Changes During Freezing
Changes During Freezing
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Lesson 28. Changes undergone by the food components during Freezing
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28.1 INTRODUCTION
Current course
Dairy and Food One of the greatest challenges for food technologists is to maintain the quality of food products for an extended period. The principles of low-
Engineering
temperature preservation have been employed for many years. It renders advantageous negative effect of reduced temperature on various chemical
Participants
and biochemical reactions responsible for food spoilage, as well as on microbial growth and spore germination. Freezing is a well-known long-
General
term preservation process widely used in the food industry. This is because changes in the nutritional or sensory characteristics of foods are small
Module 1. Dairy
Development in
if appropriate freezing and storage procedures are followed. The freezing of foods normally consists of pre-freezing treatments, freezing, frozen
India storage, and thawing, each of which must be properly conducted to obtain optimum results. A decrease in temperature generally decreases the rate
Module 2. of chemical reactions that are responsible for the deterioration in food quality over time; therefore freezing is frequently used to extend the shelf
Engineering, life of food products. When a product is frozen, the formed ice crystals may cause cell rupture and alterations in the transport properties of cell
thermal and
chemical proper... membranes, which have practical consequences in terms of leaching of cellular substances from tissues as well as water loss, leading normally to
Module 3. Unit disappointing consequences in terms of texture. There is a general acceptance that high freezing rates retain the quality of a food product better
operation of various than lower freezing rates since evidence tends to show that relatively slow freezing causes large ice crystals to form exclusively in extracellular
dairy and food...
areas, while high freezing rates produce small uniformly distributed ice crystals. The formation of ice may result in textural changes and disruption
Module 4. Working
principles of
of cell compartments that cause the release of chemically reactive components. Furthermore, the removal of water during ice formation
equipment for concentrates the solutes in an unfrozen matrix, which can affect reaction conditions, such as pH and ionic strength. Therefore in order to extend the
rece... shelf life of frozen food products, it is crucial to understand the chemical reactions that can occur in food components that can lead to quality
Module 5. Dairy deterioration.
plant design and
layout, compositi...
Module 6.
Deterioration in 28.2 EFFECT OF FREEZING ON PRINCIPAL CONSTITUENTS OF FOODS
products and their
cont...
The effect of freezing on the food components is diverse, and some components are affected more than others. For example, protein can be irreversibly
Module 7. Physical,
chemical and denatured by freezing, whereas carbohydrates are generally more stable. Other common chemical changes that can proceed during freezing and frozen storage
biological method... are lipid oxidation, enzymatic browning, flavour deterioration, and the degradation of pigments and vitamins. The main goal of the freezing process is to extend
Module 8. Changes the shelf life of a raw material or product beyond that achievable at temperatures above the initial freezing point of the material. Therefore, it is important to
undergone by the understand the modifications that can occur during freezing in food components and that can further lead to quality degradation. This chapter focuses on
food components...
chemical and biochemical reactions that affect the quality of frozen food systems. These reactions and specific examples in food are summarized in Table 28.1.
Lesson 26.
Changes
undergone by
Changes that occur in foods during freezing, storage and thawing can be both chemical and physical in nature. Various chemical, enzymatic and physical
the food changes are promoted as a result of the concentration of components (concentration effects) in the unfrozen water phase within the frozen foods. For example:
component...
Lesson 26 Quiz Chemical changes such as oxidative rancidity or oxidation of flavour components, pigments and vitamins.
Lesson 27.
Changes Enzymatic reactions such as enzymatic browning or lipolytic rancidity.
undergone by
the food Meats become tougher due to protein denaturation by chemical effects and cell breakage by ice crystals
component...
Lesson 27 Quiz In freezing foods, the objective is to promote the formation of tiny ice crystals rather than the formation of fewer but larger ice crystals that cause cellular
Lesson 28. damage. Ice crystal damage can lead to loss of water from the food product once it is thawed. The drip that is found in thawed strawberries or beef is due in part
Changes to ice crystal damage to the cells, leading to leakage of cellular fluids into extracellular spaces, and to the loss of water-holding capacity of food components as a
undergone by
result of concentration effects.
the food
component...
