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Lebensm.-Wiss. u.-Technol.

, 35, 15–20 (2002)

Chemical and Physico-chemical Changes in Processed


Cheese and Ready-made Fondue During Storage.
A Review
W. Schär and J. O. Bosset*

W. Schär: Tiger Cheese Ltd., CH-3550 Langnau - Emmental (Switzerland)


J.O. Bosset: Federal Dairy Research Station, Liebefeld, CH-3003 Berne (Switzerland)
(Received April 17, 2000; accepted July 19, 2001)

Processed cheese is often expected to be a stable product with a very long shelf-life. However, even products without any
bacteriological contamination retain their high quality only for a few months at room temperature. During storage, structure and
flavour slowly change. The following possible causes for such changes are reviewed in the present paper: loss of water vapour,
hydrolysis of polyphosphates, changes in ionic equilibria, crystal formation, oxidation, nonenzymic browning, enzymatic activity as
well as interactions with packaging materials. The changes with age of processed cheese are influenced by four main factors: product
composition, processing, packaging and storage conditions (time and temperature). No work about the changes with age of ready-
made fondue appears to have been published.

r 2002 Elsevier Science Ltd

Keywords: processed cheese; ready-made fondue; storage; ageing; shelf-life; quality

Introduction The ‘best before’ date must be declared according to the


ageing properties of their products. Processed cheese for
So far, most research studies into the problems of the export markets should retain its quality as long as
shelf-life and storage of processed cheese have dealt with possible, especially for hot countries where they are the
problems caused by microbial contamination. Modern most popular cheese types. The manufacturers collect
processing technologies and careful selection of ingre- empirical data but a better knowledge of the main causes
dients make it possible to produce bacteriologically of change and factors contributing to this change would
stable processed cheese. For this reason, processed form the basis for further improvements. However, only
cheese is often expected to be a product with a shelf- few scientific results have so far been published.
life of more than 1 y. However, even bacteriologically ‘Swiss Cheese Fondue’ (‘Fertigfondue’) is a typical Swiss
stable products in good packaging usually maintain meal including cheese, white wine and brandy (Kirsch).
their quality only for 6–12 mo at room temperature In 2000, approx. 7,400 tons of ‘Swiss Cheese Fondue’
(Chambre and Daurelles, 1997). During storage, chemi- and 13,100 tons of processed cheese were produced in
cal and physical aging processes impair flavour and Switzerland (Swiss Association of Processed Cheese
structure. A typical off-flavour, often called ‘old’ Manufacturers, 2000). Both products are mainly based
flavour, gradually appears, thus limiting the sensory on Emmental and Gruyère cheese.
quality. Structure also continuously changes, typically No published data are available about the ageing and
towards a firmer, shorter texture. Several changes can shelf-life of ‘Swiss Cheese Fondue’ and processed Swiss
occur simultaneously. Emmental cheese with citrates. Therefore, the Federal
This subject is relevant for all processed cheese Dairy Research Station (FAM) of Liebefeld/Bern and
manufacturers who have great know-how on this topic the Swiss association of processed cheese manufacturers
but have not published it for obvious reasons. They have are carrying out a collaborative study on the ageing of
to check for these changes during product development. processed Emmental cheese and ready-made Fondue.
The two main aims of that study, published in two parts,
*To whom correspondence should be addressed. E-mail: jacques- are to review the current knowledge on this topic and to
olivier.bosset@fam.admin.ch complete it on several aspects investigating a 1-y ageing
0023-6438/02/020015+06 $35.00/0 doi:10.1006/fstl.2001.0820
r 2002 Elsevier Science Ltd All articles available online at http://www.idealibrary.com on

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lwt/vol. 35 (2002) No. 1

of commercial processed Emmental cheese and ready- Clostridium butyricum, Clostridium tyrobutyricum,
made Fondue. Actual information about chemical and Clostridium sporogenes can be destroyed. Post-sterilisation
physical changes in processed cheese is summarised in infection is prevented by hot filling (85–95 1C) into the
the present review article. packing (Sturm, 1998).

