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PRACTICAL GUIDE

r e f r i g e r a t i o n
The following article was published in ASHRAE Journal, November 1999. Copyright 1999 American Society of Heating, Refrigerating and AirConditioning Engineers, Inc. It is presented for educational purposes only. This article may not be copied and/or distributed electronically or in paper form without permission of ASHRAE.

Food Preservation
By David S. Reid Member ASHRAE

o ensure a secure and steady food supply, food needs to be preserved, protected from undue deterioration, and stabilized so it can be

stored for extended periods. Extending foods shelf life requires an understanding of the factors that limit shelf life and of the processes that cause foods to become unsuitable for consumption.
There is a wide range of food preservation techniques available. These include thermal processing (e.g., cooking), refrigeration, drying, intermediate moisture preservation techniques, the use of additives, and freezing. This article discusses those techniques and explains how they work.

Food Preservation Techniques Thermal Processing. Thermal processing uses a heat treatment to stabilize the product by controlling the microbial population. Thermal methods include sterilization, pasteurization, and aseptic processing. The traditional thermal process technology is canning, which uses a sterilizing heat treatment. Canning often causes significant change in product characteristics, due to thermal damage. A more recently developed thermal process, aseptic processing, uses a reduced heat treatment and results in a product with less thermal damage. This process demands more careful handling during and before processing than sterilization. Thermal processing preserves food by destroying microbes, preventing growth. The package is designed to prevent re-contamination, and the product is stable at ambient temperature. Examples of aseptically processed foods include many of the boxed juice drinks available on the market. Also, many of the shelf-stable meals in pouches are aseptically processed. Pasteurization is less severe than canning and controls vegetative microorganisms. However, the process does not achieve sterilization. The shelf life of canned products under ambient storage conditions can be very long. The shelf life of products with a lesser thermal treat40

ment, such as aseptic processing or pasteurization, tends to be shorter. The shelf life can often be extended by refrigerated storage. Refrigeration. Refrigeration uses low temperature to preserve food. At lower temperatures, microbial growth slows. Many of the chemical reactions that deteriorate food are also slowed. Control of the refrigerated storage temperature is essential to maintaining good quality. Individual foods and individual microorganisms have their own responses to refrigerated storage. Various data sources, including Chapter 25 of the 1998 ASHRAE HandbookRefrigeration, identify the preferred conditions for storing many products that are candidates for extended refrigerated storage. While refrigeration extends shelf life, many products have limited shelf life even when refrigerated. Although storage life is limited, the quality of refrigerated produce tends to be superior to that achieved through a thermal process because no thermal degradation is incurred. Drying. Drying removes much of the solvent water in food, which slows many of the chemical degradation processes that take place in the high moisture environment of fresh foods. These chemical degradation processes often are responsible for the reduction in acceptability of fresh food after extended storage. Also, a certain level of water is required for the growth of microorganisms, so drying also may prevent microbial deterioration. Drying causes significant changes in the properties of the food. The characteristics are very different from the original fresh raw material. Nevertheless, the resulting product may be acceptable. Dried products may be consumed as they are delivered, or they may be rehydrated prior to consumption. Many traditional foods incorporate a drying step. Dried foods can be stable under a wide range of storage conditions. Examples of dried foods include pasta, beef jerky, and powdered milk. In addition to conventional air drying, freeze-drying can be used. David S. Reid, Ph.D., is a professor in the Department of Food Science and Technology at the University of California at Davis.
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This is a more expensive process, which often results in less damage to the original product. Many backpacking meals are produced by freeze-drying. Intermediate Moisture Preservation. Partial drying is used to produce foods such as raisins and semi-moist pet foods. Products using this technology are referred to as intermediate moisture foods. Their preservation is largely a result of inhibiting microbiological spoilage, although chemical change may be slowed as well. Enhanced microbiological stability often can be achieved with antimicrobial additives, such as sorbates and propionates. In addition to partial drying (i.e., removing moisture), intermediate moisture states can be achieved by adding appropriate solutes, such as glycerol or other humectants. These solutes lower the partial vapor pressure of the water in the food and as a result inhibit microbial growth. Particular microorganisms may be inhibited in specific ranges of relative vapor pressure. Food Additives. Adding compounds that slow chemical change or inhibit microbial growth is also an important preservation technology. Examples include salting, pickling, and adding antioxidant compounds. Freezing. The final method to describe, which is the primary focus of this article, is freezing. Freezing preserves foods by storing them at temperatures around 0F (18C). Since freezing uses low temperatures, it can be considered a refrigeration technique. However, ice forms on freezing, reducing the amount of liquid water in the food, thus increasing the solute concentration. In this aspect, freezing is akin to intermediate moisture foods. Hence, freezing provides preservation through two important mechanismsreducing temperature and reducing water availability. timicrobial agents such as sorbic acid. Maintain temperatures low enough to slow down or prevent growth of microorganisms. This is the primary function of refrigeration. The temperature range for control is specific to the microorganism. However, a hazard still exists for different organisms in certain temperature regions. Some microorganisms, including listeria, an important pathogen, can grow at normal refrigeration temperatures. Hurdle technology. Here a product is subjected to several different means of controlling microbiological growth as a sequence of barriers. The result tends to be more effective than one might expect by simply summing the expected effects. The temperatures used for preservation and storage by freezing are low enough to prevent the growth of all microorganisms. Indeed, at these low storage temperatures there may even be a reduction in microbial numbers. This is not, however, equivalent to sterilization, or even pasteurization. Upon warming, growth is possible. Thus, care must be taken to maintain frozen storage temperatures. Improper handling and processing prior to freezing can cause the growth of hazardous organisms before freezing. The organisms are not eliminated by freezing, but remain in the product. Therefore, proper handling is essential for microbiological safety in products prior to freezing. Otherwise, freezing provides excellent control of microbiological degradation and microbiological hazard. Chemical changes. Chemical changes are a significant source of product degradation. They can be influenced by the conditions that exist in freezing and frozen storage. Processes of particular significance are: Protein denaturation: The state of the protein in a food is important to its nutritional quality and to its textural characteristics. In many foods it is important that proteins retain their native characteristics. Freezing and frozen storage can cause some proteins to establish additional internal cross-links, denature, and lose a lot of their hydration capability. This is an important factor for some fish during frozen storage. Due to denaturation, the texture becomes tough, and the water holding capability is lost. As food freezes and ice forms, salt concentration increases. At high salt concentrations, many proteins lose solubility. This change may be irreversible. Some of the changes in protein are the result of enhanced enzyme activity under the conditions of freezing. Some products of enzyme activity can react with proteins, reducing the functionality of the proteins. Color changes: Color is an important attribute of food. A change in color can signal other deleterious alterations and may also, of itself, lead to reduced consumer acceptability. Freezing and frozen storage can result in the degradation of chlorophyll to pheophytin, a change from green to olive drab. Due to both enzymic
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Preservation Factors in Freezing To understand preservation methodology, one must understand the factors that lead to deterioration and loss of quality. Three primary types of factors influence shelf life: microbial, chemical, and physical. It is helpful to examine each of these categories to consider their influence on food quality and shelf life and to consider the means for modifying and mitigating their impact. This article discusses these mechanisms with the primary focus on their relevance to preservation through freezing. Microbiological growth. Microbiological growth leads to significant deterioration and hazard in many foods. Four primary methods of control of microbiological hazard follow: Destroy the microorganisms through heating. This method includes pasteurization, where only vegetative microorganisms are destroyed, and sterilization, which also destroys spores. Spores have a higher thermal resistance than vegetative cells. Control the growth of microorganisms by altering water availability or by controlling system composition. This method is the traditional control found in intermediate moisture foods, salted foods, and foods that contain anN o v e m b e r 19 9 9