Other undesirable changes include formation of package ice and freeze dehydration which is popularly called freezer burn and can produce unsightly food
Lesson 28 Quiz
surfaces and loss of nutrients. "Freezer burn" is a misnomer since the food does not "burn" in the freezer but rather takes on an appearance of having been
Lesson 29.
Changes burned because of the moisture loss that occurs during this freeze dehydration.
Undergone By
Fruit 28.2.1 WATER
Components D...
Lesson 29 Quiz Water is an essential constituent of most foods. It is present in a very wide range, varying, for example, from 4% in milk powder up to 95% in tomato and
Module 9. Plant lettuce. Water may exist as an intracellular or extracellular component in vegetable and animal products, as a dispersing medium or solvent in a variety of
utilities requirement. products, as the dispersed phase in some emulsified products such as butter and margarine, or as a minor constituent in other foods. The conversion of water into
References ice during freezing has the advantage of fixing the tissue structure and separating the water fraction in the form of ice crystals in such a way that water is not
Courses available as a solvent or cannot take part in deterioration reactions. On the other hand, ice crystals formed during freezing can affect quality parameters such as
color, texture, and flavor. Meanwhile, in the remaining unfrozen portion, the concentration of dissolved substances increases, while the water activity of a
product decreases. Usually, this part of water is non-freezable and, therefore, not available for chemical reactions or as plasticizers. The water that does not
freeze is normally considered to be the critical water content above which deteriorative changes may occur. Critical water is a rather unusual substance having
high boiling and low freezing points, high specific heat, high latent heats of fusion and vaporization, high surface tension, high polarity, and unusual density
changes. The considerable difference in the densities of water and ice may result in structural damage to foods when they are frozen, being more likely in plant
tissue with its rigid structure and poorly aligned cells than in muscle with its pliable consistency and the parallel arrangement of cells.
Table-28.1: Chemical Reaction of Food Components during Freezing that Affect Food Quality
Toughening and
functional changes,
particularly loss of protein
Degradation of solubility in fish,
texture and
Protein Denaturation Loss of protein solubility,
functional
emulsifying capacity
properties
Loss of water holding
capacity of meat for
processing
and interact
with other
components to
produce off
flavours,
discoloration,
and
toughening of
muscle protein
Increases the
amount of
smaller Sucrose hydrolysis
molecular
weight
components—
Carbohydrates Hydrolysis leads to lower
melting
temperatures Firmness of ice cream
decreased as hydrolysis
progressed
Change of
texture
Greenness in Brussels
Colour Green sprouts decreased
pigments chlorophyll Stability of green colour
forms in kiwifruit
olivebrown
(a) Frozen blanched spinach
Chlorophyll Pheophytinization pheophytin in had a higher amount
the
of pheophytin than fresh
presence of
acid or heat
Glucosidase
hydrolyses
glycosidic
Enzymatic
linkages and
reaction produces
sugars
Loss of anthocyanin in
and aglycone
raspberry in the late
compounds
cultivar was more severe
than the early cultivars
(b)
Anthocyanin
Depending on
the pH of the
Red colour hue of sour
food,
cherry weakened during
different forms
Structure of frozen storage
anthocyanin of anthocyanin
exist,
depends on pH
value usually from
red to blue as
pH
increases
The loss of
pigments
(c) causes fading Loss of carotenoid in
Oxidation
Carotenoids of colour and salmon
loss of
nutritive value
Effect of heat
Oxidation
Loss mainly
through leaching
When water freezes at atmospheric pressure, it expands nearly 9%. The degree of expansion varies considerably owing to the following factors:
28.2.2 PROTEINS
Proteins may undergo changes during freezing and frozen storage, primarily because of denaturation. Denaturation can be defined as a major change in the
native structure that does not involve alteration of the amino acid sequences and usually involves the loss of biological activity and significant changes in some
physical or functional properties such as solubility. Oxidative processes during storage can also contribute to protein denaturation; oxidizing agents (e.g.,
enzymes, transition metals) can react with proteins via lipid and nonlipid radicals. For example, the addition of malonaldehyde, a commonly occurring product
of lipid oxidation, to trout myosin solutions during storage at −4°C was found to accelerate protein denaturation. Fish protein is particularly sensitive to
denaturation where the protein develops cross links between adjacent protein molecules that effectively stop the thawed fish protein to reabsorb water to recreate
the pre-frozen gel structure. This denatured protein has a much tougher and rubbery texture than the native protein. The textural changes that occur in fish
proteins have been attributed to changes in the myofibrils. The rate at which fish or beef muscle is frozen also influences the degree of protein denaturation.
