19

CONTENTS

Quality and Safety of Frozen Fruits

Danila Torreggiani and Andrea Maestrelli
Istituto Sperimentale per la Valorizzazione Tecnologica dei Prodotti Agricoli (I.V.T.P.A.), Milano, Italy

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II. Factors Inuencing Fruit Cultivar Selection for Freezing . . . . . . . . . . . . . . . . . . . . . A. Agronomical Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Technological Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C. Sensory Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D. Nutritional Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . III. The Range of Pretreatment Techniques and Their Impact on Quality . . . . . . . . . . . A. Blanching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Partial Dehydration and Formulation Techniques . . . . . . . . . . . . . . . . . . . . . . 1. Texture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2. Pigments, Color, and Nutrients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3. Aroma Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV. Safety Aspects of Frozen Fruits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Raw Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Processing before Freezing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C. Freezing Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D. Frozen Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . E. Thawing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . F. Osmotic Pretreatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1. Microbial Contamination of Osmotic Solution . . . . . . . . . . . . . . . . . . . . . 2. Sanitation of the Osmotic Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

417 418 418 420 422 422 424 424 426 427 430 432 433 434 435 435 435 435 435 435 436 436 437

I. INTRODUCTION
The frozen fruit market is now taking its place among other frozen foods. Just as for the fresh market, the demanding consumer is looking for high quality, nutritious, and safe foods. Today, the average person understands the importance of having a varied diet including a large portion of fruit and vegetables as in the so-called Mediterranean diet. In the ever-developing eld of frozen fruit, there are many diverse aspects to be considered and will be covered in this chapter. It is well known that there is a deterioration of many fruit quality characteristics caused by severe or unsuitable treatments used for the recovery of the nutritional elements. Temperature reduction is the ideal choice to preserve any biological materials, and among the cooling techniques, freezing is the most valid method.
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Fruit freezing is only an apparently simple process, although it really hides some puzzling complexities. The direct, evident, and macroscopic effects of freezing on foods is the phase transition of liquid components, which crystalize and solidify. This fact determines the rupture of cell walls due to the growth of ice crystals during freezing. While thawing, the product will exhibit a loss of cellular integrity, which can manifest itself in increased drainage, shape modication, and less denite structure, so preventing a return to the initial pleasant state [1]. Several factors can infuence the quality of frozen fruit but two of them are universally accepted as being of crucial importance: raw material and pretreatments. It is inevitable that these two factors continuously overlap or they are parallel or dependent on one another. As far as freezing is concerned, fruits differ from vegetables mainly for the mechanical support organization, which in the fruit group is based on pectins, whereas in the vegetable group on ber. The pectic system is less resistant than the ber, being physically, chemically, and enzymatically susceptible to degradation. To emphasize this difference between fruit and vegetable, Table 19.1 shows how cell dimensions and particularly cell wall thickness of the two groups play an important role [2 5]. For the earlier mentioned low-resistence problems of fruit cellular structure, raw material selection for fruit freezing is becoming more and more essential to ensure an extra-high-quality nished product. The exploitation of specic characteristics (intentionally or spontaneously) in the vegetable kingdom to satisfy specic needs leads to the creation of the concept of varietal or cultivar functionality. A cultivar can be dened as a group of cultivated plants identied by any specic characteristic (morphological, physiological, cellular, chemical, etc.), which on reproduction, whether sexual or not, preserve their original characteristics. The cultivar is the lowest botanic unit. Some species of fruits and vegetables must undergo thermal treatment before storage at temperatures below zero to reach enzymatic inactivation. Even if this treatment called blanching (a term originating from the French cuisine, blanchiment, a word for not complete cooking [6]) is normally carried out for a short time and followed by rapid water chilling; its detrimental effect on the fruit structure cannot be avoided because of the noticeable fragility of fruit. Apart from blanching, there are many other pretreatments that are used for specic purposes, not only for enzymatic inactivation but also for protecting or enhancing the structure resistance, color maintenance, and vitamin retention during frozen storage. These pretreatments will be looked into further on in this chapter.

II. FACTORS INFLUENCING FRUIT CULTIVAR SELECTION FOR FREEZING A. AGRONOMICAL FACTORS
The cultivation of fruit intended for processing, particularly for freezing, has been modied over the years. In southern Europe, farms used to consist of elds of just a few hectares; the larger country zones were destined for pastures and vast private estates. In recent years, the dimension

TABLE 19.1 Average Size of Cells (mm) of Some Fruits and Vegetables
Product Strawberry (cv Sparkle) Clingstone Peach (cv Vivian) Apple (cv Red delicious) Carrot (cv N.K.) Length 161385 6480 100 5060 Cell Dimension (mm) Width Wall Thickness 53122 4560 6080 5060 1.9 4 7 1.51.9 References [2] [3] [4] [5]

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of the elds has been noticeably increased, especially in the Mediterranean area, rather than in northern Europe. This new change in dimension has the advantage of introducing mechanical tillage and harvesting and helping form a link between production and industry. Industry normally uses on line equipment with a known capacity. In contrast, the producers have to provide a regular crop to industry, without minimum or maximum peaks. Only the background of the cultural cycles of the varieties and parallely the equipment capacity can ensure this regularity. Therefore, it is crucial to achieve an integrated eld-industry system. The cultivar concept is the solution to this problem. The farmer is required to supply industry with cultivars that mature at different periods spread over a period of time, meaning that as one variety nishes production, there is another one ready to take its place. Obviously, the nutritional and morphological characteristics of cultivar have to be similar, to supply industry with qualitatively homogeneous stock. For this reason, the breeding of the specic varieties is imperative to obtain an exact type of behavior from the series of cultivar used, especially in the face of agronomical but principally climatic conditions. Such precision means that it is possible to create a ripeness calendar where the variability can be limited to a range of 2 3 days, at maximum. Figure 19.1 shows an example of a ripeness calendar for some clingstone peaches destined for Central Italy [7]. In this calendar, 0 is the reference cultivar and the negative or positive numbers indicate ripeness of early or late cultivar. For the clingstone, the reference cv is Redhaven, which is harvested from 5th to 10th of July. Soil has always played an important role but looking into the future, it can be considered as a simple substrate of the plant as it is possible to correct difcult environmental conditions using specic protective tunnels (plastic and so on; xed or temporary), which more or less give individual nutritional requirements and modify the amount of different macro-elements according to the needs of the plants ( fertigation). A fertilizer already exists in a waxy capsule form, which regulates the amount of nutrients given to the soil depending on external temperature; the hotter the weather, the more nutrients are given out, while the cooler the weather, the fewer the nutrients. Yet, these modern concepts should not go against the traditional idea of the irreplaceable link between the soil and the product. Through this unusual blood supply system, it is also easy to distribute water and pesticide, when necessary (drip irrigation). Soil-less strawberry or other berry fruit are commonly produced in tunnel and the fruit is grown on suspended peat blocks at human eye level to facilitate picking, and so on. At the moment, these agricultural models are expensive and not exactly suitable for industry [8]. In extensive agriculture, it is difcult to put these protective models into practice.

