Journal of Food Engineering 61 (2004) 467470 www.elsevier.

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Research note

Application of the Guggenheim, Anderson and De Boer model to correlate water activity and moisture content during osmotic dehydration of apples
Fr ed eric Prothon, L lia M. Ahrn e
Received 24 September 2002; accepted 6 April 2003

SIK, The Swedish Institute for Food and Biotechnology, Department of Environment and Process Engineering, Box 5401, 40229 G oteborg, Sweden

Abstract Water activity and moisture content are the most valuable characteristics for assessing the stability of dried foods. The aim of this work was to evaluate if a desorption isotherm model could be used to describe the relationship between the water activity and moisture content in the product during osmotic dehydration. This model can lead to a better understanding of how water activity of a product can be reduced during osmotic dehydration. The Guggenheim, Anderson and De Boer (GAB) model was chosen because it has been proven to best t the desorption and adsorption of foods over a large range of water activities. The studied material was apple pieces, and the osmotic medium with a water activity of 0.939 was prepared with sucrose. The osmotic dehydration process was studied by collecting moisture content and water activity data at dierent temperatures and times. The model was shown to t well the experimental points at temperatures 25, 45 and 55 C. At 65 C, however, the model is satisfactory if aw is below 0.970 but not above. The eect of temperature can be expressed on the C -parameter of the GAB model. 2003 Elsevier Ltd. All rights reserved.
Keywords: GAB model; Osmotic dehydration; Water activity prediction; Temperature

1. Introduction In the context of minimal processing, the measurement and prediction of water activity provide the best available tool for evaluating the stability of foods. The sorption isotherm, consisting of a graphic representation of water activity (aw ) against moisture content at constant temperature, is a common way of presenting the relationship between these two parameters (McLaughlin & Magee, 1998; Rahman & Labuza, 1999). Desorption isotherms are of particular importance in the design of a food dehydration process, especially in the determination of a drying end point. The end point of drying is the residual moisture content of the nal product which ensures economic viability and microbiological safety, i.e. a water activity value lower than 0.60. Desorption isotherms focus therefore on low moisture or intermediate moisture zones, because this is the range of moisture content of the food product after drying methods
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82. E-mail address: lia@sik.se (L.M. Ahrn e). 0260-8774/$ - see front matter 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0260-8774(03)00119-5

such as air-drying and freeze-drying. The eect of temperature on moisture sorption isotherms has also been reported in many studies (Vel asquez de la Cruz, Torres, & Mart n-Polo, 2001; Wang & Brennan, 1991). Numerous mathematical models have been proposed for the study of both adsorption and desorption of foods, such as the GAB, Iglesias and Chirife, BET, Oswin, and Ferro Font an models (Barbosa-Canovas & Vega-Mercado, 1996; Crapiste & Rotstein, 1982; Gekas, 1992; Wang & Brennan, 1991). There is a lack of knowledge on how the overall water activity of cellular material is evaluated near the full turgor state (Crapiste & Rotstein, 1982). The GuggenheimAndersonde Boer (GAB) model is reported to be the best for tting sorption isotherm data for the majority of food products up to aw levels of approximately 0.9 (Barbosa-Canovas & Vega-Mercado, 1996; Timmermann, Chirife, & Iglesias, 2001; Tsami, Krokida, & Drouzas, 1999). At aw > 0:9, which is the region where cellular material is still in a quasi-turgor state, the water activity was seldom accurately measured or studied. Osmotic dehydration is characterized by a more complex mass transfer process than air-drying. The transport

