1 Shelf life Testing: Procedures and Prediction Methods for Frozen Foods Bin Fu Kellogg's Battle Creek MI. Theodore P. Labuza Dept. of food Science & Nutrition, University of Minnesota 1334 Eckles Ave., St. Paul, MN 55108. 2. 1 9 . 1 Introduction The Shelf life of a food can be defined as the time period within which the food is safe to consume and/or has an acceptable quality to consumers. Just like any other food , Frozen foods deteriorate during storage by different modes or mechanisms, as summarized in Table 1. Microbes usually are not a problem since they cannot grow at freezing temperatures unless subjected to extensive temperature abuse above the freezing point. Enzymes are a big concern for Frozen foods, which can cause flavor change (lipoxygenase) in non-blanched fruits and vegetables and accelerated deterioration reactions in meat and poultry (enzymes released from disrupted membranes during precooking).
2 Cell damage or protein and starch interactions during freezing cause drip and mushiness upon thawing. Discoloration could occur by non- enzymatic browning, bleaching, and freezer burn. Vitamin C loss is often a major concern for Frozen vegetables. Physical changes, such as package ice formation, moisture loss, emulsion destabilization, recrystallization of sugars and ice of Frozen desserts are often accelerated by fluctuating temperatures. For any specific Frozen product, which mode determines its Shelf life , depends on the product characteristics (raw materials, ingredients, formulation), pre-freezing treatment, freezing process, packaging film and processes, and of course storage conditions. All of the quality deterioration and potential hazards are usually exaggerated or complicated by a fluctuating time-temperature environment ( freeze/thaw cycle) during storage.
3 On the other hand, the Shelf life of a Frozen food can be extended through ingredient selection, process modification and change of package or storage conditions, as discussed in Section 3 of this book. This chapter will focus on Shelf life testing of Frozen foods for product development and market practices. Shelf life testing consists basically of selecting the quality characteristics which deteriorate most rapidly in time and the mathematical modeling of the change. Table can be used as a reference for the selection of quality characteristics, which depends on the specific product and usually requires professional judgment. Mathematical modeling of quality deterioration will be discussed next. 3. Table Deterioration modes of Frozen foods Frozen Foods Deterioration Modes Frozen meats, poultry and seafood Rancidity Toughening (protein denaturation).
4 Discoloration Desiccation (freezer burn). Frozen fruits and vegetables Loss of nutrients (vitamins). Loss of texture (temperature abuse). Loss of flavor (lipoxygenase, peroxidase). Loss of tissue moisture (forming package ice). Discoloration Frozen concentrated juices Loss of nutrients (vitamins). Loss of flavor Loss of cloudiness Discoloration Yeast growth (upon temperature abuse). Frozen dairy products Iciness (recrystallization of ice crystals). (ice cream, yogurt, etc.) Sandiness (lactose crystallization). Loss of flavor Disruption of emulsion system Frozen convenience foods Rancidity in meat portions Weeping and curdling of sauces Loss of flavor Discoloration Package ice Frozen bakery products (raw dough, Burst can (upon temperature abuse) (dough).)
5 Bread, croissants) Loss of fermentation capability (dough). Staling (becoming leathery). Loss of fresh aroma 1 9 . 2 Modeling of quality deterioration Basic equation A Frozen food starts to degrade once it is produced (Figure ). The rate and the degree of degradation depends on both the composition and the environmental conditions during storage and distribution. In general, the loss of food quality or Shelf life is evaluated by measuring a characteristic quality index, "A". The change of quality index A with time (dA/dt) can usually be represented by the following kinetic equation: - dA/dt = k An ( ). where k is called a rate constant depending on temperature, product and packaging characteristics; n is a power factor called reaction order which defines whether the rate 4.
6 Of change is dependent on the amount of A present. If environmental factors are held constant, n also determines the shape of deterioration curve. Ao d A e a b c t Figure Quality deterioration curves: a) linear; b) exponential;. c) hyperbolic; d) quadratic; e) complex. Zero and first order kinetics Equation can also be written as: f(A) = k t ( ). where f(A) is the quality function, k and t are the same as above. The form of f(A). depends on the value of n. When n is equal to zero it is called zero order reaction kinetics, which implies that the rate of loss of quality is constant under constant environmental conditions (curve (a) in Fig. ). If n is equal to one it is called first order reaction kinetics, which results in an exponential decrease in rate of loss as quality decreases (curve (b) in Fig.
7 , which becomes a straight line if plotted on a semi-log plot). These quality functions can be expressed as follows: f(A) = Ao - A = kzt zero order ( ). f(A) = ln Ao - ln A = kft first order ( ). 5. where Ao is the initial quality value. If Ae corresponds to the quality value at the end of Shelf life , the Shelf life ( ) of the food is inversely proportional to the rate constant: = (Ao - Ae) / kz zero order ( ). = ln (Ao/Ae) / kf first order ( ). It should be noted that most chemical reactions leading to quality loss in Frozen food systems are much more complex. However, the reaction kinetics can be simplified into either pseudo-zero order or pseudo-first order kinetics. In the case of complex reaction kinetics with respect to reactants, an intermediate or a final product ( peroxides or hexanal in lipid oxidation ) could be used as a quality index.
8 There are few cases where neither zero nor first order kinetics apply. Curve (c) in Fig. shows the degradation curve for a 2nd order reaction (with single reactant), which also shows a straight on a semi-log paper. A fractional order should be used to describe the curve (d) in Fig. Sometimes, there is an induction period or lag time before the quality deterioration begins ( browning pigment formation in the Maillard reaction or a microbial growth lag phase, as shown in curve (e) in Fig. The length of the lag depends on many factors, but temperature is a predominant factor. Given this, modeling of both the induction or lag period and deterioration phase are necessary for accurate prediction of quality loss or Shelf life remaining.)
9 An example of such work has been demonstrated by Fu et al. (1991) for the growth of bacteria in milk. In certain circumstances ( A represents a sensory hedonic score), a non- kinetic approach, a statistical data fitting technique can also be used to describe the deterioration curves. Varsanyi and Somogyi (1983) found that the change in quality characteristics as a function of time could be approximately described with linear, quadratic and hyperbolic functions and that storage temperature and packing conditions affected the shape of the deterioration curves. However, the parameters determined by data fitting are difficult to use for prediction under variable storage conditions except for the linear curve. Temperature dependence of deterioration rate Arrhenius kinetics Once a Frozen product is made and packaged and starts its journey from the manufacturer's plant to warehouse, distribution center, retail store and finally 6.
10 Consumer's freezer, the rate of quality loss is primarily temperature dependent (Zaritzky, 1982). The Arrhenius relationship is often used to describe the temperature dependence of deterioration rate where for either zero or first order: k = ko exp (-Ea/RT) ( ). or ln k = ln ko - Ea/(RT) ( ). where ko is a pre-exponential factor; Ea is an activation energy in cal/mol; R is the gas constant in cal/mol K and equal to ; T is an absolute temperature in K (273 + C). Thus, a plot of the rate constant on semi-log paper as a function of reciprocal absolute temperature (1/T) gives a straight line as shown as Fig. The activation energy is determined from the slope of the line (divided by the gas constant R). A steeper slope means the reaction is more temperature sensitive, , a small change in T produces are large change in rate.