Manufacture of Processed Cheese Shelf-life of Processed Cheese


Processed cheese is produced by heating a mixture of According to Berger et al. (1989), processed cheese is not
cheese, water, emulsifying salts (mostly sodium citrates, a preserved food, but a ‘semi-preserved food’ with a
sodium orthophosphates or sodium polyphosphates) limited shelf-life. Premium grade processed cheese
and further optional ingredients such as butter or spices. should be given a shelf-life guarantee not exceeding
Mix constituents and processing conditions are selected 3–4 mo, especially when the product is packaged in
to give the desired structure, appearance, colour, flavour plastic foils. Products stored in metal cans or tubes may
and shelf-life at an acceptable cost. The mixture is have longer shelf-lives. According to Chambre and
heated in a batch cooker to 70–120 1C under a partial Daurelles (1997), processed cheese products usually
vacuum with constant agitation, until a homogeneous retain their good quality for up to 6–12 mo at room
mass is obtained, or in a continuous UHT-process at temperature. Sturm (1998) differentiates the shelf-life of
140 1C. Generally, the hot processed cheese is filled into the following products stored at room temperature:
the desired packages such as pouches or polymer-coated 8 wk for slices, 20 wk for small portions, more than 1 y
aluminium foils. Thereafter, these packages are sealed for products packed in tubes or cans. Table 1
and the products are cooled down. Several textbooks summarises the possible changes and their relevance.
and review articles on processed cheese manufacture are Ready-made fondue in multilayer aluminium pouches is
available (Meyer, 1970; Paquet, 1988; Berger et al., very well protected against loss of water vapour, gas
1989; Zehren and Nusbaum, 1992; Caric and Kalab, permeation and light transmission. It is typically
1997; Chambre and Daurelles, 1997). The influence of produced with sodium orthophosphate as an emulsify-
heating on the volatile compounds of Swiss processed ing salt. A longer shelf-life could theoretically be
cheese varieties was recently investigated (Mariaca et al., expected, but even in this case, changes in the mouth-
1998). feel are noticed: the structure continues to become more
During processing, the natural cheese, consisting mainly homogeneous and the corresponding mouth perception
of insoluble calcium paracaseinate and fat globules, is is described as becoming more creamy. An increasing
finely dispersed, homogenised and converted into a gel ‘old’ off-flavour (taste and odour) limits its sensory
in which fat is emulsified. By chelating the calcium from acceptance. Changes in fondue strongly depend on
the protein structure, the emulsifying salts contribute to storage temperature: at 5 1C, the changes are much
the dispersion of the proteins and enhance their slower than at 20 1C (Tiger Cheese Ltd., Langnau-
emulsifying properties. The structure of the processed Emmental: internal reports).
cheese depends on the type of cheese used, the fat ratio, General aspects of the shelf-life of various foods are
the dry matter and the ability of the emulsifying salt to discussed in textbooks. The following main changes will
sequester the calcium (Paquet, 1988). be described: loss of water vapour, hydrolysis of
polyphosphates, changes in ionic equlibria, formation
Manufacture of Ready-made Fondue of crystals, reactions induced by heat-stable enzymes,
nonenzymic browning, reactions induced by light and
The manufacture of ready-made fondue is similar to the oxygen as well as interactions with packaging materials.
manufacture of processed cheese. White wine, starch
and Kirsch brandy are additional ingredients. As the
tartric acid from the wine acts as a chelating agent, the Loss of Water Vapour
content of emulsifying salt is set to a maximum of
8 g/kg, whereas processed cheese contains up to 40 g/kg Usual packaging material for processed cheese provides
(Eidgenössisches Departement des Innern, 1998). Com- a good, but not a completely tight barrier against water
mercial ready-made fondue is traditionally filled into vapour. Depending on storage temperature, a consider-
multilayer aluminium pouches with a content of 400 g. able weight loss may occur, leading to a firmer texture
Recent developments include ‘microwaveable’ fondue in (Tiger Cheese Ltd., Langnau-Emmental: internal
cups. reports). Typically, processed cheese slices, stored for
1 mo at 20 1C, may present a weight loss of 2–5 g/kg
(Ney, 1988).
Microbiological Aspects