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F. Prothon, L.M. Ahrn e / Journal of Food Engineering 61 (2004) 467470 Table 1 Some characteristics of mutsu apple Dry matter (%) Brix Density (g/cm3 ) 13.9 0.8 12.8 1.0 0.839 0.014

of water out of the tissue is completed by a counter-current diusion of the osmotic agent from the solution toward the tissue. These two simultaneous transports have a depressing eect on the aw of the samples. Osmotic processes are often evaluated in terms of water loss (WL) and solid gain (SG) (Bolin, Huxsoll, Jackson, & Ng, 1983; Erba, Forni, Colonello, & Giangiacomo, 1994; Garrote, Silva, & Bertone, 1992; Hawkes & Flink, 1978). Mathematic models have been reported in the literature to describe the water transport during osmotic drying (Azuara, Beristain, & Garcia, 1992; Fito & Chiralt, 1997; Panagiotou, Karathanos, & Maroulis, 1998; Toupin, Marcotte, & Le Maguer, 1989). However, only few studies aim at representing kinetics of water activity changes (Hough, Chirife, & Marini, 1993; Monsalve-Gonzalez, BarbosaC anovas, & Cavalieri, 1993). Marcotte and Le Maguer (1991) developed a model based on the equality of aw between the osmotic solution and potato material. A mathematical model, based on the principles of desorption isotherms, can be a suitable way to predict the aw of a product during osmotic dehydration using the moisture content data. A reduction of the experimental work can therefore be reached. In addition, this model can be included in the mathematical models for description of water transport during dehydration allowing the direct prediction of the water activity in the product. The aim of this study was to evaluate if the GAB model can be used (1) to describe the relationship between aw and moisture content in the particular case of osmotic dehydration and (2) to study the eect of temperature on the parameters of this model.

were used were suitable for the microtome. The samples were disks with an average diameter of approximately 13 mm and average width of approximately 10 mm. The samples were placed on wet paper to prevent dehydration until all the samples were cut. Since the composition of foodstus greatly inuences sorption isotherms, some characteristics of Mutsu apples are gathered in Table 1. 2.2. Experimental set-up and sampling procedure A 50% w/w sucrose solution corresponding to a water activity value of 0.939 0.001 at 24 C was prepared by mixing grade sucrose with distilled water. Bottles with a volume of 250 cm3 were lled with both samples and osmotic solution. In each bottle six samples were immersed in 125 ml osmotic medium, which corresponds to a 1:8 volume ratio. Since the apple samples have a lower density than the osmotic solution, a net was used in order to keep them immersed in the solution. The bottles were placed in a shaking water bath with 80 rotations per min (rpm). Experiments were carried out at temperatures of 25, 45, 55 and 65 C. The osmotic treatment took place over a period of up to 24 h. 2.3. Measurements during processing

2. Materials and methods 2.1. Sample preparation A Swedish apple variety (Mutsu) produced in the Kivik region was purchased from a local market and stored at 4 C at a relative humidity of around 95%. In the experiments two batches of apples were used. It was always ensured that apples of satisfying and equivalent quality in terms of rmness, colour and size were chosen. In order to evaluate the quality of the apples, the degree Brix was always measured and only apples with Brix 12.8 1.0 were used. A cork borer was used to extract the samples. Only radial orientation was used, i.e. the samples were cut equatorially from the surface into the core so as to sample the parenchymatic tissue. From each radial cylinder one apple sample was produced with the help of a cutting device by cutting at the point were the vascular tissue is at its densest, thus obtaining a sample from the periphery of the parenchyma. The cutting device was specially built in order to cut cylinders without applying compression forces to the samples during the preparation stage. The blades that

After removal from the osmotic medium, the samples were washed with distilled water, to remove excess solution, and blotted with absorbent tissue to remove excess water, after which their weight, Brix and water activity were measured. Water activity was measured with a water activity meter (AquaLab Series 3 TE) with temperature control and an accuracy of 0.003. Samples were cut to tiny discs in order to ll the surface of the cups, and the water activity was measured at 24 C. The moisture content was determined by drying the two samples in a 70 C vacuum oven at 100 mmHg until a constant weight was reached (AOAC, 1995). 2.4. Moisture isotherms model The GAB equation was used to describe the dry basis moisture content (X ) as a function of water activity (aw ): X CkX0 aw 1 kaw 1 kaw Ckaw 1

where C and k are constants and X0 is described in the literature as the monolayer moisture content on dry basis (kg/kg).

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2.5. Data analysis Equation parameters were estimated by the generalized reduced gradient algorithm (Microsoft Excel Solver) for nonlinear problems. It allows optimizing the

three parameters by minimizing the sum of the residual error. The regression coecient (R2 ) was calculated for model t at each temperature. Because of the diculty in getting a unique solution, the regression procedure was repeated with dierent initial values and dierent upper and lower limits until stable and reproducible values were reached.

