be
useful the polymer matrix (such as an inner layer of a laminate) would need
to be very permeable to oxygen.
Once excited to its singlet state the oxygen can react with any electronrich acceptors, A, present in the polymer matrix (Equation 4.5) provided
they are within the distance the singlet oxygen can diffuse before it is
quenched back to the ground state (Equation 4.6). The process occurs only
within the lifetimes of the excited sensitiser (Equation 4.7) and singlet
oxygen and so requires continuous illumination. The distance singlet oxygen
can diffuse before quenching in a polymer matrix is of the order of IOOA
depending on the polymer permeability and other factors (Turro et a/.,
1981).
This chemistry has been used in the laboratory as an oxygen-scavenging
process where the polymer matrix is, for instance, cellulose acetate or ethyl
cellulose (Rooney et al., 1981; Rooney, 1982). The sensitisers include
erythrosine or me^o-tetraphenylporphine and the acceptors are bis(furfurylidene)pentaerythritol and ascorbic acid. It was found that the permeability of the polymer film is an important determinant of scavenging rate, with
the ethyl cellulose being a better matrix for rapid scavenging than cellulose
acetate. Ethyl cellulose has an oxygen permeability coefficient at 25C of 7
Barrers (cm3 (STP) cm/cm-2 s"1 cm"1 Hg x 10~10) compared with that of 0.7
Barters for cellulose acetate (Bixler, 1971). It was also found that the rate of
scavenging of oxygen from a pouch by the film is limited by light intensity
initially but becomes diffusion limited when the oxygen partial pressure
reaches low values (Rooney et al.9 1981). The light intensity used was 2 x
10 5 -7 x 105 Lux. It was subsequently shown that the rate of oxygen
scavenging reaches a maximum at a concentration of tetraphenylporphine
above 10~3 M but less than 10~2 M. When the scavenger film was used as a
roll it was found that the rate was dependent upon the length of film in the
roll consistent with increased access of oxygen to the film.
The singlet oxygen acceptor does not need to be a small molecule
dissolved in the polymer. It has been shown the double bond of natural
rubber can be photo-oxidised at a rate sufficient to bring about rapid oxygen
scavenging from the headspace of a package. Figure 4.3 shows the rate of
scavenging of oxygen from air, 20 ml, in a 10 cm x 10 cm pouch coated on
the inside with either natural rubber dyed with tetraphenylporphine, 10~3 M,
or ethyl cellulose 0.6 M with respect to PEF and 10~3 M with respect to
tetraphenylporphine. The rubber scavenged oxygen substantially faster than
the PEF in the ethyl cellulose. This was interpreted as being due to the
higher concentration of double bond (13.5 equivalentsflitre) in the rubber
than the concentration of furan rings (1.2 equivalents/litre of film) in the

% Oxygen

(bifunctional) PEF, although the higher permeability of rubber towards

oxygen (24 Barrers) than that of ethyl cellulose (7 Barrers) is also likely to
contribute. It is significant that the reaction occurring in natural rubber
occurs on the polymer chain and therefore is not dependent on the free
rotation of the acceptor. The photo-oxidation of the tacky natural rubber
layer resulted in rapid crosslinking as indicated by the loss of tack within
minutes. An unpleasant odour was also generated. The oxidation of the
rubber continued on dark storage resulting in formation of a brittle powdery
film.
The potential for use of synthetic rubbers in place of natural rubber was
investigated in order to determine whether the nature of the rubber
monomers affects the rate of scavenging. The results in Figure 4.4 show the
rate of oxygen scavenging by poly(dimethylbutadiene) (PDMB), cispolybutadiene (PB) and ra-polyisoprene (PI). Based on the reactivity of
simple low-molecular weight analogues of these polymers, it would be
expected that the more highly methylated rubber poly(dimethylbutadiene)
would react more rapidly with singlet oxygen. However, the inverse
relationship is observed, presumably due to the low oxygen permeability of
PDMB of 2.1 Barrers compared with values of 20 Barrers and 24 Barrers for
PB and PI. Thus permeability rather than reactivity can be the important

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)
Figure 4.4 Oxygen scavenging by polydienes, poly(dimethylbutadiene) +, cis-polyisoprene O, cispolybutadiene A. Coatings on inner surface of pouches of area 100 cm2, volume of air 20 ml.

variable in an oxygen-scavenging polymer system as was found to be the

case with PEF dissolved in cellulose acetate and ethyl cellulose.
The use of multiple dyes in oxygen-scavenging films has been investigated, since illumination with white light of polymer films containing only
one dye is wasteful of potentially usable energy (Rooney et ai, 1994). It has
been found that even dyes which are not photosensitisers can harvest energy
and transfer this energy to a photosensitiser also in the film. Thus curcumine,
a natural food colour and a poor photosensitiser (Chignell et ai, 1994), was
shown to enhance the rate of oxygen scavenging photosensitised by eosine
in ethyl cellulose. The effectiveness of such a film in suppressing rancidity
in sunflower oil has been investigated and found to be substantial at 230C
and 37C (Maloba et al., 1994).

4.2.4.4 Brief exposure to light for activation.

4.2.4.4.1 Chain reactions. Continuous exposure of a package to light
places an intolerable restriction on the way in which most foods would need
to be stored and distributed. It is not surprising therefore that the use of light
to activate reactive polymer-based systems has been investigated. The
problem, inherent in all oxygen-scavenging systems, of using compounds
reactive towards oxygen but stable towards thermal processing of the
packaging material needs to be addressed.
The use of autoxidation of fatty acids for oxygen scavenging has already
been claimed but this process seems likely to result in formation of the same
volatile oxidation products which are undesirable in foods (Frankel, 1982).
Some sachet patent applications describe the use of adsorbents in the sachets
to bind volatile off-flavours generated in this way. Mitsubishi Gas and
Chemical Company has claimed that activated alumina, silica gel or charcoal
absorbs any odour formed on the oxidation of fatty acids or oils catalysed by
transition metal compounds in the presence of alkaline earth bases (Inoue
and Komatsu, 1988). Toppan Printing Company (1992) claimed a similar
composition involving addition of activated clay. The benefit of such
systems is independence from water for the reaction. The research effort put
into development of photodegradable plastics packaging over the past two
decades has provided a background to one approach to this problem
Rabek and Ranby (1975) show how a transition-metal metal salt and a
photosensitiser dispersed in a plastic can cause it to degrade in darkness
once exposed to sunlight for some days. This form of photodegradation
involves a substantial extent of hydrogen abstraction from the polymer
backbone coupled with hydroperoxide formation, particularly on tertiary
carbon atoms. Subsequent breakage of the hydroperoxy bond leads to
formation of either keto or aldehyde groups which become additional
photosensitisers or result in polymer chain scission. It is in the prevention of
the latter reaction that the opportunity for development of oxygenscavenging polymers exists.
The scavenging of oxygen including oxidation of hydrocarbon polymers
impregnated with salts of transition metals has been described by Speer et al
(1993). The novelty of their method is that the oxidation process is activated
by brief exposure to light of wavelengths less than 750 nm. The optional use
of a photosensitiser is reported to increase the rate of activation, particularly
in the presence of an antioxidant.
As with the photodegradable plastics processes, the chemistry involves
initiation of the free radical process on the polymer chains by changes in the
oxidation state of the transition metal ion, preferably cobalt. The redox
reaction on the polymer chain involves either hydrogen abstraction in
polypropylene or polyethylene or oxygen attack on the double bond in the
case of poly(l,2-butadiene).

The hydroperoxide formed by reaction of either the polymer free radical

or by direct attack on the polymer decomposes to form ketones, aldehydes,
peroxides or carboxylic acids, in some cases with chain scission. In the case
of poly(l,2-butadiene) it is the aim to localise the oxidation to the side chain
containing the double bond. Speer et al. (1993) report that this polymer
retains its physical properties even when most or all of its oxidisable groups
have been reacted. Since this is a typical autoxidation that is also thermally
activated, the polymer needs to be stabilised against premature initiation in
the extruder or moulding machine in package fabrication. Antioxidants
provide this protection. The quantity of antioxidant is chosen both to provide
this protection and to retard the autoxidation chain reaction for a selected
period of time between activation and package filling. Removal of
antioxidant from the polymer appears likely to increase the likelihood of
taint formation due to unrestricted polymer oxidation. Attention should
probably be given to inclusion of odour absorbents in the composition as
proposed by Toppan (1992).
The manner in which such a system could be used is particularly broad
but one suggested is to laminate or coextrude the reactive layer with an
oxygen-barrier layer. Such an application would be appropriate for many
packaging processes such as in the storage of cheese, nuts and meats such as
beef primal cuts.
The use of such compositions at the low temperatures required for storage
of meats and cheese requires that the reactive layer be readily permeable to
oxygen. Speer and Roberts (1993) have specified that the compositions
containing their oxidisable components should be largely amorphous and
have a glass transition temperature below -15C.
4.2.4.4.2 Rapid photoreduction of a scavenger precursor. Research
into systems involving this form of triggering indicate that this approach
overcomes some of the limitations of other methods already proposed
(Rooney, unpublished results).
4.2.5 Chemical barrier to oxygen permeation
Implicit in the use of oxygen scavenging inserts (sachets) or closures is the
effect these have on the consumption of oxygen as it enters the product
during its storage life. The results in Table 4.5 show the calculated impact of
Table 4.5 Calculated life of chemical oxygen barriers
Film
_ _ _ _
PET 25 nm/LDPE 25 \x.m
PVDC-coated OPP 25 jjum
Metallised PET 12 ^m/LDPE 25 |xm

OTR
cm3 m~2 day"1 atm~l
_ _

Barrier life
(days)
_

63
9
0.5

56
362
7250

the oxygen transmission rate of packaging materials on the period of

effective oxygen scavenging by a commercial oxygen-scavenging sachet
with an absorption capacity of 50 ml of oxygen. The packages are 10 cm x
20 cm and initially contain 100 ml air. LDPE is low-density polyethylene,
OPP is oriented polypropylene, PET is polyester and PVDC is poly(vinylidene chloride). However, in a food-packaging situation where the
food is tightly packed, the sachet can be expected to deoxygenate only a
small portion of the headspace and combat permeation of oxygen that is
accessible to it.
Close-fitting packages such as vacuum packs for block cheese and meats
or aseptic cartons of beverages are examples where the headspace is very
small and oxygen permeation is the prime cause of quality loss. It is in such
circumstances that oxygen-scavenging plastics films are particularly needed.
The use of the oxygen-scavenging reaction to intercept oxygen diffusing
through the package wall is an example of a chemical barrier as distinct from
the physical barrier normally provided by aluminium foil and vacuum
metallising or crystalline polymers such as poly(vinylidene chloride).
The use of a chemical oxygen barrier offers the opportunity to cheapen
barrier packaging for relatively short shelf-life products such as wholesale or
export units or for some fresh foods. This can be achieved by using a barrier
film of intermediate performance coupled with a chemical barrier. This
combination was investigated by Rooney and Holland (1979) and the results
in Figure 4.5 demonstrate a period of total barrier to oxygen permeation
from air at 25C. A laminate of polyethylene/nylon 6/cellulose acetate
containing oxygen-scavenging reagents was used to separate the two
compartments of a glass permeability cell. When the ethyl cellulose layer
contained 0.5 M fe-furfurylidenepentaerythritol, illumination with fluorescent light resulting in a barrier life of around 30 days was followed by a
period of oxygen transmission at a rate less than that found in darkness. In
this case the chemistry used was a singlet oxygen reaction which requires
constant illumination to photo-excite the oxygen. Other chemistries can be
used to achieve similar reactions in darkness and Speer et al (1993)
identified this application for their photoinitiated chain reactions in rubbers,
and Cochran et al (1990) devised the Ox-Bar process largely for this
purpose.
The use of oxygen-scavenging sachets to allow the use of a cheaper
packaging material has been described by Alarcon and Hotchkiss (1993) and
their work is reviewed in Chapter 6.
Although use of multilayers of plastics films appears the most appropriate
approach to solving permeability problems, there have been early attempts to
carry out scavenging reactions in liquid layers. Oxygen scavenging in liquid
layers was one of the earliest processes described in the patent literature.
Cook (1969) claimed that bilayers of plastics films separated by a layer of a
solution of one of several antioxidants in high boiling point solvents

Next Page

in darkness

% Oxygen

illuminated

Time (days)

Figure 4.5 Barrier to oxygen permeation of polyethylene/Nylon 6/cellulose acetate laminate.

Cellulose acetate 26 |xm thick containing PEF (0.5 M) and erythrosine, 5 X 10~3 M. Oxygen
concentration measured in a cell on the cellulose acetate side of the laminate, air on the other
side.

demonstrated a reduced oxygen permeability. Whereas the mechanism was

unknown, all of the common antioxidant classes were claimed to be
effective.
Use of an aqueous solution of an oxygen-scavenging reducing sulfite as a
layer between two polymeric layers has been claimed by Scholle (1976). As
with the organic system of Cook (1969), the purpose was to reduce the
oxygen permeability of the laminate. In the case of Cook's system the role
appears to have been to improve shrinkable packaging, as for meat, whereas
the Scholle system was particularly suitable for bag-in-box liners since the
packages consist of, at least, a collapsible duplex which is sealed together
only at the edges where the liner forms a bag (and around the tap fitting).
Such a system requires an oxygen scavenger for oxygen-sensitive products
due to the gas space between the two film layers.
4.3 Moisture control films
Moisture affects the gas and vapour permeability of hydrophilic plastics
packaging films (Davis, 1966). Fruit cakes packed in films with an
appropriate water vapour permeability can have long shelf-lives because the
surface dries somewhat. This creates conditions unfavourable to mould
growth. Nitrocellulose-coated regenerated cellulose has been used because it

Previous Page

in darkness

% Oxygen

illuminated

Time (days)

Figure 4.5 Barrier to oxygen permeation of polyethylene/Nylon 6/cellulose acetate laminate.

Cellulose acetate 26 |xm thick containing PEF (0.5 M) and erythrosine, 5 X 10~3 M. Oxygen
concentration measured in a cell on the cellulose acetate side of the laminate, air on the other
side.

demonstrated a reduced oxygen permeability. Whereas the mechanism was

unknown, all of the common antioxidant classes were claimed to be
effective.
Use of an aqueous solution of an oxygen-scavenging reducing sulfite as a
layer between two polymeric layers has been claimed by Scholle (1976). As
with the organic system of Cook (1969), the purpose was to reduce the
oxygen permeability of the laminate. In the case of Cook's system the role
appears to have been to improve shrinkable packaging, as for meat, whereas
the Scholle system was particularly suitable for bag-in-box liners since the
packages consist of, at least, a collapsible duplex which is sealed together
only at the edges where the liner forms a bag (and around the tap fitting).
Such a system requires an oxygen scavenger for oxygen-sensitive products
due to the gas space between the two film layers.
4.3 Moisture control films
Moisture affects the gas and vapour permeability of hydrophilic plastics
packaging films (Davis, 1966). Fruit cakes packed in films with an
appropriate water vapour permeability can have long shelf-lives because the
surface dries somewhat. This creates conditions unfavourable to mould
growth. Nitrocellulose-coated regenerated cellulose has been used because it

prevents contamination with moulds and allows substantial water vapour

permeation.
There are, however, several sets of circumstances in food packaging
where greater selectivity in control of liquid and gaseous water is required.
These include:

Transpiration of horticultural produce.

Melting of ice, e.g. in fish transportation.
Temperature fluctuation in high erh food packs.
Drip of tissue fluid from cut meats and produce.

The problems which arise from these circumstances are the result of
build-up of liquid water. Alternatively, the natural water level in the tissue
can be undesirably high near the surface for microbiological stability under
the chosen storage conditions. The results of the presence of water in
unwanted quantities include bacterial (yeast) and mould growth as well as
fogging of films and mobile blood and tissue fluid. Moisture migration via
the vapour phase can result in transient formation of regions without
adequate preservative or where the aw is high even though the food is packed
at lower aw. Some of the ways of addressing these problems via packaging
are considered in detail in terms of either liquid water control or humidity
buffering.
4.3.1 Liquid water control
Temperature cycling of high erh foods has led most film manufacturers to
use heat-seal plastics with anti-fog additive. These additives are blended
with the resin before extrusion and migrate to the surface after film
formation. The additives are chosen for their amphiphilic nature with the
non-polar chain in the plastic and the polar end group at the interface. The
result is a lowering of the interfacial tension between water condensate and
the plastic film. The fog droplets therefore coalesce and form a transparent
film on the plastic. This film may even flow on sloped surfaces and gather at
the bottom of the pack in extreme circumstances.
Anti-fog treatments are a cosmetic form of active packaging, assisting the
customer to see the packaged food clearly. There is no change in the
availability of liquid water in the package and this has the potential to cause
produce spoilage unless managed by one of the processes described below.
Other active packaging systems go further in removing liquid water from
food contact.
Several companies manufacture drip-absorbent sheets, which may have a
variety of other names. Basically they consist of two layers of a microporous
or non-woven polymer, such as polyethylene or polypropylene, between
which is placed a superabsorbent polymer in the form of free-flowing
granules. The duplex sheet is sealed at the edges and is normally quilted to

allow the water absorbent to be held in place rather than aggregating towards
one edge of the sheet when tilted towards one edge.
Such sheets are then used either as pads under whole chickens or chicken
pieces to absorb drip, thereby preventing discoloration of either the meat or
the white foam tray. Given the interest in reducing the volume of solid waste
by decreasing foam polystyrene usage, the use of drip-absorbers may
become even more necessary to prevent water damage to the more
hydrophilic alternatives.
Large sheets are used for absorption of melted ice in the packaging of
seafood for air transportation. The superabsorbent polymer used in the
Thermarite Pty Ltd sheet manufactured in Australia is capable of
absorbing at least 100 times and possibly as much as 500 times its own
weight of liquid water depending dramatically upon salinity (Malouthi et al.,
1994). Another product of this type is Toppan Sheet manufactured in Japan.
A recent patent application in Japan describes a water-absorbent sheet which
has a high barrier to oxygen for use with fresh meat (Showa Denko KK,
1990), This would necessitate use of a sealed outer pack.
The preferred polymers used to absorb the water are polyacrylate salts,
although graft copolymers of starch can also be used. Such copolymers
consist of a polysaccharide backbone with synthetic polymer chains
radiating from the starch backbone. The strong association of the polysaccharide chains is disrupted allowing the starch to exercise its affinity for
water by hydrogen bonding. Such polymers tend to become slimy when
swollen with large amounts of water.
The swelling of the polymer on hydration results in substantial distortion
of the duplex sheet, an effect that is controlled somewhat by the quilted seal
pattern. This effect can be controlled by choice of the amount and the
capacity of the superabsorbent polymer.
The significance of such active packaging in seafood shipment by air lies
in the removal of the potential for spillage of salt water from cartons in
aircraft holds. The aluminium construction of aircraft makes them easily
susceptible to corrosion damage, at great cost.
4.3.2 Humidity buffering
An entirely different approach to the control of excess moisture in food
packages is to intercept the moisture in the vapour phase. This approach
allows the food packer or even the householder to reduce the surface
concentration of water in a food by reducing the in-pack relative humidity.
This can be done by placing one or more humectants between two layers of
a plastic film which is highly permeable to water vapour. An example of this
type of product is Pichit manufactured by Showa Denko in Japan. The film
duplex is described as containing an alcohol, described by Labuza (1989) as
propylene glycol and a carbohydrate, both of which are humectants.

Table 4.6 Water vapour uptake by Pichit and Toppan sheet

YimQ
(h)
__
3
4
24
26

Weight loss from petri dish (%)

Pichit
-_
2.4
3.6
15.2
22.0

Toppan sheet
_
0.7
1.2
8.4
8.8

The effectiveness of such a combination material in comparison with a

superabsorbent polymer absorbent for liquid water is shown in Table 4.6.
Distilled water 5 g was placed in each of two petri dishes (with lids) and
these were enclosed with either Pichit or Toppan Sheet (450 cm2) in a highbarrier package. The packages were opened at intervals and the petri dishes
were weighed to give the per cent loss of weight of water, shown in Table
4.6. Thus, whereas the superabsorbent polymer has a far greater capacity for
liquid water uptake, the humectant-based film more rapidly absorbs water
vapour.
Pichit is marketed for home use in roll or single sheet form for wrapping
pieces of flesh food such as fish or chicken to reduce the aw proximate to the
food. At present there is a lack of experimental verification of the
significance of this effect. Louis and de Leiris (1991) suggest two to three
days of fresh storage is possible. It has been suggested by Labuza (1989)
that the permeability of poly(vinyl alcohol) to propylene glycol may be
sufficient to allow some of the latter to diffuse to the food surface. If this is
the case, some antimicrobial action might be expected. Propylene glycol is
a GRAS substance in the USA.
Louis (1991) reports the availability of an additional moisture control film
which plays the same role as Pichit in the Japanese market. The potential for
use of such materials for quality retention in the home appears to be
considerable and this type of film should be subjected to detailed objective
evaluation for use in the domestic situation where excess portions of flesh
foods need refrigerated storage for some days. The potential for washing the
surfaces of sheets like Pichit, followed by re-use, is an attractive incentive
for active packaging use in the home provided absence of microbial
contamination can be demonstrated.
A different approach to humidity buffering has been under investigation
for use in the distribution of horticultural produce. Currently the packages
are wholesale fibreboard cartons of produce, usually with a polyethylene
liner or consisting of the very expensive waxed fibreboard without a liner. A
recent development has been the water-barrier coating of the inside of
fibreboard cartons to allow moist produce to be placed directly into the
carton. Besides the introduction of liquid water with the produce, packing
into closed spaces allows the build-up of water vapour. The produce

continues to lose water by evaporation during distribution and the relative

humidity in the lined carton can reach close to 100%. Since temperature
cycling is very difficult to avoid during handling, there is every likelihood of
condensation, and, with this, the growth of microorganisms on fruits and
vegetables.
Two widely different approaches have been taken to buffering the
humidity in the cartons in order to prevent condensation while not
concurrently causing desiccation of the produce. One is to include
microporous bags or pads of inorganic salts and the other is to line the carton
with a protected layer of a solid polymeric humectant.
The approach of using microporous sachets of inorganic salts has been
used in the US tomato market in recent years. This was proposed by Shirazi
and Cameron (1992) who showed that an equilibrium relative humidity of
around 95% above produce can be reduced to around 80% by use of sachets
of desiccant salt such as sodium chloride. The application was extended by
Hudson (1991). Both these studies involved use of heat-sealed liners which
were concurrently being evaluated for their performance to maintain
equilibrium modified atmospheres (EMA) generated by the fruit (see
Chapter 3). The control of moisture is one of the main impediments to the
introduction of EMA packaging. Indeed it is common to package potatoes in
perforated sacks to prevent unwanted build-up of condensation.
The most recent alternative involves the use of the carton as the active
package rather than an insert. This approach lends itself to combination with
EMA generation less readily as the humidity is buffered at the interface with
the fibreboard. The designs of Patterson and Joyce (1993) involve: an
integral water vapour barrier layer on the inner surface of the fibreboard; a
paper-like material bonded to the barrier and which acts as a wick; and a
layer highly permeable to water vapour but unwettable next to the fruit or
vegetable. The latter layer is spot welded to the layer underneath.
Accordingly, the multilayer of material on the inside of the carton is able to
take up water in the vapour state when the temperature drops and the RH
rises. When the temperature rises the multilayer releases water vapour back
into the carton in response to a lowering of the RH. The condensation
control system therefore acts as an internal water buffer. The critical
characteristic of the system is the capacity of the wick layer for water.
The performance of this system is demonstrated in Table 4.7 taken from
Patterson et al. (1993) which shows the results of a comparison of the free
Table 4.7 Free water in carrot packs on cooling
Packaging
Polyethylene liner
Condensation control carton
Standard error of the mean (n = 5)

Cooled from
10 to 3C

Cooled from
22 to 3C

10.1 (0.6)*
0.0 (0.0)*

22.9 (0.7)*
0.2 (0.2)*

water found in cartons of carrots with a conventional liner with the

condensation control multilayer. The cartons containing carrots, 6 kg, were
cooled to 3C from either 100C or 22C and after 3 days the amount of free
water in the boxes and on the carrots was measured. The results demonstrate
the capacity of such a system for water uptake under circumstances likely to
be found in commerce.
Shrink wrapping is an alternative approach to the use of active packaging
systems for control of condensation on spherical fruits such as citrus. BenYehoshua (1989) has reviewed this field, to which he has made such a large
contribution.
4.4 Removal of taints and food constituents
The interaction of packaging plastics with food aroma has long been
recognised, especially through the flavour 'scalping' which is of considerable 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.
4*5 Ingredient release
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 commercially 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 degradation 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
Table 4.8 Substances emitted by Active Packaging
Substance

Purpose

Carbon dioxide

antimicrobial

Ethanol
Silver ion
Organic acids
Sulfur dioxide
Benomyl
Flavours
Hinokitiol
BHT
Enzymes

antimicrobial
antimicrobial
antimicrobial
antimicrobial
antimicrobial
fortification
antimicrobial
antioxidant
various

Source
film
sachet
sachet
film
film
sachet
film
film
film
film
film

Reference
Rooney, 1989
Abe, 1990
Abe, 1990
Hirata, 1992
Hotchkiss, 1993
ICI Australia
Halek and Garg, 1988
Venator, 1986
Abe, 1990
Han et a/., 1987
Budny, 1990

flavour addition to a food fabricated from many ingredients becomes

contrary to consumer interests.
Release of very few flavours has been investigated to date, although the
ease of oxidation of many flavours suggests an opportunity to provide slowrelease flavour precursors in the packaging material. The manufacture of
flavour concentrates in the common commodity plastics has been described
by Venator (1986). Master batches of plastics with concentrations of up to
40% of the flavour have been marketed with a view to obviate the effects of
flavour scalping.
4.5.1 Antioxidant release from plastics
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, thiodipropionic 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/polypropylene/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 approximately 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.
4.6 Permeability modification
There are a number of circumstances in which it is desirable for the
packaging material to be more permeable to one substance than to another.
The importance of predicting the requirements of plastic film's permeability
to carbon dioxide and oxygen in packaging of fresh horticultural produce has
been discussed in Chapter 3. It is possible to modify the permeability of a
window in a package and to control gas exchange through this limited area.
A variety of semipermeable patches were initially developed by the Hercules
company in the USA. Subsequently the effect of sorbed water on cellulosic
patches has been claimed to give selectivity in gas permeability matched to
the respiration rates of some produce.
There are other substances which need to be selected for entry into
plastics packaging. Of particular interest is the ability to selectively transmit
smoke flavours through films which are useful as skins for ham and other
preserved meats. These are films of polyamide alloy which are highly
permeable to water and oxygen under conditions of high temperature and
high humidity and highly impermeable to oxygen at room temperature under
dry conditions (Nishini and Yoshii, 1988). Hirata (1992) described one such
type of film as having an oxygen transmission rate of 8 ml/m2/day at 200C,
60% RH and a water vapour transmission rate of (WVTR) 60 g/m2/day at
400C, 90% RH. The low oxygen permeability is necessary for colour
retention of preserved meats. This high WVTR should favour rapid
transmission of polar flavours. Kureha Chemical Co. (1986) described a
polyamide film for this purpose with an OTR in the range 50-300 ml/m2/day
for film thicknesses of 5-50 |xm.