FIGURE 19.1 Ripeness calendar in Central Italy of different clingstone peach cultivars. (From E Bellini, V Nencetti, L Conte, A Liverani, O Insero. Liste varietali fruttiferi. Pesco (pesche, nettarine, percoche). Terra e Vita 52 (18):51 70, 2001).

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There is no way in which a farmer can protect his production from severe weather conditions, particularly under excess rain and hard frost. An interesting example can be found in Spain, where 10,000 ha are occupied by only one cultivar, called Camarosa, which is suitable for retail and recently also for freezing. In 2001 and 2002, unseasonal rain and cold during the last phase of ripening seriously damaged most of the crops. The price of the crop thus fell and the product could not be competitive with the investment made. Most of the crop was eventually left in the eld, creating difcult sanitary conditions for the following year [9]. Camarosa has an excellent market value, but it would be better to include it with other varieties. There is also a market for small berry fruits which are important not only for retail and for their very interesting nutritional characteristics but also for industry. In Central Europe, these berries are grown in hilly and mountain areas (in some cases, up to an altitude of 1500 m) [10]. In such conditions, it is not rare to have very cold summer nights (below 08C, near the harvesting time). However the abnormal weather conditions should be recognized by the very highly specialized farmers. In some cases, the success of the berries production depends only on 0.58C difference in temperature, when a winning cultivar can survive and give a good yield. Table 19.2 gives an example of the harvesting period of some cv of raspberry and blueberry [11]. Table 19.3 is entirely dedicated to strawberry showing the different behavior of some quality and nutritional parameters of two very well known varieties, with respect to the place of cultivation, showing another simple and clear example of how the soil and weather conditions are linked. The earlier mentioned conditions indicate that in reality, there is only a slight line dividing the agronomical factors from the climatic conditions, both of which should be considered together.

B. TECHNOLOGICAL FACTORS
The suitability for mechanical harvesting has at last been accepted as one of the most important technological characteristics of strawberry destined to freezing. However, not all small fruits can be harvested mechanically. Wild strawberry and raspberry are too delicate and must be picked manually. In contrast, blueberry, blackberry, and redcurrant are already harvested automatically. For strawberry, the best way to pick fruit seems to be based on a rake moving slowly through the rows of strawberry [12,13], meaning that the stalk of the fruit can easily be separated. Destalking characteristic is a genetic factor inuenced by the cultivar. Figure 19.2 illustrates the force needed to destalk the fruit of three varieties. As it can be seen, all varieties are in a similar force

TABLE 19.2 Harvesting Calendar of Some Berry Cultivars

Fruit Raspberry Early Ripening Malling Exploit Glen Moy Malling Promise Williamette Lloyd George co (very early) Me Early Blue Standard Waki Gradina Puyallup Delmes da Ha va 2 Ze Goldtraube Cultivar Late Ripening Malling Admiral o Malling Le Meeker Radbound Schoeneman Rose de Cote-dOr Jersey Reowering ritage (end September) He Baron de Wavre (September) va reowering Ze

Blueberry

lection des cultivars en relation avec la transformation. In: G Albagnac, Source: Adapted from A Maestrelli, JM Chourot. Se P Varoquaux, JC Montigaud, Eds., Technologies de Transformation des Fruits, Paris (France): Lavoisier, 2002, pp. 4177. With permission.

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TABLE 19.3 Inuence of Origin and Harvesting Season on Quality and Nutritional Characteristics of Camarosa and Senga Sengana Cultivars
Quality Parameters Acidity (meq/100 g Fruit Weight) 12.30 11.60 11.80 9.60 9.63 10.50 13.90

Cultivar Camarosa

Origin Cesena, Italy

Year 1996 1997 1998 1998 1999 1999 1998 1999 2000

8 Bx 8.20 7.20 8.40 7.90 7.36 8.00 5.18 6.20 10.50

pH 3.38 3.39 2.87 3.50 2.84 3.44 3.30

Weight (g) 20.3 13.6 19.4 28.0 25.0 26.0 21.3 10.0 25.0

Penetration Force (g) 700 336 415 461 125 245

Palermo, Italy Spain Senga Sengana Cesena, Italy Cuneo, Italy Poland

range, but what really happens is better explained in the pictures (Maestrelli, personal communication). The 734 (cv Senga Sengana) shows a perfect destalking without defects, whereas only some of strawberry of 745 are destalked. The calix still remains on some of the fruits, and in others, the stalk is broken far from the fruit. The worst that can happen is what can occur to

1 0.8 Force (kg) 0.6 0.4 0.2 0 734 745 Cultivar 749 sd

FIGURE 19.2 Destalking force (kg) of three strawberry cultivars (734, Senga Sengana; 745, Mimek Sella; 749, 89.209.9 87.38.1). SD, standard deviation.

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strawberry 749, for which the stalk breaks and calix remains, but more seriously a portion of pulp is taken away by the destalking action. This is an example of physical unsuitability of sample under selection, which can also reect on the nutritional value. Danger of oxidation, mold pollution, and drip loss (also before freezing), and lack of natural resistance, which can all occur around the injured zone, all contribute to the erosion of the nutritional value. Some agronomic practices already exist which are oriented toward the improvement of the technological functionality of fruit intended for processing and particularly freezing, although these practices are always connnected to breeding programs or cultivar selection. A good example is the grafting technique for some fruits, normally used on fruit trees and owers. The main purpose of tree grafting is to defend them from the attacks of soilborne pathogens throughout the biological life (3, 5, and 10 years). The rootstock and the graft often came from different cultivar or species. Another reason is to allow the plant to stay the 2- or 3-year cultivation cycle in the same soil, without showing any signs of illness or tiredness without rotation. The principle of crop rotation is normally used as a protective measure, but in this way, it can become less rigid. The ght against mushroom illness (Fusarium sp.) of Cantalup melon has been going on for many years by grafting cultivar on specic rootstock. Supermarket is a highquality cultivar melon with good nutritional and sensory values but it is easily attacked by mushrooms. This melon is well protected when grafted onto Vector, a cv which produces mediocre quality fruit [14].

C. SENSORY FACTORS
Sensory quality of fruit is formed by a combination of different and very important subunits, such as appearance, odor, texture, taste, avor, and so on. An example of what can happen, if only one subunit is favored is given by a case observed in the United States [15], where cherry growers chose rmness and color attributes of the fruit over sugar and taste. Early harvested cherry (cv Brooks and Tulare) completely lacked taste and the consumers refused to buy them. This example is obviously referring to fresh product. It is very easy to imagine what could happen to pretreated and processed products. Spreading out the branches of technological steps can easily hide raw material that is of bad quality or where the process is carried out incorrectly, so multiplying the gray zone of the errors. The performances of processed fruit depend on suitability of cultivar and type of processing. This is conrmed by what was observed in processed melons [16]. Two cultivar of muskmelon (Rony and Mirado) were pretreated by osmotic dehydration and air dehydration before freezing and 4 months storage (2 208C). Among the different quality parameters, the most important for muskmelon is the avor, and Rony and Mirado raw varieties have the same strong avor and overall acceptance. Freezing caused an unexpected behavior: while the sensory evaluation of Rony showed a high standard, that of Mirado decreased noticeably, indicating that not only is cultivar a crucial point but also processing, which can inuence the quality. In particular, a simple unit operation like freezing that normally does not affect avor, becomes heavily detrimental for that of melon (Table 19.4) [16].