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and non-enzymic processes, brown colors may be produced. These are often accompanied by bitter flavors, particularly as the result of polyphenol oxidase activity. The action of hydrolytic enzymes, such as chlorophyllase, can lead to loss of color. Oxidation: There are many examples of quality loss due to oxidation in frozen systems. A typical test for loss of fish quality measures the amount of an early oxidation product, malondialdehyde. Some oxidation processes are catalyzed by the presence of oxidative enzymes. Lipid oxidation is a frequent problem in frozen foods, but many other important molecules are also susceptible to oxidation. Many oxidative reactions are enzyme catalyzed. Hydrolysis: Lipid hydrolysis is encountered in frozen storage of many products, with the consequential formation of free fatty acids that have an immediate flavor impact. Proteins can also degrade from hydrolytic changes initiated by proteases. In gadoid fish such as cod, enzymic hydrolysis of trimethylamine oxide leads to the production of trimethylamine, the source of the intense, unpleasant fishy odor of some poorly stored fish. Enzyme action: Many changes in biological systems are catalyzed by enzymes. In intact tissues, these processes take place in a controlled manner. However, if tissues are disrupted, uncontrolled action can result. Freezing tends to disrupt tissues. The concentration effect of removing water as ice also can lead to changed catalytic rates. There are many examples of product changes and deterioration caused by uncontrolled enzyme action. In fruits and vegetables, oxidative change can be catalyzed by polyphenol oxidase, by lipoxygenase, and many other enzymes. This results in color and flavor changes. There are many hydrolytic enzymes, including lipases, proteases, demethylases. Through their action, off flavors can develop, proteins can become insoluble, and textures can change. Unwanted enzyme action can be prevented through blanching, a heat treatment that destroys the enzymes, or with additives that can function as enzyme inhibitors. In general, the rates of all of these processes are temperature dependent, with significant rate reductions at low temperatures like those encountered during frozen storage. An exception is the rate of lipid oxidation in systems with a high amount of unsaturated fats. Here the rate may increase at lower temperatures due to a catalytic effect of high salt concentrations. Physical processes. Physical processes also influence the quality and shelf life of frozen products. Physical processes that lead to significant quality loss include: Moisture migration: The location of moisture within a product is important to product quality. In the presence of temperature gradients, water may diffuse along the concomitant water vapor pressure gradients. This can cause unacceptable change. If the moisture diffuses from the surface of the product, partial drying may occur. Defects such as freezer burn may be seen. The driving force for moisture migration in foods containing ice is
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invariably the existence of temperature gradients within the product and also within the package and the environment. Recrystallization: In a frozen product, the number of ice crystals decreases with time and the average size of ice crystal increases, due to a variety of recrystallization processes. The increase in ice crystal size can be accompanied by a loss in product quality. This is seen in many products, but is particularly evident in ice cream, and other frozen confections, where ice is an important contributor to the eating experience. Altered molecular mobility: Many physical processes are influenced by molecular motions. Hence, if molecular mobility changes, these processes will be affected. The lowering of temperature and the increasing of concentration (as water separates out as ice crystals) both lead to reduced molecular mobilities. Freezing incorporates both lowering temperature and increasing concentration. As a result, freezing has a significant influence on molecular mobility. Recent understanding of frozen storage stability involves taking into account the effect of system composition on the changing of molecular mobilities below the freezing point temperature in a frozen system.