4.7

Current use commercially

The commercial development of plastics-based active packaging has not

occurred evenly either geographically or in terms of their field of
application. The major field to date has been horticulture in which several
forms of enhanced permeability films have been commercialised for both
trade and home use. This success, in spite of a lack of soundly based
evidence of effectiveness in many cases, owes much to substantial prior
scientific research. This research into equilibrium modified atmosphere
packaging has been based on the work of Kader (1980) and earlier workers
including Jurin and Karel (1963). Since some of the active packaging
technologies currently commercial are scarcely improvements on existing
technologies there will probably be significant realignment in the marketplace. The need for active packaging solutions to problems in the storage
and distribution of horticultural produce may well ensure that the development of the most soundly based technologies is commercialised. Ethylene
scavenging, condensation control and equilibrium modified atmosphere
packaging will continue to be emphasised.
Active packaging for processed foods is still based largely on sachet
technologies, with the exception of moisture control packaging. It is in the
processed food field that commercial development of plastics-based systems
can be expected to be substantial over the next few years. Perhaps Toyo
Seikan Kaisha's planned manufacture of an oxygen-scavenging laminate for
the semi-aseptically packaged boiled-rice market by Sato Food Industry Co.
Ltd is the first example. This tray has been described as 'epoch making',
causing, as is planned, a 100 000 meals/day operation to be more cost
effective (Anon., 1994).
The substantial impact on the marketplace of oxygen-scavenging crown
seals for beverages, metallised polyester microwave susceptors and timetemperature indicator strips is discussed in other chapters.
4.8 Regulatory and environmental impacts
Since plastics-based active packaging involves not only changing current
materials somewhat but also inclusion of reactive components in some cases,
regulatory authorities must become involved in many developments. Indeed
regulatory considerations appear to have caused the delay in the introduction
of a chemical barrier to oxygen into PET beverage bottles.
The effect of environmental considerations on plastics-based active
packaging will vary with the nature of the product/package combination.
Commodity films used for produce packaging may become the object of
recycling schemes, especially in the European Union, and so additional
ingredients will need to be evaluated for their impact. Barrier packages used

for processed foods at present are generally not amenable to economic

recycling. The benefits of active packaging in terms of food quality, safety
and shelf-life extension will need to be considered in a holistic approach to
environmental impact assessment. A study by Kooijman (1994) of food
packaging in the Netherlands demonstrated that 'the packaging sub-system
cannot be studied or optimised in isolation'. Accordingly, active packaging
plastics should be judged on the basis of their contribution to the quality and
safety of food.
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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 materials 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 polysaccharidebased 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 filmforming 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 preservation 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

Food additives (e.g. antioxygen

and antifungic agents)

Diffusion
of food additives

Gas Transfers

Storage

Water Transfer

Food additives in

AOffiWOLM

SURFACE RETENTION
of food additives

CONTROL
of Gas Transfers

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.
5.2 Use of edible active layers to control water vapor transfer
Moisture transfers due to water vapor pressure or concentration gradients
have major effects on the organoleptic and microbiological qualities of food
products. For example, products such as raisins (Bolin, 1976; Kochnar and
Rossell, 1982; Lowe et a/., 1963; Marston, 1983; Watters and Brekke,
1961), candies and chocolate-coated products (Andres, 1984; Barron, 1977;
Cosier, 1957; Feuge, 1970; Jokay et al., 1967), dry crackers, biscuits, pizza
crust, and filled bakery crust (Dhale, 1983; Heiss, 1968; Katz and Labuza,
1981; Labuza, 1985) may become unsatisfactory as a result of moisture gain
or loss. Moisture exchanges are difficult to control in multicomponent foods
such as mixtures of dehydrated foods, jelly-filled cookies, pies, and pizzas.
Moisture transfer can be limited by reducing the vapor pressure gradient
between components, e.g. using aw lowering agents (salts, sugars, polyols,
etc.). However, this is not always possible and may result in drastic
modifications of the sensory and physiochemical characteristics of the
product (Guilbert, 1984, 1985; Karel, 1976). Another solution consists in
using edible films or coatings with good moisture barrier properties to
separate compartments and thus control further moisture transfer (Guilbert,
1986; Kamper and Fennema, 1985). Surface drying on some fresh and
frozen foods or, inversely, moisture uptake in dry or semi-moist foods, can
also be hindered by using films with a low water permeability (as
schematized in Figure 5.1).
Permeability is defined as a state which permits the transmission of
permeants through materials (Mannheim and Passy, 1985). When there are
no pores, faults or membrane punctures, permeability P, is equal to the
product of the diffusion coefficient D, representing the mobility of permeant
molecules in the polymer, and the solubility coefficient S, representing the
permeant concentration in the film in equilibrium with the external
pressure:
P = DxS
In practice, water, gas or solute permeability, P, through a membrane is
determined by steady-state measurements:
P =

AWx

AtAAp

where AW is the permeant weight that passes through a film of thickness x

and area A; where At is the time and Ap is the differential partial pressure
across the film. The diffusion coefficient can be obtained by taking

measurements before the steady state is reached. The solubility coefficient

can either be calculated from P and D, or measured in a separate experiment
(sorption isotherms).
The diffusion and solubility of permeants are affected by temperature and
by the size, shape and polarity of the diffused molecule. Moreover, these two
parameters depend on film characteristics, including the type of forces
influencing molecules of the film matrix, the degree of cross-linking between
molecules, the crystallinity, the presence of plasticizers or additives, etc. (De
Leiris, 1985; Gontard et ah, 1993; Kumins, 1965; Pascat, 1985; Schwartzberg, 1985).
Permeability is only a general feature of films or coatings when the
diffusion and solubility coefficients are not influenced by permeant content,
i.e. when Fick's and Henry's laws apply. In practice, for most edible films,
the permeant interacts with the film and the D and S coefficients are
dependent on the difference in partial pressure. For instance, in relation to
the water vapor permeability of hydrophilic polymer films, the water
solubility and diffusion coefficients increase when the water vapor differential partial pressure increases because of the moisture affinity of the film
(nonlinear sorption isotherm) and because of increased plasticization of the
film due to water absorption (Gontard et ai, 1993; Schwartzberg, 1985). The
film thickness can also influence permeability when using film-forming
materials that do not behave ideally. The permeability of an edible film is
thus defined as a property of the film-permeant complex, under specified
temperature and water activity conditions.
Water vapor permeabilities of some edible and synthetic films are given in
Table 5.1. Permeability is clearly high in edible films formed from
hydrophilic materials. These films can only be used as protective barrier
layers to limit moisture exchange for short-term applications or in lowmoisture foods such as dried fruits (Forkner, 1958; Swenson et aLy
1953).
Lipidic compounds are often used to make moisture barrier films and
coatings (Table 5.1). For instance, coating fresh fruit and vegetables with
wax reduces desiccation-induced weight loss during storage by 40-75%
(Kaplan, 1986). Water is not very soluble or mobile in lipid-based films
because of the low polarity and dense, well-structured molecular matrixes
that can be formed by these compounds.
Moisture resistance of lipid films is inversely related to polarity of the
lipids. Hydrophobic alkanes and waxes, such as paraffin wax and beeswax,
are the most effective barriers. More hydrophilic lipids, such as fatty acids,
are less resistant to water vapor transmission since their polar groups attract
migrating water molecules and thereby facilitate water transport. The
moisture barrier capacities of different films can be classified in increasing
order of efficiency, as follows: liquid oils < solid fats < waxes (Gontard et
ah, 1994a; Kamper and Fennema, 1984b). This efficiency order has been

Table 5.1 Water vapor permeability of various films

Film
Starch, cellulose acetate(1)
Wheat gluten(3)
Casein-gelatin(20)
Wheat gluten(l5)
Sodium caseinate(2)
Cornzein(33>
HPC and PEG(I8)
MC and PEG(I8)
MC and PEG(5)
Corn zein(18)
HPMC(13)
Glycerol monostearate(16)
MC (I6)
Wheat gluten and glycerol(9)
Wheat gluten and oleic acid(10)
Wheat gluten and carnauba wax(l0)
Wheat gluten(8)
HPC (I9)
Wheat gluten and soy protein(7)
Wheat gluten and mineral oil(8)
Corn zein and oleic acid(12)
HPMC and palmitic acid(l4)
Dark chocolate(4)
MC and beeswax bilayer<n)
LDPE(17)
HPMC/MC and beeswax bilayer(15)
Beeswax(6)
Wheat gluten-beeswax bilayer<9)
Carnauba wax(6)
HDPE(!2)
Beeswax(16)
Aluminium foil(17)

Water vapor
permeability
(X 10'2 mol m m~2 s"1 Pa"1)

T
(0C)

Thickness
(X 103m)

RH %
conditions

142
69.7
34.3
34.2
24.7
22.8
13.7
13.6
7.78
6.45
5.96
5.85
5.23
5.08
4.15
3.91
3.11
2.89
2.84
2.28
1.48
1.22
0.707
0.199
0.0482
0.0360
0.0320
0.0230
0.0185
0.0122
0.0122
0.000289

38
26
30
21
25
26
21
21
25
21
27
21
30
30
30
30
23
30
23
23
38
25
20
25
38
25
25
30
25
38
25
38

1.190
0.250
0.400
0.130
0.100
0.025
0.200
0.019
1.750
0.075
0.050
0.050
0.050
0.127
0.075
0.075
0.125
0.040
0.040
0.610
0.025
0.051
0.100
0.090
0.100
0.025
0.120
0.025

100-30
100-50
60-22
85-00
100-00
100-50
85-00
85-00
52-00
85-00
85-00
100-75
11-00
100-00
100-00
100-00
11-00
11-00
11-00
11-00
95-00
97-67
81-00
100-00
95-00
97-00
100-00
100-00
100-00
97-00
97-00
95-00

(According to Allen et al, 1963a(1); Avena-Bustillos and Krochta, 1993(2); Aydt et al, 1991(3);
Biquet and Labuza, 1988(4); Donhowe and Fennema, 1993a(5); Donhowe and Fennema, 1993b(6);
Gennadios et al, 199(F; Gennadios et al, 1993a(8); Gontard, 1991(9); Gontard et al, 1994a(10);
Greener and Fennema, 1989a(ll); Guilbert and Biquet, 1989(l2); Hagenmaier and Shaw, 1990(13);
Kamper and Fennema, 1984a(l4); Kester and Fennema, 1989a(15); Landman et al, 1960(16); Myers et
al, 1961(17); Park and Chinnan, 1990(l8); Park et al, 1991(19); Schultz et al, 1949(20).)
(HPC = hydroxypropylcellulose; HDPE = high-density polyethylene; HPMC = hydroxypropyl
methylcellulose; LDPE = low-density polyethylene; MC = methylcellulose; PEG = polyethylene
glycol; RH = relative humidity; T = temperature).

confirmed by Kester and Fennema (1989a) in a study on the resistance of

various lipids, heated and adsorbed into filter papers, to water vapor
transmission. Composition, fusion and solidification ranges, lipid crystalline
structure, in addition to the interaction with water, oxygen and other
components of the food product influence the physico-chemical, functional
and organoleptic properties of lipid-based films (Fennema et al, 1994;
Kamper and Fennema, 1984a, b; Kester and Fennema, 1989a).

In general, the rate of transmission of water through a lipid film increases

as the length of the lipid hydrocarbon chain is decreased and the degree of
unsaturation or branching of acyl chains is increased (Archer and Lamer,
1955; Fettiplace, 1978; Fettiplace and Haydon, 1980; Kamper and Fennema,
1984b and 1985). This is a consequence of enhanced mobility of
hydrocarbon chains and less efficient lateral packing of acyl chains caused
by a reduction of interchain van der Walls' interaction (Jain, 1972; Taylor et
al., 1975).
However, specific information on the water vapor barrier properties of
films of more hydrophobic lipids is lacking, and almost all the information
available has been gathered using a 100-0% RH gradient which is not
commonly encountered during storage of foods under commercial conditions.
The water vapor barrier properties of a lipid-hydrocolloid composite film
is generally determined by the potentials of its component parts (Table 5.1).
The coating operation used, i.e. emulsion (suspension or dispersion of nonmiscible compounds), successive layers (multilayered films) or solutions
with a common solvent, affects the water vapor barrier properties of these
films (Table 5.2).
According to Schultz et al (1949), Martin-Polo et al (1992), Debeaufort
et al (1993) and Gontard et al (1994a), who investigated the moisture
permeability of multicomponent films composed of methylcellulose, pectinate or gluten and various lipids (waxes, fatty acids, etc.), it is better to form
two successive layers than to apply a dispersion in solvent. Kamper and
Fennema (1984a, b) carried out detailed studies of films, composed of
soluble cellulose esters and a mixture of palmitic and stearic acids, and
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
(X 108 mol m~2 s'1 Pa'1)
_

T
(0C)
_

MC and paraffin wax (emulsion)(1)

MC and paraffin wax (bilayer)(1)

7.39
0.251

25
25

0.090
0.130

84-22
84-22

Glutten(2)
Gluten and beeswax (emulsion)(2)
Gluten and beeswax (bilayer)(2)

10.1
0.727
0.0257

30
30
30

0.050
0.120
0.090

100-00
100-00
100-00

25
25
25

0.040
0.040
0.125

85-00
85-00
85-00

Film
_ _

HPMC(3)
HPMC and fatty acids (emulsion)(3)
HPMC and fatty acids (bilayer)(3)

8.02
0.00643
17

Thickness
RH %
(X 103 m) conditions
_ _
84_22

(According to Debeaufort et al., 1993(l); Gontard et aLy 1994a(2); Kamper and Fennema,
1984b(3).)
(HPMC = hydroxypropylmethylcellulose; MC = methylcellulose; RH = relative humidity; T =
temperature.)

demonstrated that application of emulsions resulted in reducing moisture

permeability by 10-fold relative to bilayer systems. Variations in homogeneity and/or structure (size, form and orientation of the crystals) of the lipid
layer related to the film-forming process and to coating operation, could
explain this discrepancy.
Permeability of composite films decreases substantially when the proportion of lipids increases. For instance, an increase of glyceride sucro ester
(beeswax, stearic acid or monoglycerides) contents in gluten- (caseinate- or
hydroxypropyl methylcellulose-) based composite films, causes a substantial
reduction in water vapor permeability (Figure 5.2), (Avena-Bustillos and
Krochta, 1993; Gontard et al, 1994a; Hagenmaier and Shaw, 1990). The
number of hydrophobic residues (from lipid derivatives) in the matrix affects
the water interaction potential, and consequently the barrier properties.
Solidification of lipids (especially saturated) in a densely organized
crystalline structure results in a very significant reduction in moisture
permeability (Kamper and Fennema, 1984b; Kester and Fennema, 1989b;
Landman et ai, 1960; Watters and Brekke, 1961).
Water vapor permeability variations relative to aw reveal the non-Fickian
behaviour of biological materials. At low aw, water diffusion, and especially
the water solubility coefficient, remains relatively low: film permeability is
minimal at this point. As expected in a hydrophilic film (Barrie, 1968;
Biquet and Labuza, 1988; Kamper and Fennema, 1984a; Crank, 1975; De
Leiris, 1985; Pascat, 1986; Schwartzberg, 1985), increasing aw leads to an

Water Vapor Permeability (i ltf2 mol. m . m*. s l . Pa *)

Lipid Materials Content (%w/w)

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 temperature 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 variations 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 Vapor Transmission Rate (WVT), (x 108 mol. m . iff2. r 1 )

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

Water Vapor Permeance (WVP), (x 10* mol.m . m 2 . s l )

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.
5.3 Use of edible active layers to control gas exchange
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 permeability 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 properties. 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

Film
_ _ _

O2 Permeability
(X 1O18HIoImIn-2S-1Pa-1)
__

HDPE (3)
Rigid PVC (II)
PET<3)
Polyamide 6(3)
PVDC (3)
Cellophane(3)
EVOH (H)
Polybutadiene<3)
Polypropylene(3)
LDPE (l3)
Flexible PVC
film(3)
Uncoated cellulose 0}
HDPE (3)
HDPE (I)
Cellophane (H)
Polyvinyl alcohol(1)
PET (3)
PET
Nylon 6 (I)
Cellophane (l4)
EVOH (I3)
MCandPEG ( I O )
MCandPEG ( 1 0 )
MC and beeswax<9)
Beeswax<5)
HPC and PEG(IO)
HPC and PEG(IO)
MC and palmitic
acid (l2)
Carnauba wax(5)
Corn zein(2)
Cornzein (2)
Wheat gluten and
glycerin(6)
Cornzein ( l 0 )
Wheat gluten
protein (l0)
Wheat gluten
protein (l0)
Corn zein(10)
Wheat gluten protein(2)
Soy protein(6)
Wheat gluten and
mineral oil(7)
Wheat gluten(8)
Wheat gluten and soy
protein(4)
Wheat gluten protein(2)
Pectin<8)
Wheat gluten(8)
Wheat gluten(8)

T
(0C)
__

0 0

972
37.6
19.5
7.65
-

23
23
23
23
23
23
23

0.0
0.0
0.0
0.0
0.0
0.0
0.0

703
-

23
23
23
23
23
23
23
23
23
23
23
23
23
23

0.50
0.50
0.50
0.50
i.00
0.50
1.00
0.95
1.00
0.50
1.00
1.00
0.50
0.95

29900
28900
-

30
21
25
25
30
21
24

0.0
0.0
0.0
0.0
0.0
0.0
0.0

81.1
34.8
19.6

216
-

25
38
23
23

0.0
0.0
0.0
0.0

16.1
8.92

30
30

0.0
0.0

119

21

0.0

285
16.0
11.9
11.6
1.86
1.34
0.155
19400
1170
961
682
406
227
224
130
50.8
24.3
12.2
10.2
8.27
6.20
522
499
480
470
190

CO2 Permeability
(X 1018 mol m m 2 s 1 Pa 1 )
_ _

aw

3.50
2.30
1.70

95.0
-

21
38
23
23

0.0
0.0
0.0
0.0

1.24
1.19

25
25

0.0
0.0

1.20
21300
36700
24500

23
25
25
25

0.0
0.96
0.95
0.91

1340
1290
982

Table 5.3 Continued

Film
Wheat gluten and
beeswax (8)
Chitosan(8)
MC and palmitic
acid(12>

O 2 Permeability
CO 2 Permeability
T
( X 10 l 8 molm HT2S-1 Pa"1) ( X 1018 mol m m"2 s"1 Pa"1) (0C)

aw

687

6614

25

0.91

472
407

8010
-

25
24

0.93
0.79

(According to Ashley, 1985 (l) ; Aydt et al., 1991 (2) ; Bakker, 1986(3); Brandeburg et al, 1993(4);
Donhowe and Fennema, 1993b(5); Gennadios et al, 1990(6); Gennadios et al, 1993a(7); Gontard et
al., 1994b(8); Greener and Fennema, 1989a(9); Park et Chinnan, 1990(l0); Poyet, 1993 (n) ; Rico-Pena
and Torres, 1990 (l2) ; Salame, 1986 (l3) ; Taylor, 1986(l4).)
(aw = water activity; EVOH = ethylene-vinyl alcohol; HDPE = high-density polyethylene;
LDPE = low-density polyethylene; MC = methylcellulose; PEG = polyethylene glycol; PET =
polyester; PVDC = poly(vinylidene chloride); PVC = poly(vinyl chloride); T = temperature.)

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
Oxygen Permeability (x 10* mol. m. m 2 . s 1 . P a ! )

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
Table 5.4 Gas selectivity coefficient of various films (CO2/O2)
Gas selectivity
coefficient (CO2/O2)

T
(0C)

aw

PP(2)
PA(2)
PVC(2)
Wheat gluten(3)
Corn zein(3)
HPC and fatty acid(3)
MC and PEG(3)
HPC and PEG(3)

4.0
4.2
5.8
7.5
9.5
23.7
31.6
40.6

23
23
23
25
25
25
25
25

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0

Gluten(I)
Gluten(1)
MC and beeswax(l)
Gluten and beeswax 0}
Pectin(l)
Chitosan(1)
Gluten(l)
Gluten*'>

4.0
4.5
6.7
9.6
16.0
17.0
25.0
2$A

25
25
25
25
25
25
25
25

0.35
0.62
0.56
0.91
0.96
0.93
0.91
0.95

Film

(According to Gontard et aL, 1994b(1); Lefaux, 1972(2); Park and Chinnan,

1990(3).)
(aw = water activity; HPC = hydroxypropylcellulose; MC = methylcellulose; PA =
polyamide; PEG = polyethylene glycol; PP = polypropylene; PVC = poly(vinyl
chloride).)

oxygen and carbon dioxide between fruit or vegetables and the environment
is a basic element in the post-harvest physiology of fruit (Burton, 1974,
1978; Cameron and Reid, 1982). The type of coating material applied alters
the relative effects on the skin permeability to oxygen and carbon dioxide
(Trout et a/., 1953). For example, waxing increased the carbon dioxide
content and decreased the oxygen content of the orange's internal atmosphere (Eaks and Ludi, 1960). The coating of peach surfaces with beeswaxcoconut oil emulsion decreased oxygen gas transfer (Erbil and Muftugil,
1986). Chitosan coatings retarded ripening and prolonged storage life of
tomatoes, cucumber and bell pepper fruit without affecting their ripening
characteristics (El Ghaouth et a/., 1990, 1991). Lowings and Cutts (1982)
reported that an edible composite coating (carboxymethylcellulose, sucrose
fatty acid esters and mono- and diglycerides) would produce a semipermeable modified atmosphere within fresh fruit after application. The
post-storage uses of these coatings were investigated on apples (Chu, 1985;
Drake et a/., 1987; Elson et al., 1985; Smith and Stow, 1984), on pears
(Elson et al.y 1985), on bananas (Banks, 1983, 1984; Lowings and Cutts,
1982), on limes (Motlagh and Quantick, 1988) and on mangoes (Dhalla and
Hanson, 1988). For example, the selective gas permeability properties of
these films applied on bananas can reduce oxygenfluxfivefold,while carbon
dioxide flux is only decreased by about half (Banks, 1984). Other examples
of gas permeability control by edible active layers are gelatin films used to
protect frozen meats from rancidity (Klose et ah, 1952), to coat candies
and dried products (Grouber, 1983) and to microencapsulate flavors
(Anandaraman and Reineccius, 1980).
The development of edible active films with selective gas permeability
seems have considerable potential applications for achieving a modified
atmosphere effect for fruits and vegetables.
5.4 Modification of surface conditions with edible active layers
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 preservative 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.

Guilbert (1988) determined the retention rate of a-tocopherol in gelatinbased films formed on intermediate moisture foods and margarine (Figure
5.6). The rapid decrease of tocopherol content in the gelatin layer in contact
with margarine is due to the high apparent solubility of tocopherol in fatty
material. The low solubility of tocopherol in water, and so its low diffusivity
value, explains the retention effect exerted by the gelatin layer in contact
with aqueous model food. Cross-linking treatment with tannic acid increases
tocopherol retention by the gelatin layers in contact with margarine. These
active layers enriched with tocopherol could be used to reduce the oxidative
deterioration in some food products.
Guilbert (1988) also investigated the retention of sorbic acid in gelatin and
casein films treated respectively with tannic and lactic acid, and placed over
an aqueous model food system (aw = 0.95). After 35 days at 25C, a
retention of 30% was observed with the treated casein film. Swelling and
poor retention were observed with the gelatin film (30% retention after 10
days).
Sorbic acid retention has been studied in zein-based (Torres et aL, 1985b)
and casein-based films (Guilbert, 1986, 1988), gluten-based and pectinbased films (De Savoye et aL, 1994), and in composite polysaccharide-lipid
derivative films (Vojdani and Torres, 1990). The sorbic acid permeability
values determined for these films can also be compared with published
apparent diffusion values for sorbic acid in food systems. In an intermediate

Table 5.5 Apparent coating diffusion coefficients for sorbic acid in intermediate moisture model food (agar model or cheese analog) at 24C and aw =
0.88, in agar gel (with sucrose or glycerol) at 25C and aw = 0.88, and in
cheese analog coated with edible zein films
Diffusion coefficient
(m2 s~')

Experiment
Agar gel and sucrose(1)
Cheese analog(2)
Agar model(2)
Agar gel and glycerol(1)
Cheese analog and zein
Cheese analog and two zein

0.5
1.0
2.0
3.5
film(2)
films(2)

X
X
X
X

IO"10
IO"10
10"10
10"10

3.3 X 10~13
6.8 X 10~13

(According to Giannakopoulos and Guilbert, 1986a(l); Torres et al.,

1985b(2).)

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
Film
Chitosan
MC
HPMC
MC and palmitic acid (weight ratio 3:1)
HPMC and palmitic acid (weight ratio 3:1)
Zein

Sorbic acid permeability

(x 108 g mm m"2 s'1 (g/1)"1)
0.865
0.334
0.830
0.120
0.205
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 methylcellulose 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.
Sorbic Add Permeability
(xlO f g.m.nr 2 .* 1 .**/!)- 1 )

Sorbic Add Diffusivity

(xlO lf m ' . s 1 )

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 RicoPena 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).

An increase in temperature causes a decrease in film sorbic acid barrier

properties (Figure 5.8). These variations can easily be analysed through
Arrhenius-type representations. Vojdani and Torres (1989b) noted that
activation energy is affected by the solvent embedding the film, which
suggests that the diffusion process in the film occurs mainly through the
aqueous phase. Consequently, the performance of edible coatings controlling
surface preservative concentration will depend strongly on the composition
of the aqueous phase of the coated food.
The sorbic acid permeability of edible films varies according to pH
(Figure 5.9). At constant aw and temperature, sorbic acid permeability
decreases when pH increases. An increase in pH lowers permeability,
possibly due to a change in the sorbic acid formed around the pKa (equal to
4.8), thus modifying the diffusion properties. Longer surface retentions of
sorbic acid are possible at higher pH (and also at lower aw and lower
temperature). It should be noted that the higher retention at higher pH would
help balance the lowering of sorbic acid effectiveness as pH is increased
(Eklund, 1983).
The microbiological analyses carried out have confirmed the sorbic acid
retention efficiency of zein-based edible films, formed on the surface of
intermediate moisture cheese analogs, relative to microbial stability of the
food product (Torres et al., 1985b; Torres and Karel, 1985). These edible

Sorbic Add Permeability (SAP), (x 10f g. m. m2 . s '. (g / W )

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 RicoPena 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
(days)

aw
0.71

aw
0.75

aw
0.84

aw
0.90

Control (non coated)

(a)
(b)

>40
>40

>40
>40

13
3

4
1

Coated with casein

(a)
(b)

>40
>40

>40
>40

12
2

4
2

Coated with casein and sorbic acid

(a)
(b)

> 40
>40

> 40
>40

22
>40

10
17

Coated with carnauba wax

(a)
(b)

> 40
>40

> 40
>40

> 28
>40

10
14

Coated with carnauba wax and

sorbic acid

(a)
(b)

> 40
> 40

> 40
> 40

32
> 40

10
> 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
Contamination: togN (cells / cm2)

(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 changes 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 procedure must be realizable on the industrial scale and be easily integratable in
the food processing line.
Acknowledgements
Dalle Ore Florence (CIRAD-SAR, Montpellier, France), Thibaut
Romain (CIRAD-SAR, Montpellier, France), Aymard Christian (CNRS,
Montpellier- CIRAD-SAR, Montpellier, France) and Cuq Jean Louis
(Universite de Montpellier II, France) are gratefully acknowledged for
helpful discussions and technical assistance. Part of the work presented here
was supported by the EC project: AIRl - CT92 - 0125.
References
Albrigo, L.G. and Brown, G.E. (1970) Orange peel topography as affected by a preharvest
spray. Horticultural Science 5, 470-2.
Allan, CR. and Hadwiger, L.A. (1979) The fungicidal effect of chitosan on fungi of varying
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surfaces. III. Effects of surface preservative concentration and surface pH control on
microbial stability of an intermediate moisture cheese analog. Journal of Food Processing
and Preservation, 9, 107-19.
Torres, J.A., Motoki, M. and Karel, M. (1985b) Microbial stabilization of intermediate
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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 temperature 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 generators, 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.

6.2 Oxygen absorbents

One novel and innovative method of oxygen control and of atmosphere
modification involves the use of oxygen absorbents. Oxygen absorbents can
be defined as 'a range of chemical compounds introduced into the MAP
package (not the product) to alter the atmosphere within the package' (AgriFood Canada, personal communication). Developed in Japan in 1976,
oxygen absorbents were first marketed by the Mitsubishi Gas Chemical Co.,
under the trade name Ageless (Table 6.1). Several other Japanese companies
also produce oxygen absorbents with the best known being the Toppan
Printing Company which produces a range of oxygen absorbents under the
label Freshilizer Series (Smith et al., 1990). In 1989, almost 7000 million
sachets were sold in Japan with sales of absorbents growing at a rate of 20%
annually. The Mitsubishi Gas Chemical Co. dominates the oxygen absorbent
market (73%) while the Toppan Printing Co. has about 11% of the market
with nine other companies sharing the remaining 16% of the market.
Oxygen absorbent technology has been successful in Japan for a variety of
reasons, including the hot and humid climate during the summer months
which is conducive to mold spoilage of food products. Another important
factor for their success is that Japanese consumers are willing to pay higher
prices for preservative-free products with an increased shelf-life. Several
years after the Mitsubishi Gas Chemical Co., successfully launched oxygen
absorbent technology onto the marketplace, Multiform Desiccants in the
United States introduced FreshPax, the first North American oxygen
scavenger (Table 6.1). Like its predecessors, FreshPax is extremely effective
in lowering package oxygen from 20% to less then 0.05% in about 36 hours.
However, unlike the Japanese market, acceptance of oxygen scavengers in
Table 6.1 Major companies producing oxygen absorbents
Company

Product name

Mitsubishi Gas Chemical Co., Japan

Toppan Printing Co., Japan
Multiform Desiccants, US

Ageless
Freshilizer
Freshpax

North America and Europe has been slow, although several major
companies in both continents are now using this technology.
Oxygen absorbents comprise of easily oxidizable substances usually
contained in sachets made of air-permeable material. These sachets come in
a variety of sizes capable of absorbing 20-2000ml of headspace oxygen.
When placed inside the packaged food, they actively modify the package
headspace and reduce the oxygen levels to < 0.01% within 1-4 days at
room temperature. However, some are designed to scavenge oxygen at
refrigerated or frozen storage temperatures and are used to further extend the
shelf-life and keeping quality of muscle foods. This oxygen-free environment protects the food from microbiological and chemical spoilage and is
also effective in preventing damage by insects. A combination of some or all
of these factors helps maintain the quality and freshness of food, which
facilitates the marketing of oxygen absorbents. The classification and the
main types of oxygen absorbents will now be briefly reviewed.
6.2.7

Classification of oxygen absorbents

Oxygen absorbents can be classified into several different categories as

shown in Table 6.2. Each category will be briefly reviewed.
6.2.1.1 Classification according to material. In theory, any material that
reacts easily with oxygen can be used as an oxygen scavenger. However,
because the technology involved is used mainly for food preservation, the
material used inside the sachet must meet the following criteria prior to
approval by regulatory agencies.

It
It
It
It
It
It
It

must
must
must
must
must
must
must

be safe.
be handled easily.
not produce toxic substances or offensive odors/gases.
be compact in size.
absorb a large amount of oxygen.
have an appropriate oxygen absorption speed; and
be economically priced (Harima, 1990).

Iron powder and ascorbic acid are commonly used in existing oxygen
absorbers with powdered iron being most frequently used either alone or in
conjunction with other specific chemical compounds in dual function
absorbents (Table 6.2).
6.2.1.2 Classification according to reaction style. Water is essential for
oxygen absorbents to function. In the self-reaction types, water required for
the chemical reaction is added and the absorbents must be handled carefully
as the oxygen absorbing reaction commences as soon as the self-reacting
absorbent is exposed to air. In moisture dependent types, the oxygen

absorption reaction only takes place after moisture has been absorbed from
the food; these type of absorbents are easier to handle as they do not react
immediately upon exposure to air. However, they absorb oxygen quickly
after sealing and oxygen can be absorbed within 0.5-1 day in certain
products. Examples of self-reacting and moisture dependent types of oxygen
absorbents are shown in Table 6.2.
62.13 Classification according to reaction speed.. Oxygen absorbents
can be classified as immediate effect, general effect, and slow effect types
(Harima, 1990). The average time for oxygen absorption is 0.5-1 day for the
immediate type; 1-4 days for the general type; and 4-6 days for the slow
Table 6.2 Classification of oxygen absorbents
Function
O2I

Reactant
Iron

Catechol

Application

Absorption
speed

Product

Dry
aw < 0.3
Tea; nuts

4 to 7 days

Ageless Z-PK
Vitalon T

Medium aw
aw < 0.65
Dried beef

1 to 3 days

Ageless Z
Keplon TS

High aw
aw > 0.65
Cakes
Bakeries

0.5 days

Ageless S
Sequl CA

Frozen temp
+ 3 to - 25C
Raw fish

3 days at
- 25C

Ageless SS

Moisture
dependent type

High aw
aw > 0.85
Pastas

0.5 days

Ageless FX
Vitalon LTM

Self-working type

Medium aw
aw < 0.65
Nuts

Tamotsu A

High aw
aw > 0.65
Cakes
Roasted coffee

Tamotsu P

Self-working type

O2I &
CO2I

Iron + Calcium

Self-working type

O2I &
CO2T

Ascorbic acid

Self-working type

Medium aw
0.3 < aw < 0.5
Nuts

Ascorbic acid +
Iron

Moisture
dependent type

High aw
aw > 0.85
Cakes

O2I &
Iron +
EthanolT Ethanol/Zeolite

Moisture
dependent type

High aw
aw > 0.85
Cakes

3 to 8 days

Ageless E

1 to 4 days

Ageless G
Toppan C
Vitalon GMA

Negamold

O2 concentration (%)

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.