D. NUTRITIONAL FACTORS
Fruits have always been considered as important components of a healthy diet, especially when refering to macronutrients: their role in the prevention of vitamin deciency; adequate folic acid intake; a quick energy boost from easily digestable sugars and their important source of dietary ber. However, in recent years, the role of phytochemical activity of fruits has come to light. Phytochemicals are complex plant chemicals which could act as protective factors in a wide range of chronic disorders. Once consumed, phytochemicals are subjected to enzymatic and bacterial degradation to produce an even wider range of products available for absorption. As previously discussed, regarding the link between agronomical and climatic factors, there exists a strong connection between sensory and nutritional factors. The classication of nutritional compounds

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TABLE 19.4 Flavor and Overall Acceptance Scores of Melon Spheres Cultivars Rony and Mirado, not Pretreated (Raw) and Pretreated (Air Dehydrated to 50% Weight Reduction, AD; Osmodehydrated for 60 min, at 258 C at Atmospheric Pressure in 60% (wt/wt) Sucrose Solution, DIS), after 0 (T0) and 4 (T4) Months of Frozen Storage at 2 208 C
Storage (Months) Cultivar Raw Flavor 50.75Bb 37.67Ba 40.75Bb 37.75Ba Overall acceptance 53.58Bb 39.25Ba 44.17Bb 39.67Aa AD DIS

0 4

Rony Mirado Rony Mirado Rony Mirado Rony Mirado

34.83Aa 34.42ABa 33.17Aa 33.50Aa 33.58Aa 35.33ABa 30.08Aa 30.17Aa

40.17ABb 36.42Ba 38.42Ba 36.33Ba 40.25Bb 37.42Ba 36.67ABa 35.42Aa

0 4

Note: Different letters (uppercase: among the different pretreatments for a single cultivar; lowercase: between the two cultivars for the same pretreatment) indicate signicant difference (P 0.05). Source: Adapted from A Maestrelli, R Lo Scalzo, D Lupi, G Bertolo, D Torreggiani. Journal of Food Engineering 49: 255260, 2001. With permission.

in macronutrients and phytochemicals can help us to describe the crucial inuence of cultivar and agronomical and processing factors on maintaining high nutritional levels. As for macronutrients, among the 2000 varieties of strawberry known around the world, the balance of the nutrients signicantly change and contribute to establishing the real qualitative difference. The ratio between sugar and acid content has always been considered as both a technological and nutritional index. It identies very important characteristics such as maturity stage, harvesting index, sensory acceptance (described by the correct harmony between two sensory parameters: sweet and sour), and balanced nutritional intake. In Table 19.5, sugar/acid ratio of ve strawberry varieties harvested in 1999 is shown (Testoni and Lovati, personal communication).

TABLE 19.5 Average Content (mg/100 g fr. wt.) of Acids and Sugars and Total Sugars/Total Acids Ratio of Some Strawberry Cultivars
Content (mg/100 g) Acids Cultivar Andana Cigaline Red Chief Cigoulette Kimberly Qui 227 334 262 195 173 Mal 472 382 597 228 731 Cit 792 880 1135 977 638 Asc 39 56 41 43 37 Suc 830 410 630 300 390 Sugars Glu 1600 2430 2060 1620 1300 Total Sugars/Total Acids Ratio 2.74 3.35 2.48 2.63 2.05

Fru 1770 2700 2340 1880 1550

Note: Qui, quinic; Mal, malic; Cit, citric; Asc, ascorbic; Suc, sucrose; Glu, glucose; Fru, fructose.

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A further interesting example is the importance of the sugar/acid ratio in oranges, which indicates the suitability of both the cultivar and the quality level for juice production. To obtain high quality red orange juice, the ratio 8Bx/acidity should not be lower than 8.0, independently from the cultivars (Moro, Tarocco, and Sanguinello) [17]. As for phytochemicals, an important step torward this new research area has been the screening of fruit cultivar to identify the variety with the highest and most stable phytochemical activity. Until now, cultivar selection has been made by industry with the specic goal of extracting from the fruit single nutrients such as vitamins, antioxidant compounds, and so on. Today, it is understood that a daily consumption of fruits is far more important to have a regular intake of protective factors. Indeed, it has been clearly demonstrated that the in vivo activity of whole consumed fruit is higher than that of single extracted molecules [18]. An example fruit showing the variability of antioxidant capacity related to variety is presented in Table 19.6 [19].

III. THE RANGE OF PRETREATMENT TECHNIQUES AND THEIR IMPACT ON QUALITY A. BLANCHING
Some fruit species need a treatment of enzymatic inactivation before freezing and low-temperature storage, which is much more important for horticultural products than for fruit. Table 19.7 shows advantages and disadvantages of immersion blanching as a prefreeze treatment [20]. Enzymatic inactivation (blanching) is carried out normally using heat, particularly boiling water or steam, where the heat action must be intense and quick, being more efcient if the product is divided into small pieces such as cubes, spheres, slices, disks, and halves. The length of time and intensity of the thermal effect must be accurately calculated and, when terminated, has to be immediately stopped often by spraying with or immersing in cold water. The treatment time

TABLE 19.6 Antioxidant Activity, Anthocyanin, and Phenolic Contents of Acetonitrile Extracts of Berries from Different Commercially Available Cultivars of Vaccinium Species
Cultivar (State) ORACROO a (mmol TE/g) Anthocyaninb (mg/100 g) Phenolicsc (mg/100 g)

Bluecrop (MI) Jersey (MI) Jersey (NJ) Rubel (MI)

Vaccinium corymbosum L. (Northern Highbush) 17.0 + 1.0 (70.5) 93.1 + 1.6 20.8 + 0.6 (63.2) 100.1 + 2.3 21.4 + 0.4 (91.9) 116.6 + 1.1 37.1 + 0.5 (182.8) 235.4 + 6.1 Vaccinium corymbosum L. (Southern Highbush) 16.8 + 1.9 (105.0) 92.6 + 4.6

189.8 + 10.9 206.2 + 4.1 221.3 + 4.3 390.5 + 6.5

ONeal (NC)

227.3 + 6.9

Note: MI, Michigan; NJ, New Jersey; NC, North Carolina.

a

Oxygen radical absorbance capacity expressed as micromole Trolox equivalents per gram of fresh fruit. Data in parentheses expressed per gram of dry matter. Concentration based on cyanidin-3-glucoside as standard expressed per gram of fresh weight.

b c

Concentration based on gallic acid as standard expressed per gram of fresh weight.

Source: Adapted from RL Prior, G Cao, A Martin, E Soc, J Mc Ewen, C OBrien, N Lischner, M Ehlenfeldt, W Kalt, G Krewer, CM Mainland. Journal of Agricultural and Food Chemistry 46:2686 2693, 1998. With permission.