Although rapid freezing generally results in less denaturation than slower freezing, intermediate freezing rates can be more detrimental than slow freezing, as
judged by textural changes and the solubility of actomyosin. For example, cod fillets frozen at intermediate rates developed intracellular ice crystals large
enough to damage the cellular membranes.
Freezing and frozen storage do not significantly affect the nutritional value of meat and fish proteins. However, on thawing frozen meat and fish, substantial
amounts of intra- and extracellular fluids and their associated water-soluble proteins and other nutrients may be lost (the so-called drip loss). The volume of drip
loss on thawing of meat and fish is highly variable, usually of the order of 2%–10% of net weight; however, in exceptional circumstances, up to 15% of the
weight of the product may be lost. Nevertheless, it was observed for fish that if the product is stored for an appropriate short time and at a sufficiently low
temperature, the subsequently thawed fish would rehydrate with the protein returning to its original gel condition. The caseinate micelles of milk, which are
quite stable to heat, may also be destabilized by freezing. On frozen storage of milk, the stability of caseinate progressively decreases and this may lead to
complete coagulation. Enzymes have also been linked to protein denaturation, as it is known that low temperature decreases the activity of enzymes in tissue,
but does not inactivate them.
28.2.3 LIPIDS
Lipids in food exhibit unique physical and chemical properties. Their compositions, crystalline structure, melting properties, and ability to associate with water
and other nonlipid molecules are especially important to their functional properties in many foods. During processing, storage, and handling of foods, lipids
undergo complex chemical changes and react with other food constituents, producing numerous compounds both desirable and deleterious to food quality. The
process of auto oxidation and the resulting deterioration in flavor of fats and fatty foods are often described by the term rancidity. In particular, the unsaturated
bonds present in all fats and oils represent active centers that, among other things, may react with oxygen. This reaction leads to the formation of primary,
secondary, and tertiary oxidation products that may make the fats or fat-containing foods unsuitable for consumption.
Lipids can degrade in frozen systems by means of hydrolysis and oxidation. Lipid oxidation is indeed one of the major causes of food spoilage. It is of great
economic concern to the food industry because it leads to the development of various off flavors and off-odors. In addition, oxidative reactions can decrease the
nutritional quality of foods. Lipids in foods can be oxidized by both enzymatic and non enzymatic mechanisms. One of the enzyme that is considered important
in lipid oxidation is lipoxygenase, which has recognition for its off-flavor development in vegetable. Lipoxygenase is the main enzyme responsible for pigment
bleaching and off-odors in frozen vegetables; if the enzyme is not inactivated before freezing by blanching, it can generate offensive flavors and loss of pigment
color. At temperatures below −10°C, both enzymatic and non enzymatic reactions associated with lipid oxidation are decelerated. However, in the range from
0°C to −10°C, decreased oxidative stabilities have been noted. Unless the rate is very slow, the rate of freezing has been found to have little influence on the
oxidative stability of frozen products. Instead, storage temperatures play a dominant role in dictating the stability of food products, including muscle foods. The
order of time/temperature holding treatments, on the other hand, markedly influences the development of rancidity. The hydrolysis of lipids or lipolysis results
in the release of free fatty acids. Freezing can facilitate lipid oxidation, partly because the competing reactions of microbiological spoilage are avoided and
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14/06/2022, 09:28 Dairy and Food Engineering: Lesson 28. Changes undergone by the food components during Freezing
partly because of the concentration effects. Thus, lipid oxidation is relatively more important in frozen muscle tissue than in fresh tissue. Lipid degradation can
be reduced in frozen foods by lowering the storage temperature, excluding oxygen (e.g., use of vacuum packaging), adding antioxidants (e.g., butylated
hydroxytoluene or BHT as well as natural vitamin E), and supplementing the diet of animals with antioxidants.