O2 concentration (%)

reacting type (Harima, 1990). The reaction time depends on storage

temperature and water activity (aw) of the food. The effect of storage
temperature on oxygen absorbing speed is shown in Figures 6.1 and 6.2.
Most oxygen absorbents are used with foods stored at ambient temperature.

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 lowtemperature 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.
6.2.1.4 Classification according to use. Oxygen absorbents can be used
for a variety of foods with different moisture contents ranging from very
moist to very dry food products. In general, foods with a high moisture
content are more susceptible to mold spoilage. Therefore, an immediate
effect absorbent would be used with these products to rapidly absorb oxygen
and extend the mold-free shelf-life of the product. General type absorbents
are used with intermediate moisture food products where a moderate speed
of oxygen absorption is required. For low moisture food products, which are
not susceptible to microbial spoilage but to chemical spoilage, a slow effect
oxygen absorbent can be used. Examples of the application of the various
categories of oxygen absorbents are shown in Table 6.2.

02 concentration (%)

6.2.1.5 Classification according to function. The majority of absorbents

have only one function - absorption of oxygen. However, dual functional
absorbents have been developed for use in specific products. These include
oxygen-carbon dioxide absorbents for use in coffee, and oxygen absor-

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.
6.2.2 Main types of oxygen absorbents
6.2.2.1 Ageless. Ageless, made by the Mitsubishi Gas Chemical Co.,
consists of a range of gas scavenger products designed to reduce oxygen
levels to less than 100 ppm in the package headspace. While both organic
types (based on ascorbic acid) and inorganic types (based on iron powder)
are available, the inorganic types are most commonly used in the Japanese
market. The basic system is made up of finely divided powdered iron which,
under appropriate humidity conditions, uses up residual oxygen to form nontoxic iron oxide, i.e., it rusts. The oxidation mechanism can be expressed as
follows (Harima, 1990; Smith et ai, 1990; Smith, 1992):
Fe -> Fe2+ + 2e
^O2H- H2O + 2e -> 2OHFe2+ + 2(OH)- -> Fe(OH)2
Fe(OH)2 + J^O2 +\ H2O -> Fe(OH3)
To prevent the iron powder from imparting color to the food, the iron is
contained in a sachet (like a desiccant). The sachet material is highly
permeable to oxygen and, in some cases, to water vapor.
Since Ageless relies on a chemical reaction and not on the physical
displacement of oxygen as in gas packaging, it completely removes all traces
of residual O2 and protects the packaged food from aerobic spoilage and
quality changes.
Several types and sizes of Ageless sachets are commercially available and
are applicable to many types of foods including those with a high moisture
content, intermediate moisture products, low moisture product foods and
foods containing or treated with oil. The main types of absorbents are types
Z, S, FX, E and G. Three new types of Ageless are commercially available
in Japan. These are Ageless types SS, FM and SE (Table 6.3).

Table 6.3 Types and properties of Ageless oxygen absorbents

Water activity

Absorption speed
(day)

Type

Function

Moisture status

Z
S
SS

Decreases O2
Decreases O2
Decreases O2

Self-reacting
Self-reacting
Self-reacting

<0.65
> 0.65
> 0.85

FX
FM
E

Decreases O2
Decreases O2
Decreases O2
Decreases CO2
Decreases O2
Increases CO2
Decreases O2
Increases ethanol

Moisture dependent
Moisture dependent
Self-reacting

>0.85
> 0.85
< 0.3

1-3
0.5-2.0
2-3 (0-4 0 C)
10 ( - 2 5 0 C )
0.5-1.0
0.5-1.0
3-8

Self-reacting

0.3-0.5

1-4

Moisture dependent

>0.85

1-2

G
SE

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 microwaveable 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

Type

Function

F Series (ferrous metal)

Decreases O2
FD
Decreases O2
FH
Decreases O2
FT
C Series (Non-ferrous metal)
C
Decreases O2
Increases CO2
Decreases O2
CW
Increases CO2
Decreases O2
CV
Decreases CO2

Water activity

Absorption speed
(day)

<0.8
0.6-0.9
> 0.8

1-3
0.5-1.0
0.5-1.0

Self-reacting

< 0.8

3-5

Self-reacting

0.8-0.9

2-3

Self-reacting

< 0.3

3-8

Moisture status
Self-reacting
Self-reacting
Moisture dependent

Courtesy of Toppan Printing Co., Tokyo, Japan.

6.2.2.2 Freshilizer series. The Freshilizer Series of freshness keeping

agents made by Toppan Printing Co., Japan, consists of the F series and the
C series (Table 6.4). Series F Freshilizers use mainly ferrous metal and
absorb only oxygen. Three types are commercially available - types FD, FH
and FT. Type FD is designed for use in food products with aw values less
than 0.8 (nuts, tea, chocolate) while type FH is suitable for use in products
with a range of aw values ranging from 0.6 to 0.9 and is used mainly with
beef jerky and salami to maintain the color of these products. Type FT
works best in foods with water activities greater than 0.8 such as pizza
crusts. Series F absorbents can absorb 20-300 ml O2 corresponding to a
package volume of 100-1500 ml of air (Toppan Technical Information,
1989).
The Freshilizer C series of absorbents comprises types C, CW and CV.
These sachets consist of non-ferrous metal particles and can therefore be
used in products which must pass through a metal detector. Types C and CW
absorb oxygen and generate an equal volume of CO2 thereby preventing
package collapse. Type C is used in foods with an aw of 0.8 or less (nuts)
while type CW is suitable for foods with higher aw values (i.e. > 0.8). Type
CW is commonly used to prevent mold growth in sponge cakes. Type CV
absorbs both oxygen and carbon dioxide and was developed for use with
roasted or ground coffee (Table 6.4; Toppan Technical Information,
1989).
6.2.2.3 FreshPax. FreshPax is a patented oxygen absorbing system
developed by Multiform Desiccants, a leading manufacturer of desiccants
and other protection products for more than 30 years. Manufactured in the
United States, FreshPax, like other oxygen absorbent technology provides an
alternative to gas/vacuum packaging to extend the shelf-life and keeping
quality of products while simultaneously reducing costs and increasing

Table 6.5 Types and properties of Freshpax oxygen absorbents

Type

Function

Moisture status

Type B
Type D

Decreases O2
Decreases O2
at 2 to - 200C
Decreases O2

Moisture dependent
Self-reacting

Decreases O2
Increases CO2

Moisture dependent

Type R
Type M

Self-reacting

Water activity

Absorption speed
(day)

> 0.65
< 0.7

0.5-2.0
0.5-4.0

0.3-0.95

0.5-1.0
(depending on temp.)
0.5-2.0

> 0.65

Courtesy of Multiform Desiccants, Buffalo, NY.

profitability. Produced in sachet form, FreshPax absorbs headspace oxygen

to < 0.1% using safe, non-toxic ingredients (mainly iron oxide) that rapidly
absorb oxygen before the food deterioration process begins. Four main types
of FreshPax are commonly available - type B, type D, type R and type M
(Table 6.5). Type B is used with moist or semi-moist foods while type D can
be used with dehydrated or dried foods. Type R can be used to scavenge
oxygen at refrigerated or frozen storage temperature and is similar to
Ageless type SS. It is mainly used to extend the shelf-life and keeping
quality of muscle foods. Type M is used with most or semi-moist gas
flushed products to maintain package volume and to remove all traces of
residual oxygen (Table 6.5; FreshPax Technical Pamphlet, 1994).
6.2.3

Factors influencing the choice of oxygen absorbents

Oxygen absorbent sachets come in a range of sizes capable of absorbing 5

ml to 2000 ml of oxygen. Several interrelated factors influence the choice of
the type and size of absorbent selected for shelf-life extension of food
products (Harima, 1990; Smith et ai, 1990; Smith, 1992). These are:

The
The
The
The
The
The

nature of the food, i.e., size, shape, weight.

aw of the food.
amount of dissolved oxygen in the food.
desired shelf-life of the product.
initial level of oxygen in the package headspace.
oxygen permeability of the packaging material.

The latter parameter is critically important for the overall performance of the
absorbent and shelf-life of the product. If films with high O2 permeabilities
are used, e.g., > 100 cm3 mil m~2 day"1 atm"1, the oxygen concentration in
the container will reach zero within a week but then returns to ambient air
level after 10 days due to the fact that the absorbent is saturated. However,
if films of low O2 permeability are used, e.g., < 10 cm3 mil m 2 day 1 atm 1
such as PVDC coated nylon/LDPE, the headspace O2 will be reduced to 100
ppm within 1-2 days and remain at this level for the duration of the storage

Table 6.6 Examples of films used with oxygen absorbents (Freshpax

Technical Pamphlet, 1994)
Film laminates
including

OTR
(ml/m2/d)

MVTR
(g/m2/d)

Long-term preservation

Aluminium
EVOH
PVDC

< 0.6
< 3
< 15

< 0.6
< 4
< 8

Short-term preservation

Nylon
PET

< 16
< 15

< 40
< 100

Not appropriate

Cellophane
PP
PE

< 200
< 2000
< 3000

<20
< 6
< 5

OTR = oxygen transmission rate; MVTR = moisture vapor transmission

rate; EVOH = ethylene vinyl alcohol; PVDC = polyvinylidene chloride;
PET = polyester; PP = polypropylene; PE = polyethylene.

period providing packaging integrity is maintained. Examples of appropriate

packaging materials for use with oxygen absorbents and their permeability
characteristics are shown in Table 6.6.
A rapid and efficient method of monitoring package integrity throughout
the storage period is through the incorporation of a redox indicator, e.g.,
Ageless Eye. When placed inside the package alongside an Ageless sachet,
the color of the indicator changes from blue (oxidized state) to pink (reduced
state) when the oxygen content of the container reaches < 0.005%. If the
indicator reverts back to its blue color, it is indicative of poor packing
integrity caused by poor sealing of the film or minute pin holes in die film.
Similar redox indicators are made by the Toppan Printing Company.
6.2.4 Application of oxygen absorbents for shelf-life extension of food
6.2.4.1 In Japan. Several studies have reported significant extension in
the chemical and microbiological shelf-life of low, intermediate and high
moisture food products using oxygen absorbent technology (Nakamura and
Hoshino, 1983; Abe and Kondoh, 1989; Harima, 1990; Minakuchi and
Nakamura, 1990). As a result of these studies, oxygen absorbent technology
is being used extensively in Japan to prevent chemical problems, e.g.,
discoloration problems in highly pigmented products, such as cured meat
products and tea, and rancidity problems in high fat foods, such as peanuts,
fried rice cake and chocolate covered almonds (Figures 6.4 and 6.5; Table
6.7). Oxygen absorbents are also used effectively to inhibit growth of
aerobic spoilage microorganisms, especially molds, in intermediate moisture
and high moisture bakery products. Examples of products found in Japanese
supermarkets with extended chemical and microbiological shelf-life as a
result of oxygen absorbent technology are summarized in Tables 6.8-6.11.
More detailed information on the use of both Ageless and Freshilizer oxygen

Total Vitamin C (mg/100g)

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
POV (peroxide value : meq/kg)

N 2 gas

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.
Ageless

O2(%)
POV almond
POV chocolate
Flavor score

Air

O2(%)
POV almond
POV chocolate
Flavor score

40 days

3 months

6 months

0.01
2.3
1.1
5

0.01
1.2
1.0
5

0.01
1.5
1.0
4

18.2
7.8
0.9
4

13.3
16.4
1.2
3

9.5
23.5
2.1
2

(Almond without chocolate coating)

Air
O2(%)
14.3
POV almond
14.0
Flavor score
2

6.7
21.1
1

1.7
28.8
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

Type of food
Cheesecake
Buttercake
Plain sponge cake
Egg bread
Pumpernickel bread
Pita bread
Tortilla chips
Custard cakes
Blueberry cheesecake
Soy bean pie
Bean/jam cake
Steamed bean/jam cake

Water activity of
food

Packaging materials

Type and size of

Ageless

0.88-0.92
0.9
0.86-0.88
0.9
0.9
0.9
<0.6
0.92-0.94
0.88-0.9
0.93
0.85
0.9

KON
KON
KON
KON
KON
KOP
KON/Box
PET/PVDC/PE
KON
KON
KON/PS Tray
PP/EVAL/KON/PE

S200
SIOO
S200
SlOO
FXlOO
SlOO
Z200
S50
S200
S10-15
ZPTl 00-200
S200

Prevents
Mold growth/oxidation
Oxidation/mold growth
Mold growth
Mold growth
Moid growth
Mold growth
Oxidation
Mold growth
Mold growth
Mold growth
Mold growth
Mold growth

Shelf-life @ RT*
1 month
1 month
1 month
1 month
3-4 weeks
3-4 weeks
6 months
7-10 days
1 month
1 month
2 months
2-3 weeks

*RT = Room temperature

PET = polyester; PE = low-density polyethylene; AC = acrylonitrile; KON = PVDC-coated nylon; KOP = PVDC-coated polypropylene; PVDC = polyvinylidene chloride; PP = polypropylene; EVAL = ethylene vinyl alcohol; PS = polystyrene.

Table 6.9 Use of Ageless for shelf-life extension of fish products

Type of food

Water activity of
food

Dried seaweed
Dried salmon jerky
Dried sardines
Dried shark's fin
Dried rose mackerel
Dried cod
Dried squid
Fresh yellow taile
Sliced salmon

<0.3
0.7-0.8
< 0.6-0.88
0.8
0.7-0.8
< 0.6
0.7-0.8
0.99
0.99

Dried/smoked salmon
Dried octopus leg
Dried bonito
Salmon roe
Dried squid/vinegar/
soybean sauce
Sea urchin

0.8
< 0.85
0.6-0.7
0.8-0.9
0.7-0.8

* RT = Room temperature

0.98

Packaging materials

Type and size of

Ageless

Prevents

PET/AC/PE
KON
KON
KON
KON/PET Tray
KOP
KON
Nylon/PVDC/PP
KON

ZlOO
Z50
Z100-200
S200
S2000
ZlOO
ZlOO
SSlOO
FXlOO

Oxidation/Discoloration
Oxidation/Discoloration
Oxidation
Oxidation/Mold growth
Oxidation
Oxidation
Oxidation/Mold growth
Oxidation/Discoloration
Discoloration

KON
KON
KON
KON
KOP

ZlOO
FXlOO
TypeZ200+100%N 2
SSlOO
Z200

Mold growth/Discoloration/Oxidation
Oxidation/Mold growth
Oxidation/Discoloration
Discoloration
Oxidation/Mold growth

1 year
3 months
6 months
1-2 months
1 month
6 months
3 months
1 week at - 30C
6 months at
-200C
1 month at 100C
1 month
3-6 months
6 months at - 3C
3 months

Wood Tray/KON

SSlOO

Discoloration/Bacterial growth

2 weeks at - 50C

Shelf-life @ RT*

Table 6.10 Use of Ageless for shelf-life extension of meat and deli products
Type of food
Pizza crust
Pizza
Fresh carved sausage
Pre-cooked hamburgers
Pre-cooked chicken nuggets
Salami slicks
Sliced salami

Water activity of
food
~ 0.94-0.95
0.99
0.99
0.99
0.99
0.8-0.85
0.8-0.85

Packaging materials

Type and size of

Ageless

Prevents

KON
KON
KON
PS Tray/KON
KON
KON
KON

FX200
S200
FX50
SlOO
FXlOO
Z50
SlOO

Mold growth
Mold growth/Discoloration
Discoloration/Rancidity
Discoloration/Rancidity
Discoloration/Rancidity
Discoloration
Discoloration

Shelf-life @ RT
2 months at 50C
2 weeks at 50C
3 weeks at 0-40C
3 weeks at 0-40C
3 weeks at 0-40C
1-2 months
1 month

Table 6.11 Use of Ageless for shelf-life extension of miscellaneous products

Type of food
Rice crackers/fried bean
Peanuts
Peanut butter/chocolate coated
Chocolate peanuts
Candy-type cheese
Smoked cheese
Soy bean paste
Bakery food (milk powder)
Green tea
Flavored tea
EVA = ethylene vinyl acetate.
RT = Room Temperature.

Water activity of
food

Packaging materials

<0.3
<0.3
0.5-0.6
0.5-0.6
0.9-0.95
0.9
0.8-0.85
< 0.3
<0.3
0.5-0.6

Tin/Plastic/Aluminium lid
KON
KON/Paper box
KON
KON
KON
Paper/AC/EVA
Tin can
Tin can
KON

Type and size of

Ageless
ZlOO
GlOO
Z200
Z30-100
FX50+100%N2
S30-50
FX20
ZlOO
Z50
Z50

Prevents
Oxidation/Rancidity
Oxidation/Rancidity
Oxidation/Rancidity
Oxidation/Rancidity
Oxidation/Rancidity
Oxidation/Mold growth
Discoloration
Oxidation/Rancidity
Oxidation
Oxidation

Shelf-life @ RT
1 year
6 months
9 months
9 months
1 month at 0-40C
1 month at 0-40C
3 months
6-12 months
1 year
1 year

Table 6.12 Use of oxygen absorbent technology in USA

_ _ Product

(months @ RT1)

Maxwell House coffee

Ener-Getic gluten-free bread
MRE2 bread
MRE bread/buns

12-36
12
36
6

Company
General Foods
Ener-G Foods
Sterling Foods
Franz Bakery
The Famous Pacific
Dessert Company

Fruit tortes

6-9

1
2

RT = room temperature
MRE = meals, read-to-eat

uses Ageless oxygen absorbents to prevent rancidity and mold problems in

packaged tortes (Table 6.12). Clearly, there is an increasing interest by many
companies, particularly baking companies, in the use of oxygen absorbent
technology as an alternative or adjunct to gas packaging to prevent the perennial
problem of mold growth.
6.2.4.3 Research activities in oxygen absorbent technology. Although the
use of oxygen absorbent technology has not been accepted commercially
with the same enthusiasm in North America compared to Japan, there is,
however, tremendous interest and ongoing research in this innovative
method of atmosphere modification.
Studies in our laboratory have shown oxygen absorbents to be three times
more effective than gas packaging for increasing the mold-free shelf-life of
crusty rolls (Smith et al., 1986). While the mold-free shelf-life of crusty rolls
can be extended by packaging in 60% CO2 and 40% N2, mold growth still
occurred after 19 days due to the oxygen permeability of the packaging film.
Studies have shown that Aspergillus and Penicillium species, the major spoilage
isolates of crusty rolls, can tolerate and grow in < 1% (v/v) headspace oxygen
even in the presence of elevated levels of CO2. However, when Ageless (Type
S or Type FX) was packaged alongside crusty rolls, either alone or in
conjunction with gas packaging, headspace O2 never increased beyond 0.05%
and the product remained mold-free for > 60 days at ambient storage
temperature (Smith et al., 1986). While a longer extension in the mold-free
shelf-life was possible using oxygen absorbents, mold problems occasionally
arose in the Ageless packaged product. This was due to absorption of headspace
gas and package collapse resulting in some products being tightly wrapped
with the packaging film. This created pockets of localized environments
between the product surface and the film where the oxygen concentration may
have increased to a level sufficient to permit mold growth. This clearly
demonstrates the need for a free flow of gas around the product if Ageless
is to be totally effective as an oxygen scavenger (Smith et al, 1986).
More recently, Ageless oxygen absorbents have been used in our
laboratory to extend the mold-free shelf-life of fresh bagels and pizza crusts.

with the packaging film. This created pockets of localized environments

between the product surface and the film where the oxygen concentration may
have increased to a level sufficient to permit mold growth. This clearly
demonstrates the need for a free flow of gas around the product if Ageless
is to be totally effective as an oxygen scavenger (Smith et a/., 1986).
More recently, Ageless oxygen absorbents have been used in our
laboratory to extend the mold-free shelf-life of fresh bagels and pizza crusts.
Furthermore, the use of specific types of absorbents appeared to have an
anti-staling effect on bagels. Further studies are now underway to compare
the anti-staling effects of oxygen absorbents with other methods of
atmosphere modification for shelf-life extension of bakery products.
The use of absorbent technology for shelf-life extension of food has also
been extensively studied by Cryovac, a world leader in vacuum packaging
technology. Cryovac in the US has been given the distribution rights to
Ageless in North America by the Mitsubishi Gas Chemical Company.
Researchers at Cryovac have found that oxygen absorbent technology can be
used to prevent mold growth, discoloration and flavor changes in cooked
cured sausage, cooked poultry and smoked poultry chops. Using a
combination of oxygen absorbent technology and Cryovac's high barrier
shrink film, headspace oxygen (which can reach 4-7% due to entrapped
oxygen in the foam tray) is reduced to < 0.3% before products are exposed
to retail display lighting. Thus, oxygen absorbent technology can be used to
inhibit photodegradation of meat pigments in cured meat products thereby
enhancing consumer appeal for such products (Cryovac, personal communication). Oxygen absorbent technology has also been investigated to inhibit
mold growth and rancidity problems in fresh pasta and pizza crusts. Other
areas of applied research by Cryovac involving oxygen absorbents include
prevention of rancidity problems in snack food; prevention of flavor changes
in wine stored in oxygen permeable PET bottles using a barrier pouch
overwrap with an oxygen absorbent; and master packaging of fresh meat and
poultry. This latter concept is in response to consumer concerns about
absorbents being visible inside the packaged food product. In the MasterPak,
retail cuts of meat/poultry are packaged in trays with an oxygen permeable
overwrap. These are placed inside a cardboard carton with a high gas barrier
film and absorbents added. The system is then evacuated, gas flushed and
heat sealed and distributed under refrigeration to the retailer where the
individual packs are removed from the MasterPak and displayed on retail
shelves. Color or 'bloom' returns to the meat/poultry due to the low barrier
characteristics of the overwrap.
Extensive research on Freshilizer absorbents has been conducted by
Multiform Desiccants in conjunction with Dr Joe Hotchkiss at Cornell
University. Studies by Alarcon and Hotchkiss (1993) have shown that
FreshPax oxygen absorbents can prevent mold growth in preservative-free
white bread and low moisture, low fat mozzarella cheese for 8 weeks at

ambient/refrigerated temperature. Furthermore, oxygen absorbents were also

effective in reducing the oxidative formation of rc-hexanal (an indicator of
off-flavor development) in both sunflower seeds and cornchips. Sensory
panel analysis also showed that absorbents inhibited the formation of
undesirable rancid odors during accelerated storage tests (Alarcon and
Hotchkiss, 1993). These authors also reported that FreshPax oxygen
absorbents were also effective in controlling permeated oxygen, and hence
iiiold growth ai/id rancidity problems, in bread and cheese packaged in
jnedium barrieij films with an OTR of about 32 ml/m2/day. Therefore,
medium barrier] films could be substituted for a high barrier and more
expensive film if an oxygen absorber pack was included in the package
(Alarcon and Hotchkiss, 1993).
6.2.5 Advantages and disadvantages of oxygen absorbents
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 compounds.
Maintain product quality without additives.
Increase product shelf-life and distribution radius.
Allow a long time between deliveries and allow fewer, longer deliveries.
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.

6.2.5.1 Consumer resistance to sachets. The two main consumer concerns about sachets being placed inside the packaged food product are: fear
of ingestion even although the contents are safe and the label clearly says
'Do not eat'; and spillage of sachet contents into food and consequent
adulteration of the food product. These concerns have been addressed by the
Mitsubishi Gas Chemical Company by producing the deoxidizer in a tablet
form or in a board form and affixing it to the lid or to the bottom of
packages. This approach has been successfully used for health foods sold in
bottles and with individually wrapped teacakes in the Japanese marketplace.
An alternative method is to package the primary packages inside a secondary
packaging containing the absorbent. This is the principle behind the
MasterPak system, i.e., bag-in-box system, designed to hold 12-48 consumer-size primary packages made of material with a higher oxygen
transmission rate than for secondary containers, as discussed in the previous
section. The main advantage of this approach is that the consumer never sees
the absorbents, thus eliminating the possibility of consumers misusing the
packets or reacting negatively to the absorbents (Smith, 1992).
Another approach to overcome consumer resistance to sachets is to
incorporate the oxygen scavenging capacity in the form of a package label.
This approach has been developed by both Mitsubishi Gas Chemical
Company and Multiform Desiccants. This latter company currently markets
both Type B and Type M absorbents in the form of labels marketed under
the trade name FreshMax. This label can be backed with various adhesives
for different product applications. The technology has a printed surface and
is contact acceptable (oil/grease resistant). The label can be applied at
conventional line speeds and is compatible with both moist and dry food
products. The prototype FreshMax is 2.5" x 2.5" and 15 mil thick. It is
capable of absorbing 100 ml of oxygen in 24 h and can be made into various
shapes. The labels can reduce headspace oxygen to less than 0.01% (100
ppm) and can be used to retard both chemical and microbiological spoilage
in stored products. Marks & Spencer Ltd., London are now using FreshMax
labels to extend the shelf-life and keeping quality of deli meats. The new

labels cover only one third of the lid surface, providing consumers with a
clearer view of the product yet absorb oxygen and protect products from the
adverse oxidizing effect of light and oxygen on meat pigments (Multiform
Desiccants, personal communication).
6.2.5.2 Public health concerns. Another consumer and regulatory concern about oxygen absorbent technology is that the anaerobic environment
created inside the package may be conducive to the growth of facultative
anaerobic or strictly anaerobic food pathogens. These concerns are justified
in view of the ability of many food pathogens to grow at refrigerator
temperatures, e.g. Listeria monocytogenes and Clostridium botulinum type
E; the inhibition of aerobic microorganisms as indicators of spoilage; and
the potential for temperature abuse. Recent studies have shown that average
temperatures of retail cases in supermarkets were about 12C while
temperatures of domestic refrigerators ranged from 2 to 200C (Palumbo,
1986). Nakamura and Hoshino (1983) reported that an oxygen-free
environment alone was insufficient to inhibit the growth of Staphylococcus
aureus, Vibrio species, Escherichia colif Bacillus cereus and Enterococcus
faecalis at ambient storage temperature. For complete inhibition of these
microorganisms they recommended combination treatments involving oxygen absorbents with thermally processed food or refrigerated storage or a
CO2 enriched atmosphere. Using this latter combination, i.e., low O2-high
CO2 gas atmosphere, they found that this modified atmosphere inhibited the
growth of S. aureus and E. coli but promoted the growth of E. faecalis.
While low levels of CO2 (20%) failed to inhibit the growth of B. cereus,
higher concentrations (100%) completely inhibited the growth of this
microorganism in an oxygen-free environment. When similar studies were
done with Clostridium sporogenes, some interesting results were obtained,
as shown in Table 6.13.
These studies demonstrated that an O2/CO2 absorbent will inhibit the
growth of C. sporogenes while an O2 absorbent-CO2 generator will enhance
its growth, indicating the importance of selecting the correct absorbent to
control the growth of Clostridium species in MAP food. In challenge studies
with C. botulinum type A and B spores, Lambert et al. (1991a) observed that
Table 6.13 Effect of various gas atmospheres on the growth of C. sporogenes
(adapted from Nakamura and Hoshino, 1983)
Packaging conditions
_
Ageless oxygen absorbent generating carbon dioxide
Ageless oxygen absorbent not absorbing carbon dioxide
Ageless oxygen absorbent absorbing carbon dioxide

Growth of
C. sporogenes
_
4+
2+
1+

- = no growth; 1+ = slight growth; 2+ = medium growth; 3+ = heavy

growth; 4+ = extensive growth.