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TABLE 19.7 Advantages and Disadvantages of Immersion Blanching as Pretreatment

Advantages Inactivating enzymes responsible for browning and off-colors Partially destroying microorganisms Decreasing pesticide Specic applications Reducing volume of pieces increasing storage capacity Leading to exclusion of air from tissues Increasing extraction of antioxidants in juice production (blueberry and orange) Disadvantages Leading to the death of cellular tissue with high possible deterioration of texture Higher sensitivity to microbial growth afterwards Loss of foods own solutes resulting in pollution of the blancing bath and decrease of nutritional value Absorption of water by food and modication of yield High water consumption

Source: Adapted from D Torreggiani, T Lucas, AL Raoult-Wack. In: CJ Kennedy, Ed., Managing Frozen Foods, Cambridge (England): Woodhead Publishing Limited and CRC Press LLC, 2000, pp. 5780. With permission.

depends on the kind and the vitality of the enzymes and on the type of raw material and its maturity stage. A dualistic effect acts in botanical eld as the fruit system is made up of, on one hand, oxidation catalyzer compounds, and on the other hand antagonist antioxidant compounds. The more the technological process is correctly targeted (including blanching), the more the integrity of the protective compounds (antioxidants) is expected. Lipids are the most susceptible substances to oxidation in the food system and many heterogeneous factors (chemical, physical, and biological) can create a lot of problems when lipid oxidation must be controlled. Even blanching as a specic protective pretreatment inuences oxidative reaction in a contradictory way. The most important oxidative catalyzers present in vegetable cells are enzymatic and nonenzymatic, and they are active, preferably, against the unsaturated fatty acids. The lypoxygenase enzyme favors the attachment of oxygen on fatty acids [21,22]. This enzymes activity can provoke at least three undesired effects: destruction of essential fatty acids, production of free radicals (reactive against vitamins and proteins), and development of off-avours. These effects justify the need to completely inactivate the lipoxygenase before freezing. The hemoproteins are other catalytic agents, which are important enzymes in the vegetable world (such as peroxidase and catalase). However they react with fatty acids because of their physical structure; this reaction occurs through the intervention of the iron atom inside their porphyrin ring (heme group), which is hidden within the hydrophobic fessure of the proteic area. During blanching, heating denaturates hemoproteins, facilitates the exposure of the heme group, and reveals the porphyrin ring. In this way, the fatty acids can come into contact with the iron atoms (specic mineral, catalytic agent), allowing it to express its catalytic ability. This can be called as nonenzymatic activity. For this reason, enzymes like peroxidase and catalase, which have no specic action on fatty acids, can aid the lipids oxidation through the nonenzymatic activity of their prosthetic group [23,24]. It would seem that the lipoxygenase inactivation may not be enough to control or stop the oxidation of fatty acids. The enzymatic role of vegetables hemoprotein is still not clear, whereas the peroxidase role is very clear as an indicator of the inactivation level of the enzymes during blanching. The technological importance of peroxidase comes from its thermal resistance, which is higher than that of other enzymes [25].

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Nevertheless, some factors should be considered to indicate the lipoxygenase as key enzyme suitable for evaluating the blanching effect. Among these factors are (1) technological trend limiting the thermal treatment intensity and (2) a better understanding of the biochemical phenomena involved in the quality loss of processed fruit. These factors show that there is a delicate equilibrium inside different enzymatic activities and the nonenzymatic activities. It is very difcult to foresee the potential lipid oxidation by enzymes and hemoproteins. The forecast is more and more approximate, as the enzymatic activities are contrasted by natural antioxidant activities. Most fruits contain antioxidant compounds such as avonoids, anthocyanins, tocopherols, carotenoids, and ascorbic acid, acting as reducing factors or free radical chelators. These compounds are present, for example, in aromatic herbs, berries, and citrus fruit. In this biological world, there exists the speed in which the activity of the two antagonistic agents decay. As the speed can be different for both agents, there is a shifting from the left or from the right of the following reaction: Antioxidant activity ) Pro-oxidant activity Therefore, the ideal fruit thermal treatment can be achieved by (1) knowing the parameters of the lipoxygenase thermal inactivation and simultaneously controlling the nonenzymatic oxidant activity of lipids and (2) studying the blanching effect on natural antioxidant activity. The blanching inuence on antioxidant activity in fruit can be explained with two examples: blueberry and orange. The addition of a blanching step of the fruits in juice processing proved to be a very important factor when evaluating processed blueberry products for their possible health benets. In fact, the inactivation of polyphenol oxidase through steam blanching signicantly increased the anthocyanin and cinnamate recovery when blueberries were pressed into juice [26]. Besides having a higher content in phenolic compounds, juices obtained from blanched blueberry were more blue due to the positive effect of the thermal treatment on the extraction of the most soluble anthocyanin pigments, which are also the most intense blue. The higher recovery of phenolic compounds led to a signicant increase of the radical-scavenging activity of the juice. Blanching can be even advantageous for blood oranges, in fact, the antiradical activity of cv Moro blood orange juice obtained from blanched orange segments was signicantly higher when compared with that of the nontreated one [27]. This phenomenon could be linked to a better extraction of compounds with antioxidant and radical-scavenging activity, such as free and bound hydroxycinnamic acids and anthocyanins, as already observed in blueberry. During frozen storage of blanched products, the cryolability of the catalytic agents, which is in itself favorable, does not occur with any regularity. As nonenzymatic activity in some blanched and frozen vegetables dramatically increases over some weeks of storage at 2 208C and then diminishes [28], it would be also interesting to follow this pattern in fruit. The revealing exposition of the heme group, probably arising during blanching, can continue through frozen storage, caused by the denaturating effect of low temperature on proteins. Although all this happens, the inactivated lipoxygenase tends to naturally disappear. Blanching pretreatment could be applied correctly by taking into account the great number of variables (species, cultivar, storage stage, way of cutting, handling before pretreatment, time and temperature of treatment, etc.).

B. PARTIAL DEHYDRATION AND FORMULATION TECHNIQUES

Currently, there is renewed interest in implementing partial dehydration and formulation stages before freezing. The reason for this is the versatility of these techniques, which make it possible to reduce water content, improve quality, and develop new products. Partial removal of water from the fruit leads to (1) concentration of cytoplasmatic components within the cells; (2) depression of the freezing point; (3) increase of supercooling and