Factors That Influence Stability Given the importance of chemical and physical processes to the stability of frozen products, it is important to consider them in light of the principal factors that influence the stability of a frozen product. These factors are the storage temperature, temperature fluctuation during storage, the composition of the product, the existence of vapor spaces and barriers within the product structure, the presence of crystal growth inhibitors, and the changing mobility of the constituent molecules as a function of temperature, particularly the temperatures at which that mobility becomes severely constrained. Temperature and temperature fluctuation. The temperature of a frozen system governs the concentration relationships. This is best illustrated by the use of phase and state diagrams (Figures 1 and 2). Figure 1, a binary phase diagram, illustrates that as temperature is reduced below the freezing point, the composition of the unfrozen phase increases. Like a solution of molten metals, the increase in concentration as temperature goes down follows the liquidus. In an ideal system, when the unfrozen solution reaches saturation, at Point E of Figure 1, the solute precipitates, and a solid eutectic system ensues. Crystallization of the solute may be inhibited for many reasons. If this is the case, ice alone will continue to separate beyond Point E, and the unfrozen solution composition will follow an extension of the liquidus, as shown in Figure 2. Eventually, the solution reaches a point where no more ice can separate. This point appears as Point C in Figure 2. At this point, where we have achieved maximum freeze concentration of the unfrozen matrix, it
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enters a glassy, or immobile state. In this state, the mobility of the larger molecules is severely constrained, and the rates of reactions that require these molecules to be mobile drop off to near zero. Figure 2 also shows that temperature changes the composition of the unfrozen phase, and hence the amount of ice. Region B of Figures 1 and 2 represents the region where ice and unfrozen phase coexist. The amount of ice at any temperature can be estimated from a tieline: PQ. QX/QP is the fraction of ice in the system. QX/XP is the ratio of amount of ice to amount of unfrozen phase. For any fixed overall composition, temperature fluctuation will change the amount of ice. The resulting melting and refreezing is an im- Figure 1: In Region B, bounded by the liquidus, and the x-axis, which also portant contributor to the recrystallization pro- represents pure water (ice below the liquidus), the system exists as a mixture of ice and unfrozen solution. At Point E, the eutectic point, pure solute cess. It must also be noted that, due to the also separates out. E is the junction of the liquidus and the solubility curve. physical properties of water and ice, the warming process is faster than the cooling process between sub-zero temperatures and around 22F (6C), but the cooling process is more rapid than the warming process between 22F (6C) and room temperature. Thus, temperature fluctuations can lead to product temperatures hovering in the 22F to 25F (6C to 4C) range for extended time. Many chemical and physical reactions proceed at a maximum rate in this temperature range due to the combined effects of temperature reduction and concentration increase associated with freezing. As a result, excessive temperature fluctuation can accelerate loss in quality. In addition to this kinetic effect, temperature fluctuation necessarily leads to temperature gradients, thus causing significant moisture migration, which further deteriorates quality. Product composition. Since freezing is accompanied by an increase in the concentra- Figure 2: If in a binary system, solute fails to separate out at E, ice will tion of the unfrozen phase, the composition continue to separate out, and the solution composition will follow an extension of the liquidus, EQC, until it reaches Point C, where no more ice of the product can be very important. The can separate. The temperature at C is the mobility temperature, and the amount of ice at a given temperature can be composition is that of the maximally freeze concentrated matrix. For an reduced by adding additional solutes, often overall system composition ST, the tie-line PQ allows the ratio of ice to called cryoprotectants. Sugars are common solution to be estimated. It is given by QX/XP. cryoprotectants. By reducing the amount of ice that separates out of the food, salt concentration in the fuse to the area of lowest temperature. Migration through food does not increase, thus reducing damage that would a vapor space tends to be more rapid than migration result from increasing ionic strength. The relative amount through the solid. In a solid, the diffusion channels can of soluble biopolymer can influence the freezing diagram be traversed in both directions. Therefore, as a gradient by influencing the overall pattern of molecular mobili- reverses, moisture can return to its original location. Once ties. This can lead to enhanced product stability. into a vapor space, however, the likelihood of water Vapor spaces and barriers. Moisture migration re- molecules returning to the micropore from which they sults in loss of quality. Moisture migration is influenced were released is slight. This is an effect of probabilities by the internal structure of the product and by the pres- and can also be interpreted as a consequence of the ence of vapor spaces and barriers to moisture diffusion. greatly increased entropy if the vapor is dispersed through Driven by temperature gradients, moisture tends to dif- a large volume.