package headspace was not significant in affecting the time until toxin
production (Lambert et al, 1991b,c).
In more recent agar plate studies with Listeria monocytogenes, high CO2
levels (> 60%) promoted the growth of this pathogen at 10-150C (Morris et
al, 1994). However, when an oxygen-free environment was achieved using
Ageless SS, growth of L. monocytogenes was completely inhibited even at
mild temperature abuse storage conditions. Further studies are now
underway to determine the antimicrobial efficacy of Ageless SS and gas
packaging on L. monocytogenes in packaged pork.
6.2.6 Effect of oxygen absorbents on afiatoxigenic mold species
While the use of oxygen absorbent technology may fail to completely inhibit
the growth of facultative or strictly anaerobic pathogenic bacteria, it is very
effective in controlling the growth of Aspergillus flavus and Aspergillus
parasiticus. In inoculation studies with these aflatoxigenic molds in peanuts
packed in air alone and with an oxygen absorbent, mold growth and
aflatoxin were completely inhibited in absorbent packaged peanuts while
~1000 ppb (1000 ng) of aflatoxin B1 were detected in all air-packaged
samples after only 6 days at room temperature (Ellis et al, 1993). Similar
control of A. parasiticus has also been reported in inoculation studies with
peanuts using oxygen absorbent technology (Ellis et al, 1994). However,
this control was dependent on both the OTR of the packaging films used and
storage temperature. While packaging in high-medium barrier films
inhibited aflatoxin B1 production, aflatoxin was detected in all absorbent
packaged peanuts using a low barrier film (OTR -4000 ml/m2/day).
However, when absorbent packaged peanuts were packaged in medium
barrier films (OTR - 5 0 ml/m2/day), aflatoxin production occurred in all
peanuts stored at 300C (Ellis et al, 1994). This was attributed to the greater
permeance of the film to oxygen at higher storage temperatures, resulting in
saturation of the absorbents, a concomitant increase in headspace oxygen,
and subsequent mold growth and aflatoxin production. Similar results were
obtained with a CO2 generating oxygen absorbent (Ageless G), indicating
the importance of packaging film permeability to ensure the efficacy of
oxygen absorbents and the public health safety of absorbent packaged
peanuts.
6.3 Ethanol vapor
The use of ethanol (ethyl alcohol) as an antimicrobial agent is well
documented. Alcohol was used by the Arabs over 1000 years ago to preserve
fruit from mold spoilage. However, alcohol is most commonly recognized as
a surface sterilant or disinfectant. In high concentrations (60-75% v/v),

ethanol acts against vegetative cells of microorganisms by denaturing the

protein of the protoplast (Seiler and Russell, 1993). Lower concentrations of
alcohol (5-20% v/v) have also been shown to have a preserving action
against food spoilage and pathogenic microorganisms in agar model
systems. In tests with surface inoculated agar medium containing concentrations of ethanol ranging from 4 to 12% (v/v) ethanol was shown to be
effective in controlling 10 species of mold including Aspergillus and
Penicillium species; 15 species of bacteria including S. aureus and E. coli;
and 3 species of spoilage yeasts (Freund Technical Information, 1985). Most
molds were inhibited by 4% ethanol while yeasts were more resistant and
required 8% ethanol for complete inhibition. However, S. aureus required
12% ethanol for complete inhibition (Freund Technical Information, 1985).
Shapero et al. (1978) reported that the effectiveness of ethanol against S.
aureus was a function of water activity (aw). They reported that in broth
media adjusted to aw 0.99, 0.95 and 0.9 with glycerol, inhibition of S. aureus
occurred at 9, 7 and 4% of ethanol respectively. A similar synergism
between aw and the antimicrobial efficacy of ethanol against A. niger and R
notatum has been observed by Smith et al. (1994). In studies with
unadjusted Potato Dextrose Agar (PDA) plates a concentration of 6%
ethanol was required for complete inhibition of these common mold
contaminants of bakery products. However, complete inhibition of A. niger
and P. notatum was observed with 4 and 2% of ethanol respectively in plates
adjusted to aw 0.95 and 0.9 with glycerol. These results confirm previous
observations that lower concentrations of ethanol can be used to extend the
mold-free shelf-life of food products with a low aw.
The antimicrobial effect of low concentrations of ethanol for shelf-life
extension of bakery products has also been demonstrated. Plemons et al.
(1976) showed that the mold-free shelf-life of pizza crusts could be extended
for about 20 weeks at ambient temperature by spraying the crusts with 95%
ethanol and overwrapping in a large unsealed polyethylene bag (Seiler,
1978; Seiler, 1988). Seiler and Russell (1993) also reported a 50-250%
increase in the mold-free shelf-life of cake and bread sprayed with 95%
ethanol to give concentrations ranging from 0.5 to 1.5% by weight of
product. Both these studies indicate the potential of ethanol as a vapor phase
inhibitor. However, a more practical and safer method of generating ethanol
vapor is through the use of ethanol vapor generating sachets, which will now
be discussed in greater detail.
6.3.1 Ethanol vapor generators
A novel and innovative method of generating ethanol vapor, again
developed by the Japanese, is the use of ethanol vapor generating sachets or
strips. These contain absorbed or encapsulated ethanol in a carrier material
and enclosed in packaging films of selective permeabilities which allow the

Table 6.14 Manufacturers of ethyl alcohol generators

6J.I

Trade name

Manufacturer

Antimold
(Ethicap)
Negamold
Oitech
ET Pack

Freund

Sachets/yr
60m

Entered
1978

Freund
Nippon Kayaku
Ueno Seiyaku

9m
1m

1982
1980
1988

Ethanol vapor generators

A novel and innovative method of generating ethanol vapor, again

developed by the Japanese, is the use of ethanol vapor generating sachets or
strips. These contain absorbed or encapsulated ethanol in a carrier material
and enclosed in packaging films of selective permeabilities which allow the
slow or rapid release of ethanol vapor. Several Japanese companies produce
ethanol vapor generators, with the most commercially used system being
Ethicap or Antimold 102 produced by the Freund Industrial Co., Ltd., Japan
(Table 6.14).
Ethicap consists of food grade alcohol and water (55% and 10% by
weight respectively) adsorbed on to silicon dioxide powder (35%) and
contained in a sachet made of a laminate of paper/ethyl vinyl acetate
copolymer. To mask the odor of alcohol, some sachets contain traces of
vanilla or other flavors as masking compounds. The sachets are labelled 'Do
not eat contents' and include a diagram demonstrating this warning. Another
type of ethanol vapor generator is Negamold (Table 6.15), which scavenges
oxygen as well as generating ethanol vapor. Negamold, like its competitor,
Ageless type SE, can be used to extend the shelf-life and keeping quality of
bakery products. However, Negamold is not widely used since it does not
generate as much ethanol vapor as Ethicap (Freund Technical Information,
1985).
Sachet sizes of Ethicap range from 0.6 to 6 G or 0.33 to 3.3 g of ethanol,
which can be evaporated. The actual size of the sachet used depends on the
weight of food; aw of food; and the desired shelf-life of product. This
interrelationship is shown in Figure 6.6. For example, if the aw of the product
is 0.95 and a 1-2 week shelf-life is desired, then a 2 G size of Ethicap
Table 6.15 Types of alcohol generators
_
Type

Function

Application

Ethicap (Antimold 102)

Generates EtOH vapor

Negamold

Absorbs O2
Generates EtOH vapor

Moisture dependent Cakes/

Bread
Moisture dependent Cakes/
Bread

products
> 0.85
> 0.85

Required sachet size of ETHICAP per 10Og of food

(~ 1.1 g ethanol) should be used per 100 g of product. However, if a longer

shelf-life is desired (2-3 months), a 4 G size of Ethicap should be used for
the same product (Freund Technical Information, 1985).
When food is packed with a sachet of Ethicap, moisture is absorbed from
the food, and ethanol vapor is released from encapsulation and permeates the
package headspace. However, both the initial and final level of ethanol vapor
in the package headspace is a function of sachet size and water activity, as
shown in Figure 6.7. Smith et al. (1987) examined this relationship in PDA
plates adjusted to aw 0.95 and 0.85 with glycerol and packaged in a film of
low ethanol vapor permeability with a 1 G and 4 G (E1 and E4) size of
Ethicap respectively. After day 1, the level of headspace ethanol generated
from a 1 G sachet of Ethicap (E1), ranged from 0.7% v/v at a water activity
of 0.99 to 0.5% v/v at a water activity of 0.85 (Smith et al, 1987). However,
after 7-10 days' storage, headspace ethanol was approximately 0.4% v/v at
a water activity of 0.85 compared to 0.2% v/v at the highest water activity
under investigation and remained at these levels for the duration of the
storage period (Smith et al., 1987). A similar, higher trend was noted for
headspace ethanol generated from 4 G of Ethicap, E4 (Smith et al., 1987).
These studies indicated the importance of product aw on the vaporization of
ethanol into, and absorption of ethanol from, the package headspace.

for long term

for short term

Water activity of food

Figure 6.6 Relationship between aw of food and required size of Ethicap sachet. Short term, 1-2
weeks; long term, 8-13 weeks. (Reproduced with permission from the Freund Technical Co., Ltd.,
Japan.)

-I*

O
Z
<
Z
Ul
Ul
O
(0

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.

Another important factor in using Ethicap as a food preservative is to

package the product in a film with a high or medium barrier to ethanol
vapor. The ethanol vapor permeabilities of appropriate packaging materials
are shown in Table 6.16. Generally, a film with an ethanol vapor
permeability of < 2 g/m2/day @ 300C is recommended (Freund Technical
Information, 1985).
6.3.2 Uses of Ethicap for shelf-life extension of food
Ethicap is used extensively in Japan to extend the mold-free shelf-life of
high ratio cakes and other high moisture bakery products. A 5-20 times
extension in mold-free shelf-life has been observed for high ratio cakes
depending on the size of Ethicap used (Freund Technical Information,
1985). Results also showed that products with sachets did not get as hard as
the controls and results were better than those using an oxygen scavenger to

Table 6.16 Ethanol vapor permeability of certain plastic films (adapted from Freund Technical Information,
1985)
Film
_ _ _ _ _

Ethanol vapor permeability

(g/m2/day) @ 300C
___

OPP/EVOH/LDPE
PVDC/PET/PP
PVDC/OPP/PP
AL/PET/LDPE
PP/PVDC/PP
PET/PP
OPP/PP
HDPE
OPP
PP
LDPE
EVA/LDPE

0.8
0.9
1.0
1.2
1.5
1.8
2.0
4.1
4.7
8.0
19.0
56.1

PVDC = polyvinylidene
chloride;
PA = nylon;
OPP = oriented polypropylene; PP = cast polypropylene; PET = polyester; AL = aluminium; HDPE =
high-density polyethylene; LDPE = low-density polyethylene; EVA = ethylene vinyl acetate.

inhibit mold growth, indicating that the ethanol vapor also exerts an antistaling 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")
Food

Size of
Ethicap

Packaging
material

0.92
0.85
0.83
0.80
0.76
0.72

IG
3G
3G
2G
4G
2G

OPP
OPP/PP
OPP
OPP/PP
OPP/PP
OPP/PP

1 week
2 months
20 days
6 months
2 months
6 months

0.85
0.68
0.69
0.63

IG
0.6G
0.6G
IG

OPP
OPP
OPP/PE
OPP

3
3
2
3

aw of food

Shelf-life @ RT

Bakery products
Bread
Cupcake
Jam doughnut
American cake
Rice cake
Chocolate sponge cake
Fish products
Smoked squid
Boiled squid
Boiled & dried squid
Boiled & dried small fish

months
months
months
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 wellknown 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 concentrations on the microbiological and chemical shelf-life of fresh packaged
pork.
63 A Advantages and disadvantages of ethanol vapor generators
According to Smith et al. (1987) the advantages of Ethicap are:

Ethanol vapor can be generated from sachets without having to spray

ethanol directly onto product surface prior to packaging.
Sachets can be conveniently removed from packages and discarded at the
end of the storage period.
It eliminates the need for preservatives such as benzoic acid or sorbic
acid to control yeast spoilage.
It can control mold spoilage and delay staling in bakery products.
A disadvantage of using ethanol vapor for shelf-life extension is its
absorption from the package headspace by product. However, the concentration of ethanol found in apple turnovers (1.45-1.52%) was within the
maximum level of 2% by product weight when ethanol is sprayed onto pizza
crusts prior to final baking (Smith et al., 1987). However, the level of
ethanol in apple turnovers can be reduced to < 0.1% by heating product at
375 F prior to consumption. Therefore, while a longer shelf-life may be
possible by packaging product with Ethicap, its use as a food preservative
may be limited to 'brown & serve' or microwaveable products. Another
disadvantage is cost, which limits its use to products with higher profit

margins. Nevertheless, Ethicap is a viable alternative or supplement to gas

packaging to extend the shelf-life of baked bakery products in relation to
both mold and yeast spoilage and to prevent staling.
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 shelflife and keeping quality of a variety of products, their use to date in the
North American market is limited due to the cost of the sachets, consumer
resistance to the inclusion of sachets in packaged products and lack of
regulatory approval for Ethicap. Nevertheless, the use of gas absorbents/
ethanol vapor generator sachets or labels offers the food industry a more
viable alternative method of interactive packaging than vacuum/gas flushing
for shelf-life extension of its products.
References
Abe, Y. and Kondoh, Y. (1989) Controlled/Modified Atmosphere/Vacuum Packaging of Foods,
Food & Nutrition Press PubL, Trumbull, CT, pp. 149-58.
Alarcon, B. and Hotchkiss, J.H. (1993) The effect of FreshPax oxygen-absorbing packets on
the shelf-life of foods. Technical Report, Dept. of Food Science, Cornell University, NY,
1-7.
Anon. (1988) Ener-Getic all year long. Packaging Digest, 8, 70, 72, 75.
Black, R.G., Quail, K.J., Reyes, M., Kuzyk, M. and Ruddick, L. (1993) Shelf-life extension of
pita bread by modified atmosphere packaging. Food Australia, 45, 387-91.
Ellis, W.O., Smith, J.P., Simpson, B.K., Khanizadeh, S. and Oldham, J.H. (1993) Control of
growth and aflatoxin production by Aspergillus flavus under modified atmosphere packaging
(MAP) conditions. Food Microbiology, 10, 9-21.
Ellis, W.O., Smith, J.P., Simpson, B.K. and Doyon, G. (1994) Effect of films of different gas
transmission rates on aflatoxin production by Aspergillus flavus in peanuts packaged under
modified atmosphere packaging (MAP) conditions. Food Research International, 27,
505-12.
FreshPax Technical Pamphlet (1994) Protect and preserve your products and profits with
FreshPax. Multiform Desiccants, Buffalo, NY.
Freund Technical Information (1985) No-mix-type mould inhibitor Ethicap. Freund Industrial
Co., Ltd., Tokyo, Japan, pp. 1-14.
Harima, Y. (1990) Food Packaging, Academic Press PubL, London, UK, pp. 229-52.
Lambert, A.D., Smith, J.P. and Dodds, K.L. (1991a) Combined effect of modified atmosphere
packaging and low-dose irradiation on toxin production by Clostridium botulinum in fresh
pork. / . Food Protection, 54, 97-104.
Lambert, A.D., Smith, J.P. and Dodds, K.L. (1991b) Effect of headspace CO2 on toxin
production by Clostridium botulinum in MAP, irradiated fresh pork. / . Food Protection, 54,
588-92.
Lambert, A.D., Smith, J.P. and Dodds, K.L. (1991c) Effect of initial O 2 and CO2 and low-dose
irradiation on toxin production by Clostridium botulinum in MAP fresh pork. / . Food

Protection, 54, 939-44.

Minakuchi, S. and Nakamura, H. (1990) Food Packaging, Academic Press PubL, London, UK,
pp. 357-78.

Morris, J., Smith, J.P., Tarte, I. and Farber, J. (1994) Combined effect of chitosan and MAP
on the growth of Listeria monocy togenes. Food Microbiology; (Submitted for publication).
Nakamura, H. and Hoshino, J. (1983) Techniques for the preservation

of food by the

employment of an oxygen absorber. Mitsubishi Gas Chemical Co., Tokyo, Japan, 1-45.
Ooraikul, B. (ed.) (1993) Modified Atmosphere Packaging of Food, Ellis Horwood Publ, New
York, NY, pp. 49-117.
Pafumi, J. and Durham, R. (1987) Cake shelf life extension. Food Technology in Australia, 39,
286-7.
Palumbo, S.A. (1986) Is refrigeration enough to restrain food borne pathogens? /. Food
Protection, 49, 1003-9.
Plemons, R.F., Staff, CH. and Cameron, F.R. (1976) Process for retarding mold growth in
partially baked pizza crusts and articles produced thereby. US Patent 3979525.
Powers, E.M. and Berkowitz, D. (1990) Efficacy of an oxygen scavenger to modify the
atmosphere and prevent mold growth in meal, ready-to-eat pouched bread. /. Food
Protection, 53, 767-71.
Rooney, M. (1992) Reactive Packaging Materials for Food Preservation. In: Proceedings of
the First Japan-Australia Workshop on Food Processing, Tsukuba, Japan, pp. 78-82.
Seiler, D.A.L. (1978) The microbiology of cake and its ingredients. Food Trade Review, 48,
339-44.
Seiler, D.A.L. (1988) Microbiological problems associated with cereal based foods. Food
Science and Technology Today, 2, 37-41.
Seiler, D.A.L. and Russell, NJ. (1993) Food Preservatives, Blackie Academic & Professional,
Glasgow, UK, pp. 153-71.
Shapero, M., Nelson, D.A. and Labuza, T.P. (1978) Ethanol inhibition of Staphylococcus
aureus at limited water activity. /. Food Science, 43, 1467-9.
Smith, J.P., Ooraikul, B., Koersen, WJ. and Jackson, E.D. (1986) Novel approach to oxygen
control in modified atmosphere packaging of bakery products. Food Microbiology, 3,
315-20.
Smith, J.P., Ooraikul, B., Koersen, WJ., van de Voort, F.R., Jackson, E.D. and Lawrence,
R.A. (1987) Shelf life extension of a bakery product using ethanol vapor. Food
Microbiology, 4, 329-37.
Smith, J.P., Ramaswamy, H. and Simpson, B.K. (1990) Developments in food packaging
technology. Part 2: Storage aspects. Trends in Food Science and Technology, 1, 112-19.
Smith, J.P. (1992) MAP Packaging of Food - Principles and Applications, Academic and

Professional Publ., London, UK, pp. 134-69.

Smith, J.P., Lyver, A. and Morris, J. (1994) Effect of ethanol vapor on the growth of common
mold contaminants of bakery products. Food Microbiology; (Submitted for publication).
Toppan Technical Information (1989) Freshness keeping agents. Toppan Printing Co., Ltd.,
Tokyo, Japan, pp. 1-8.
Young, L.L., Reviere, R.D. and Cole, A.B. (1988) Fresh red meats: a place to apply Modified
Atmospheres. Food Technology, 42, 65-9.

7 Enzymes as active packaging agents

A.L. BRODY and J.A. BUDNY

This chapter discusses the role of enzymes in active packaging, especially as

oxygen scavengers.
Almost all mechanisms in which packaging structures function in
response to a stimulus involve physical, chemical or physiochemical actions.
In a physical action, the active element of the material, which is usually
external, opens, expands, closes, contracts, etc. as one or more variables are
changed. In chemical or physiochemical reactions, a component of the total
package reacts with the package structure or component, usually in an
irreversible manner, with the result that the active component is effectively
consumed or changed as the internal package environment is changed.
However, in catalytic processes physiochemical or chemical reactions
occur in which the catalyst remains effective and intact. Enzymes, which are
biological catalysts, accelerate chemical reactions but are not consumed as a
result of the reactions. Within limits, for as long as reactants or substrates are
present, enzymes will function to catalyze chemical, or more specifically
biochemical, reactions. When the proper enzymes are introduced under the
proper conditions, they are capable of catalyzing reactions which can either
prevent the product from being changed or extend the function of packaging
beyond its accepted or previously understood functions by actively serving
as a processing unit.
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 nonenzymatic 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 temperature 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.
7.2 Potential roles of enzymes in active packaging
In many commercial situations, enzymes may be viewed as chemicals to be
added to the product to catalyze a reaction as one way to affect batch
processing. The addition can occur to the in-plant batch or individual
package. For in-package situations, the enzyme may be added directly to the
product to effect a reaction or may be incorporated into the package
structure. To function within a package material, the enzyme must be
immobilized and the substrate, reactant or a constituent circulated past the
site to initiate a reaction. Immobilization of an enzyme, or placing it in a
static position where it may function for an indefinite period, may be
accomplished by making the enzyme an integral part of the packaging
material.
Active packaging in general often involves the incorporation of a

chemical into the package material. Active packaging employing one or

more enzymes involves the incorporation into the package material of the
specific enzymes in much the same manner as the incorporation of a more
conventional chemical to create the active package. The key differences are
that the enzyme is not changed by the reaction and can continue to function
indefinitely; the enzyme is vulnerable to variations in temperature, pH, etc.;
and the range of environmental conditions for the functioning of the enzyme
is a relatively narrow band. These key considerations which affect the ability
of the enzyme to function require special processes and techniques for
incorporating enzymes into packaging materials. Often, harsh manufacturing
processes, geometric configurations, etc. that are adequate and even
appropriate for non-enzyme packaging components render the use of
enzymes inappropriate. Consequently, new and innovative methods are
likely to be required for the incorporation of enzymes into packaging
materials.
Although a broad range of enzymatic reactions stemming from enzyme
incorporation into package materials can be conceived, only a relatively
small number have actually been attempted on a practical basis. Examples of
those that have been actively pursued include:
Oxygen removed by means of glucose oxidase plus catalase.
Removal of products of microbiological degradation by glucose oxidase/
catalase.
Incorporation of lactase to remove lactose from milk.
Incorporation of cholesterol-changing enzymes to remove cholesterol
from liquid egg or milk.
Time-temperature integrator indicators which are triggered enzymatically.
Examples of enzymatic reactions that have not found general use but
which might have some future potential and require development include:
Conversion of sugar into alcohol and carbon dioxide in secondary
fermentations of wine to produce champagne-like products.
A United Kingdom patent application (Thomas and Harrison, 1983)
which describes an in-package secondary fermentation system using
immobilized yeast within a liquid porous container immersed in an
alcoholic beverage. In one manifestation, the container was a flexible
pouch. Further, the inventors refer to isolated enzyme complexes as
being useful as yeast substitutes. The objective here was to consume the
residual fermentable sugars, converting them into carbon dioxide and
water.
In-package production of lactic acid for pickles, sauerkraut or sour dairy
products.
Production of 'natural' antimicrobial agents such as benzoic or propionic
acids to help preserve the product contents.

Destruction of natural toxins in foods.

Removal of undesirable respiratory end products such as ethylene that
accelerate the respiratory processes of fresh fruits and vegetables.
Removal of undesirable end products of microbiological or endogenous
enzymatic reactions such as polypeptides, carbonyls, ketones, volatile
acids, etc.
Tenderizing of fresh meat such as beef by proteases such as papain.

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.
7.4 Oxygen removal
As is documented elsewhere in this book, oxygen is a highly reactive gas
which can cause deterioration of almost all food products in terms of flavor,
color, nutritional value and safety. Further, the presence of oxygen is
essential to the growth and potential deteriorative effects of aerobic
microorganisms including most bacteria, yeasts and molds. Thus, minimization or removal of oxygen is an important factor in prolonging the quality
retention of many food products.
According to Baker (1949, but evidently conceived in 1944) the addition
of an oxidase to liquid-containing food products such as beer, peas, corn,
milk, apple cider or orange juice, protects them from oxidation. 'In some
instances, it is better to produce in the product a substrate for the oxidase
that is to be introduced rather than to use a substrate already present.' For
example, glucose originally present or added can be oxidized to gluconic
acid. Baker's patent indicates that if the oxidase produces an objectionable
end product such as hydrogen peroxide, then an additional enzyme might be
introduced to remove the undesirable end product.
Among the interesting aspects of this early patent is the notion that as the
oxygen in the product is removed, free oxygen in the headspace is further
dissolved by equilibrium dynamics, thus removing oxygen from the
headspace. The reaction, now very well known, is
2G + 2O2 + 2H2O -> GO + 2H2O2
where G is the substrate. Since hydrogen peroxide is a very good oxidizing
agent, it is 'just as objectionable, or even more so, than is the original
molecular oxygen.' Thus, catalase is introduced to break down the hydrogen
peroxide
2H2O2 + catalase - 2H2O2 + catalase
The sum of these two reactions yields half the oxygen originally present and
therefore ultimately the free oxygen approaches zero.
Baker's invention was implemented by introducing one or more pellets of
the enzyme into the product such as beer or orange juice. The patent also
mentions the incorporation of lactase to hydrolyze lactose into glucose and
galactose which are then oxidized in the presence of oxidases. Perhaps
without realizing the significance of this assertion, the patent suggested the
use of enzymes to reduce the lactose content of milk.
The patent does not explicitly describe precisely how the enzymes are
incorporated. The inference is that the enzymes are introduced directly into

the product. Expressed differently, this patent does not indicate that the
enzymes are either part of the package structure or in an independent packet
within the primary package. Thus, although the 1949 patent described
perhaps for the first time the employment of enzymes to eliminate inpackage oxygen, it did not indicate that the enzymes were part of the
package material or structure.
This concept of enzyme incorporation into a package material was first
overtly described in a 1956 patent (Sarett, 1956). (Sarett, incidentally, was
the assignee for the Baker patent.) In this patent, the same basic enzymatic
reactions as in the Baker patent were reiterated as a reference, but the
enzymes glucose oxidase and catalase in a solution were impregnated into or
on a moistureproof or fabric sheet. The enzyme was bound to the sheet with
a water-dispersible adhesive such as polyvinyl alcohol, starch, casein or
carboxymethyl cellulose. The enzyme-coating face must contact the moist
product to ensure that the requisite oxygen reduction reactions take place.
The enzyme system was indicated to serve as a barrier to oxygen which
would otherwise be transmitted through the sheet. Products described as
being benefited by this system of oxygen reduction include cheese, butter,
frozen foods subject to browning, etc.
Although during the period of the patent a Kraft packaging paper called
moistureproof (which, as it happens, was not actually moistureproof) was
often used to package butter and cheese, the patent does not indicate the use
of this material. Rather, the package material is described as having \ .. an
exposed surface covered with a gas-permeable packaging material and
having an inter layer between and in contact with packaging material and . . .
food . .. inter layer providing an oxygen barrier. . . . ' The specific package
materials identified were moistureproof cellophane, paper, rubber hydrochloride with impregnation employed for the papers and coating for the plastic
and cellulose films. Also cited as being suitable substrates were wax paper,
styrene, polyethylene and vinyls.
Experiments discussed in the body of the patent indicated results in which
oxidation of cheese surfaces was retarded by the presence of the enzymecontaining package material.
In 1958, Scott (co-inventor on the 1956 Sarett patent) of Fermco
Laboratories, published a paper on Enzymatic Oxygen Removal from
Packaged Foods in which enzymes were incorporated into packaging
materials or introduced into packets. Fermco Laboratories was a manufacturer of enzymes, one category of which was labeled Fermcozyme
antioxidants, and of the packets which were named Oxyban. This paper
marked the first publication to our knowledge on the use of packets of
chemicals in packages.
The glucose oxidase/catalase systems were derived from mold mycelia
which were disrupted, filtered and further purified. To be effective in

reducing oxygen, glucose oxidase/catalase systems must be used in gas-tight

packages. Among the applications indicated were:
Aqueous foods

direct incorporation, in mayonnaise or carbonated beverages;

surface treatment in canned dog food;
in packets in situations in which the enzyme and the product should be
kept separate.
Non-aqueous foods
direct incorporation;
in packets, as for chow mein noodles.
The mayonnaise and carbonated beverage examples involved incorporation of the enzyme system directly into the products, with oxidative rancidity
delayed in the former class of products and color fading (e.g., grape-flavor
carbonated beverages) as well as flavor oxidations delayed in the latter. The
dog food example was also a direct addition to retard surface discoloration
on the top of the dog food in retorted cans.
As a coating, the dried enzyme system was coated on the surfaces of
package materials for processed cheese. Deposition of the enzymes was in
solution form or via incorporation into a dry starch mixture prior to 'dusting'
the package material surface. When the dry and therefore inactive enzyme
picked up moisture from the product, it was activated and was a sufficiently
good oxygen interceptor to control the formation of brown ring. Another
series of experiments focused on obviating oxidative gray coloration on the
surfaces of luncheon meats.
Fermco's Oxyban product was a dry glucose oxidase/catalase/glucose/
buffers blend to be incorporated into products to reduce headspace and
occluded and dissolved oxygen in dry foods such as coffee or soup. In
another manifestation, the Oxyban was placed in small packets in which it
reacted with oxygen in packages of roasted and ground coffee, smoked yeast
or egg solids. Exactly how the enzyme was activated without moisture was
not indicated, but clearly some moisture from the product was required. The
author noted that this in-package packet was analogous to the desiccant
packet.
Three years later, Scott, then with Hammer (Scott and Hammer, 1958),
elaborated on the oxygen-scavenging packet for in-package deoxygenation.
Using the same glucose oxidase/catalase packet system described earlier
from their laboratory experiments, they proceeded forward to a more
commercially viable mechanism. Among the problems they enumerated
were:

Oxygen-scavenger surface area owing to the gas phase reaction.

The need for moisture (cited above).
Necessity to neutralize gluconic acid to avoid enzyme deactivation.

Package material structure allowing passage of oxygen but not moisture.

The gluconic acid problem was obviated using phosphate buffers. As little as
15 g of Oxyban enzyme mix in a packet was capable of removing all
measurable oxygen from a sealed No. 2 size can held at ambient
temperature. Once again, the type of package material used for the packet
was not indicated.
An interesting side note was an exploration of the use of glucose oxidase
alone which, of course, led to an increase in the amount of hydrogen
peroxide which would, in turn, slow the subsequent rate of oxygen
uptake.
The products benefited by the total system were primarily dry milk, potato
granules and ice cream mix.
An international patent application (Lehtonen et ai, 1991) described a
package material containing an enzyme system to remove oxygen from the
interior of the package by enzymatic reaction. By removing the oxygen, the
growth of aerobic microorganisms was significantly retarded, and so this
technology was favorable to shelf-life from both microbiological and
chemical standpoints. The enzyme, for example, glucose oxidase, was
incorporated into a package material with a gas-impermeable layer on the
exterior and a gas permeable layer on the interior, i.e., the layer containing
the oxygen-consuming enzyme was sandwiched between two plastic film
layers.
The background of this patent cited a 1969 German publication describing
the use of glucose oxidase in package materials for the surface protection of
meats, fish and cheese products but without elaboration. And, of course, the
classical review paper by Labuza et al. (1989) described a similar
technology of coating plastic film with glucose oxidase catalase, with the
enzyme system activated by moisture from the food as Scott had previously
cited.
This patent application from Cultor Ltd. of Helsinki, Finland, details a
flexible package structure containing an enzyme system in the liquid phase
trapped between films, the outer of which might be polyamide or
polyvinylidene-coated polyester. The inner film would be polyethylene
which is generally not a good gas barrier.
The enzymes of choice were oxidases of the oxidoreductase family using
oxygenases and hydroxylases which bind oxygen to oxdizable molecules.
The enzyme solution contains a buffer and a stabilizer, and may also be
mixed with a filler. The enzyme layer was applied on the film by gravure or
screen technique with the layer thickness being about 12 fim. The enzyme is
not directly in contact with the contents.
The film produced was employed either as the cover film layer or as the
thermoformable bottom layer for tray-type packages.