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microcrystallization; and (4) lower ratio of ice crystals to unfrozen phase. There is consequently a reduction of the detrimental phenomena of loss of cellular structure and drip loss caused by freezing in fruit tissues [29]. Simple it may be, yet it is the choice of the dehydration method that is the key point because of the great variability of fruit tissue structure linked to species and cultivar. The dehydration methods that can be used include air dehydration, osmotic dehydration (also dened as dewatering impregnation soaking in concentrated solutions, DIS) and a combination of both. Partial dehydration is generally achieved by air drying. The resulting process is termed dehydrofreezing. The advantages over conventional freezing include (1) energy saving, as the water load to the freezer is reduced, leading to a reduction in transport, storage, and wrapping costs and (2) better quality and stability as well as better thawing behavior (lower drip loss). When using partial air dehydration, food ingredients of high water activity are generally obtained, as water removal is limited to 50 60% of the original content. Conventional air drying can be substituted by (or combined with) DIS, mainly for fruits, whose color can be affected by heat modication under any form of air dehydration, as DIS is effective at room temperature and operates away from oxygen. This process involves placing the solid food (whole or in pieces) into solutions of high sugar or salt concentration [30 32]. Soaking gives rise to at least two major countercurrent ows: an important outow of water from the food into the concentrated solution and a simultaneous transfer of solute from the concentrated solution into the food. However, the main unique feature of DIS compared with other dehydration processes is the penetration of solutes into the food material, making it more suitable for freezing process [33]. As a result, it is possible to adapt further the nutritional properties of the dehydrofrozen fruit and thereby formulate new fruit products suitable for various industrial uses. This can be done by (1) adjusting the physicochemical composition of food by reducing water content or adding water activity lowering agents; (2) incorporating ingredients or additives with antioxidant or other preservative properties (spices, sugars, ascorbic acid, etc.) into the food before freezing; (3) adding solutes of nutritional or sensory interest; and (4) providing a larger range of food consistency. There is vast literature that indicates the usefulness of partial water removal before freezing for numerous species of fruits [31]. Keeping the fruit rmness and structural integrity is important not only for fruit quality but also for preventing the loss of nutrients, which is manifested through exudate loss at thawing. The quality characteristics of frozen fruit, which could be improved through the application of a dehydration step, are numerous and will be analyzed here. 1. Texture Moisture reduction has been proved to be useful even to improve quality of a delicate tissue such as that of strawberry. The structural collapse after thawing rehydration of strawberry slices is reduced by adopting partial removal of water through air dehydration, DIS, or their combination [34]. A reduction in moisture content of at least 60% is needed to improve the texture characteristics of thawed rehydrated fruits, irrespective of the dehydration method used. These ndings were conrmed by the results of microscopic analysis performed on predehydrated and freezethawed strawberry slices [35]. The results clearly showed that the freezing damage is reduced due to the decrease in moisture content. Predehydrated strawberry slices retain the tissue structure after thawing, whereas the untreated ones show a denite continuity loss and thinning of cell wall. Even though osmotic treatments have been proved to be a useful tool in fruit and vegetable cryoprotection, the changes in mechanical properties caused by the process itself have to be taken into account [36]. Different factors contribute to mechanical properties of plant tissue: cell turgor, which is one of the most important ones, cell bonding force through middle lamella, cell wall resistance to compression or tensile forces, density of cell packaging that denes the free

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spaces with gas or liquid, and some other factors, which are also common to other products such as sample size and shape, temperature, and strain rate [37]. As an example, treatment using DIS alone for 4 h at atmospheric pressure is needed to obtain texture improvement of strawberry slices, but at the same time, structural modications in the fruit tissue occur [38]. Light photomicrographs of DIS-treated strawberry tissues show that there is a deterioration in the cell links and that the cell walls already lose their shape after 4 h of DIS treatment (Figure 19.3). Considering the good agreement obtained between structural and texture changes for strawberry, the DIS pretreatment has to be shorter than 2 h and combined with air dehydration if texture improvements must be obtained. The combined dehydration is proposed because through the incorporation of sugars, it could be possible to improve color, avor, and vitamin retention, during frozen storage.

1.5 1.2 Maximum force (kg) 0.9 0.6 0.3 0 R O2 O4 Treatment O6 sd

O2

O4

O6

FIGURE 19.3 Photomicrographs and texture values, expressed as shear press cell maximum force (kg) on dry basis, of strawberry slices before (R) and after osmotic dehydration for 120 (O2), 240 (O4), and 360 min (O6) in 60% (wt/wt) sucrose solution, at 258C at atmospheric pressure. Bars: 100 mm. SD, standard deviation.

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Referring to the DIS pretreatment, it should be kept in mind that the earlier mentioned results refer to a specic cultivar, that is, the cultivar Chandler. Therefore, if other cultivars were used, different results might be obtained. In fact, as shown in Figure 19.4, the cultivar inuenced the solid liquid exchanges during DIS treatment applied for 240 min in a 50% (wt/wt) glucose syrup at atmospheric pressure, showing the great importance of the tissue structure, size, and architecture of the intercellular spaces [39]. Furthermore textural properties of fruits are closely linked to cellular structure and pectic composition, and solid liquid exchanges can inuence the texture characteristics of the end product. DIS causes a slight decrease in texture values of strawberry correlated with a decrease in the soluble oxalate and residual pectin (protopectin) fractions, which are correlated with fruit rmness. The analysis of how differently soluble pectin fractions of strawberry slices are modied by air dehydration or combined osmo-air dehydration applied before freezing, and freezing itself, indicated that protopectin (residual insoluble pectin fraction) content signicantly decreases during air dehydration, with the osmotic step reducing the loss [40]. Freezing causes a signicant reduction of protopectin content, which is the biggest effect occurring in strawberry that is not predehydrated before freezing. The different losses of protopectins in different predehydrated fruits could explain the differences in texture observed in freezethawed fruits. Osmotic treatments using selective solutes can also allow cryoprotection of the cell during freezethawing [41]. Another interesting treatment is vacuum infusion with cryoprotectants (sugars from concentrated grape must) and cryostabilizers (HM pectin), which was applied to reduce ice crystal damage in frozen apple cylinders and to improve the fruit resistance to freezing damage through a notable reduction of freezable water [42,43]. Addition of cryoprotectants and cryostabilizers in the formulation changed the glass-transition temperature (Tg0 ) of the maximally cryoconcentrated food liquid phase and the freezable water content of strawberry impregnated under vacuum or at atmospheric pressure, with sucrose and sorbitol acqueous solutions with or without the addition of ascorbic acid [44]. The analysis of the product microstructure by light transmission electron microscopy showed that tissues subjected to vacuum had higher cellular tissue integrity and the ascorbic acid addition preserved the cellular tissue better in all the samples.
45 SG and WL Pectin: Galacturonic acid content (mg/10 g fr. wt.) Texture: (kg) 40 35 30 25 20 15 10 5 0 SG WL Pectin Parameter Texture Addie Linda Nike

FIGURE 19.4 Solid gain (SG) and water loss (WL) expressed on 100 g of initial fresh fruit, after DIS treatment of three cultivars of strawberry slices. On the same cultivars, after DIS treatment, insoluble pectin fraction (mg galacturonic acid/10 g fresh weight) and texture values expressed as shear press cell maximum force (kg). (Adapted from E Forni, A Sormani, D Torreggiani. In: S Porretta, Ed., Ricerche e innovazioni nellindustria alimentare, 4th CISETA (Congresso Italiano di Scienza e Tecnologia degli Alimenti). Pinerolo, Italy: Chiriotti Editori, 2000, Vol. 4, pp. 750 762. With permission.)

