Journal of the Science of Food and Agriculture

J Sci Food Agric 85:13971404 (2005) DOI: 10.1002/jsfa.2126

Rehydration process of Boletus edulis mushroom: characteristics and modelling

1 Jose Bon,1 Jose E Carreres2 and Pablo Garc a-Pascual,1 Nieves Sanjuan, Antonio Mulet1
1 Departamento 2 AINIA,

de Tecnolog a de Alimentos, Universidad Politecnica de Valencia, Camino de Vera s/n, E-46020 Valencia, Spain Parque Tecnologico de Valencia E-46980 Paterna, Spain

Abstract: Rehydration of air-dried Boletus edulis mushrooms was investigated at six temperatures (25, 30, 40, 50, 60 and 70 C). To describe the rehydration kinetics, two empirical equations, Peleg and Weibull, and a diffusion model for a slab were considered. The empirical models described the rehydration process properly, while the diffusion model also described experimental data adequately when considering the moisture-dependent effective diffusion coefcient. The equilibrium moisture content increased in line with temperature up to 60 C, then decreased. The kinetics constants of the Peleg and Weibull models, k1 and respectively, were affected by temperature. This inuence of temperature can be expressed in term of an Arrhenius relationship, with an average activation energy of 19.2 kJ mol1 . 2005 Society of Chemical Industry

Keywords: Boletus edulis mushroom; rehydration; diffusion; Peleg; Weibull; Lewicki

INTRODUCTION Boletus edulis is one of wild mushrooms the most widely valued by consumers. Owing to its short shelflife linked to a high moisture content and seasonal nature, drying is a useful method to extend availability. One of the main quality parameters in dehydrated foods is the rehydration behaviour. Rehydration of vegetables is usually carried out by soaking the dry material in large amounts of water, although, instead of this, some authors have used air with high relative humidity, either statically or in a drying chamber with air circulation.1 5 The changes that dried material experiences when left in water are the result of water uptake and soluble solid loss. Both are kinetic phenomena highly dependent on temperature, diffusion being the main mechanism.6 8 In addition, the ultrastructure of the product will change after drying and rehydration, leading to changes in the water absorption capacity and moisture retention that can be conrmed and assessed by microscopy.9,10 When simulation or optimization studies are undertaken, the kind of model considered is important; thus addressing different models and knowing their capacity to describe the process could be important. In order to model the rehydration kinetics, different models can be used. Among the empirical ones, Pelegs and Weibulls models have been widely

used. The Peleg equation11 is a two-parameter, non-exponential, empirical model for the description of moisture sorption curves. This model has been applied to rehydration of different foods.3,11 15 The Weibull model has been applied to describe the water adsorption kinetics of rice and tobacco seeds1,5 and the rehydration kinetics of puffed breakfast cereals.16,17 On the other hand, diffusion models have also been used to describe rehydration processes, through Ficks second law. Depending on the hypotheses assumed, this equation may be solved analytically or by an appropriate numerical method.2,18 Studies on the rehydration of edible mushrooms are scarce. Krokida and Maroulis4 studied the rehydration kinetics of Agaricus bisporus and other vegetables in an air dryer at 50 C and 80% air humidity. Their main nding was that the common mushroom showed a low rehydration ratio and left pores unlled. Pal and Chakraverty19 dried samples of Pleurotus ostreatus in a thin layer dryer under different conditions of air temperature and air velocity. Afterwards, they rehydrated the samples in cold (28 C) and hot (100 C) water for 30 min, nding that the rehydration ratio was higher in hot water than in cold water. Mart nez-Soto et al 20 studied the effect of pretreatment and kind of drying on the quality of P ostreatus. They found that the blanching

Correspondence to: Antonio Mulet, Departamento de Tecnolog a de Alimentos, Universidad Politecnica de Valencia, Camino de Vera s/n, E-46020 Valencia, Spain E-mail: amulet@tal.upv.es Contract/grant sponsor: CICYT Contract/grant sponsor: FEDER; contract/grant number: 1FD97-0196-C02-02 Contract/grant sponsor: Microscop a Electronica, Universidad Politecnica de Valencia (Received 3 June 2004; revised version received 11 October 2004; accepted 20 October 2004) Published online 21 February 2005

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pretreatment yielded a more compact structure of the product after dehydration and, subsequently, this factor adversely inuenced rehydration. In addition, the rehydrated freeze-dried samples attained physical characteristics that could be rated as close to the fresh mushrooms, while the quality of hot air- and vacuumdried mushrooms after rehydration was lower. This is not in accordance with the ndings of Li-Shing-Tat and Jelen,9 who found that there were no statistical differences between P sajor-caju vacuum- and freezedried samples, although vacuum-drying provided the closest quality parameter values to the fresh products. Krokida and Marinos-Kouris21 rehydrated A bisporus and other vegetables by immersion in water at 40, 60 and 80 C. They found that the equilibrium water content increased with temperature and the rehydration ratio of mushrooms was the lowest of all the products considered. Except for this last reference, which modelled the experimental data using a rst-order kinetic model, different authors evaluated the absorption capacity of mushrooms through the moisture content reached after a long time, but they did not propose kinetic models to describe these phenomena. The aim of this work is two-fold: to study the effect of rehydration temperature on air-dried samples of B edulis mushrooms, and to obtain models that properly describe the process for gaining insight into the rehydration process of mushrooms.