The scope of this review is limited to publications Hydrolysis of Polyphosphates


dealing with bacteriologically stable products. Micro-
biological hazards can be eliminated by UHT pro- Linear polyphosphates (with  4 phosphates) are ob-
cessing: even temperature-resistant spores such as tained from very pure orthophosphates (monophosphates)

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Table 1 Chemical and physical changes in processed cheese during storage


Influence on
Practical Improvement
Effect Cause Flavour Texture significance possibilities
Loss of water Packaging not Noa Becomes Depends on the Tighter packaging
vapour completely tight firmer packaging properties Storage at lower
temperatures
Polyphosphates Unstable polypho- Noa Yes Only in products con- Storage at lower
hydrolysis sphates in aqueous so- taining polyphosphates temperatures
during storage lutions, hydrolysed to
short-chain poly- and
orthophosphate
Changes in ionic Interaction of emulsi- Noa Becomes Mainly in processed Optimised mixture of
equilibrium fying salts with ions firmer cheese spreads with emulsifying salts
and polyphosphates Storage at lower
proteins temperature
Crystal formation Solubility of the No Yes Depends on product Optimised mixture and
ionic components such composition and process quantity of emulsifying
as calcium, amino acids salts
and emulsifying salts Avoid ripe cheese
including crystals
Reactions induced Even after processing Yes Yes Depends on ingredients Careful selection of in-
by heat-stable heat-stable and heat treatment gredients
enzymes enzymes might during processing Higher heat treatment
remain active during processing
Storage at lower
temperatures
Nonenzymic Reaction of reducing Yes Not Products with a signifi- Lower lactose content
browning sugars with amino significant cant amount of lactose Less severe heat treat-
acids (1–6%) become yellow/ ment Storage at lower
brown temperatures
Reactions induced Traces of oxygen Yes Not Depends on composition Tighter packaging
by light and in the package. Oxidation significant (oxidising, antioxidative with lower oxygen
oxygen Permeation of flavour components), light and permeation
oxygen through packaging properties Packaging with a good
the package. light barrier
Storage at lower
temperatures
Interactions with Migration of packa- Yes No Depends on Selection of optimal
packaging ging components, cor- packaging packaging material.
materials rosion of aluminium materials Storage at lower
foil temperatures
a
Indirect effect possible because of different texture and mouth-feel.

by high-temperature condensation (Chambre and improve calcium binding (Berger et al., 1989; Caric and
Daurelles, 1997). They are hydrolysed in an aqueous Kalab, 1997). The rheological properties of various
solution (Berger et al., 1989). This reaction begins processed cheese slices were measured during 1 mo of
during melting and continues during the storage of storage at 4, 13 and 20 1C (Ney, 1988). A measuring
processed cheese (Ney, 1988). The hydrolysis quickly device was developed, which bends the slices until they
leads first to triphosphates and diphosphates (pyropho- break. The breaking angles generally decreased during
sphates) then more slowly to orthophosphates which are storage and were not caused by pH or loss of water
excellent pH buffers (Mair-Waldburg, 1958; Ruf and vapour. The results were described as a hardening effect
Gläser, 1971). A part of added polyphosphates is and related to the hydrolysis of polyphosphates
already hydrolysed during the melting process. The rest (Ney, 1988).
is completely hydrolysed after 7–10 wk of storage (Caric Klostermeyer (1990) reported measurements of the
and Kalab, 1997). The hydrolysis of oligo- and firmness, viscosity and elasticity of various processed
polyphosphates creates new acid functions thus lowering cheeses. Products containing phosphates first showed,
the pH-value of the product and inhibits an eventual pH however, a decreasing resistance after production. After
increase (Chambre and Daurelles, 1997). The buffering about 3 wk a minimum was reached, thereafter the
capacity of polyphosphates depends on the chain length: measured resistance rose again. This effect was not
the higher the chain length, the lower the buffering observed with products containing citrates as emulsify-
capacity. Commercial mixtures of emulsifying salts ing salt. The curves presenting minima or maxima often
often contain short-chain oligophosphates with the result from opposite processes, likely a slow destruction
required good balance of calcium binding and buffering of the primary gel structure and the formation of a
properties. Long-chain polyphosphates are added to secondary structure. The author supposes that these