The inventors noted that with increasing temperature, the gas permeability
of package materials increases and so also does the ability of the enzyme
system to reduce the oxygen content from the 20.9% of air to about 1% at
ambient temperature within 24 hours.
From technological and potential commercial perspectives, this Finnish
work is so precise as to imply a major advance in the ability to implement
the principles of enzymes as active package components.
Co-author Budny and his company PharmaCal, Ltd. have been actively
researching enzymes for active packaging since the 1980s. The contribution
of PharmaCal, Ltd. to enzymes in active packaging was to expand the
concept of packaging beyond the two long-regarded functions of packaging:
containment of the product; and protection of the contents. These requirements originally were embodied in wine skins that ancient goat- and sheepherders used for their sustenance beverages. Throughout history, while there
have been advancements in materials and approaches, there have not been
any fundamental changes or additions to the necessary requirements for
containers or packages. Whether they are animal skins, a lid or a multi-layer
stock, they should protect the contents and not leak.
PharmaCal, Ltd. added a third dimension to packaging by allowing an
individual package to become a processing unit or to perform a process step
or function that previously was limited to in-plant operations. With a
combination of patent applications and proprietary technology, PharmaCal,
Ltd. has been able to expand the concept of packaging to include processing
steps, value-addition to packaged products and increased processing efficiencies.
PharmaCal, Ltd. has developed a two-enzyme system involving glucose
oxidase and catalase to intercept oxygen and has applied the technology for
enzymes in active packaging to improve the proven concept of oxygen
removal with the dual enzyme system of glucose oxidase and catalase. The
use of the enzymes to remove oxygen has been acknowledged as not new,
but their role in enzyme-based active packaging has been regarded as a more
advanced application. Figure 7.1 illustrates the mechanism in which
packaged liquid reacts enzymatically with glucose in the package wall to
form gluconate. The resulting hydrogen peroxide is enzymatically reacted
with catalase to produce oxygen and water that re-enter the contained
product liquid.
A container with an internal reactor, in reality an integral section of the
package wall through which the liquid contents may flow, permits the
enzymes to be retained for a reaction described in a 1989 patent application
(Budny, 1989).
A 1991 patent (Ernst, 1991), described a glucose/glucose oxidase enzyme
mixture in a porous precipitated silica acid carrier. Calcium carbonate,
calcium hydrogen phosphate, magnesium carbonate or disodium hydrogen

Head
space

Gluconate

Glucose
oxidase
enzyme

Glucose
Packaged
liquid

Catalase

Outside
of
container

enzyme

Inside of container
Container wall

Figure 7.1 Oxygen removal from liquid products.

carbonate may also be employed as carriers or reaction accelerators. The

oxygen scavenger may be in the interior of in-package sachets.
A 1991 patent (Copeland et al, 1991) describes the incorporation of
oxygen scavenging cell membrane fragments which contain an electron
transfer system in solutions containing alcohol or acids to reduce oxygen to
water. Although neither purified nor crude enzymes, the active component of
membrane fragments in this technology must constitute the enzyme
system.
The inventors note that the major mechanism to effect the reaction is
incorporation of the membrane fragments into the product, and that these
active components may also be made part of the package structure. Sources
of the membrane fragments were cell membrane of bacteria such as
Escherichia coli and/or mitochondrial membranes.
Examples of products from which oxygen might be removed by the
system include beer, wine, fruits, juices and a variety of non-food products.
Both red and white wines were treated with materials supplied by Oxyrase,
Inc., which is also the patent assignee. Dissolved oxygen was removed
within 16 minutes at 37C. Less than 12 minutes was required to remove
100% of the oxygen from beer or tomato juice. A five-fold increase in the
time to the onset of browning of cut surfaces of bananas and apples was
observed at ambient temperature.
Developers from chewing gum producer, William Wrigley, Jr., have
described the use of porous polymeric beads containing glucose oxidase in
multilayer flexible package materials (Courtright et al, 1992). The porous
particles are made from styrene divinyl benzene, with the enzyme incorporated mechanically. The beads are then blended into a thermoplastic coating
in the multilayer film.

Labuza and Breen (1989) have analyzed the issues involved in the
incorporation of glucose oxidase into package materials.
To counteract the quantity of oxygen passing through an aluminum foil
lamination an enzyme surface will have to react with oxygen in the
following manner:
Rate = permeability X area X oxygen pressure difference
between the outside and inside
Rate = 0.1 X 1 [0.21-0.01] = 0.2 ml per day per m2
= 20 jxl/day
The calculation above assumes air outside and < 1% oxygen inside. For the
worst case and with a pinhole or cracked score, there would be the need to
scavenge 1 ml/day. A film could be made equivalent to a barrier by binding
the oxygen scavenging enzyme to the inside surface of the film to react with
the excess oxygen.
Glucose oxidase transfers two hydrogens from the -CHOH group of
glucose to oxygen with the formation of glucono-delta-lactone and hydrogen
peroxide. The lactone then spontaneously reacts with water to form gluconic
acid. One mole of glucose will consume one mole of oxygen and so a
package with 500 ml headspace is required, to reach zero oxygen, with only
0.0043 mole of glucose needed as a substrate. The major factors are the
speed at which the enzyme works, the amount of glucose available, and the
rate at which oxygen permeates into the package. In the presence of catalase,
a normal contaminant of commercial glucose oxidase, the hydrogen
peroxide is broken down, and so with catalase one mole of glucose will react
with only a half mole of oxygen, decreasing the overall effectiveness of the
system. Pure glucose oxidase without catalase is reportedly expensive.
If no surface exists for the peroxide for diffusion, the glucose oxidase will
be inactivated, precluding this application. Since many foods may have
minimal contact with the package surface, except on the sides and bottom,
this may not be the best approach for oxygen scavenging.
At 30-400C, pure glucose oxidase has a rate of oxygen consumption of
about 150 000 (il/h/mg. Based on this, and spreading 1 mg per m2 on a film,
this would be equivalent to reacting with all the oxygen passing through a
film with an oxygen permeability of about 18 000 ml/day m2 atm.
Thus at room temperature, a i m square surface with 1 mg of enzyme
spread out on it should be able to handle all the oxygen passing through any
package film. One advantage is that both polypropylene and polyethylene
are good substrates for immobilizing enzymes. One factor to take into
account is the stability of the enzyme when bound to the film. An unknown
factor is how stable the enzyme will be on the film over time. Glucose
oxidase bound to a plastic surface has been shown to undergo a 50% drop in
activity in 2-3 weeks followed by little loss over the next four weeks.

The Japanese have worked on binding of enzymes to chitosan, which is an

insoluble polymeric carbohydrate from shellfish shells, but a 70% loss in
activity for bound glucose oxidase has been reported. Glucose oxidase
immobilized on polyethylenimine-coated glass beads retained 78-87% of its
activity and was more stable to heat inactivation. Since the enzyme is a
protein and can serve as a nutrient for microbes along with the glucose
substrate, a microbial inhibitor may be needed in the film.
Besides glucose oxidase mentioned previously, other enzymes have
potential. One such enzyme is ethanol oxidase which oxidizes ethanol to
acetaldehyde. The reaction is extremely rapid. Hopkins et a/. (1991) describe
a package in which alcohol or oxidase or cellular extracts of Pichia pastoris
cells containing alcohol oxidase are the enzymes used for oxygen scavenging in dry foods. An alcohol substrate either from the product or introduced
into the package from the exterior is required to remove the oxygen from the
package headspace.
7.5 Antimicrobial effects
The use of enzymes in active packaging to control microbial growth and
subsequent packaged-product degradation can be achieved by two independent approaches. By controlling the amount of available oxygen, selective
control of aerobic bacteria can occur. However, this method of bacterial
control can, under certain circumstances, allow the overgrowth of pathogenic anaerobic bacteria which, from a human view, may be worse than
aerobic bacterial overgrowth. A second approach that has been implemented
by several investigators is non-specific relative to oxygen requirements and
is a direct attack on the organisms present, independent of whether the
organisms are aerobic or anaerobic. This second approach can be either by
a direct attack on bacteria (both aerobic and anaerobic) or by the production
of broad-spectrum antimicrobial agents.
Neither the literature nor the memories of the authors indicates the
commercial implementation of the Fermco products. Meanwhile, the use of
immobilized enzymes in commerce has increased significantly. During the
1970s, Scott (1975), in his continuing research on the technology of glucose
oxidase, noted that catalase-free glucose oxidase might exert antimicrobial
effects due to the production of hydrogen peroxide. At the University of
Rhode Island, Rand and his co-workers conducted research and development
on catalase-free glucose oxidase as a food preservative, especially with
regard to fish (Field et aL, 1986).
The enzymes (not coincidentally, supplied by Fermco) were applied to
fresh flounder fillets or whole fish by dips, immersion in ice or by enzyme/
algin blankets. In some experiments, the enzyme system included catalase
and/or glucose. The university researchers' experiments (which had begun

during the early 1980s) demonstrated that the enzyme treatments retarded
the onset and magnitude of adverse microbiologically triggered spoilage
odors. The researchers explained the result as due to reductions in surface
pH under the refrigerated conditions of the test. These changes influenced
the metabolism of putrefactive microorganisms. They also suggested that the
generation of hydrogen peroxide might inhibit the growth of psychrotropic
microorganisms which are reported to be sensitive to the chemicals used.
Other possible microbistatic agents include gluconic acid, reportedly a metal
complexing agent, and gluconolactone, reported to be a binding agent for
water and metal ions. Another factor reported by the group was an altered
gaseous microenvironment in which oxygen in the muscle interstices was
depleted by the enzymatic action thus retarding the growth of aerobic
psychrophiles. This last, of course, is synergistic with the oxygen removal
aspects of the enzyme system.
The authors cited a Japanese patent in which catalase-free glucose oxidase
was demonstrated to be effective in preserving other proteinaceous foods
such as ground chicken and tofu (Fukazawa, 1980).
Although the Rand et al. work did not specifically state the incorporation
of enzymes into package materials, the implications were sufficiently clear
in the examples of the enzyme-containing ice and the enzyme-containing
algin blanket. Either of these could have been relatively easily substituted
with a skin package material which had been surface tested with the enzyme
system. The notion of hydrogen peroxide as an intentional active antimicrobial agent is somewhat of a contradiction since this chemical is quite
reactive with many food constituents, especially lipids, and residual free
hydrogen peroxide is not readily accepted by regulatory officials. If the
hydrogen peroxide is fully reacted with microorganisms as in aseptic
packaging, however, perhaps the proposed system may warrant further
consideration. Unfortunately, work at the University of Rhode Island on this
topic has been discontinued.
A German patent assigned to Continental Group (Anon. 1977) describes
incorporation of biologically active enzymes into polymers on the interiors
of package structures to destroy microorganisms of contained products. The
enzymes were intended to destroy microorganisms by breaking cell walls
and also to consume oxygen, thus increasing shelf-life without heat. The
applicable products were beer and fruit juices.
Enzymes such as muramidase for cell wall destruction and glucose
oxidase for oxygen interception were attached to the internal polymer by
covalent bonds. 'Non-essential' functional groups such as NH2, COOH, OH
phenol, imidazole and sulfhydryl were cited as examples.
The polymer was described as a terpolymer of monomer alkyl acrylate
and vinyl aromatic applied to the interior of a glass container from a solvent
and dried by heat. The enzyme was subsequently applied as a coating from
an aqueous dispersion.

Tests indicated highly significant reductions in oxygen concentrations

within the glass jars due to the conversion of glucose to gluconate in an
oxidative enzymatic reaction.
This appears to be the first reference to actually incorporating an enzyme
into an interior package wall to achieve an enzymatic antimicrobial
effect.
7.6 Time-temperature integrator-indicators
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 experience, 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 temperaturechange 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.

7.7 Lactose removal

Lactose intolerance is a dietary problem affecting a minor but nevertheless
substantial fraction of the population. Individuals affected by this problem
suffer from a lack of the enzyme lactase in their intestinal wall. Lactase is
necessary to break the disaccharide lactose, or milk sugar, into its
component parts glucose and galactose. Since lactose cannot be absorbed
from the gastrointestinal tract, its presence can cause discomfort in the form
of cramps, bloating, flatulence and diarrhea. Persons with lactose intolerance
either avoid milk or introduce lactase enzyme into their milk prior to
consumption.
A British patent assigned to Tetra Pak International AB (Anon., 1975)
describes incorporation of lactase into pasteurized or sterilized milk prior to
packaging to split the lactose after packaging. The lactose must be sterile
and is added aseptically. The patent notes that the milk must remain for
about a day at a temperature of at least 80C for the lactase to function.
The Tetra Pak approach differs from the previously discussed examples of
active packaging because the enzyme has no relationship to the packaging
material. Rather, a solution of enzyme is added directly to the individual
package just prior to sealing. In reality, the Tetra Pak approach is batch
processing done on a miniature scale, within the individual container.
However, this approach does point out that an active enzymatic process can
be carried out in a sealed container.
PharmaCal, Ltd. extended and improved the Tetra Pak approach and made
the process a true enzymatic active packaging process. Budny, at PharmaCal, Ltd. (1990) incorporated the lactase, using proprietary technology of
PharmaCal, Ltd. with the result that 30-70% of the lactose was removed in
24-36 hours at 3-4C. PharmaCal, Ltd. has proprietary designs and
approaches for commercializing this active package (Figure 7.2).

7.8 Cholesterol removal

The widespread information on the effects of excess cholesterol in the diet
does not require discussion here. To demonstrate the awareness in the USA
of the cholesterol content of foods, all food packages in the United States
must be labeled for cholesterol content.
Co-author Budny (1990) suggests the removal of cholesterol which is
present in whole milk by incorporating the enzyme, cholesterol reductase, in
the package structure. Using much the same proprietary technology of
PharmaCal, Ltd. as he employed for enzymatic oxygen removal or lactose
splitting, the fluid milk contents are exposed to the enzyme to convert its
cholesterol to coprosterol which is not absorbed by the intestine.
This system, illustrated in Figure 7.3, reduces the extensive in-plant
processing required by supercritical fluid extraction systems to produce
cholesterol-reduced fluid milk products. Rather, active packaging and the
technology of PharmaCal, Ltd. allows untreated fluid milk to be packaged,

Milk

Lactase
enzyme

Glucose

Galactose

Lactose

Outside
of
container

Container
wall

Inside of container

Figure 7.2 Lactose removal from liquid products.

Milk

Cholesterol
reductase
enzyme

Coprosterol

Cholesterol
Outside
of
Container

container
wail

Inside of container

Figure 7.3 Cholesterol removal from liquid products.

and in the time taken to transport the package to the consumer, it

conceivably could become free of cholesterol. While the commercial
implementation has not yet been completed, the component elements of the
application have been successfully demonstrated.
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 Biological 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.

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 isoascorbic 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.
8.2 Oxygen measurements
8.2.1 Techniques for measuring the oxygen content of bottles
Before withdrawing gas samples from a bottle for measurement, the bottle
should be equilibrated by shaking. The foam should be allowed to settle. For
a gas sample, this might require several hours. The sample is withdrawn
with a Zahm-Nagel device. Oxygen and nitrogen can be measured in a gas
sample directly by gas chromatography or by removing carbon dioxide,
separating the other gases and measuring with a mass spectroscopy detector.
Using chromatography, assumptions and corrections must be made to
determine oxygen. The advantage of the mass spectroscopy detector is that

argon is detected directly. Because nitrogen and argon do not react with the
bottle contents, other data can be gained by comparing the ratios of the three
gases. The total oxygen and nitrogen can be calculated from the measured
headspace, the temperature, and the oxygen and nitrogen concentration in
the head-space.
Liquid samples can be withdrawn and measured with polarographic
techniques. Again, the bottle should first be equilibrated. The total oxygen of
the bottle can be calculated.
Since the Zahm-Nagel device pierces the closure, each bottle can only be
sampled once. In order to follow the changes in the bottles, it must be
assumed that all the bottles were the same at bottling. This requires the most
reproducible conditions possible.
8.2.2 Results of measurements
Depending upon the equipment capability of the brewer, the oxygen content
of bottled beer can be seen to correspond to three categories of brewer:

Brewers incapable of performing a final blow down with purified carbon

dioxide and without new high technology fillers. The initial oxygen in
the package is about 1700 ppb. This decreases by 30% during
pasteurization, 42% the first day, 54% the second day, and 95% in a
week. The reaction of oxygen with the bottle contents is rapid. These
brewers usually compensate by adding 10 ppm or more of sulfur dioxide
to the beer.
Brewers capable of good oxygen control up to the last step, but do not
have new high technology fillers. These brewers provide an initial
oxygen content of about 900 ppb. The oxygen depletion in the bottle
proceeds at the same percentage rate as in the first category.
Brewers that use the best equipment available. The initial values vary
because maintaining the lower value requires the filler to be in top
condition. An initial value of 400 ppb is common. Brewers using 10 ppm
or more of sulfur dioxide obtain values of 200 ppb oxygen; brewers with
8 or less ppm sulfur dioxide experience values of 350-800 ppb of
oxygen depending on the maintenance of the equipment. The oxygen
depletion in the bottle proceeds at the same percentage rate as for the
other two classes.

The effect on flavor deterioration of bottling under different conditions is

difficult to gauge. Each beer is different, so comparisons must be made on
different crowns under the exact same bottling conditions on the same batch
of beer. The few valid comparisons made prior to the introduction of
scavenging crowns indicated that beer bottled with less oxygen had better
shelf-life.

8.2.3 Oxygen ingress

Closure of the bottle does not mean that the battle with oxygen is over. For
years a crown or closure was defined as a hermetic seal. Wisk and Siebert
(1987) at Stroh and Heyningen et al. (1987) at Heineken separately
challenged this assumption and came to the same conclusion: crowns allow
oxygen ingress. ZapatA Industries studied oxygen ingress in crowns;
Teumac, Ross and Rassouli (1990) confirmed the earlier conclusions, and
recommended some improvements to eliminate oxygen ingress. This work
was extended to include both plastic and aluminum closures (1991). The
concept of oxygen ingress into the bottle gained slow acceptance because it
is difficult to envision how oxygen will penetrate a bottle with 3
atmospheres of pressure within from an ambient pressure of 1 atmosphere.
The phenomenon has, however, been proven using several techniques by
several workers in the references cited above. It is based on a well
established equation that describes permeability through a permeable
polymer (the liner or gasket).
(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.
8.2A

Combining the effect of initial and ingress oxygen

The bottler must consider both the oxygen trapped in the bottle at filling and
oxygen ingress. For example, a brewer with good oxygen control techniques
will fill bottles with beer containing 50 ppb oxygen and entrap another 440
ppb. The initial oxygen level would be 490 ppb. A crowned 12 ounce bottle
will allow another 750 ppb to ingress in 3 months or 2000 ppb in 8 months.
The amount of oxygen available to react with the product can be calculated
from measurements and extrapolated.
The amount of oxygen that has reacted with the product can then be
calculated by subtracting the measured oxygen from the total oxygen

Hot melt
lueor
min. epoxy

Brass mtg. plate

Solder

Figure 8.1 Schematic of Mocon apparatus.

exposure (initial + ingress). The instruments cited are capable of making

meaningful measurements that reveal the oxygen chemistry taking place in
the bottle. All of the oxygen that gets into the bottle is either measurable or
has reacted. In other words:
OXYGEN (Initial+ Ingress) = OXYGEN (Measured) - OXYGEN (Reacted)
8.3 Oxygen scavenger liners
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.
8.3.2 Commercial activity
PVC compounds lend themselves particularly well to use as scavenger
additives. Plasticized PVC can tolerate fillers without significant loss of

properties and is sufficiently permeable to oxygen and water vapor to allow

good reaction rates. Polyolefins have sufficient oxygen permeability, but are
less permeable to water vapor.
(i) W.R. Grace, through Tapon France (a crown manufacturer), introduced
a scavenger product in a polyolefin liner to Heineken in the Spring of 1989.
Heineken dropped scavengers when they became more interested in other
aspects of crown performance.
Grace has published and been granted several patents on their scavenger
system. Essentially, they describe using ascorbates and similar chemicals
with or without sodium sulfite in a thermoplastic matrix. By reading the
patents and analyzing liner materials, it is evident that the Grace scavengers
contain up to 7% sodium sulfite and up to 4% sodium ascorbate. The
ascorbates by themselves are very weak scavengers, so the sulfite is required
for the rate of activity. For some beers the low activity is not a disadvantage
and may even be an advantage.
The exact extent of Grace's commercial success is not known outside of
Grace. It appears that a PVC compound is being used on a low alcohol beer,
Foster's Special Bitter. Courage Beer uses Daraform 6490 for the AnheuserBusch beer produced under license in the UK. Daraform 6490 is a polyolefin
liner compound containing an oxygen scavenger. A PVC compound from
Grace is being intensively tested at one major Canadian brewer and several
smaller US brewers. Trials are being performed with Daraform 6490 at
several European brewers.
(ii) Aquanautics Corporation, now Advanced Oxygen Technologies, Inc.,
had developed some expertise in removing oxygen from sea water and
recognized an opportunity in removing oxygen from bottles of beer. An
elaborate business plan was developed and eventually sold to ZapatA
Industries, Inc.
A joint effort was launched in early 1989. A system was developed that
was based on the beer chemistry described earlier. Several patents have been
granted and applications are in the process of being approved.
The new technology employs ascorbic acid as the reducing agent.
Alternatively, alkali metal ascorbates, alkali metal erythorbates, or erythorbic acid can be used. The addition of very small amounts of metal
catalysts to ascorbate or erythorbate-containing liners greatly enhanced the
rate of reaction with oxygen. The preferred catalysts are copper and iron
salts, but all transition metal salts increase the reaction rate. The amount of
ascorbate or erythorbate determines the oxygen reduction capacity; the type
and amount of catalyst determines the reaction rate. Placing the same
materials in a plastic liner earlier placed in beer greatly minimizes the fear
of product contamination. The small amount of catalyst enclosed in the
plastic liner yields undetectable amounts of leach in beer. Separating the
scavenger system from the beer, besides keeping it out of the beer, gives a
surprising benefit. Different reactions occur. Earlier workers had observed a

reversal of the benefits of adding ascorbates directly to beer; this is not

observed when the ascorbate is placed in the liner. Another surprising
benefit is that the reaction rate is significantly increased by placing the
scavenger in the liner. The reaction with oxygen is enhanced by the paucity
of moisture found in the liner.
The Aquanautics-ZapatA liner, Smartcap, was introduced in a controlled manner in 1991. There was concern that the new conditions created
in the bottle would cause off-flavors to be created. The brewers that started
using the liners commercially in 1991, and those that have started
subsequently, have not had a documented incident of off-flavor development
attributable to the liner. Smartcap and the improved PureSeal crowns are
marketed by ZapatA Industries and affiliated companies in other countries.
In 1993, over 1 billion PureSeal crowns were sold. Other crown manufacturers have been provided with lining compound for crown trials. ZapatA
provides trial recommendations and an oxygen testing service for PureSeal
trials. Trials at 60 brewers have proven that the liners always reduce the
oxygen level in the bottle and usually reduce oxygen damage to the beer
during storage. The difference is first noticeable between 1 and 3 months of
storage and is maintained to between 9 and 12 months.
8.3.3 Health and environmental concerns
This history implies ready acceptance by health authorities; each supplier
will document the acceptability to potential customers. The commercially
employed oxygen scavenging chemicals have not been listed as environmentally harmful.
8.4 The effect of scavenging closures on beer flavor
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).
8.5 The advantages of oxygen control bottles
The advantages are most obvious to exporters. There is little similarity
between beer purchased in the area of origin and that purchased elsewhere.
Beer carefully brewed to have certain flavor characteristics can now be
delivered to customers all over the world in shipments in the same
condition.
The effect on the bottle of day-to-day variations in oxygen level at the
filling line or between filling lines can be minimized. Most large brewers
have rigid standards on initial oxygen levels and dump beer that exceeds the
limit. Oxygen control bottles would allow raising of the limit.
Most beer is sold through distributors. Brewers lack the control they
would like on the distribution of their beer; by extending the expected shelflife, they can now lessen the concern on how long beer is on the shelves or
give the distributors more leeway.
Production departments can use oxygen control bottles as a tool to solve
manufacturing problems; for example, the limiting factor on how fast a
filling machine can operate is often the initial oxygen level.
Limitations of filling lines, the amount of oxygen, and the amount of
headspace place limitations on package design; with oxygen control bottles,
new packages can be designed for the same filling line.
Properly designed oxygen control bottles will provide a fresher tasting
beer compared to a bottle with a standard crown after approximately 30
days.
There is some evidence that reduction of oxygen in a package can reduce
spoilage caused by organisms. Acidic beverages, like beer, can be protected
by less severe heat or additive treatment. In fact, total removal of some
organisms has been achieved by rapid depletion of oxygen in the bottle. This
provides more freedom of design in the product, processing, package,
packaging materials, and distribution.
8.6 The future of oxygen scavenging closures
The use of oxygen scavenging crowns for beer is increasing rapidly.
Brewers will become more comfortable with this trend. At the same time,
the cost premium over standard crowns will diminish with increased
volume. Oxygen control liners should be used in the standard crown

employed by the beer industry. Oxygen control liners have been introduced
for aluminum roll-on closures to complete the closure requirements for
beer.
The use of oxygen control for other beverage products is a new frontier.
It is a relatively new industry involved in this field, differing in many
respects from the beer industry. Until recently, refined constituents such as
sugar, corn syrup, artificial flavors, and citric acid have been used. There
were relatively few substances that had the potential of becoming oxidized
to off-flavors. As beverage makers begin to use more natural materials such
as fruit juice, the potential for organoleptic problems increases. These
problems can be off-set with additives, but additives must be listed on the
label.
Wines and coolers also contain hundreds of organic compounds that can
react with oxygen. Wine chemistry has dealt with oxygen for centuries.
Wine makers understand the role of oxygen in maturation and/or spoilage in
wine; it is a matter of how much oxygen at what stage. Oxygen scavenging
closures can be part of the oxygen control procedure of a winery.
Many food products are damaged by oxygen. Damage might be in the
form of discoloration, change in texture, loss of flavor, or the generation of
off-flavors. The effect is obvious and well understood by food processors.
Sacrificial reduction of metal and use of preservatives are becoming less
acceptable. Package oxygen control affords a different means of protecting
food from oxygen damage.
Measuring techniques and equipment are now available for evaluation of
the control of oxygen in any package. Nonetheless, 'quick and dirty'
methods are commonly found. This lack of precision will lead to faulty
conclusions or indicate no significant difference. Control of the initial
oxygen content and a valid means of measuring a change in properties are
essential features. The food scientist should become familiar with the latest
developments and only then very carefully plan and execute experiments.

References
Gray, P., Stone, 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.

Commercial applications in North America

S. SACHAROW

9.1 Packaging overview

Packaging exists because it performs four basic functions which may vary in
importance depending on the nature of the products and their modes of
distribution.
The classic functions are:
1.
2.
3.
4.

Protection
Containment
Information
Utility of use

In recent years, these properties have been expanded to include both the
environmental disposability of the package material as well as the ability of
the package to perform far beyond the inherent property of the package
media. This may include characteristics such as enhanced shelf-life, the
ability to 'cook' the product or other changes in the product caused by the
packaging material.
Active packaging is the term used for a package that changes the
characteristics of the product packaged. Examples of active packaging
existing in the North American marketplace will be discussed in this
chapter.
9.2 Marketplace susceptors
In its classical definition, an active package (within the microwave field) is
one that changes the electric (or magnetic) field configuration and ultimately
the heating pattern of the product packaged (Packaging Gp., 1987).
Susceptors (also sometimes called receptors) are materials which convert
sufficient microwave energy into heat to result in temperature increases that
exceed those produced by either the direct heating of foods or the boiling of
water into moisture vapour. Temperatures high enough to produce drying,
crisping and ultimately browning result, thereby yielding the desirable
effects associated with conventional infrared oven cooking. Microwave
cooking alone produces temperatures limited by the temperatures developed
by the food components, especially water, sugar and fats, in response to
excitation.

Foods containing mostly water, such as vegetables, thus reach boiling

temperature. If heating continues in the absence of sufficient relief of
internally-generated pressures, bursting can result. Thus potatoes baked
in the microwave are first deeply pierced so moisture has exits.
Foods containing fat, such as bacon, reach temperatures of frying, which
may exceed 2000C (392F).
Foods containing mixtures of water and sugars or fats achieve temperatures determined by the concentrations and distributions of ingredients, limited of course by the exposure time. This complicates the
heating of meals made up of foods differing in response to microwaves,
such as vegetables with gravy-covered meat, mashed potatoes and a
dessert of cherry cobbler.

Foods that require surface drying include pastries, breads, pizza crusts, and
other dough-based compositions. Crisping and sometimes browning is
needed in some of these same foods and additionally in certain meat
products as well as roasts.
Microwaves are not yet suited for crisping and browning. They must
rather be implemented with some method of raising local temperatures to
1500C or higher (3000F or higher) to make them function as do browning
dishes and conventional ovens or frying pans. Methods include (1) use of a
browning element, an infrared heating source such as a heating coil, in the
oven to provide air at temperatures up to 2500C (4800F); and (2) a surface,
a susceptor, which reacts to microwaves by becoming hot enough to create
the desired temperature.
The characteristic temperature-time curves for foods in a microwave oven
vary over a considerable range. Among dry foods, watery and high moisture
foods, foods containing fats and oils, and sugary foods, there can exist orders
of magnitude differences in heating rate, exacerbated by initial temperature
and specific composition. Susceptors help to overcome these differences.
Two outcomes are desired of a susceptor:

rapid rise to the required temperature

constant temperature thereafter

Only the first of these has been achieved in practice, but self-limiting
susceptors that satisfy the second are receiving considerable research
attention and should be on the market within a few years.
9.2.7

Susceptor types

In the parlance of deposited films, 'thick' and 'thin' are differentiated by the
form which the deposited material takes during the deposition process.

thin films are direct condensations of individual atoms, ions or molecules

onto a substrate

thick films are deposits onto a substrate from dispersions of the material
as, for example, from a paste

Thin films may be only a few angstroms up to a thousand or more angstroms

(1 angstrom = 10~8 cm = c. 4 x 10~9 inch) in thickness; as deposition
continues, thickness increases.
The most interesting and potentially most useful effects pertaining to
aluminium in microwave packaging are those which occur at thicknesses
corresponding to Macbeth optical densities (OD) between 18 and 28. These
coatings are largely transparent to visible light (% transmission c. 50%) and
in fact overlap the lower end of the range of thicknesses used in window
films. In this range, particles form a discontinuous film of non-uniform
thickness - an array of electrical resistances - which responds to microwaves by becoming increasingly hot, through ohmic heating. At thickness
yielding OD = 35, arcing occurs.
Thickness is a misleading term to apply to these extremely thin coatings because
their surfaces are quite irregular; perhaps the root mean square thickness might be
more apropos.
Early susceptors (c. 1986 - 1987) yielded promising heating results which
produced the desired cripsing and browning, but they also produced
problems in some cases, which since that time have been largely corrected
or eliminated entirely. Two examples are:
(i)

(ii)

A strong unpleasant odour, emitting from the oven or on opening the

door after heating, emanated from the paperboard substrate, the
adhesive, the film base or metal or combinations;
Uneven crisping, or lack of crisping in some areas of the food when
other areas were done, detracted from the favourable impression this
new technology offered.