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Partial dehydration before freezing could even enhance the resistance of texture of frozen strawberry slices and apricot cubes to a thermal treatment [45,46]. For fruit to be incorporated as a food ingredient, for example, in yogurt, a heat treatment should be applied, but this causes texture damage and so does freezing. As shown in Figure 19.5 for strawberry, the most delicate but most requested fruit for yogurt, the fruit undergoes several thermal shocks (two cooling and two heating steps) during processing. The texture measurement data, obtained with a dynamometer, emphasize that the major rheological damage occurs at freezing. Even a drastic treatment such as pasteurization does not determine any further texture decrease. To reach a texture improvement after the proposed heat treatment, a moisture reduction of at least 50% before freezing is needed for both strawberry and apricot, irrespective of the dehydration method used. This percentage of moisture reduction is what is required to reduce the freezing damage of the fruits at thawing [34], so conrming that the freezing step is the most crucial point in the production process of thermally stabilized strawberry and apricot ingredients. If the freezing damage is limited, then the fruit texture can be improved even after heat treatment.

2. Pigments, Color, and Nutrients Together with a texture improvement, during frozen storage, the penetration of solutes combined with a dehydration effect due to the DIS pretreatment could modify the fruit composition and improve retention of pigment, color, and nutrients such as vitamin and antioxidant substances. According to the kinetic interpretation based on the glass-transition concept, physical and chemical stability is related to the viscosity and molecular mobility of the unfrozen phase, which in turn depends on the glass-transition temperature [47,48]. When the temperature is at or

Texture Strawberry 14.25 kg Harvesting Selection

Freezing 8.44 kg Sizing Storage

I.Q.F. T=-40C/-50C

T=-20C/-30C

Heat treatment in sugar and pectin solution 7.97 kg

Heating to 60C in 10min Heating to 98C in 2min Holding at 98C for 3min Cooling Bulk storage Final Bx = 40

Preparation of strawberry yogurt

FIGURE 19.5 Production ow sheet of strawberry ingredients destined for yogurt. Texture values expressed as shear press cell maximum force (kg).

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below Tg0 , diffusion controlled changes occur at very slow rates, that is, the stability if based on diffusion-controlled events is excellent. Yet, it should be remembered that many chemical changes are not diffusion controlled. The rates of presumed diffusion controlled reactions are considered proportional to the difference between Tg0 , which is also called mobility temperature [49] and the temperature of study. Manipulation of mobility temperatures through composition could therefore inuence reaction rates. Therefore, if through DIS the fruit formulation can be modied and thereby an increase in glass-transition temperature could be obtained, then there could also be an increase in the storage stability. Although the kinetic interpretation based on the glass-transition temperature holds for chlorophyll and vitamin C stabilization in kiwi fruit, for anthocyanin in strawberry and blueberry, a simple relationship does not exist between the loss of these antioxidant phytonutrients and the amplitude of the difference between the storage temperature and the glass-transition temperature of the maximally freeze-concentrated phase. The incorporation by DIS of different sugars into kiwifruit slices modied their low-temperature phase transitions and signicantly increased chlorophyll and vitamin C stability during frozen storage at 2 108C [50]. Kiwifruit pretreated in maltose and thus having the highest Tg0 values showed the highest vitamin C retention (Figure 19.6). Strawberry and blueberry juices, added with different sugars and used as a model, show anthocyanin retention signicantly higher than that observed in the juices frozen without the addition of sugar, but no differences were observed among the juices added with different sugars, thus having different glass-transition temperatures [51,52]. The sorbitol-added strawberry and blueberry juices, which have the lowest glass transition temperature, show the same anthocyanin retention as the sucrose and maltose added juices (Figure 19.7). Other factors such as the pH of the unfrozen phase and the specic chemical nature of sorbitol could have inuenced the anthocyanin degradation. These results on model systems such as juices were conrmed on strawberry halves osmodehydrated in different sugars [53,54]. Sugar incorporation improved the health benet of fruit, increasing the stability of the antioxidant activity linked to anthocyanin pigments. An osmotic step could also improve the stability of vitamin C and color during air drying and frozen storage of osmodehydrofrozen apricot cubes by the modication of sugar composition

60 50 Ascorbic acid content (mg/100g fr.wt.) 40 BF 30 20 10 0 F SO Treatment SU MA 10C 20C

FIGURE 19.6 Ascorbic acid content of kiwi fruit slices, not pretreated (F) and pretreated for 120 min, at 258C at atmospheric pressure, in 65% (wt/wt) sorbitol (SO), sucrose (SU), and maltose (MA) solution, after 9 months of frozen storage at 2 108C and 2 208C; BF, content before freezing. (Adapted from D Torreggiani, G Bertolo. Journal of Food Engineering 49:247 253, 2001. With permission.)

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80 70 Anthocyanin content (mg/100g fr. wt.) 60 50 40 30 20 10 0 Raw NT Mix Treatment 41.38 42.32 41.38 44.70 44.70 Strawberry Blueberry 43.20

Quality and Safety of Frozen Fruits

44.00 44.62 33.48

35.10

SO

MA

FIGURE 19.7 Anthocyanin content of strawberry and blueberry juices, not added (NT) and added with 20% (wt/wt) glucose fructose mixture (Mix), sorbitol (SO), and maltose (MA), after 6 months of storage at 2 108C. Raw, content of the fresh juice. Tg0 values (8C) are reported at the top of each bar.

[55,56]. The higher the sugar enrichment, the higher the protective effect on vitamin C during air drying at 658C, with maltose being the most effective carbohydrate. 3. Aroma Compounds Aroma is one of the major determinants of fruit quality, however, it can be easily modied or even greatly reduced during processing. One of the most interesting fruits displaying this property is muskmelon, whose aroma is a very complex mixture and is highly inuenced by both the cultivar and harvest time. The retention or loss during DIS and air dehydration applied before freezing was investigated on muskmelon spheres to obtain high-quality innovative frozen products [16,57]. The results ascertained the crucial importance of the cultivar, which had a great inuence on the quality characteristics of the end products. Among the pretreatments, air dehydration caused a signicant increase of alcohols, whereas these negative aroma compounds responsible for the fermented taste were stable in the DIS-treated fruits (Figure 19.8). Furthermore DIS prevented the increase of alcohols during the freezing process. This nding could explain the higher sensory acceptability of the fruit pre-DIS when compared with those pre-air-dehydrated. These considerations are also dealt with in the section on sensory factors (Section IIC) to emphasize the link between cultivar and pretreatment (Table 19.4). The effect of freezing and frozen storage together with that of osmotic process conditions was also analyzed on the volatile fraction of strawberries [58]. Treatments with 65% (wt/wt) sucrose solutions showed the same behavior as that observed by Di Cesare et al. [59] and Escriche et al. [60,61]: there was an increase in some ethylesters and furaneol but a decrease in isobutylester and hexanal, with the changes being slightly lower in pulsed vacuum osmotic treatments (PVOD). Freezing and frozen storage implied losses in all components, although in predehydrated strawberries, the concentration of some esters (and furaneol) remained greater than in the fresh ones due to the formation of these esters promoted during the osmotic step. Osmotic dehydration also caused changes in the volatile prole of kiwi fruit, depending on the treatment conditions applied [62]. With osmotic dehydration, the concentration of the ester fraction increased, whereas aldehydes and alcohols decreased. After 1 month of frozen storage of kiwi fruit slices, a severe reduction of all compounds (esters, aldehydes, and alcohols) occurred, which resulted in very small differences in the volatile prole of fruit directly frozen and

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800 600 400 200 0 BF 8000 Alcohol content g/g dry matter) 6000 4000 2000 0 BF Treatment T0 NT AD DIS T0 NT AD DIS

433

FIGURE 19.8 Ethylester and alcohol content of melon spheres (left bars of each twin set refer to cv Rony and right bars to cv Mirado) not pretreated (NT) and pretreated (air dehydrated to 50% weight reduction, AD; osmodehydrated for 60 min, at 258C and at atmospheric pressure in 60% (wt/wt) sucrose solution, DIS), before freezing (BF), and immediately after freezing (T0). (Adapted from A Maestrelli, R Lo Scalzo, D Lupi, G Bertolo, D Torreggiani. Journal of Food Engineering 49:255 260, 2001. With permission.)

previously dehydrated in different conditions. The sensory impact of these differences needs to be analyzed.