6.0

25C
5.0 X (g moisture/ g DM) 4.0 3.0 2.0 1.0 0.0 0.940 0.945 0.950 0.955 0.960 0.965 0.970 0.975 0.980 0.985 aw 6.0 X (g moisture / g DM) 5.0 4.0 3.0 2.0 1.0 0.0 0.940 0.945 0.950 0.955 0.960 0.965 0.970 0.975 0.980 0.985 aw 6.0 X (g moisture / g DM) 5.0 4.0 3.0 2.0 1.0 0.0 0.940 0.945 0.950 0.955 0.960 0.965 0.970 0.975 0.980 0.985 aw 6.0 X (g moisture / g DM) 5.0 4.0 3.0 2.0 1.0 0.0 0.940 0.945 0.950 0.955 0.960 0.965 0.970 0.975 0.980 0.985 aw

3. Results and discussion Desorption isotherm graphs of apples during osmotic dehydration with sucrose solution at four dierent temperatures are presented in Fig. 1. As it can be observed the t of the GAB model is good and it is quantied with the regression coecient R2 (Table 2). At 65 C, however, the model is satisfying below 0.970 but not above. The GAB parameters at each temperature are also gathered in Table 2. The so-called monolayer value X0 looses here its original meaning since it was derived from desorptionadsorption theories and not in the special case of osmotic dehydration. Thus, in this approach all GAB parameters can be called empirical constants. Table 2 shows that only the C constant increases with the temperature and this correlation is also demonstrated by the principal components plot in Fig. 2. The fact that the C -point and T -point are very close to each other means that they are correlated. Whenever required the correlation between C and T can be described by a second-order polynom: C 0:0014 T 2 0:1545 T 1:6754 2

45C

55C

65C

In the prediction of parameters X0 and k it is recommended to use an average value. It is important to point out that any comparison of the osmotic desorption with sorption isotherms developed for traditional drying must be very carefully veried. In fact, in the case of traditional sorption isotherms, samples are put in a chamber with known vapour pressure and constant temperature until equilibrium is reached (Labuza, 1968). Sample moisture content is then measured and plotted against the corresponding water activity. In our study the samples were surrounded with a liquid osmotic media at dierent temperatures, for dierent times, and the water
Table 2 GAB parameters and regression coecients for moisture desorption of apple in osmotic medias at dierent temperatures Temperature (C) 25 45 55 65 GAB parameters X0 0.051 0.057 0.039 0.051 C 1.322 2.563 2.606 2.614 K 1.009 1.007 1.011 1.007 R2 0.9497 0.9821 0.9855 0.9199

Fig. 1. Comparison of experimental (r) and predicted (full line) water desorption data of apple samples subjected to osmotic dehydration. The GAB model is described in Eq. (1).