In addition, the rapid growth in use of compact ovens, typically less than
500 W and 201 capacity (0.7 cf) sharply increased demand for convenience
foods most likely to require crisping and browning. The accompanying rush
to formulate suitable foods and packages led to some sub-optimal results.
Most of the recent offerings of susceptor-crisped foods seem to overcome
the early problems, though some remain, especially in the frozen category
where uniform temperature attainment is difficult at best. In tests of oval
cross-section frozen dough-encased pasties (meat pies), centre line temperatures from middle to ends after the recommended heating time varied
from 71-27C (160-80 0 F) and were not improved with additional heating up
to the maximum recommended using the sleeve susceptors provided.
Moreover, the susceptor efficiency was noticeably better at the base of the
pies than at the upper surfaces. Standing time of 5 min narrowed the
difference between highest and lowest temperatures from 44 to 33C (80 to
60 0 F).

Further advances in susceptors technology are anticipated. A key need is

a susceptor the temperature of which rises quickly to the desired value and
holds it nearly constant for the time required. Such a self-limiting device
may be found in current early stage research and development activities.
Susceptors are made of either aluminium or stainless steel deposited on
substrates. Other metals may be used in the future. The practical application
of microwave-susceptible materials to heating of foods is to produce
crisping and browning (see Table 9.1). Two classes of materials are
available for producing susceptors;
(i)

Resistive coatings, i.e. materials whose electrical resistance in the form

in which they are deposited is high enough to produce ohmic
heating;
(ii) Ferromagnetic/electric materials.
Resistive coatings are currently used exclusively in susceptors, but the
second class may become important when the expected technology is
developed during the next five years. These latter offer the possibility of
setting specific upper temperature limits on susceptors, thus overcoming
some of the disadvantages of resistive coatings, such as local hot spots, and
charring. In an experiment with a sleeve susceptor around a frozen waffle,
the time of microwaving was extended by one-fourth with the result that the
sleeve and the waffle began to char.
Susceptor substrates thus far have been limited to polyester films and
paperboard. Other materials may find use for specific reasons, not least of
which could be greater resistance to heat as higher temperature performance
is achieved. Engineering thermoplastics including the liquid crystal polymers, polysulfones, polyarylenes, nylons, and others listed among high
temperature tray materials for dual oven ware, are potential candidates.
9.2.2 Field intensification devices
Field intensification devices focus microwave energy to increase local
intensity above that which would otherwise exist. FIDs therefore function in
a manner similar to optical focusing lenses. The extent of intensification
depends on the geometrical design of the focusing system - a metal antenna
- and the distance of the target plane(s) from the antenna.
Alcan, Ltd., calls their MicroMatch system for field intensification a
field management system which focuses and directs the incoming energy. In
development of the MicroMatch container, Alcan found that efficient
designs consisted of patches of aluminium arranged on a polymeric,
microwave-transparent, snap-fit dome used as a cover for the food tray. The
dome positions the aluminium array with respect to the food and, by virtue
of an overlap of the tray, precludes direct contact of the tray with oven walls,
thereby reducing the chance for arcing to occur.

Table 9.1 Comparative performance of various susceptor technologies

Technology
name

Even
heating

Commercial
status

Depends on product
packaged

Excellent

Limited success.
Now being licensed
under technical
agreeemnt. Presently
there are two paid
licensees in North
America. Only one
commercial product
in North America,
'Meals on Wheels'.

Cumbersome
Expensive
Over-engineered
No tray use

Good

Good

1. Excellent
2. Excellent
3. Good

'Accu-Crisp is the
mainstay' as a
'patterned susceptor'.
Other two are not yet
commercial.

Gaining one
customer per month

Printpak, Inc.
Deposition Technologies,
Inc. (San Diego, CA)

Good

Excellent rapid
heating

Good

Only use is in pizza

boxes (Healthy
Choice brand).

Rapid heating for

French fries and
pizza

Dupont, Inc.
1. Cello-based
demetallized
2. PET stainless
steel metallized
film

Printpak, Inc.
(licensees)

Good

Good

Not yet commercial;

however, one product
on market has been
withdrawn.

Still somewhat on
drawing board

'Micromet'
(pattern
susceptor)

Lawson Mardon
Midsomer North (UK)

Excellent

Only limited
commercial trials. No
market success.

About to be taken
off R & D program

Firm

Browning

Crisping

'Micro-Match'

Alcan, Ltd (Montreal

PQ)

Good

1. 'Acan-Crisp'
2. Accu-Wave'
3. 'BarrierWave'

Printpak, Inc.
Advanced Dielectric,
Inc.
(Taunton, MA)

'Susceptor Film'
'InconaT (Alloy
metal)

Excellent

Good
Good

Comments

No commercial application for MicroMatch is yet in place, but licensing

is reportedly underway in the USA and Germany. Alcan has concluded that
acceptance would be enhanced if packaging companies better known in the
food industry were to handle commercialization.
Aspects of the system which appear to make it attractive include:

the ability to design the antennae to provide optimal focusing on

different areas of food, thereby facilitating heating of each food in a
multi-component meal to its proper temperature
faster heating
relatively direct application in manufacturing and ease of changing the
required patterns to fit individual food suppliers' needs
functioning from above and without direct contact with the food makes
possible the browning and crisping of foods having soft and sticky
surfaces, which is not feasible with contact susceptors

Use of the MicroMatch container does not always obviate the need to rotate
the food to achieve even heating - many cheaper MW ovens have no mode
stirrer.
The aluminium tray is coated to lend greater assurance against arcing.
Coating increases the electrical potential required for arcing from 30 000 V
to c. 50 000 V, but arcing can occur in either case. Another reason for
coating that is not usually mentioned is that coating improves appearance
and corresponding consumer appeal.
Thus, a FID dome on an aluminium tray directs and focuses energy to
provide both control for uniformity and a means of regaining the speed lost
by virtue of the tray's inability to transmit MW energy. A FID dome on an
aluminium composite tray in which the tray base is plastic or paperboard
would overcome the speed loss and would supposedly heat food faster than
the same tray without the field intensification.
Cost of the FID dome will no doubt be a major factor in determining its
market niche. The extra space required to accommodate the dome shape and
its manufacturing cost will likely limit its use to the more expensive meal
offerings. Consumers will require convincing evidence of resulting better
quality.
9.2.3 Susceptor applications
There are numerous packages in the supermarket that utilize susceptors from microwaveable popcorn (reducing the amount of unpopped kernels) to
microwaveable pizza (offering a crisp crust). In addition, entrees, fruit pies,
meat pies and various 'crust' items lend themselves quite well to susceptor
utilization. Susceptors have been used in Israel for bourekas, New Zealand
for French Bread, the UK for pappadums, and in Sweden for frozen meat
entrees.

9.3 Application of temperature indicator to microwaveable

packaging
An interesting American microwave innovation not utilizing a susceptor, but
still an * active package' form is a microwaveable polypropylene bottle for
pancake syrup.
Squat PP jugs of Hungry Jack pancake syrup to be heated in household
microwave ovens feature thermographic 'temperature indicator' labels that
tell consumers when the syrup is hot.
Developed by Pillsbury Co., Minneapolis, MN, the microwave-ready
bottles are currently in supermarkets across the USA.
The 24 oz bottles stand 16.8 cm (6 in) high 13.0 cm (5 g in) wide, and
7.0 cm (21 in) deep. Like their counterparts, the MW bottles incorporate front
and back paper spot labels. But, on the MW bottles, the face of the front labels
features an illustration of a microwave oven. On the shelf, the door of the oven
appears black. But, when the bottle is put in an oven and heated to bubbling
according to directions on the black label, the black oven door on the front
label fades to yellow and the word 'HOT appears in the centre.
Extrusion blowmoulded by Continental Can Co., Syosset, NY, the squat
PP bottle incorporates a fat, hollow handle that is pinched closed where it
joins the container's body and shoulder. The handle design is meant to warn
consumers and prevent them from burning themselves when handling the
heated bottle.
9.4 Active packaging - produce
9.4.1 Oya produce bags
Evert-Fresh, a company in Houston, Texas makes a new kind of bag for storing
produce (Evert-Fresh, 1994). The greenish polyethylene bags are impregnated
with a finely ground stone of the zeolite family that has high absorption
properties. (Similar minerals are used to make products like Odor Eaters for
shoes.) In the bags, the mineral absorbs ethylene gas, which is given off by
many fruits and vegetables and hastens ripening. By absorbing the gas, the
bags slow down the ripening process and keep foods fresh longer.
The bags also have minute pores that allow the gas to escape and prevent
the accumulation of moisture that could result in the development of
bacteria. The bags are re-usable if rinsed and turned inside out to dry.
'Evert-Fresh Bags' are reported to be impregnated with processed Oya
Stone which has its origins in a cave in Japan. The cave has been used for
three centuries to store fresh produce. The success of this cave as an ideal
storage space can be attributed to constant levels of high humidity, static
temperature, darkness and, most importantly, the ability to absorb the gases
discharged by the stored produce. The study of the caves gave scientists the

key to developing the Evert-Fresh film that absorbs ethylene, maintains

humidity, is permeable to other gases, and, when refrigerated, maintains
temperature control. AU of these are major factors in successful long-term
storage of produce.
9.4.2 Oya test results
A substantial portion of the vitamins and minerals in the American diet come
from fruits and vegetables. Approximately 50% of the vitamin A and over 90%
of vitamin C come from this food group. Stability of vitamins in produce is
affected by a number of factors, including heat, light, oxygen and pH.
For example, testing with vegetables, such as whole cabbage and green beans,
has demonstrated that the susceptibility to heat destruction of 3-carotene, which
is a pre-cursor for vitamin A, can depend upon the nature of the vegetable.
Control of temperature and humidity are necessary since if low humidity
conditions prevail, rapid transpiration occurs and vegetables wilt. Under these
conditions, vitamin C and (3-carotene losses in leafy vegetables are well over
50%. Also proven is the use of modified atmosphere storage to control the
carbon dioxide and oxygen levels which affect vitamin C retention.
It is reported that this bag does effectively reduce vitamin loss.
Specifically, the bag is green in colour to reduce light transmission and made
breathable to enhance the transpiration of gases (O2 and CO2). Combine
these two elements with modern refrigeration (temperature) and three of the
four factors that affect vitamin retention are excluded. Storage evaluations of
leaf spinach, lettuce, broccoli, cabbage and green beans indicated that
vitamin C loss was reduced in excess of 50% using the Evert-Fresh bag for
long term storage.
Tests regarding vitamin C retention using the Ever-Fresh bag and ordinary
polythylene bags were conducted in Japan by the Consumer's Products
Company. The Vitamin C contents were determined using the Indophenol
Method.
Broccoli
After 3 days
After 6 days
After 12 days

Evert-Fresh
95%
90%
77%

Polyethylene
90%
80%
50%

Final results indicated that Evert-Fresh reduced vitamin C loss by 54% over
a 12 day storage period during the broccoli test.
Crown Daisy
Evert-Fresh
Polyethylene
After 12 days
60%
40%
Final results indicated that Evert-Fresh reduced vitamin C loss by 50% over
a 12 day storage period during the Crown Daisy test.
CROWN DAISY is an edible flower popular in Japan

9.4.3

Modified atmosphere produce

With the exception of the Oya type consumer produce bags, the trend toward
fresh produce has resulted in products such as fresh cut packaged vegetables.
These are prepared using ultra-clean processing and packaging. The rate of
package material gas permeation is controlled to allow for natural respiration
to occur with the product distributed under refrigerated conditions. While
not strictly an 'active' package form, the concept does utilize controlled
permeation.
9.5

Oxygen absorber food applications

In 1977, Mitsubishi Gas Chemical introduced 'Ageless' oxygen absorbers in

Japan, and now reportedly command over 70% of the 10 billion unit per year
Japanese market; the remaining 30% is shared by approximately 15 other
Japanese producers. In 1988 Multiform Desiccants introduced Fresh Pax
oxygen absorbers (Figure 9.1), as the first US producer of oxygen absorbing
packets. Between 1988 and 1994 Multiform developed a family of products
to meet the specific needs of the North American marketplace (Multiform,
1994). Products are designed to be moisture-activated preventing primary
oxidation until time of use, while others are for dry applications, or for

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

9.5.1 Bottle closures - oxygen scavengers

This subject has been extensively discussed in Chapter 8. Aquanautics Corp
is the developer of 'Smartcap', marketed by ZapatA Industries, and used in
various beer bottle crown liners. At present, an estimated 20 microbreweries
use the Pureseal liner in various applications. No large volume beer
application yet exists; however, ZapatA is actively pursuing this market
(ZapatA, 1994). Microbreweries using ZapatA's PureSeal include Sierra
Nevada Brewing Co., Cellis Brewing Co., Abita Brewing Co., and Full Sail
Brewing Co.
9.6 Other applications
International Paper, Purchase, NY, has developed an odour-trapping paper in
conjunction with UOP, Des Plaines, IL supplier of Abscents deodorizing
powder.
The powder, which absorbs odours instead of masking them, makes up
30-35% of the paper's weight, replacing clay and other fillers typically used
in paper. Paper made with Absents powder has been tested in surgical face
masks, feminine hygiene products, and filters. International Paper is still
investigating uses to see if paper with Absents is a viable, cost-effective
product.

International Paper foresees applications in the medical industry, food

packaging and household deodorization. The company is also testing uses
for automotive products.
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

Time-temperature indicators are part of the developing interest in intelligent

packaging, and there has been considerable interest in small temperature
indicators (TIs) and time-temperature indicators (TTIs) for monitoring the
useful life of packaged perishable products. There are over 100 patents
extant for such indicators based on a variety of physico-chemical principles;
however, widespread commercial use has been very limited for a number of
reasons. For example, TTIs must be easily activated and then exhibit a
reproducible time-temperature dependent change which is easily measured.
This change must be irreversible and ideally mimic or be easily correlated to
the food's extent of deterioration and residual shelf-life.
TTIs may be classified as either partial history or full history indicators,
depending on their response mechanism. Partial history indicators will not
respond unless some temperature threshold has been exceeded, while full
history indicators respond independent of a temperature threshold. This
chapter reviews some of the physico-chemical principles utilised by different
types of indicator, and discusses the various issues concerning their
application, including consumer interests. Similar principles are being used
in indicator systems for validating heat processes, and some of the latest
research directions are highlighted.
10.1 Introduction
Time-temperature indicators are one example of intelligent packaging, and
interest in this is growing because of the need to provide food manufacturers, retailers and consumers alike with assurances of integrity, quality
and authenticity. Other intelligent product quality indicators might include
microwave doneness indicators, microbial growth indicators, and physical
shock indicators. No microbial growth indicators are commercially available
yet, but they are likely to be based on the detection of volatile microbial
metabolites such as CO2, alcohols, acetaldehyde, ammonia and fatty acids.
Tamper evidence and pack integrity indicators are perhaps the most well
developed category. The most familiar types include the physical barriers
such as plastic heat shrink sleeves and neck bands; tape and label seals; and
paper/plastic/foil inner seals across the mouth of a container. More
sophisticated systems include Vapor-Loc introduced by Protective Packaging Ltd. (Sale, UK) which provides a tamper evident recloseable pouch that

combines the security of a barrier pouch with the ease of a recloseable zipper
seal. Secondary tamper evident features rely on subtle devices based on
chemical reactions, biological markers, and concealing techniques. Some
that are now commercially available utilise pattern adhesive labels and tapes,
solvent soluble dyes and encapsulated dyes, optically variable films and
holographic tear tapes.
A number of other developments are on the horizon, including the
application of smart cards within caps, magnetically coded closures and
electrochemical devices. However, gas sensing dyes are the most advanced,
especially for modified atmosphere packs. For example, a CO2 sensing dye
could be incorporated into the laminated top web film of a modified
atmosphere pack, and this could be designed to change colour when the CO2
level falls below a set concentration. In the area of product authenticity and
counterfeiting, there is a large range of intelligent package devices which are
being developed for use in various industrial sectors. Some of these will be
applicable to the food industry and include the use of holograms,
thermochromic and photochromic inks, IR and UV bar codes, biotags,
optically variable films, computer scrambled imaging, electromagnetic ink
scattering, and so on.
There is continuing interest in the monitoring of temperature in the food
distribution chain from factory to the consumer, and temperature monitoring
and measurement, particularly of chilled foods, have been discussed by
others (Woolfe, 1992). As part of the approach to assuring product quality
through temperature monitoring and control, attention has focused on the
potential use of indicators. Temperature indicators may either display the
current temperature or respond to some predefined threshold temperature
such as a freezing point or a chill temperature such as 80C. TTIs usually
utilise a physico-chemical mechanism that responds to the integration of the
temperature history to which the device has been exposed. Many different
types of indicator have been devised over the years and general reviews have
been presented by several authors, including Schoen and Byrne (1972)
covering patent literature from 1933 to 1971, Cook and Goodenough (1975),
Kramer and Farquhar (1976), Olley (1976, 1978), Farquhar (1977), Schoen
(1983), Ulrich (1984), Selman and Ballantyne (1988), Bhattacharjee (1988),
and Selman (1990).
In general terms, indicators must be able to function in order to monitor
one or more of the following.

Chill temperatures (go/no go basis).

Frozen temperatures (go/no go basis).
Temperature abuses.
Partial history (response over threshold).
Full history (continuous response).

In order to achieve the monitoring objectives, there are several important

requirements for indicators, including:

Ease of activation and use.

- Indicator may need to be stored and stabilised below threshold
temperature for several hours before use
Response to temperature or to cumulative effect of time and temperature.
Response accuracy, time and irreversibility.
Correlation with food deterioration.
Correlation with distribution chain temperature/time.
The sensory quality of food deteriorates more rapidly at higher temperatures
due to increasing biochemical reaction rates. Such increasing reaction rates
are often measured in terms of Q10 (the ratio of the rate at one temperature
to that at a temperature 100C lower). For many chemical reactions Q10 has
a value around 2, i.e., the reaction rate approximately doubles for each 100C
temperature rise. As different foods lose quality at different rates, it may
therefore be important that the indicator reaction has an activation energy
that is similar to that of the food deterioration (Taoukis and Labuza, 1989a;
1989b). This is important for two reasons: firstly, the deterioration rates of
stored foods follow similar patterns, although Q10 values may be higher, say
from 3 to 20; and secondly, chemical reactions can be used in indicator
systems so that by design the reaction rate can be made similar to that of the
rate of deterioration of the food. Tables of product activation energies or Q10
values have been given by Hu (1972) for ambient shelf-stable foods, by
Schubert (1977) and Olley (1978) for frozen products, and by Labuza
(1982), and Hayakawa and Wong (1974) for the scientific evaluation of
shelf-life.
10.2 Indicator systems
There are a variety of physico-chemical principles that may be used for
indicators, including melting point temperature, enzyme reaction, polymerisation, corrosion, and liquid crystals. Using these systems, many indicators
give one of three responses: colour change, movement, or both colour
change and movement. A variety of patents have been recorded and some of
these are summarised in Table 10.1; a number of types of labels are
discussed below.
Liquid crystal graduated thermometers may be familiar to some (e.g.
those manufactured by Liquid Crystal Devices Ltd., Ruislip, UK), and they
can be engineered in different ways, e.g. as a sticky-backed paper label
(Avery Label Systems Ltd., Maidenhead, UK) or designed to show selected
temperatures as with the Hemotemp II (Camlab, Cambridge, UK). The

Table 10.1 Some recent patents - Cold chain monitoring systems

Thaw Indicators - Based on Ice Melting
Bigand, F.M.

French Patent 2626-668A 29.01.88

This device reveals an indicator when the frozen liquid thaws

Fauvart, J.

French Patent 2616-596A 06.01.89

This is a defrost indicator which consists of blotting paper that

becomes coloured by afrozenaqueous dye when it thaws

Gradient, F.

French Patent 2641-61IA 09.01.89

A defrost indicator for frozen foods; it uses a windowed packaging

system to observe change of shape due to thawing

Holzer, W.

W. German Patent 3716-972A

20.05.87

This device makes use of an ice tablet and an empty chamber which
willfillup with water if the temperature rises

Holzer, W.

W. German Patent 3731-268A

17.09.87

This device consists in developingfrozenhemispheres of ice on the

surface. When these thaw they lose their shape

Japanese Patent 0031-809 21.07.82

This device consists of an evaluation indicator which is stable when

frozen but separates on thawing

British Patent 2209-396A 04.09.87

This indicator uses an irreversible change of state system: once a

temperature change occurs it is recorded

Minnesota Mining MFG

European Patent 310-428A

02.10.87

This consists of a microporous sheet which becomes wetted when the

liquid thaws. The process is irreversible and operates quickly

Mitsubishi Heavy Ind. KK

Japanese Patent 2021-229A

08.07.88

Use of vegetable leaves to indicate thawing - green colour turns to

black; irreversible on thawing

Perez Martinez, F.

European Patent 2002-585A

10.03.87

This device is a sealed unit containing ice which changes shape on

thawing

Perinetti, B.

French Patent 2625-599A 28.01.88

Sphere of ice suspended in the centre of a capsule

Toporenko, Y.

French Patent 2626-072A 20.01.88

This device has a geometrically shaped column of ice coloured with

phosphorescent material at the centre. Loss of geometry indicates
thawing

Uberai, B.S.

French Patent 2441-076A 23.12.88

Solvent/membrane indicator; when solvent melts colour is developed

Wanfield-Druck KaId

W. German Patent 2824-903C

13.10.88

Bi-metal stripflexesto display colour to indicate critical temperature

reached

KAO Corp.
Levin, D.

Table 10.1 Continued

Electrochemical Time-Temperature Devices
Grahm, I.

World Patent 9004-765A 24.10.88

Also US Patent 4929-020A

Temperature history indicating label; the electrodes of a galvanic circuit

form a temperature-responsive device

Johnson Matthey

US Patent 4804275 14.02.89

Tungsten trioxide electrode/weak acid

Toppan Printing KK

Japanese Patent 1141-973A

28.11.87

This is a time indicator to show the expiry of foods started at ambient

temperature. The device consists of a dye diffusing into a gel; the rate
is determined by time and temperature

Toppan Printing KK

Japanese Patent 1250-090A

03.12.87

Twin lapse display. Dye diffusion in agar. With retarder, e.g. albumin

Badische Tabakmanuf

W. German Patent 3907-683A

09.03.89

Time-temperature indicator based on colour development with time

when two chemicals are brought into contact, e.g. amino compounds,
hydroquinones, quinones and nitro compounds

Bramhall, J.S.

US Patent 4825-447A 21.09.87

This sytem comprises liposomes containing a quenched fluorescent dye.

Thefluorescenceis released by lysis when the product temperature
fluctuates. It measures positive and negative temperature deviations

Lifelines Tech. Inc.

US Patent 4892-677 19.12.84

Diacetyiene monomer which polymerises to a dark compound, the

intensity of which depends on time-temperature exposure

Rame, P.

French Patent 2613-069A 25.03.88

A thermal inertia temperature indicator which reacts at a certain preset

threshold temperature. It is enclosed in a transparent case. It does not
react to short temperature changes

Three S Tech BV

Japanese Patent 1012-237A

22.06.87

This device consists of a microcapsule layer containing an achromatic

lactone compound pigment precursor and solvent. The sheet indicates
the time elapsed at 50C temperature intervals

Dry Diffusion in Gels

Chemical Reactions

Freezewatch indicator (PyMaH Corp., Flemington, NJ, USA) is, by contrast,

a simple irreversible indicator based on some threshold temperature,
compared to the reversible technology exhibited by liquid crystals. When
frozen, the liquid inside the ampoule freezes, causing it to break. If the
temperature rises to -4C, the liquid thaws and flows out, staining the
backing paper.
Chillchecker operates by means of a meltable, dyed compound contained
in a porous reservoir (Thermographic Measurements Ltd., Burton, UK). In
the inactivated form, a domed indicator paper is separated from a reservoir
by a small distance. When the dome is pressed, the two materials come into
contact, allowing wicking to occur when the melt temperature is reached.
The Chillchecker can be designed for different threshold temperatures, e.g.
+ 9 or + 200C. Thermographics (see above) have now launched the
Thawalert, a self-adhesive label (18 mm in diameter) which utilises
temperature sensitive paints chosen to respond at a variety of threshold
freezing and chilling temperatures. The above types are based on simple
colour development; others quantify the change.
Ambitemp (Andover Monitoring Systems Corp., Andover, USA) was a
time-temperature integrator which functioned with a fluid that has a specific
melting point related to the product to be monitored. Under abuse conditions
the melted liquid moves along the capillary tube. Tempchron (Andover
Laboratories Inc., South Weymouth, USA) was a more recent version of
Ambitemp which gave a read-out in degree minutes that could be interpreted
from a chart. Although these two did semi-quantify the changes, their size
and cost did not meet the further important requirements for the indicators to
be simple, small and inexpensive.
3M Monitormark indicators consist of a paper blotter pack and track
separated by a polyester film layer (3M Packaging Systems, Bracknell, UK).
Incorporated into the paper blotter pad are chemicals of very specific melting
points and a blue dye. The indicator is designed as an abuse indicator which
yields no response unless a predetermined temperature is exceeded. The
response temperature of the indicator is therefore the melt point of the
chemical used. To activate this partial history indicator, the polyester film
layer is removed, allowing the melted chemical and dye to diffuse
irreversibly along the track. The higher the temperature above the response
level, the faster the diffusion occurs along the track. If the temperature falls
below the response level of the tag, then the reaction stops. Each indicator
has five distinct windows which allow an estimate of exposure time above
present values to be made. Before use the indicator has to be preconditioned
by storing at a temperature several degrees below the response temperature
of the indicator, so that at the start of the reaction the chemical/dye mix is
solid. Response of the indicator is measured by the progression of the blue
dye along the track, and this is complete when all five windows are blue. An
indicator tag labelled 51, for example, would indicate a response temperature

(melt temperature) of 5C with a response time of 2 days. This response

refers to the time taken to complete blue colour for all five windows at a
constant 2C above the response temperature of the tag. Similarly, response
times of 7 days and 14 days are available on tags, with response
temperatures varying from -170C to + 48C (Byrne, 1976; Manske, 1983,
1985; Taoukis and Labuza, 1989a, 1989b; Morris, 1988; Ballantyne,
1988).
I Point labels are 'full history' indicators showing a response independently of temperature threshold (I Point A/B, Malmo, Sweden). The device
consists of a two-part material, one part containing an enzyme solution, the
other a lipid substrate and pH indicator. To activate, the seal between the
two parts of the indicator is broken and the contents become mixed. As the
reaction proceeds, the lipid substrate is hydrolysed and a pH change results
in colour change through four colour increments (0-3, green to red). This
reaction is irreversible and will proceed faster as temperature is increased
and slower as temperature is reduced. Each label has a colour scale to be
used as a matching reference, which can also be expressed as a percentage
of set time-temperature tolerance (TTT) elapsed (colour 1: 80% TTT; colour
2: 100% TTT; colour 3: 130% TTT). These labels have been the subject of
several studies (Byrne, 1976; Blixt and Tiru, 1977; Blixt, 1984; Singh and
Wells, 1987; Grisius et ai, 1987; Ballantyne, 1988; Taoukis and Labuza,
1989).
An alternative I Point indicator (type B) is also available. Each indicator
model is provided with the same time-temperature characteristics as type A,
but the difference occurs in the colour change interval. In model B only two
visible colours are seen: green and yellow. Only in the final 5% of preset
TTT (95-100%, time to colour in type A) does the indicator change from
green to yellow. So, whilst responding to the temperature history, the
indicators actually remain green for most of the storage life. The development of a yellow colour then indicates product approaching the end of its
shelf-life. This single colour change was designed to reduce variability in
colour determination by different personnel, which was a common complaint with type A models. A range of indicators (A and B with varying
TTT) are available, lasting from 2 years at -18C to 2 days at + 300C.
Activation energies of the models 2140, 2180 and 2220 range from 14.0 to
14.3 kcal/g mole (Wells and Singh, 1988c). The biochemical solutions must
be accurate; results may tend to become less reproducible at longer intervals.
Using the same technology, I Point have made a freezer indicator. Another
enzyme based time-temperature indicator has been experimentally developed by Boeriu et ah (1986). This is based on enzymic reactions taking
place many orders of magnitude faster in liquid paraffins than in solid ones.
The device works as a thaw indicator by triggering off an enzymic colour
reaction when the solid paraffin melts.