28.2.4 VITAMINS
Freezing is considered as one of the best food preservation methods when judged on the basis of nutrients retention. However, it is well known that significant
amounts of some vitamins can be lost from processing prior to freezing (e.g., peeling and trimming, leaching especially during blanching), chemical
degradation, and thawing. The stability of vitamins in foods is generally influenced by pH and the presence of oxygen, light, metals, reducing agents, and heat. It
has been reported that for some frozen foods such as strawberries, the total and biologically active ascorbic acid remain at essentially the same level for a year or
longer if the foods are stored below −18°C, although vitamin C losses have also been found to occur at temperatures as low as −23°C. The conversion to the
partially active dehydroascorbic acid and the totally inactive 2,3-diketogulonic acid increases with increasing storage temperature; complete conversion
practically occurs in 8 months at −10°C and in less than 2 months at −2°C. Such findings were instrumental in establishing −18°C as the upper limit for frozen
food storage and for using biologically active ascorbic acid as a general indicator of quality deterioration during frozen storage. For peaches and boysenberries,
a 10°C rise in the temperature from −18°C to −7°C caused the rate of vitamin C degradation to increase by a factor of 30–70. Vitamin C and thiamine (vitamin
B1) have been studied extensively since they are water soluble, highly susceptible to chemical degradation, and present in many foods; they are also required in
the diet and are sometimes deficient in the diet. Therefore, it is generally assumed that if these vitamins are retained, all other nutrients would also be well
retained.
28.2.5 CARBOHYDRATES AND MINERALS
Carbohydrates occur in plant and animal tissues in many different forms and levels. In animal organisms, the main sugar is glucose and the storage carbohydrate
is glycogen; in milk, it is almost exclusively the disaccharide lactose. In plant organisms, approximately 75% of the solid matter is carbohydrate. The total
carbohydrate content can be as low as 2% of the fresh weight in some fruits or nuts, more than 30% in starchy vegetables, and over 60% in some pulses and
cereals. In plants, the storage carbohydrate is starch, while the structural polysaccharide is cellulose. The nutritive value of carbohydrates is not significantly
affected during handling of fresh foods and the subsequent processing and distribution of frozen foods. In general, carbohydrates are susceptible to hydrolysis
during frozen storage, which can still occur at temperatures as low as −22°C. Like B vitamins and proteins, carbohydrates are less affected by process and more
by loss through drip following a freeze–thaw cycle. Sugar hydrolysis increases the number of solutes in the food matrix, resulting in a reduction in the amount of
ice in the product, which may alter certain physical properties; for example, the firmness of ice cream was found to inversely relate to the degree of hydrolysis.
Blanching and freezing can cause changes in texture and the pectic composition of certain foods. Both treatments produce a gradual breakdown in the
protoplasmic structure organization, with a subsequent loss of turgor pressure, release of pectic substances, and final softening effect.
Minerals present in any form (e.g., chemical compounds, molecular complexes, and free ions) can dramatically affect the color, texture, flavor, and stability of
foods. Minerals are chemically stable under typical conditions of handling and processing, and nutrient losses are negligible, provided that losses by physical
means (e.g., leaching) are avoided. Nevertheless, no changes were observed in six mineral elements (Ca, Cu, Mg, Mn, Ni, and Zn) between fresh and frozen
artichokes, green beans, and peas; boiled fresh vegetables and boiled frozen vegetables also exhibited similar mineral contents.
28.3 CONCLUSION
Freezing is complex process involving physical and chemical changes that might greatly affect the food quality. Further to minimize the changes in food
components during freezing it is imperative to to freeze a product quickly to –18°C and store it at the same temperature throughout the cold chain.
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