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phenomena are related to precursors in the submicelle of cheese analogues made from rennet casein. The
range. plasmin content significantly influenced the proteolytic
and rheological changes during 1–35 wk of storage.
Beta-casein was more extensively hydrolysed than as1-
Changes in Ionic Equilibria casein. As rennet (EC 3.4.23.4) is a relatively heat-
sensitive enzyme, its activity in processed cheese seems
After the melting and cooling of processed cheese, the negligible (Mulvihill and McCarthy, 1993). Heat-stable
ionic equilibria and hence the pH settle slowly. During lipases may also be active: processed cheese made with
storage, the loss of water vapour and the hydrolysis of ripe Camembert cheese may develop a noticeable
polyphosphates in turn influence the ionic equilibria in lipolysis during storage (Morgenthaler, M. Gerber
processed cheese. In addition, interactions between Cheese Ltd., Thun, Switzerland: pers. comms., 2000).
protein, emulsifying salt, sodium and calcium influence
water binding and texture. Processed cheeses typically
become firmer during storage. Spreadable, ‘creamed’ Nonenzymic Browning
products should be stored below 20 1C, preferably at
10–15 1C, to avoid a firmer, shorter texture (Chambre Nonenzymic browning (‘Maillard reaction’) is an im-
and Daurelles, 1997). portant and widely occurring reaction in foods. The
primary reaction is the carbonyl-amine addition between
reducing sugars and amines (usually the e-amino groups
Formation of Crystals of lysine). It is followed by rearrangements, scissions,
hydrolyses and other carbonyl-amine reactions, as well
Crystals are due to compounds with a low solubility. as numerous further reactions (Feeney and Whitacker,
The following possible crystals have been reviewed 1982). The Maillard reaction and its prevention
(Berger et al., 1989; Caric and Kalab, 1997; Uhlmann have been reviewed (Feeney and Whitacker, 1982;
et al., 1983): calcium phosphate, calcium diphosphate, Pizzoferrato et al., 1998; Yaylayan, 1997). Its relevance
calcium lactate, lactose, crystalline amino acids such as in processed cheese was discussed by Berger et al. (1989).
tyrosine, and calcium tyrosinate. Crystals of emulsifying It plays a key role in products containing high amounts
salts may be observed in processed cheese as a result of of lactose (10–80 g/kg). During storage, especially at
(i) an excess of emulsifying salt, (ii) an unsuitable elevated temperatures, the formation of a brownish
mixture of emulsifying salts or (iii) insufficient dissolu- colour and an off-flavour limit the shelf-life of the
tion of the latter in the mixture during processing. product. The extent of Maillard reactions is reduced by a
Tyrosine or other crystals may act as nuclei for the lower lactose content, less severe heating conditions and
formation of further crystals (Berger et al., 1989; a lower storage temperature (Berger et al., 1989;
W. Berger, pers. comms., 2000). In general, the Piergiovanni et al., 1989). The influence of manufactur-
formation of crystals is favoured by excessive amounts ing procedures and composition of stirred-curd Cheddar
of emulsifying salts or lactose, a high calcium content in cheese were investigated for their effects on the non-
the natural cheese, a high pH-value and a long storage enzymic browning of processed cheese (Bley et al., 1985).
of the processed cheese at low temperatures (Caric and The correlation between galactose content of Cheddar
Kalab, 1997). and the brown colour intensity in process cheese was
Crystallisation on the surface of processed cheese slices very high. Faster cooling of processed cheese reduced the
is influenced by mechanical treatments as well as the intensity of brown colour. In another study, non-
phosphates/citrates ratio in the emulsifying salt (Uhl- enzymic browning of processed cheese was examined in
mann et al., 1983). Small white crystals, identified as a model system. The processing temperature and storage
calcium citrate or tertiary sodium calcium citrate, may temperature were found to be more important factors
occur on the surface of processed cheese slices (Berger than the concentrations of protein and lactose. The
et al., 1989). results indicated the advisability of storing processed
Microcrystals of calcium phosphate and calcium pyro- cheese at low temperature (approx. 5 1C), since otherwise
phosphate dihydrate have been described (Pommert the Maillard reaction continues during storage (Piergio-
et al., 1988). These microcrystals do not affect the taste vanni et al., 1989).
and the appearance of the processed cheese, in contrast
with the other crystals responsible for spots or lines on
the product surface. Reactions Induced by Light and Oxygen