Lifelines' Fresh-Scan labels provide a full-history TTI, again showing a

response independently of a temperature threshold. The Lifelines system
consists of three distinct parts: a printed indicator label incorporating
polymer compounds that change colour as a result of accumulated
temperature exposure; a microcomputer with an optical wand for reading the
indicator; and software for data analysis (Lifelines Technology Inc., Morris
Plains, USA).
The indicator label consists of two distinct types of bar code. The first is
the standard bar code, providing information on product and indicator type,
and the second is the indicator code containing polymer compound that
irreversibly changes colour with accumulated temperature exposure. The
colour change is based on polymerisation of diacetylenic monomers, which
proceeds faster at higher temperatures, leading to more rapid darkening of
the indicator bar (Fields and Prusik, 1983,1986; Byrne, 1990). Initially,
reflectance of the indicator code is high (approximately 100%), subsequently
falling during storage as the reaction proceeds and the colour darkens. Once
manufactured, Lifelines' labels immediately start reacting to environmental
temperature. Therefore, to maintain high initial reflectance values, indicators
must be stored at temperatures of - 200C and below. Studies have found that
the colour changes correlate well with quality loss in tomatoes and UHT
milk, with activation energies for the indicators ranging from 17.8 to 21.3
kcal/g mole (Wells and Singh, 1988a, 1988b). The portable hand-held
computer reads both the bar codes and the indicator codes. The software
package has been designed to correlate reflectance measurements to
predetermined time-temperature characteristics. Data from the hand-held
computer are transferred to a host computer, product freshness measurements are entered into the system, and a comparison is made between the
product freshness curve and the response kinetics of the Lifelines labels
(ZaIl et al., 1986; Krai et ai, 1988). A mathematical model can then be
prepared to compensate for the differences in reaction rates of indicators and
product degradation and allow prediction of product quality from one
indicator reading. Trials at Campden and Chorleywood Food Research
Association found these labels to be more reliable than I Point indicator
labels (Ballantyne, 1988).
The Lifelines Fresh-Check indicator has been developed for the consumer
in a simple visual form (Anon., 1989). A small circle of polymer is
surrounded by a printed reference ring. The polymer, which starts out lightly
coloured, gradually deepens in colour to reflect cumulative temperature
exposure. Again, the higher the temperature, the more rapidly the polymer
changes. Consumers may then be advised on the pack not to consume the
product if the polymer centre is darker than the reference ring, regardless of
the use-by date (Fields, 1989). Once again the required polymer response
can be engineered. During the last two years several American companies
have been using these labels on a trial basis, and the system has been found

useful for determining shelf-life expiry when products are held under proper
refrigerated conditions. However, use is still limited by the lack of response
to short periods of temperature abuse, and the polymerisation reaction is
influenced to some extent by light. The latest types are light-protected by a
red filter. There is at present considerable interest in these indicators, for
example for fresh eggs where short time-temperature rises may not directly
affect quality. Lifelines Inc. also claim good correlation with the quality life
of cooked ready meals, fresh chicken and yoghurt. During 1991, Lifelines
continued to evaluate their polymer-based indicators used in both the food
and pharmaceutical industries, and their Fresh-Check label has been trialled
in some of the department stores of the French company Monoprix, where
they have been applied to over a dozen types of chilled retail products
(Monoprix, 1990). The most prominent of the indicators to date have been
the three referred to above, i.e., 3M Monitormark, the I Point type, and the
Lifelines Fresh-Scan and Fresh-Check. These have been the subject of a
number of independent validation tests, and the test systems and references
are given in Table 10.2.
Marupfroid (Paris, France) has developed a partial history freezer label
based on the melting point of ice. The part of the tag containing the redcoloured ice is located inside the pack next to the frozen food, with a hazard
warning area visible externally. If thawing has occurred, the red dye moves
along the label and exposes a warning printed in hydrophobic white ink. One
very important point must be highlighted here, and that is that all other
indicators are placed on the outside of a pack and therefore respond to the
environmental temperature. The packaging itself may provide the food with
some insulation from the environment and the food temperature will
therefore lag behind any changes in outside temperature. In the case of this
label, the indicator system is placed inside the pack but with its response
change visible externally.
Johnson Matthey has patented a system based on the corrosion of an
indicator strip (US Patent, 1989). It consists of a film of electrochromic
material (in this case tungsten trioxide), with a metal overprint at one end,
printed onto a card. The dissolution of the metal anode in acid is temperature
sensitive and results in a colour boundary which moves down the strip at a
rate governed by the temperature. The indicator can be engineered to
respond to short total times and shows some promise in this respect, and the
potential exists for miniaturisation of such indicators.
Oscar Mayer Foods Corp. (Madison, USA) have developed a quality
freshness indicator. This is based on pH-sensitive dyes in contact with a dual
reaction system which simultaneously produces acid and alkali to maintain
a constant pH. When one of the substrates becomes depleted, a rapid pH
change occurs, resulting in a sharp visual colour change (green to pink). A
rise in temperature causes a shift in the equilibrium and the colour
changes.

Table 10.2 Validation tests on time-temperature indicators

Model
Lifelines
Fresh-Scan
Fresh-Check

I Point

System test

Reference
0

Tomato firmness (10-20 C)

Microbial growth in pasteurised milk (0-50C)
Green tomato maturity (10-200C)
UHT sterilised milk (5-37C)
Fruit cake
Lettuce
Pasteurised milk (pallet)
Milk, cream and cottage cheese
Orange juice
UHT milk freshness
Orange juice concentrate (frozen)
Fresh produce (chilled)
Hamburger patties
UHT milk freshness (21-45C)
Orange juice (7.2C)
Response to isothermal conditions (4-300C)
Response to non-isothermal conditions (4-300C)
Response to temperature (0-370C)
Response to temperatures (5C and 100C)

Wells and Singh (1988a)

Grisius et al. (1987)
Wells and Singh (1988b)
Wells and Singh (1988b)
Wells and Singh (1988b)
Wells and Singh (1988b)
Malcata (1990)
Chen and ZaIl (1987a)
Chen and ZaIl (1987b)

Green tomato maturity (10-200C)

UHT sterilised milk (5-37C)
Fruit cake
Lettuce

Wells
Wells
Wells
WeUs

ZaHetal. (1986)
Krall et al. (1988)
Krall et al (1988)
Singh and Wells (1986)
Taoukis and Labuza (1989a)
Taoukis and Labuza (1989b)
WeUs and Singh (1988c)
Fields (1985)
Fields (1985)
Ballantyne (1988)
and
and
and
and

Singh
Singh
Singh
Singh

(1988b)
(1988b)
(1988b)
(1988b)

Table 10.2 Continued

Model

System test

Reference
0

3M Monitormark

Unspecified (two models)

Pasteurised whole milk (0 C, 5C and 10 C)

Hamburger rancidity (frozen)
Hamburger rancidity
Strawberries (- 12 to + 350C)
Seafood salad (pallets) (- 20 to - 100C)
Codfish(frozen) (pallets)
Steak, beef patties, macaroni cheese (pallets) (- 20 to + 300C)
Pizza (- 20 to + 300C)
Milk (4.4-100C)
Response to isothermal conditions (4-300C)
Response to non-isothermal conditions (4-300C)
Response to isothermal conditions
Response to isothermal conditions (- 18 to + 5C)
Response to isothermal conditions (+ 2C, + 100C, - 12C, -100C)

Grisius et al. (1987)

Wells et al. (1987)
Singh and Wells (1985a)
Singh and Wells (1987)
Singh and Wells (1985b)
Olsson (1984)
Olsson (1984)
Kramer and Farquhar (1977)
Mistry and Kosikowski (1983)
Taoukis and Labuza (1989a)
Taoukis and Labuza (1989b)
Wells and Singh (1988c)
Wells and Singh (1985)
Ballantyne (1988)

Hamburger rancidity (>- 17C)

Steak, beef patties and macaroni cheese (pallet loads) (- 23.4 to - 15C)
Milk (4.4-100C)
Response to isothermal conditions (4-300C)
Response to non-isothermal conditions (4-300C)
Response to isothermal conditions (4 - 1O0C)

Wells et al. (1987)

Singh and Wells (1986)
Wells and Singh (1985)
Kramer and Farquhar (1977)
Mistry and Kosikowski (1983)
Taoukis and Labuza (1989a)
Taoukis and Labuza (1989b)
Ballantyne (1988)

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 thermochromic 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.
10.3 Indicator application issues and consumer interests
It is generally agreed that there are a number of potential applications for
which the above-mentioned indicators could be used regarding the monitoring of various aspects and parts of the chilled and frozen distribution chains
(Singh and Wells, 1990). However, the industry has been expressing concern
regarding several issues about all types of indicator. TIs and TTIs represent
new applications of technology, with little or no history of successful and
reliable application, and until recently there has been no standard against
which their performance could be assessed. Also, the proliferation of TIs and
TTIs now being offered, involving many different forms of indication, is of
concern as this is likely to confuse the consumer. Provided these concerns
are addressed by a given indicator for a specified product (or range), the
potential exists for indicators to be used in several ways, including on pallets
or consumer packs, for stock rotation, parts or all of the distribution chain,
retail shelf-life, and as a simple consumer guide.
Ideally, chilled and frozen foods should be stored at the appropriate
temperature, which should remain constant. However, there may be several
points in the distribution chain where the environmental temperature is
raised. Such periods may be short, from a few minutes to several hours. To
date, most indicators will not react rapidly enough to respond to such
regimes. For example, a Lifelines indicator subject to 24 hours at 5C, six
hours at 100C, and two hours at 200C did not show a response that was
significantly different to the control at 5C (Ballantyne, 1988). Lifelines
have done work over the last two years and now claim that a dual chemistry
system can be engineered to specifications required. Therefore, there may be
some important limitations of some indicators that must be recognised, in
particular relating to reliability and reproducibility, sensitivity to short-timetemperature abuse, response to environment temperature but not necessarily
food temperature, and cost benefits. For example, in 1988 Lifelines bar code
labels cost 30-70p each (scanning system US$20 000), I Point labels 15-2Op
each, and the 3M Monitormark about 1.50, for small trial quantities. In
1991, Lifelines' prices in the USA ranged from 7.5 to 3.50 for bar code
labels and 3.5 to 1.250 for Fresh-Checks. The latter lower cost related to
production runs in excess of 10 million units.

To be effective and of value to manufacturer and consumer, TIs and TTIs

must provide an indication of the end-life of the product. This should be no
less clear and unambiguous to the great majority of the population than the
current minimum durability instruction. In particular, some consumers may
have difficulty in detecting the difference between two colours, or shades of
one colour, where this forms the end point. Related to this, the point at
which product life starts can be clearly defined for the purposes of declaring
a 'best before' or 'use by' date. It is essential that the start point of the life
of the TTI, i.e. when it is activated, can also be known for certain, with selfindication that this has occurred, and no reasonable possibility of preactivation, partial activation, or especially post-activation. The legal
requirement for a best before and use by date on the pack will continue for
the foreseeable future. Therefore, consumer instructions on the pack will
need to clearly indicate the action to be taken when there is conflict between
end of product life indication as given by the best before and use by date and
the TTI. There is also concern that where TIs and TTIs may have a role to
play with regard to product quality over life, unsubstantiated claims should
not be made regarding any role in relation to safety.
TTIs in general do not measure product temperature. Only one commercially available type is known, which is claimed to measure food surface
temperature. None is known to measure food centre temperature. Almost all
respond to temperatures on the outside of the pack, where there may be
some thermal insulation between product and indicator (Malcata, 1990).
Measurement at this point may be of value, but the limitations in terms of
usefulness and relevance of such measurement need to be made clear to the
user and the consumer. A TI or TTI which reflects product temperature
would be of far greater value and relevance than one which responds to the
temperature on the outer surface of the pack. A TI or TTI also needs to be
able to cope with fluctuating temperatures (including elevated temperatures
for a short time) and to respond accurately and reproducibly at the extremes
of temperature likely to be experienced by the product. A TTI may need to
mimic the growth of food spoilage microorganisms, or whatever other timetemperature related factor is liable to affect the quality of the foodstuff, over
the full range of temperatures likely to be experienced and when the
temperature fluctuates.
The quality management of the manufacture, distribution and storage of
the TTI and the reproducibility of its performance must be of at least as high
an order as the food product it seeks to monitor. In addition, there is concern
that the wrong TI or TTI may be applied to a given product. An incorrectly
applied date mark is self-evident, at least to the manufacturer at the point of
application. As manufacturers may be producing simultaneously a range of
products with different predicted lives, they will require a range of TIs or
TTIs designed with related performance characteristics. Hence, every
indicator should be supplied with a clear indication to the manufacturer,

distributor, retailer, and the enforcement authorities of the precise temperature threshold or time-temperature integration to which the indicator
will respond. The TI or TTI needs to be no less resistant to malpractice and
tampering than is the printed date on the pack. The indicator or the package
should self-indicate if removed from the product; at the same time, if
removed it should damage the packaging in such a way that a fresh indicator
cannot be applied without detection. Finally, TIs and TTIs in themselves
must not represent a hazard to the consumer, e.g. if swallowed. In particular,
care needs to be taken to make the indicator 'child-proof.
In order to address these issues of concern, the industry concluded
recently that a specification was required which could be common to all
types of TIs and TTIs, and which could be used by manufacturers of such
indicators in order to meet the requirements of the industry and of the
consumer. Such a specification would address the basic technical requirements for the performance of such indicators, although it is accepted that
commercial reasons may influence the decision to use indicators for a
particular application. A joint Ministry of Agriculture, Fisheries and Food
(MAFF)/industry working party met during 1991 at the Campden and
Chorleywood Food Research Association, and has completed a food
industry specification (George and Shaw, 1992). It is hoped that this will
provide a basis for indicator manufacturers to design the performance of
their indicators to meet the needs of the food industry, and at the same time
provide a basis for the users of such indicators to check the indicator
performance against their requirements. This specification defines the testing
scope for indicator type and application. It refers to the quality management
of the indicator manufacture, the indicator compatibility with food, the need
for evidence of tamper abuse, and indicator labelling. It then outlines test
protocols for indicator response to temperature, including temperature
cycling and abuse, and the evaluation of the kinetic constants of the
indicator. It covers evaluation of the accuracy of indicator activation point,
and the clarity and accuracy of end point determination, and finally
simulated field testing.
A survey of 511 UK consumers, carried out by the National Consumer
Council (MAFF, 1991), indicated that almost all respondents (95%) thought
that TTIs were a good idea, but only grasped their concept after some
explanation, indicating that substantial publicity or an education campaign
would be required. Use of TTIs would have to be in conjunction with the
durability date, with clear instructions about what to do when the indicator
changed colour. The relationship and possible conflict between the indication of the TTI and the durability date on the food was considered a problem.
In the retail situation, nearly half those questioned would trust the TTI
response if it had not changed but the product was beyond its durability date.
If the TTI changed before the end of the durability date when stored at
home, the majority of respondents (57%) would use their own judgement in

deciding whether a food was safe to eat, with at least 25% putting some of
the blame on the food suppliers. However, the value of TTIs was recognised
for raising confidence in retail handling, and improving hygiene practices
when food is taken home and stored in refrigerators. It is clear that there is
a future for TTIs in monitoring the chill chain. Development of different
indicators is still in progress and technical difficulties have to be overcome
by carrying out the appropriate tests (George and Shaw, 1992). However, the
consumer can appreciate the concept, and the advantages and benefits of
increased food safety for the higher-risk foods that would result.
10.4 Chemical indicators for thermal process validation
Similar approaches to temperature indication have been taken for assessing
pasteurisation and sterilisation processes, and some examples of commercially available indicator systems are summarised in Table 10.3. Most of
these tend to give qualitative indications. Current research is directed
towards evaluating new systems which may give precise quantitative
indication. Hendrickx et al (1993) have conducted an extensive review and
have classified time-temperature indicators, as shown in Figure 10.1, in
terms of working principle, type of response, origin, application in the food
material, and location in the food.
For biological TTIs, the change in biological activity such as of
microorganisms, their spores (viability) or enzymes (activity) upon heating
is the basic working principle. The use of inoculated alginate particles is an
example of the use of spores (Gaze et al, 1990). Recent studies on enzyme
activity have shown potential for the use of a-amylase, using differential
scanning calorimetry to measure changes in protein conformation (De Cordt
et al, 1994). Brown (1991) studied the denaturation of several enzymes and
suggested that an approach which measures the status of a number of
enzymes in terms of pattern recognition would be better than using a single
enzyme to indicate retrospectively the heat process that had been applied.
Brown (1991) also determined the feasibility and potential for ELISA
techniques for retrospective assessment of the heat treatment given to beef
and chicken. Marin et al (1992) studied the effects of graded heat treatments
of 30 min from 40 to 1000C on meat protein denaturation. They measured
the remaining antigenic activity of the meat proteins and found this was
significantly correlated with the heating temperature. Varshney and Paraf
(1990) used specific polyclonal antibodies to detect heat treatment of
ovalbumin in mushrooms, and could identify whether the ovalbumin had
been heated to lower than 65C or higher than 85C.
In terms of chemical systems, potential has been shown for correlating the
loss of food pigments such as chlorophyll, and changes in anthocyanins,
with heat treatment (El Gindy et al, 1972). Other food compounds may

Table 10.3 Commercially available time-temperature thermal process indicator/integrators

Manufacturer

Trade name

Colour

Change characteristics

3M Industrial Tapes and Adhesives

(Manchester, UK)

Autoclave Tape

White to black (stripes)

121C for 10-15 min and 134C for 3-4 min for
fully developed colour change

3M Industrial Tapes and Adhesives

(Manchester, UK)

Thermometer Strips

Silver to black

Immediately temperature reached

Albert Browne Ltd. (Leicester, UK)

TST

Yellow to mauve

Set to 121C for 15 min or 134C for 5.3 min

Albert Browne Ltd. (Leicester, UK)

Steriliser Control
Tube

Red to green

Steam autoclaves - colour change over 100-1800C

for a range of exposure times
Dry heat = 1600C for 120 min to 1800C for 12
min

Ashby Technical Products Ltd. (Ashby

de Ia Zouch, UK)

ATP Irreversible
Temperature
Indicators

Silver to black

Self-adhesive segmented labels giving colour

change when temperature exceeds set point by
1C

Cardinal Group (Tiburon, CA, USA)

Easterday

Black to red

Set at 2400C for 20 min, ketone based

Colour Therm (Surrey, UK)

Colour-Therm

White to black or red

Immediately temperature is reached

PyMaH Corp. (Flemington, NJ, USA)

(Temperature Indicators Ltd., Wigan,
UK Agent)

Cook-Chex

Purple to green

Irreversible indicator, eight ranges selectable, semiintegrators using chromium chloride complex for
different temperatures (110-126.70C) and times
(0-150 min) calibrated against spore destruction

PyMaH Corp. (Flemington, NJ, USA)

(Temperature Indicators Ltd., Wigan,
UK Agent)

SteriGage
Thermalog S

A blue colour front diffuses along

a transparent window of an
accept/reject band

The presence of saturated steam lowers the melting

point of a chemical tablet
Diffusion of the blue colour front has been
calibrated against spore destruction (B.
stearothermophilus) over a range of timetemperature combinations

Reatec AG (Switzerland) (Barbie

Engineering, Twickenham, UK Agent)

Reatec

White to black

Immediately temperature is reached: 54.4-1040C

Table 103 Continued

Manufacturer

Trade name

Colour

Change characteristics

Redpoint (Swindon, UK)

Spectratherm

From light blue to a colour in the

spectrum donating maximum
temperature

Liquid crystal colour change immediately

temperature is reached

S.D. Special Coatings (Barking, UK)

Temperature Tabs

Spirig Earnest (Germany) (Cobonic

Ltd., Surrey, UK Agent)

Celsistrip
Celsidot
Celsipoint
Celsiclock

Irreversible colour labels, 40-2600C; lacquers,

40-lOloC; reversible strips, 40-700C

SteriTec (Colorado, USA)

(Temperature Indicators Ltd., Wigan,
UK Agent)
SteriTec (Colorado, USA)
(Temperature Indicators Ltd., Wigan,
UK Agent)
Thermindex Chemicals & Coatings
Ltd. (Deeside, Clwyd, UK)

White to black

Immediately temperature is reached: 40-2600C

Mauve to green

Three-stage semi-integrator using chromium

chloride

Brown to black

Selected precise time and temperature, 121 to

134C

White to black

Adhesive strips 40-2600C

For crayons and paints, a range of

colours dependent on temperature
reached

Reversible and irreversible inorganic pigment

colour change either immediately temperature is
reached or after a few min exposure, 50-10100C

Integraph

Cross-checks

Thermindex

Thermographic Measurements Ltd.,

Burton, S. Wirral, UK (Temperature
Indicators Ltd., Wigan, UK, European
Agent)

Pasteurisation
Check

White to black or white to red

Immediately temperature reached: 71, 77, 82C and

88C ratings 1C. Other temperature ratings on
request

Thermographic Measurements Ltd.

(Burton, S. Wirral, UK)

Thermax

Silver grey to black

Adhesive strips, irreversible colour change paints,

37-2600C

Thermographic Measurements Ltd.

(Burton, S. Wirral, UK)

Autoclave Indicator

Red to green

Autoclave ink. Change set for 30 min at 116C or

15 min at 127C

TLC Ltd. (Deeside, UK)

TLC 8

Red to black

Organic thermo-chromic ink; colour changes

immediately temperature is reached

exhibit heat-induced changes. For example, Kim and Taub (1993) have been
studying the thermally produced marker compounds 2,3-dihydro-3,5-dihydroxy-6-methyl-(4H)-pyran-4-one and 5-hydroxymethylfurfural. Both these
compounds are produced when D-fructose is heated, and glucose yields only
the latter compound. Hence, where a food contains either of these sugars,
there is some basis for assessing heat treatment received as the kinetic
characteristics make them suitable as markers for bacterial destruction. As
before, the kinetic response requirement which a TTI should fulfil can be
derived theoretically and should match the response of the target index, such
as a spore or a nutrient, when subjected to the same thermal process.
Potential exists for multicomponent TTIs in the evaluation of thermal
processes (Maesmans et al, 1994).
Regarding the origin of the TTI, an extrinsic TTI is a system added to the
food, while intrinsic TTIs are intrinsically present in the food. In terms of the

Working principle

Response

Origin

Application

Location

Chemical

Biological

Dispersed

Volume average

Physical

Single

Multi

Intrinsic

Extrinsic

Permeable

Isolated

Single point

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.

11.2 Packaging and food safety

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).
Table 11.1 Types of food safety problems associated with packaging
Examples
Microbial contamination
Loss of integrity
Anaerobiosis

Chemical contamination
Migration
Environmental contamination
Recycled packaging
Insect contamination
Post packaging

Consequences
Seal rupture, leaking cans, incomplete glass finishes allow contamination by pathogenic m.o.
Low oxygen environment resulting from product
or microbial respiration. Can lead to toxin formation by anaerobic pathogenic microorganisms
Transfer of package components to foods
Environmental toxicants can permeate films
Examples include preservatives used in wooden
pallets, diesel exhaust
Contamination of post-consumer packaging is
transferred to foods after recycling
Some insects can bore through many common
packaging materials

Foreign objects

Glass shards, metal pieces

Injury
Exploding pressurized containers
Broken containers

Soft drinks, beer in glass, etc.

Cuts, lacerations

Environmental impact

Disposal, recycling, CFCs

Loss of nutritional and sensory

quality

Aroma and nutrient sorption by polymers

Tamper evidency

Malicious and innocuous

Inadequate processing
Conventional
Aseptic

Underprocessing can lead to food poisoning

Loss of integrity or insufficient sterilization of
packaging can lead to food poisoning

11.3 Passive safety interactions

11.3.1 Barriers to contamination
The major safety and quality function of packaging is to act as a barrier
between food and the environment. The purpose is to prevent contamination
(or re-contamination after processing) of the food from both environmental
chemicals and pathogenic microorganisms. With glass and metal food
packaging, which are, for practical purposes, absolute barriers, preventing
contamination is usually a function of closure integrity. Considerable
experience with such closures has resulted in a remarkably low risk
packaging system.
The economic and functional disadvantages of metal and glass have led to
the development of polymeric packaging materials. The barrier properties of
these polymeric materials has been the central focus of packaging development in recent years. Polymers which are high barriers to both oxygen and
water vapor are now available. Very recent efforts have focused on
improved aroma/flavor barriers.
Post-packaging microbial contamination of foods is now not only a
function of closure integrity and material integrity (Downes et a/., 1985).
There are two aspects of package integrity: strength and completeness.
Strength implies that the closure or seal is sufficiently strong to withstand
the rigors of distribution without failure. Completeness means that there are
no gaps, holes, tears, etc. in the material or the seal. A seal or material can
be strong yet incomplete or can be complete yet have insufficient strength
for distribution. In some cases, flexible materials can contain minute pinholes which allow entry to microorganisms yet still not show signs of
leakage (Chen et aL, 1991). Flexible packaging can also develop pin holes
during shipping.
Strength and integrity have become important issues because foods are
transported further and stored for extended periods. The canning industry
has had considerable experience with double seam closure for metal cans,
making a container sealed in this way one of the safest available. The lack
of such long-term experience with the heat seal as a means of closure has
raised safety concerns. Flexible materials are also more prone to failure
during transport and storage. As the change to polymeric packaging has
occurred, concern for the integrity of the container has increased. Research
has been undertaken in an attempt to improve the testing of integrity of
polymer-based packages. Gnanasekharan and Floros (1994) have reviewed
methodology for detecting leaks in flexible food packaging. No currently
available method is entirely satisfactory for all situations.
Increased potential for chemical contamination has become a concern
because polymers are permeable to organic vapors, and foods which are
hermetically sealed in polymer-based containers can absorb environmental

contaminants. The transfer to foods of potentially toxic compounds used to

preserve wooden shipping pallets and wooden container floors has been
reported and is exacerbated by the increase in long-distance shipment of
foods (Whitfield et al, 1994). In addition to toxicological concerns, many
environmental organic compounds which permeate films impart undesirable
odors to foods.
As the pace in the use of recycled materials has gained momentum,
concern over microbiological contamination of fiber based packaging
materials has also increased (Klungness et al., 1990). The paper making
process inactivates most vegetative cells but does not inactivate microbial
spores. Foods packaged in recycled materials have the potential to have
acquired high spore loads from the packaging (Vaisanen et al, 1994). It is
likely that in some cases potentially pathogenic spores could be transferred
to foods from recycled materials.
Packaging also protects the nutritional and organoleptic quality of foods.
While not directly safety issues, foods which have lost their nutritional
attributes or are not consumed because of poor taste or appearance, become
a health issue. Nutrients and organoleptic properties can be adversely
affected in several ways. For example, nutrients can be destroyed when
oxygen or light enters a package or when the product is exposed to excessive
heat. The loss 'of vitamin C in orange juice when stored in low barrier
packaging is a prominent example. Sorption of nutrients by the packaging
material is also a mechanism of loss.
11.3.2 Prevention of migration
The second major safety function of packaging is to limit the transfer (i.e.,
migration) of packaging components to foods. Considerable research has
been conducted into the migration of packaging materials to foods (Crosby,
1981). Migrants include inorganic toxicants, primarily lead from soldered
cans, as well as organic toxicants such as vinyl chloride monomer which is
a known human carcinogen. Both the theoretical and empirical aspects of
migration have been studied in detail and in most cases the process is
scientifically understood.
Concern over migration has been recently heightened because of the use
of recycled materials or refillable containers for food and beverage
packaging (Begley and Hollifield, 1993). At least two potential problems
exist. One is that non-food grade plastics which may contain additives or
monomers that are not intended for human food use will enter the recycle
stream. These additives or monomers could then migrate to foods. The
second problem is the potential contamination of food grade polymeric
packages by consumers (gasoline and pesticides are commonly mentioned as
potential contaminants). These contaminants could then migrate to foods
packaged in containers made from recycled materials.