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F. Prothon, L.M. Ahrn e / Journal of Food Engineering 61 (2004) 467470 In G. V. Barbosa-Canovas, & H. Vega-Mercado (Eds.), Dehydration of foods (pp. 2999). NY: Chapman and Hall. Bolin, H. R., Huxsoll, C. C., Jackson, R., & Ng, K. C. (1983). Eect of osmotic agents and concentration on fruit quality. Journal of Food Science, 48, 202205. Crapiste, G. H., & Rotstein, E. (1982). Prediction of sorptional equilibrium data for starch-containing foodstus. Journal of Food Science, 47, 15011507. Erba, M. L., Forni, E., Colonello, A., & Giangiacomo, R. (1994). Inuence of sugar composition and air dehydration levels on the chemicalphysical characteristics of osmodehydrofrozen fruit. Food Chemistry, 50, 6973. Fito, P., & Chiralt, A. (1997). Osmotic dehydrationAn approach to the modeling of solid food-liquid operations. In P. Fito, E. OrtegaRodr guez, & G. V. Barbosa-C anovas (Eds.), Food engineering 2000. New York: Chapman and Hall. Garrote, R. L., Silva, E. R., & Bertone, R. A. (1992). Osmotic concentration at 5 degree and 25 degree of pear and apple cubes and strawberry halves. Lebensmittel Wissenschaft und Technologie, 25, 133138. Gekas, V. (1992). Characterization and properties of foods and other biological materials. In V. Gekas (Ed.), Transport phenomena of food and biological materials (pp. 63110). Boca Raton, USA: CRC Press Inc. Hawkes, J., & Flink, J. M. (1978). Osmotic concentration of fruit slices prior to freeze dehydration. Journal of Food Processing and Preservation, 2, 265284. Hough, G., Chirife, J., & Marini, C. (1993). A simple model for osmotic dehydration of apples. Lebensmittel Wissenschaft und Technologie, 26, 151156. Labuza, T. P. (1968). Sorption phenomena in foods. Food Technology, 22, 1519. Marcotte, M., & Le Maguer, M. (1991). Repartition of water in plant tissues subjected to osmotic processes. Journal of Food Processing and Preservation, 13, 297320. McLaughlin, C. P., & Magee, T. R. A. (1998). The determination of sorption isotherm and the isosteric heats of sorption for potatoes. Journal of Food Engineering, 35, 267280. Monsalve-Gonzalez, A., Barbosa-C anovas, G. V., & Cavalieri, R. P. (1993). Mass transfer and textural changes during processing of apples by combined methods. Journal of Food Science, 58, 1118 1124. Panagiotou, N. M., Karathanos, V. T., & Maroulis, Z. B. (1998). Mass transfer modelling of the osmotic dehydration of some fruits. International Journal of Food Science and Technology, 33, 267284. Rahman, M. S., & Labuza, T. P. (1999). Water activity and food preservation. In M. S. Rahman (Ed.), Handbook of food preservation (pp. 339382). New York: Marcel Dekker. Timmermann, E. O., Chirife, J., & Iglesias, H. A. (2001). Water sorption isotherms of foods and foodstus: BET or GAB parameters? Journal of Food Engineering, 48, 1931. Toupin, C. J., Marcotte, M., & Le Maguer, M. (1989). Osmoticallyinduced mass transfer in plant storage tissue: A mathematical model. Part I. Journal of Food Engineering, 10, 1338. Tsami, E., Krokida, M. K., & Drouzas, A. E. (1999). Eect of drying method on the sorption characteristics of model fruit powders. Journal of Food Engineering, 38, 381392. Vel asquez de la Cruz, G., Torres, J. A., & Mart n-Polo, M. O. (2001). Temperature eect on the moisture sorption isotherms for methylcellulose and ethylcellulose lms (Research Note). Journal of Food Engineering, 48, 9194. Wang, N., & Brennan, J. G. (1991). Moisture sorption isotherm characteristics of potatoes at four temperatures. Journal of Food Engineering, 14, 269287.

Fig. 2. Principal component analyses showing correlation level of temperature (T ) with the three GAB parameters (C , k , X0 ).

activity measurements of the pieces were made separately at 24 C. In the case of traditional desorption the water activity equilibrate with the surrounding atmosphere.

4. Conclusions The GAB model showed a good t with experimental data at nearly all the studied temperatures, and at 65 C it was suitable for water activities below 0.970. A strong correlation was found between the C constant in the GAB model and temperature. It should, however, be borne in mind that the model is only an empirical model, which was not derived from any set of physical laws or diusion theories. Accordingly, despite its demonstrated success, therefore, its general applicability cannot be taken for granted and it needs to be established independently for any system where its use is considered. The model could, however, be used to compare the behaviour of dierent food products, sugar solutions and processing methods in decreasing the water activity of the product during osmotic dehydration, leading to a better understanding of the osmotic process.

References
AOAC (1995). Ocial methods of analysis 16th edition. J Assoc O Anal Chem 37, 110. Azuara, E., Beristain, C. I., & Garcia, H. S. (1992). Development of a mathematical model to predict kinetics of osmotic dehydration. Journal of Food Science and Technology, 29, 239242. Barbosa-Canovas, G. V., & Vega-Mercado, H. (1996). Physical, chemical and microbiological characteristics of dehydrated foods.