Ethylester content ( g/g dry matter)

IV. SAFETY ASPECTS OF FROZEN FRUITS

Frozen fruits have an excellent safety record and there have never been any cases of food poisoning, because microorganisms do not grow when the temperature is 2 108C or lower. However, freezing does not eliminate microorganisms or microbial toxins present in the food product before freezing, yet in most fruit bacterial growth is inhibited by the pH 4.5 (Table 19.8). There are few exceptions which have higher pH values, thereby requiring particular attention as poisoning and spoilage microorganisms can proliferate [63]. Besides this important factor along the food chain there are inevitably some levels of contamination that have been identied by the well-known system called Hazard Analysis Critical Control Points (HACCP), which includes the following steps: (1) identication and evaluation of severity of hazards plus risks from raw material, processing steps, any packaging, storage conditions up to nal use of the product; (2) determination of critical control points (CCPs); (3) specications of limits of physical (e.g., temperature), chemical (e.g., pH), or biological (sensorial/microbiological) nature that indicate if a certain CCP is under control; (4) monitoring each CCP through visual inspection test measurements to check whether it is under control; (5) corrective intervention to be put into action when a particular CCP is not under control; (6) verication plus documentation of the system.

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TABLE 19.8 Average pH Values of Different Fruit Cultivars

Fruit Apricot Cultivar Tonda di Costigliole S.Castrese Boccuccia Navel Tarocco Moro Red Yellow Vittoria Durone nero Royal Ann Mailot Marasca di Chieti Schateen Morelle Tethis Chandler Camarosa Senga Sengana Abbot Hayward pH 3.51 3.43 3.41 4.02 3.57 3.51 4.67 5.15 3.84 3.72 3.82 3.50 3.40 3.40 3.57 3.55 3.38 3.30 3.20 3.20 Fruit Raspberry Cultivar Zeva I Williamette Lloyd George Delicious Golden Delicious Casaba Honey Dew Berkeley Bluehaven Jersey Black Satin Thornfree Williams Bartlett Andross Baby Gold 6 Vivian Blue Green Gage Damson pH 3.38 3.38 3.40 3.90 3.42 5.89 6.34 3.27 3.09 3.12 3.35 3.70 3.70 4.05 3.80 3.55 3.77 3.10 3.95 3.00

Orange

Apple Melon Blueberry

Banana Cherry

Blackberry Pear Clingstone peach

Sour cherry

Strawberry

Plum

Kiwi

This system not only addresses microbiological safety, which is its primary objective, but it should also address other quality parameters and safety aspects that are not microbial [64]. If HACCP is applied correctly to the entire chain, there are many benets to both consumer and industry. Emphasis is moved from retrospective quality control to preventive quality assurance.

A. RAW MATERIALS
Just as for chilled foods, fruit safety may be compromised in several ways, apart from microbial contamination. An important consideration is the time and temperature between harvest and receipt of fruits into the factory: short time and low temperature would be the most suitable. Raw fruits may contain pesticides, herbicides, heavy metals, and so on, that are above permissible legal limits, which is considered totally unacceptable by health authorities and increasingly by the consumers. Some large industries and supermarkets already consider this as a CCP, together with the presence of foreign matter. Some of the latter are esthetically unacceptable, but others such as metallic pieces and glass or wood splinters are dangerous. Apart from the metal detector for iron, the only way to detect and eliminate such objects is by visual inspection.

B. PROCESSING

BEFORE

FREEZING

Microbial growth is highly dependent on time and temperature, therefore, the time that each lot of fruit spends in each part of the plant, including chill rooms, must be recorded according to specications and should be included in HACCP. Normally, fruit is sorted, graded, and washed. An accurate washing must be carried out, particularly for fruit such as strawberry, which grows near or just above the soil. Sometimes,

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the fruit is peeled and sliced; these operations must be carried out in a separate room from the preliminary sorting, and so on. As the low pH protects fruit from the growth of pathogens, blanching is not normally necessary and it is only used when enzyme inactivation is required (Section IIIA). If fruit undergoes the blanching process, then it must be considered as a CCP.

C. FREEZING PROCESS
During the freezing process, most of the microorganisms in fruit are inactivated, thus the process itself should not present a risk. However, to inhibit prefreezing growth, the time until the initiation of freezing may be critical and may be a CCP. If fruit is kept for too long above chill temperatures before being transferred to the freezing equipment, a pronounced microbial growth or toxin formation may take place. Another critical point is when the fruit is overloaded in the freezer tunnels, even though there is an appropriate air circulation and air temperature is under 2 308C. The inner parts of the mass of the fruit take much longer to freeze, resulting in microbial or enzymatic risk of deterioration before the freezing process is completed.

D. FROZEN STORAGE
Microbial growth does not take place during frozen storage; therefore, it is not a food safety problem. For fruit, it is common practice to use bulk packaging immediately after harvesting and freezing. Retail packaging is carried out at intervals and it may be regarded as a CCP to ensure that the fruit does not thaw at any time during repackaging.

E. THAWING
Frozen fruits must be thawed and heat-treated before consumption. They require no special precautions, especially if prepared directly from the frozen state. Thawed fruits should be treated as carefully as unfrozen fruits to prevent cross-contamination from one foodstuff to another. Because, when thawing, there will normally be drip loss, cleaning and disinfecting of food contact surfaces, dishes, knives, and so on should adequately reduce the microbial population. If fruits are not utilized frozen, the thawing process may be as important as the freezing process.

F. OSMOTIC PRETREATMENTS
When partial removal of water is applied before freezing using osmotic dehydration, the microbial contamination of the solution in contact with the fruit and its sanitation have to be taken into account and be considered as a CCP. 1. Microbial Contamination of Osmotic Solution Different sources of contamination can affect the microbial stability of the solutions, although the water activity values, ranging around aw 0.90 0.95, should be able to limit the growth of nonosmotolerant bacteria and yeasts [65,66]. During the processing of fruit with a pH 4.5 yeasts, molds, and lactic bacteria are the most frequent microorganisms released from the product into the solution. In this situation, pathogenic bacteria are not able to grow. Depending on the environmental process conditions, the microbial load after several osmotic cycles can range from 2 102 CFU ml21 [65] to high levels of yeast and fungi only after the 15th cycle [65] and 105 CFU ml21 after 8 h of continuous treatment [67]. The use of ozone has been proposed for hygenic management of the osmotic solutions in continuous systems [66]; the spoilage is minimized by destroying bacteria and off-odors in several treatments [68].