Several solutions to the post-consumer contamination of recyclable

plastics have been proposed. First is the use of equipment to detect
contaminated containers prior to refilling. These are commonly referred to as
'sniffers' and are designed to sample the air inside the container and
determine if volatile organic compounds such as might be found in gasoline
are present. Commercial sniffers are available and in use. The second
solution is to chemically break down the polymeric structure and subsequently reform the basic polymer. Any contaminants would be removed
during this processing. The third solution is to construct containers in which
the recycled polymer is separated from the product by a functional barrier.
Such functional barriers are intended to prevent the migration of contaminants from recycled polymers to products. Combining virgin and
recycled PET by co-extrusion into a PET bottle has been commercially
undertaken. The virgin PET is expected to be a functional barrier to potential
contaminants in the recycled layer. The major question is, How effective is
this virgin layer at preventing migration?
Other treatments of polymers such as cross-linking can retard migration.
Migration is also affected by the chemical and physical nature of the
migrant. Active packaging materials which can minimize or eliminate
migration would be of substantial interest as the concern over the
environmental cost of packaging increases.
A second recent packaging migration safety concern has resulted from the
use of polymer-based packaging as containers for food during heating such
as in processing low acid foods in a retort or heating foods in microwave
ovens. Initially, food polymer-based containers were designed to store
products at ambient or sub-ambient temperatures. Thus, most laboratory
work on migration was undertaken at room temperature or lower over
extended periods. The advent of the microwave oven has meant that foods
are heated in plastic vessels and on plastic surfaces. Heating plastics has two
effects on migration. First, migration in general follows Arrhenius-type
kinetics and increasing temperature increases migration rates in an exponential fashion. The second effect is that elevated temperature can cause
degradation of the polymer and additives which can result in migration of
the breakdown products. Each of these issues has been addressed by several
regulatory agencies in the USA and Europe.
11.4 Active safety interactions
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.
11.4.2 Active packaging and migration
Many active packaging systems incorporate functional additives in food
contact materials. These may be as simple as iron oxides which absorb O2 or
as complex as systems which react with singlet oxygen (Rooney, 1994). In
each case, the potential for and consequences of migration need to be
assessed. For example, there has been some reluctance in some parts of the
world to allow the use of ethanol emitters in foods which will be consumed
without further cooking or processing. The residual ethanol might be
considered a food additive and thus be required to undergo the rigors of
complete toxicological testing. For those active packaging systems which
indirectly add components to foods, the governmental regulatory and health
issues will be similar to those related to migration of residual monomers or
other polymer components (Crosby, 1981). Laboratory investigations will be
required to determine the potential for migration and to quantify the amount
of migration. If the amount of additive migrating is considered of potential
significance, toxicological testing may be required.
In some cases, active packaging systems may involve migrants for which
there is little concern in food systems. For example, approved antimycotic
agents such as sorbic, benzoic, or propionic acids, would likely be of little
regulatory or safety concern if incorporated into antimicrobial films (Giese,
1994). However, in most cases active components and additives will not be
common food additives and potential toxicological concerns will need to be
addressed. The addition of antimicrobial metal ions to food contact surfaces

is likely to result in the migration of small amounts of the metals to foods

(Ishitani, 1994). While these metal ions may be of low toxicity, the metals
may be classified as food additives and require rigorous toxicological
testing. The regulatory consequences of intentional addition of even low
amounts of metals will need addressing.
In some cases, the use of functional barriers to prevent migration of the
active components will be required. Incorporating absorbers or scavengers
into the adhesives used to bind layers of inert film as a means of 'burying'
the additive is an example.
11.4.3 Barrier to contamination
In addition to migration, active packaging systems must fulfill the safety
requirement of acting as a barrier to microbial and chemical contamination.
The addition of active ingredients to films could decrease their mechanical
properties resulting in a higher failure rate during transport. Such failures
become safety concerns if they allow for contamination by pathogenic
microorganisms or toxic chemicals. For example, the addition of inorganic
compounds such as metal-coated zeolites, desiccants, or oxygen scavengers
will likely reduce the mechanical properties of films raising the possibility
that the contamination barrier will be reduced.
The addition of packets or sachets to packages of food raises concern that
they will be inadvertently ingested. While sachets and packets have been in
use for several years without apparent problems, caution about adding nonedible items to packages should be taken. Incorporation of active ingredients
directly into the packaging rather than as sachets seems prudent.
11.4.4 Indirect effects on safety
Active packaging often has indirect as well as direct effects on food safety.
For example, packaging which absorbs oxygen from inside a package with
the goal of reducing deteriorative affects will affect both the types and
growth rate of the microorganisms in products. The inclusion of antimicrobial agents in the contact layer of a packaging material may have
similar effects. This will result in a change in the microbial ecology of the
food. The type of microorganisms present on a product will thus be different
from the same product packaged in a conventional manner. This change in
microbiology will indirectly influence safety. In some cases, safety may be
enhanced such as when carbon dioxide is added to high pH cheeses such as
cottage cheese (Chen and Hotchkiss, 1993). In other cases, safety may be
compromised as when the growth of Clostridium botulinum is favored.
The effect of such changes in the microbial ecology of foods has not been
investigated in detail and only a few reports on changes in microbial ecology
have been published (Reddy et al.9 1992). Smith and co-workers have

investigated the effects of MAP on the microbiology and toxin production

by Clostridium botulinum in meats (Lambert et al9 1991). Somewhat
surprisingly, toxin was produced most rapidly in samples packaged in air
(i.e., 20% O2). This confirms an earlier observation we had made in cooked
beef inoculated with both Pseudomonas and Clostridia spp. It is likely that
this occurred because the aerobic Pseudomonas grew rapidly and consumed
the oxygen rapidly leaving a highly anaerobic environment for the
Clostridia. MAP in high carbon dioxide atmospheres inhibited the Pseudomonas inoculum and left traces of unconsumed O2 which inhibited the
Clostridia. These results point out that large changes in microbial populations can result indirectly from altering the gases inside a package. These
changes can both detract from safety but can also improve safety.
11.4.5 Indicators of safety/spoilage
In addition to decreasing the safety of food, active packaging holds the
promise of reducing risks from certain foods compared to conventional
packaging. One example is the use of packaging which shows or in some
way indicates the condition or history of a product. One currently available
technology is time-temperature indicators. These devices integrate the time
and temperature history of a product and give a visual indication if the
combination has exceeded some standard or desirable amount (Taoukis et
al9 1991). Shelf-life is related not only to how long a product is stored, but
just as importantly, to the conditions, such as temperature, under which the
product is stored. For example, pasteurized milk will last weeks at O0C but
only a few hours at 35C.
Time-temperature indicators can be used on individual packages to warn
consumers that a product has been exposed to a combination of time and
temperature which may compromise safety or they may be used on shipping
cartons to alert store personnel of potential quality/safety problems or allow
stock rotations based on both time and temperature. Such devices would be
especially useful when combined with other shelf-life technologies such as
MAP or sub-sterilization radiation.
The next generation of safety/quality indicators may be more specific than
integrating time and temperature. In the future it may be possible to directly
detect the presence of specific toxins in packaged foods using biosensors.
Immunologically based sensors coupled to packaging could find applications
in food safety, food processing, and detection of adulteration (Deshpande,
1994). Such sensors could, for example, detect the presence of bacterial
toxins in packaged foods. They could also be used to determine if a food had
been properly pasteurized or contained enzyme activity. Biosensors which
combine electronics with biological specificity and sensitivity may find use
in packaging as monitors of safety and quality (Deshpande and Rocco,
1994). In time, it may be possible to incorporate these or similar biosensors

into food packaging systems for which the risk of toxin formation exists.
Reportedly, methods to quantify the presence of microorganisms on fresh
meats are near commercialization (Bsat et #/., 1994). Such systems could
eventually be incorporated directly into food packaging.
It may likewise be possible to detect the presence of toxic chemicals using
similar technologies. The presence of specific pesticides or other environmental contaminants could be detected with immunological-based systems
(Deshpande, 1994). Lastly, packaging should provide a margin of safety
against tampering. Tamper-indicating packaging has been discussed in detail
since several malicious incidents of tampering with drugs and foods have
occurred (Hotchkiss, 1983). Several simple and complex tamper-evident
packaging systems have been developed and a few implemented for
foods.
11.4.6 Direct inhibition of microbial growth
Microbial contamination and growth are the major factors in food spoilage
and responsible for food-borne disease outbreaks. Two general approaches,
heat sterilization and direct addition of antimicrobial additives, have been
used to eliminate or minimize microbial growth. In conventional thermal
processing, foods are sealed in a package and the combined productpackage thermally processed. This is the basis of the canning industry. More
recently, the process of the package and the product being sterilized
separately then filled and sealed aseptically has been used. This is known as
aseptic packaging. Foods can also be dried to reduce microbial growth.
Another method to reduce microbial growth is to add antimicrobial
additives directly to foods. This approach usually does not inhibit all growth
but is selective for certain types of microbial growth, molds for example.
The use of these additives is regulated and their use, in most cases, must be
stated on the label.
11.4.7 Modified atmosphere packaging
Recently, the development of alternative methods of inhibiting microbial
growth has resulted from a consumer desire for fresher and more natural
foods. The most successful alternative to canning or the direct addition of
antimicrobial agents has been modified atmosphere packaging (MAP). The
number and type of microorganisms present on a food is governed by five
general variables: time, temperature, substrate (food) composition, microbial
load (type and number), and gas atmosphere. For a given food product
which must be held above freezing, alteration of the gas atmosphere
surrounding the product is the most accessible method of inhibiting
microbial growth. However, inhibition is not uniform for all types of
microbes. In general (although there are exceptions) Gram-negative rods are

inhibited by a modified atmosphere containing more than 10% CO2 while

Gram-positive organisms are not inhibited and their growth can be
promoted.
The major goal of MAP is to reduce the growth rate of microorganisms
which cause the product to become organoleptically unacceptable. However,
organisms which cause disease (i.e., pathogens) do not, in many cases, cause
organoleptic changes in foods. Increasing the shelf-life by suppressing
spoilage organisms might allow for the growth of pathogenic organisms
without development of the normal organoleptic cues of spoilage that warn
consumers that a product may not be wholesome (Farber et ai, 1990). Thus,
the major safety concern with MAP and controlled atmosphere packaging or
other technologies which selectively change the microbiology of a food is
that suppression of organoleptic spoilage (i.e., extension of shelf-life) will
decrease competitive growth pressure and provide sufficient time for slow
growing pathogenic organisms to become toxic or reach infectious numbers
(Hotchkiss and Banco, 1992). The knowledge gained over the last decade
about pathogenic microorganisms which are capable of surviving and
growing at common refrigeration temperatures increases concern about the
safety of refrigerated extended shelf-life foods (Gormley and Zeuthen, 1990;
Farber, 1991). The effect that this change in microbiology might have on the
risk of food-borne disease has been debated (Gormley and Zeuthen,
1990).
There are several methods of creating a modified atmosphere inside a
package. One is the use of selective or engineered barriers which are used
for respiring products such as fruits and vegetables. The combination of
product respiration rate (i.e., rate OfCO2 formation and O2 consumption) and
CO2 egress and O2 ingress results in the formation of an equilibrium
concentration of gases which, if properly designed, will reduce senescence
and extend shelf-life. Alternatively, a specific gas mixture can be directly
introduced into the package after removal of the air and before sealing. A
third method is to use an additional material contained in a sachet or
incorporated into the film which will alter the gas composition after sealing.
In each case, the change in atmosphere will affect both the growth rate and
type of microorganisms present. However, temperature will affect the
respiration rate to a much greater extent than the permeability. If the product
is stored at an elevated temperature, respiration rates will increase and the O2
content of the package may approach zero. At the same time the growth rate
of pathogenic microorganisms substantially increases with the increase in
temperature. This could allow for the growth of anaerobic pathogens such as
Clostridium botulinum.
For example, Lambert et al (1991) have shown that toxigenesis occurs
more rapidly in aerobically packaged pork samples compared to anaerobically packaged samples when Pseudomonas spp. were present along with
the Clostridium botulinum inoculum. It was presumed that the Pseudomonas

rapidly consumed the oxygen allowing the C. botulinum to become toxic.

These results agreed with earlier results of Hintlian and Hotchkiss (1987)
who made a similar observation.
11.4.8 Antimicrobial films
Packaging may directly affect the microbiology of foods in ways other than
changing atmosphere. In solid or semi-solid foods, microbial growth occurs
primarily at the surface. Surface treatment by spraying or dusting with
antimicrobial agents for products such as cheeses, fruits, and vegetables is
widely practised. Antimycotic agents are commonly incorporated into waxes
and other edible coatings used for produce items (Peleg, 1985). More
recently, the idea of incorporating antimicrobial agents directly into
packaging films which would come into contact with the surface of the food
has been developed.
Antimicrobial films can be divided into two types: those containing an
antimicrobial agent which migrates to the surface of the food and those that
are effective against surface growth without migration of the active agent(s)
to the food. Several commercial antimicrobial films have been introduced,
primarily in Japan. One widely discussed product is a synthetic zeolite
which has had a portion of its sodium ions replaced with silver ions. Silver
can be antimicrobial under certain situations. This zeolite is incorporated
directly into a food-contact film. The purpose of the zeolite apparently is
allow for the slow release of silver ions to the food. Only a few scientific
descriptions of the effectiveness of this material have appeared and the
regulatory status of the deliberate addition of silver to foods has not been
clarified in the US or in Europe.
Several other synthetic and naturally occurring compounds have been
proposed and/or tested for antimicrobial activity in packaging (Table 11.2).
For example, the antimycotic (i.e., antifungal) agent, imazalil, is effective
when incorporated into LDPE for wrapping fruits and vegetables (Miller et
Table 11.2 Some antimicrobial agents of potential use in food packaging
Class

Examples

Organic acids
Bacteriocins
Spice extracts
Thiosulfinates
Enzymes
Proteins
Isothiocyanates
Antibiotics
Fungicides
Chelating agents
Metals
Parabens

Propionic, benzoic, sorbic

Nisin
Thymol, p-cymene
Allicin
Peroxidase, lysozyme
Conalbumin
Allylisothiocyanate
Imazalil
Benomyl
EDTA
Silver
Heptylparaben

al, 1984; Hale et al.> 1986). We have demonstrated that the same compound
is effective at preventing mold growth on cheese surfaces when incorporated
into LDPE films (Weng and Hotchkiss, 1992). Although imazalil is not
approved for cheese, this work established that antimycotic films could be
effective for control of surface molds in foods. Halek and Garg (1989)
chemically coupled the antifungal agent benomyl, which is commonly used
as a fungicide, to ionomer film and demonstrated inhibition of microbial
growth in defined media. While not directly addressed by the authors, the
method used to determine inhibition of growth indicated that the benomyl
migrated from the film to the growth media. It is unlikely that benomyl
would be approved for food use for toxicological reasons.
Reports have appeared which demonstrate the effectiveness of adding
common food-grade antimycotic agents to cellulose-based edible films
(Vojdani and Torres, 1990). Films were constructed of cellose derivatives
and fatty acids in order to control the release of sorbic acid and potassium
sorbate. These films would seem to have the greatest application as fruit and
vegetable coatings. Cellulose films are not heat sealable are not good
barriers in high humidity situations.
We have spectroscopically demonstrated that propionic acid, which is a
common approved food antimycotic agent, could be coupled to ionomeric
films but that antimycotic activity could not be demonstrated on rigorous
testing (Weng, 1992). Direct addition of simple antimycotic acids such as
propionic, benzoic, and sorbic acids to polymers such as LDPE was
unsuccessful because of lack of compatibility between the acid and the nonpolar film. This incompatibility is likely to be due to differences in polarity.
We have solved this problem by first forming the anhydride of the acid
which removes the ionized acid function and decreases polarity (Weng and
Hotchkiss, 1993). Anhydrides are stable when dry and relatively thermally
stable yet become hydrolysed in aqueous environments such as foods.
Hydrolysis leads to formation of the free acid which in turn leads to
migration from the surface of the polymer to the food where the free acids
can be effective antimycotics. This is an example of 'switched on'
packaging; the active ingredient remains in the film until the film comes into
contact with a food. The activity is initiated by the moisture in the food.
Future work in antimicrobial films may focus on the use of biologically
derived antimicrobial materials that are bound or incorporated into films and
do not need to migrate to the food to be effective. For example, a group of
substances known as bacteriocins, which are proteins derived from microorganisms in much the same way as penicillin is derived from mold, have
been described in the literature (Hoover and Steenson, 1993). Bacteriocins
are effective against organisms such as Clostridium botulinum and one such
compound, nisin, has been approved for food use. These peptides could,
theoretically, be attached to the surface of food-contact films. Whether or not
such bound bacteriocins would be effective remains unclear.

Antimicrobial enzymes might also be bound to the inner surface of foodcontact films. These enzymes would produce microbial toxins. Several such
enzymes exist, such as glucose oxidase which forms hydrogen peroxide.
A third possibility for antmicrobial films is to incorporate radiationemitting materials into films. Reportedly, the Japanese have developed a
material which emits long-wavelengt IR. This is thought to be effective
against microorganisms without the risks associated with higher energy
radiation. However, little direct evidence for the efficacy of this technology
has been published in the scientific literature.
In general, several questions, including those dealing with safety, should
be considered in developing antmicrobial films:

What is the spectrum of organisms against which the film will be

effective? Films which may inhibit spoilage without affecting the growth
of pathogens will raise safety questions similar to those of technologies
such as a MAP.
What is the effect of the antimicrobial additives on the mechanical and
physical properties of the film? It is likely, for example, that effective
levels of antimicrobial agents will reduce seal strength. This may
adversely affect safety.
Is the antimicrobial activity a reduction in growth rate (yet still a positive
increase in cell numbers) or does it cause cell death (decline in cell
numbers)?
To what extent does the antimicrobial agent migrate to the food and
what, if any, are the toxicological and regulatory concerns?
What is the effect of food product composition? Some antimicrobial
agents, for example, are effective only at acid pH while others might
require certain product compositions (e.g. aw9 protein, glucose, etc.) to be
effective.

Each of these questions need addressing before the safety consequences of

antimicrobial packaging can be understood.
11.4.9 Rational functional barriers
As pointed out, one major safety function of packaging is to act as a
chemical and biological barrier. Films are frequently selected for food use
based on the highest degree of oxygen and/or water vapor barrier at the
lowest cost. More recently, the concept of rational design or engineering of
film permeability has evolved. These so-called 'smart' films have barrier
properties which are designed to adapt or change permeabilities according to
conditions such as a change in gas composition or temperature.
These engineered barriers have at least two important safety-related
applications. The first is to act as a barrier to permeation of contaminants.
Packaged foods can be exposed to contaminants from environmental sources

or from the use of recycled plastics in food packaging. Common environmental sources of toxic permeants include chemicals used to treat shipping
containers and pollutants. Chlorinated wood preservatives readily permeate
through common films and cause taint in foods (Whitfield et al, 1991).
Common environmental pollutants such as diesel exhaust and industrial
solvents used in printing also permeate many common food-packaging
films.
The second use of engineered barriers is in passive MAP systems in
which an equilibrium in the gas mixture is achieved through the combination
of product respiration and package permeability. This equilibrium results
from the consumption of O2 and evolution of CO2 by the food product at the
same time that O2 is permeating into the package and CO2 is permeating out
at a given temperature. At some point these respiration and permeation rates
will reach an equilibrium concentration. Selection of a film with the proper
permeability will result in the desired gas mixture. Several mathematical
models have been developed which predict the proper permeation rates
given by a specific product respiration rate (Mannapperuma et ai9 1991).
There are two difficulties with this concept. The first is that respiration
rates of most produce items vary widely, even within the same type of item.
Thus, permeation rates will have to be tailored for each individual product
item. The second problem is that CO2 permeation rates for common
packaging films is 2-A fold or more higher than for O2. This means that CO2
may egress at a faster rate than O2 will enter, making the atmosphere
anaerobic. Engineered films which can independently select CO2 and O2
permeation rates as well as films that change permeation at the same rate that
fruits and vegetables change respiration rate with temperature, would be
desirable. As pointed out above, the rate of gas change will determine the
type of microorganisms on the products and, probably, the safety of such
foods.
We have recently devised equations for achieving optimum atmosphere
concentrations for extending the shelf-life of fresh corn on the cob and head
lettuce, each of which illustrates some of the problems with engineered
barriers. Head lettuce respires relatively slowly and films which will allow a
passive modified atmosphere to be established are commercially available.
However, about 90 hours are required for establishment of a suitable
atmosphere (Morales-Castro et al, 1994a). During this time considerable
deterioration can occur. Sweet corn, on the other hand, respires rapidly and
the establishment of a desirable steady-state atmosphere is not possible with
normal films because the permeabilities are too low even for very low
barrier films (Morales-Castro et aL, 1994b).
MAP products such as lettuce and corn or other vegetables could become
safety concerns if the atmosphere were to become anaerobic. This might
occur if products were stored at a higher than expected temperature. This
would cause an increase in respiration beyond that expected and the oxygen

might be substantially depleted. This would leave open the possibility of

growth of anaerobic pathogens such as Clostridium botulinum.
11.4.10 Combined systems
The most successful active packaging materials are likely to combine
different technologies. A few examples of such combinations have appeared
in the literature. For example, Fu and Labuza (1992) have suggested that
MAP might be combined with time-temperature indicators as a means of
extending the shelf-life of perishable foods while at the same time
minimizing food-borne disease risks. MAP would reduce the deterioration of
food while the time-temperature indicator would insure that the product was
stored and handled within the time and temperature window for which the
product was designed, to insure safety. Labuza et al (1992) have suggested
that predictive microbiology should be used to evaluate the safety of MAP
foods.
Low dose irradiation and MAP have been combined to extend shelf-life
(Thayer, 1993). Irradiation reduces the numbers of spoilage and pathogenic
vegetative organisms while a modified atmosphere reduces the likelihood
that those not destroyed will grow significantly in number. Lambert et al
(1992) have demonstrated a substantial increase in the shelf-life of fresh
pork treated with both irradiation and MAP.
Other combinations such as antimicrobial films combined with MAP or
oxygen absorbers combined with antimicrobial films may find commercial
uses. Zeitoun and Debevere (1991) have suggested that combining a simple
lactic acid dip combined with MAP would enhance the shelf-life of fresh
poultry.
11.5 Conclusions
It can be expected that safety will continue to be an important attribute for
foods. New packaging technologies which improve quality, usefulness, or
reduce environmental impact will also be required to maintain a high level
of safety. Active packaging systems will not be an exception.
Those active packaging systems which reduce the risks associated with
foods may find niche markets for products at the highest risk of
deterioration. MAP of non-sterile foods is one example where additional
safety measures such as use of microbial inhibitors or indicators of
temperature abuse would be useful. Recycled materials for food packaging is
another.
Active packaging systems which provide benefits for foods will have to
adhere to governmental regulatory standards in most of the world. This will
inhibit the introduction of some active systems. Antimicrobial films are a

prime example. Developers of such materials should understand the safety

and regulatory implications of their work early in the process if they expect
to be successful.

References
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Index
Index terms

Links

A
absorbers
food constituents

99

100

100

213

free oxygen see oxygen absorbents

odours and taints
activation energy
permeation

68

respiration model

65

active packaging
chemical

21

composite

definition

do-it-yourself

17

economic benefit

76

future potential

32

history

horticultural

limitations

31

literature

10

multiple effects

origins

physical

20

reasons for

24
2

143

203

252

regulatory considerations

33

reviews

10

252

This page has been reformatted by Knovel to provide easier navigation.

256

257

Index terms

Links

active packaging (Continued)

scope

12

terminology
whole packages

10

29

active packaging plastics

and safety

243

combined effect

82

commercial use

106

effects on foods

74

environmental considerations

107

migration from

243

regulations

106

106

Ageless
and aw

150

capacity

150

chemistry

149

types

149

aldehydes

100

almonds rancidity
and oxygen absorbent
amines

155
100

anaerobic respiration
antimicrobials

68
243

enzymic

250

silver zeolite

248

antimycotics

244

248

249

ascorbic acid
and oxygen absorbent
Aspergillus spp

154
159

This page has been reformatted by Knovel to provide easier navigation.

258

Index terms

Links

B
bacteriocins

249

bakery products
and oxygen absorbent

156

ethanol releasing sachets

166

169

mould growth

159

160

barriers
functional

250

beer
commercial oxygen scavenger closures

198

oxygen concentration in

194

oxygen ingress

195

blueberry

65

broccoli

65

196

69

C
calcium carbonate
as filler

69

cans
tinplate

238

carbon dioxide
permeability

123

carnauba wax

132

carrots packaging
condensation control
cauliflower

98
65

casein films
sorbic acid in

128

This page has been reformatted by Knovel to provide easier navigation.

259

Index terms

Links

cheese
antimycotic films for

249

Clostridium botulinum

244

Clostridium sporogenes
effect of Ageless

163

closure
beer bottles

193

benefits

199

beverage bottles

193

oxygen scavenging
with ascorbic acid

198

with sodium sulfite

168

composite films
sorbic acid barrier
consumer resistance to sachets

130
162

contamination
barriers to
controlled atmosphere (CA)

240

244

55

corn
gas atmospheres for

251

crusty rolls
and oxygen absorbents

159

D
deoxidisers see oxygen scavengers
desiccant
retorting

75

79

This page has been reformatted by Knovel to provide easier navigation.

260

Index terms

Links

E
edible coatings see edible films
edible films
as active packaging

113

as food

112

bilayer

117

composite

111

food surface modification

126

formation

112

gas exchange with

121

moisture barrier

114

multilayer

117

permeability

114

plasticisation

120

energy transfer

90

environment

117

107

enzymes
active packaging

176

antimicrobial

186

binding

105

function

174

history

178

oxygen scavenging

174

release

105

equilibrium modified atmosphere (EMA)

247

177

251

see also passive modified atmosphere packaging

Clostridium botulinum in

247

generation

56

packaging

Pseudomonas spp in

55

247

This page has been reformatted by Knovel to provide easier navigation.

66

261

Index terms
ethanol oxidase

Links
186

ethanol vapour
absorption

167

antimicrobial effects

165

and aw

165

in bakery products

165

and food spoilage

171

and food poisoning

171

171

generators
advantages

171

aw effects

166

disadvantages

171

required sizes

166

types

166

uses

168

ethylene
adsorption

40

chemistry

38

degradation

39

effects

41

interaction with other gases

44

sources

45

46

synthesis

38

39

ethylene scavengers
activated carbon

47

activated earth

48

novel approaches

50

potassium permanganate

46

This page has been reformatted by Knovel to provide easier navigation.

262

Index terms

Links

F
films
antimicrobial

248

ceramic filled

70

condensation control

98

controlled diameter holes to humidity buffering

96

for MAP

67

microporous

68

moisture control

94

perforated

68

temperature-compensating

70

with oxygen absorbents

92

153

fish products
and oxygen absorbents
flavour scalping

157
99

foods
oxygen absorbents for

155

Freshilizer
and aw

151

reaction speed

151

types

151

FreshMax

212

Fresh Pax
and aw

151

reaction speed

152

types

152

uses

211

fruits
edible coatings
gas atmosphere for

126
57

This page has been reformatted by Knovel to provide easier navigation.

263

Index terms
functional barriers

Links
250

G
gelatin films
sorbic acid retention

128

tannic acid crosslinked

128

tocopherol retention

128

glucose oxidase

181

gluten films
with beeswax
green pepper

124
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
oxygen concentration

245
2

safety

245

spoilage

245

temperature

209

This page has been reformatted by Knovel to provide easier navigation.

264

Index terms

Links

indicator (Continued)
time-temperature see Time-Temperature Indicators
interactive packaging see active packaging
intermediate moisture food see IMF

L
lettuce
gas atmosphere for
limonin

251
99

Listeria monocytogenes

163

ethanol vapour effect

171

M
mathematical modelling

251

limitations

64

parameters

71

steady state

66

unsteady state

65

variables

66

70

meat colour
and oxygen absorbents

160

meat packaging
oxygen scavenging
methylcellulose
with palmitic acid

158
130
132

microbiological stability
carrageenan effect

134

lactic acid effect

133

surface pH effect

133

microencapsulation

85

This page has been reformatted by Knovel to provide easier navigation.

265

Index terms
microwave susceptors

Links
203

field intensifiers

206

reflectors

206

microwaveable bottle

209

migration
from active packaging

243

from heated plastics

242

from recycled plastics

242

of preservatives

127

prevention of

241

modified atmosphere packaging (MAP)

active

55

and Clostridium botulinum

245

definition

143

and ethanol vapour

170

experimentation for

60

film selection

66

gas concentration boundaries

58

gas tolerance limits

61

feasibility study

59

films for

67

flow chart

56

and irradiation

57

optimisation

60

passive

55

pathogens in

246

and Pseudomonas

247

regulation of

67

252

literature review

quality criteria

247

59
252

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266

Index terms

Links

modified atmosphere packaging (MAP) (Continued)

and Time-Temperature Indicators

252

moisture transfer
ice cream-wafer

121

mould growth
on bakery products

75

on cheese

75

mozarella cheese
and oxygen absorbents
mushrooms

160
69

O
odours
from oxygen scavengers
organic acids
Ox-Bar

82

91

243
82

oxygen
concentration measurement

193

permeability of closure liners

195

194

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

This page has been reformatted by Knovel to provide easier navigation.

267

Index terms

Links

oxygen absorbents (Continued)

function
history

148
4

in Japan

144

153

in USA

155

159

market statistics

144

reaction speed

146

reactions in

145

requirements for

145

research with

159

oxygen absorbers see oxygen absorbents; oxygen

scavengers
oxygen permeation
aw effect
chemical barrier
edible films
oxygen scavengers

124
92

185

123
1

see also oxygen absorbents

Advanced Oxygen Technologies, Inc.

198

Ageless

211

Aquanautics Corp.

198

ascorbic acid

85

ascorbic acid plus sodium sulfite

86

beer bottle closures future

200

beer flavour and

199

bottle closures

213

chemistry of

83

closure liner theory

197

composite systems

erythorbic acid

198

198

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Index terms

Links

oxygen scavengers (Continued)

fatty acids

82

food applications

212

FreshMax

212

Fresh Pax

211

history

91

hydrogen/catalyst

84

iron see oxygen absorbents

Mitsubishi Gas and Chemical Co

211

Multiform Desiccants Inc.

211

novel designs

Ox-Bar

83

OxyBan

181

patent applications

plastics vs. sachets

81

PureSeal
release of carbon dioxide rubbers
and odours
SmartCap
sulfite oxidation

199
89

90

82

91

199
85

86

198

oxygen scavenging
activation see triggering
and aflatoxin production

164

and microbial growth

163

by autoxidation
enzymic

91
179

peroxide formation

86

purposes

75

oxygen scavenging packaging

forms of

76

81

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269

Index terms
oxygen scavenging plastics

Links
77

forms of

76

history

80

light-energised

80

light triggered

91

metal-catalysed photosensitised

91

MXD-6 nylon

83

permeability effects

99

photoreduction-reoxidation

92

photosensitised

87

potential applications

75

singlet oxygen mechanism

87

81

oxygen scavenging sachets see oxygen absorbents

Oya Stone

209

broccoli packaging and

210

Evert-Fresh Bag

209

P
package integrity

240

packaging
active constituent impact on
antimicrobial

27
243

244

246

intelligent

215

216

interactive

modelling

64

modified atmosphere

safety problems

239

tamper evident

246

with oxygen scavengers

92

246

153

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Index terms

Links

patents
oxygen scavenging

pectin films

128

Penicillium spp

159

81

perforated films
computer simulation

69

permeability
activation energy

68

composite films

118

edible films

114

effect on oxygen scavenging

78

humidity effect

79

modification
ratio

89

105
67

71

125
116
169

smoke

105

table

68
123

78
124

temperature effect

120

130

to ethanol

169

to water vapour

115

peroxide value
and oxygen absorbent

154

photosensitisation

87

Pichit

97

pizzas
and oxygen absorbents

160

plastics
definition

74

for oxygen scavenging

77

functional barrier

242

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117

271

Index terms

Links

plastics (Continued)
iron in

78

recycled

242

poly(1,2-butadiene)

77

poly(1,3-butadiene)

89

polydimethylbutadiene

89

80

91

46

55

209

252

polyethylene
antimycotics in
polyisoprene
potassium sorbate

248
89
127

processed foods
and oxygen absorbents
produce packaging

158
9

propionic acid

249

propionic anhydride

249

Q
Q10

62

R
radiation
far infra-red
regulation

70

250

106

242

243

179

181

release
antimicrobial agents

102

antioxidants

103

butylated hydroxytoluene

104

enzymes

105

ethanol vapour

165

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Index terms

Links

release (Continued)
flavours

103

food ingredients

102

fumigants

104

hinokitiol

102

Maillard reaction products

104

permethrin

104

silver ions

248

sorbic acid

126

removal
aldehydes

100

amines

100

cholesterol

190

lactose

189

styrene

101

respiration rate
circulation

62

closed system

63

flow-through

61

measurement

62

temperature effect

61

respiratory quotient

61

retortable packaging

63

79

S
Saccharomyces cerevisiae
ethanol vapour effect

170

sachets
combined effect

146

consumer resistance

162

150

151

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152

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Index terms

Links

sachets (Continued)
ethanol releasing
ethylene-removing

165
46

oxygen scavenging see oxygen absorbents

and public health

163

safety with

244

safety
active interactions

242

and packaging

238

indirect effects on

244

passive interactions

240

scalping

99

sheets
drip-absorbent

95

shelf life
with oxygen absorbents

153

silica
as filler

69

silicone film

69

smart films

sodium chloride
sorbic acid

98
126

diffusivity

129

permeability

129

Staphylococcus aureus

250

163

strawberries

69

sulfites

79

superabsorbent polymers

96

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Index terms

Links

T
taints

99

251

see also odours

Time-Temperature Indicator (TTI)
activation

228

bar code

222

classification of

233

consumer attitudes

229

definitions

215

enzymic

188

operating principles

217

reasons for

216

requirements of

217

specifications

229

thermal process validation with

230

validation tests

224

toxicology

245

243

triggering
chain reaction
of propionic acid

91
249

oxygen scavenging plastics

83

photoreduction

92

V
vegetables
gas atmospheres for

59

vitamin C see ascorbic acid

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Index terms

Links

W
water activity (aw)
and ethanol generators

68

Y
yeast growth
ethanol effect

oxygen absorber

170

Z
zein films
lactic acid retention

128
134

This page has been reformatted by Knovel to provide easier navigation.