Typical packaging materials for processed cheese


Reactions Induced by Heat-stable Enzymes include aluminium foils for portions, multilayer foils
for slices, steel cans and cups (Sturm, 1998). Bosset et al.
Most enzymes are denatured and deactivated during (1993) and recently Borle et al. (2001) reviewed light-
processing. Nevertheless, denatured proteases may induced reactions in milk and milk products. These
rearrange and exhibit a certain degree of proteolytic reactions may be relevant for slices in transparent foil,
activity. Mulvihill and McCarthy (1993, 1994) examined but do not occur in opaque packaging materials such as
proteolytic and rheological changes during the storage aluminium foils or steel cans. Processed cheese slices in

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transparent foil are usually conditioned under a content. Other compositional factors such as lactose
protective atmosphere (nitrogen/carbon dioxide) with content or emulsifying salts also influence the shelf-life.
an oxygen content below 20 mL/L. Oxidative reactions Most changes with age can be slowed down by lower
leading to colour change (Kristensen et al., 2001) and storage temperatures.
the formation of off-flavour due to methional and While these global effects of storage on processed cheese
carbonyl compounds as well as cholesterol oxides are well known, this review clearly highlights the need
depend on processed cheese composition (oxidising for further research on specific topics such as changes in
and antioxidative components), light expose (emission equilibria and interactions between the product compo-
spectrum, intensity, duration) and properties of the nents. The chemistry of the system during the ‘hard-
packaging. Studies on various milk products, including ening’ of processed cheese as well as discrepancies
processed cheese, show, that the formation of cholester- between effects noted by various authors in different
ol oxides is negligible under normal processing and studies should still be experimentally explored and
storage conditions (Bosset et al., 1993). The influence of explained. Moreover, two main fields should be
different packaging materials (tin cans, polystyrene investigated: the storage of ready-made fondue, which
cups, LDPE tubs) and storage temperature was exam- was never dealt with, and the relationship between
ined in an Indian study (Goyal and Babu, 1991). storage duration and storage temperature.
Samples packaged in tin cans had the least chemical
changes.
Acknowledgements
Interactions with Packaging Materials
We are grateful to Mr Wolfgang Berger (Römerberg,
Germany), Mrs Annie Imbert (Fromageries Bel, Ven-
A typical aluminium foil (11–15 mm) for processed
dôme, France), Mr Robert Sieber (FAM) and Mrs
cheese is coated with a protective polymer and a
Gerda Urbach (Australia) for their careful review of the
polyvinyl co-polymer with a sealing temperature of
manuscript.
65–75 1C (Sturm, 1998). This coating protects the
aluminium from corrosion due to salts and acids present
in the matrix and also prevents the undesirable
migration of aluminium into the cheese body. Factors References
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