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2. Sanitation of the Osmotic Solution If the osmotic process is carried out in a nonsterile environment and the restoring of the concentration takes place by evaporation at low temperature or by nonevaporative processes, the sanitation of the solution comes out as a priority, so as to maintain the microbial load at low level. The necessity of microbial assessment during and at the end of the process allows the optimization of the heat treatment. Microbial targets have to be individualized to assure the safety and to save the solution from over heating. Plate heat exchangers can be used even if the solution is of high viscosity [67]. Nevertheless, an adequate pumping apparatus must be implemented to assure the desired solution ow. One of the main problems related to heat treatment is nonenzymatic browning, such as caramelization and Maillard reactions, since some amino acids or proteins can be extracted from the fruit. The susceptibility to thermal degradation mainly depends on the presence of reducing sugars used as osmotic agents and on the pH of the solution. For this reason, the use of corn syrup instead of mono- or disaccharides solutions has been proposed [32]. The use of high molecular weight saccharides while preventing nonenzymatic browning, reduces the rate of heat inactivation of microorganisms. Yeasts can grow at relatively low aw, high sugar concentration, and low pH; they also show increased heat resistance in dry foods [69]. Furthermore, the heating medium, besides increasing heat resistance, also inuences the extent of sublethal injuries and repair of thermally stressed cells [70]. The rate of heat inactivation varies in function of the type of sugar and decreases with decreasing aw in glucose and fructose but not in sucrose solutions. Moreover, at any aw, the order of susceptibility to inactivation of yeast cells is consistently fructose, glucose, and sucrose. In fructose, a large proportion of the survivors exhibit sublethal injury. Depending on the raw fruit characteristics, the right balance between high and low-molecular-weight saccharides in the osmotic solution should be dened. In this way, both avoidance of enzymatic browning and microbial inactivation can be achieved.

V. CONCLUSIONS
The most important factors on which quality and safety of frozen fruits depend are raw material and pretreatments, whose interaction is essential for extra-high-quality nal products. Through a correct cultivar selection for freezing, it is possible to enhance the nutritional and sensory quality of frozen fruits and to improve suitability of fruits to further processing with a good compatibility with environmental aspects. Yet, this selection is made very difcult by the great variability among cultivars and environments where the cultivar is grown. Future perspectives of fruit cultivar selection should include the creation of a multidisciplinary research sector that is involved in selection, cultivation, and quality assessment of new or old fruit varieties ideally suitable for freezing. Within this sector, it would be very interesting to understand whether known and newly available cultivars could be ideal for organic cultivation, and consequently, to evaluate the suitability to freezing of the cultivars grown organically. The gap that exists between fruit production and processing is even wider when considering organic cultivation and hardly any research has been made concerning freezing. In parallel, and strictly connected with cultivar selection, there is the application of dehydration pretreatments. Just as cultivar selection, combined air-osmotic dehydration pretreatments are aimed at the improvement of the suitability of fruit to freezing, reducing structural damage. Furthermore through the addition of solutes of nutritional and sensory interest, it is possible to improve quality and even increase stability of the pigments, vitamins, and aroma compounds during frozen storage. Such an advantageous step requires small investment as simple equipment is required, and it is a low-cost process which needs reduced energy input over traditional drying processes (4050% energy cost reduction). It can even be considered as a minimal processing, as thermal stress is

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minimized it is compatible with environmental aspects of food processing. Pretreatments could also be a tool to develop new products and to prepare fruit ingredients with functional properties tailored for specic food systems, so opening up a tremendous market potential for high-quality frozen fruit products and ingredients, and an increased variety of value-added frozen fruits available to the consumer. The weakness of the proposed combined system pretreatments freezing is the difculty to dene a general predictive processing model, owing to the great variability of plant materials (species, cultivar, maturity stage, etc.). There is also a lack of adequate responses to problems related to the management of the osmotic solution (reconcentration, reuse, microbial contamination, reutilization and discharge of the spent solution, etc.). Future in-depth studies should be made on how to manage the solution and how to maintain at low level the microbial load of fruits destined for freezing. To avoid sanitary problems, a control system such as HACCP has to be implemented, together with the reduction of the volume of solution involved in processing and the reduction of the amount of discharged spent solutions. The effective monitoring of products safety and quality is based on the fact that the microbiology of frozen fruits is not very different from that of unfrozen (chilled) ones, but frozen fruits have the distinct advantage that microorganisms cannot grow at such low temperatures. However, for frozen fruit safety, HACCP system should be used to identify and monitor the critical points. The actual freezing process should be considered as the particular control point and there should be as little delay as possible in initiating the process and ensuring a rapid freezing time. Even the thawing process should be carefully monitored, to ensure that there is a minimum of microbial growth during and after the process. Yet, further studies are necessary in this eld also regarding the quality and shelf life of thawed fruits as there is some doubt about the opinion that microbial growth is similar in thawed and unfrozen foods.

REFERENCES
1. OR Fennema, Chilled and frozen biological materials: the lesson of roses. In: Proceedings of 19th International Congress of Refrigeration, The Hague, The Netherlands, 1995, Vol. 1, pp. 13 20. 2. AS Sczesniak, BJ Smith. Observation on strawberry texture. A three-pronged approach. Journal Texture Studies 1:41 44, 1969. ` es, son importance. Revue general du Froid 3. VX Nguyen, PA Phan. Exsudation de peches congele 5:479 486, 1973. 4. C Sterling. Effect of low temperature on structure and rmness of apple tissue. Journal of Food Science 33 (6):577 580, 1968. 5. G Van Hulle, O Fennema, WD Powrie. A comparison of methods for the microscopic examination of frozen tissue. Journal of Food Science 30 (4): 601 603, 1965. 6. E Pauli. Technologie Culinaire. 1st ed. Lucerne (Switzerland): Union Helvetia, 1976, pp. 209 210. 7. E Bellini, V Nencetti, L Conte, A Liverani, O Insero. Liste varietali fruttiferi. Pesco (pesche, nettarine, percoche). Terra e Vita 52 (18):51 70, 2001. ` delle fragole in tre sistemi di coltivazione. 8. LF DAntonio, R Fiori, G Baruzzi, W Faedi. La qualita Frutticoltura 12: 69 76, 2000. 9. Anonimous. Fragola ultimo rapporto. Weekly Report of CSO (Centro Servizi Ortofrutticoli) Week 28:1 6, 2001. 10. G Bonous. Piccoli frutti. Bologna: Edizioni Agricole, 1996, pp. 434 442. lection des cultivars en relation avec la transformation. In: G Albagnac, 11. A Maestrelli, JM Chourot. Se P Varoquaux, JC Montigaud, Eds., Technologies de Transformation des Fruits, Paris (France): Lavoisier, 2002, pp. 4177. 12. A Dale, EJ Hanson, DE Yarborough, RJ McNicol, EJ Stang, R Brennan, JR Morris, G.B. Hergert. Mechanical harvesting of berry crops. Horticultural Review 16:255 382, 1994.

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