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Refrigeration
Molecular mobility. By considering the role of molecular mobility, our understanding of frozen storage stability has improved. As ice forms and the concentration of the unfrozen phase increases, molecular motion for the solutes becomes increasingly more difficult due to collisions and entanglements. As the amount of solvent water decreases, the volume available to the solutes for motion decreases as well. At the point of maximal freeze concentration, the solute molecules have lost their translational mobility. The water molecules are still mobile, but no more ice can form because adding another water molecule to an ice crystal requires a solute molecule to diffuse away. This cannot happen once the solute molecules become immobile. The temperature where no more ice can form is conveniently termed the mobility temperature. Since the solute molecules become immobile, reaction rates are slow. If the solute molecule is larger, this makes the space requirements more onerous, so the mobility temperature is increased. Therefore, increased content of soluble polymers can raise the mobility temperature and enhance product stability. An increase in polymer content may be achieved by breeding, or by choosing the level of maturity at harvest. In formulated products, higher molecular weight additives such as maltodextrins can be chosen. The rates of diffusion-limited reactions depend on the difference between the storage temperature and the product mobility temperature. As a result, the product mobility temperature serves as a reference temperature. In a range of similar products, those with the higher mobility temperature are likely to be more stable. Table 1 lists observed mobility temperatures for some typical frozen foods. Crystal growth inhibitors. In situations where ice recrystallization is a problem, such as ice cream and other frozen desserts, crystal growth inhibitors could extend shelf life, and also provide protection against the damage caused by temperature fluctuations. Many hydrocolloids, such as carrageenans and alginates are claimed to inhibit ice crystal growth, but evidence for this is limited, except at temperatures close to the mobility temperature. Hydrocolloids do, however, influence the initial freezing patterns. In recent years, a class of biological molecules that can inhibit ice formation have been identified. These molecules are called antifreeze proteins and glycoproteins. These molecules also have an important ability, at low concentrations, to inhibit the recrystallization of ice. While not used at present, as new methods become available to manufacture these materials at lower cost, they are likely to become an additional ingredient available to the food formulator.
Product A rtichoke A sp a ra g us A voca d o Broccoli Brussel Sp routs Ca rrot Ca uliflower G re e n B e a n Okra Green Pea Sp ina ch Pota to Sweet Corn Bla ckb erry Blueb erry Cherry Pea ch Stra wb erries Cod Sa l m on Ma hi Ma hi Shrim p B eef Turkey
*d ep end s on extent of p rocessing **d ep end s on va riety a nd extent of p rocessing

Mobility Temperature ( F/ C) 4/20 11/24 27/33 11/24 13/25 15/26 7/22 10/23 15/26 13/25 20/29 4 to +17*/20 to 8* 13 to +14**/25 to 10** 24/32 22/30 24/32 25/32 27/33 14/26 15/26 17/27 20/29 11/24 8/22

Table 1: Estimates of mobility temperatures.

Conclusion Temperature control is important to maintain quality in frozen foods. If minimal product change during storage is required, it will be necessary to store at or below the mobility temperature. Storage of ice cream at the manufacturing plant is often at or below the mobility
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temperature. Mobility temperatures can be measured most easily by following the change in electrical capacitance of a product as it is warmed up from very low temperatures. At the mobility temperature, the capacitance can be seen to start to increase rapidly, as a consequence of the increased molecular mobility. Since the cost of maintaining such low temperatures is high, the other use for mobility temperatures is as a reference temperature. It enables comparison of the potential frozen storage stability of a range of similar products at any particular storage temperature. Products with higher mobility temperature are likely to have the longest storage life.
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