Figure 1. Fresh sample of Boletus edulis mushroom.

Figure 2. Scheme of sample slicing.

MATERIALS AND METHODS Raw material Fresh raw samples of B edulis mushrooms (see Fig 1), picked in the forests of the Pyrenees (Spain) 2 days previously, were purchased locally. The mushrooms were previously selected by visual inspection according to their homogeneity in size, shape and ripeness. Ripeness was evaluated by inspection of hyphae. The initial moisture content22 was 86.1 0.2 kg H2 O kg1 . Slices of 5 mm thickness (Fig 2) were dehydrated in a cabinet dryer with through ow at 50 C and 1 m s1 . The moisture content of the dried product22 was 0.052 0.004 kg H2 O kg1 dry matter (dm). Measurement of moisture uptake Dried raw material was stored in glass containers at 4 C until it was used in the rehydration experiments. An initial amount of 2.4 0.5 g of dried mushrooms was used in each trial. Samples were rehydrated by immersion in a container lled with 12 l of stirred distilled water. Six rehydration temperatures were used: 25, 30, 40, 50, 60 and 70 C (0.2 C). Samples were periodically weighed and, before weighing, the samples surface water was removed gently with tissue paper. Rehydration was stopped after 2 h or when water gain rate was lower than 0.0001 kg H2 O s1 kg1 dm. Each experiment was performed at least in duplicate, including slices from different mushrooms.
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Modelling To describe experimental data, three models were considered. The Peleg equation is as follows:11 W = W0 + t k1 + k2 t (1 )

where W is the average moisture content at time t (kg H2 O kg1 dm), W0 is initial moisture content, t is the time (s), k1 is a kinetic parameter (s kg dm kg1 H2 O) and k2 (kg dm kg1 H2 O) is a characteristic constant for each product, according to the literature. If time of treatment is long enough, the equilibrium moisture content (We ) is given by: We = W0 + 1 k2 (2 )

where k2 is the equilibrium moisture content. For drying or rehydration processes a power law equation based on the probabilistic Weibull model is as follows:23 Y= t (W W e ) = exp (W 0 W e )

(3 )

where and are the scale and the shape parameters, respectively. The scale parameter is a kinetic coefcient.
J Sci Food Agric 85:13971404 (2005)

Rehydration process of Boletus edulis

If water transport is assumed to take place by diffusion, then Ficks second law for a slab like shape is: Wl Wl = De (4 ) t x x where Wl is the local moisture content at time t (kg H2 O kg1 dry material) and De is the effective diffusion coefcient (m2 s1 ). The assumptions necessary to solve equation (4) analytically are one-dimensional diffusion, uniform initial moisture distribution, negligible external resistance to heat and mass transfer, constant effective diffusion coefcient and no shrinkage. The solution is a series development, and by integration the average moisture can be computed:24 Y= (W W e ) = (W 0 W e )
n=0

where M is the mass, s is the dry matter content, and subscripts d, 0 and r refer to dried, before drying and rehydrated, respectively. The dry matter holding capacity (DHC), which expresses the ability of the matrix to hold soluble solids after the rehydration process, gives an idea of the extent of tissue damage and its permeability to solutes, and may be calculated as: DHC = Mr sr Md sd (9 )

8 ( 2 n + 1 )2 2 (5 )

Finally, the rehydration ability (RA) is a measure of the ability of the product to rehydrate and, according to this author, represents the total damage incurred by the tissue during drying and rehydration processes. It is given by: RA = WAC DHC (10) Statistical methods Tests for signicance differences were carried out using analysis of variance (ANOVA) and Fishers leastsignicant-difference (LSD), protected and unprotected procedure, with a signicance level of = 0.05.28 Analysis of sample microstructure Sample microstructure was observed by Cryo-SEM in a Jeol JSM-5410 microscope. The specimens for Cryo-SEM were taken from the centre of the cap of dried slices. Square samples of 4 4 1 mm were rehydrated for 15 min at 22 and 70 C; afterwards they were cryo-xed by immersion in slush nitrogen (210 C), fractured, etched (at 90 C, 105 Torr for 15 min), gold coated and viewed in the SEM coldstage. The fracture surface of the cryo-xed samples was viewed directly while it was maintained at 130 C or lower.

exp (2n + 1)2 2

De t 4L2

In order to take into account the necessary number of terms of the series, 30 terms were used in the calculations. Ficks equation was also solved considering that the effective diffusion coefcient is moisture-dependent. In that case, the diffusion model cannot be solved analytically. The nite element method (FEM) was used in order to identify the parameters. The relationship between the effective diffusivity and the product water content considered was:25 De = exp(a + bW ) (6 )

where a and b are the parameters of equation (6). The parameters of the models were estimated by the nonlinear least squares method.26 Two criteria were used to evaluate the goodness of the t to experimental data: the explained variance (VAR)18,26 and the mean relative error (MRE).21 The kinetic parameters of the models were assumed to be temperature-dependent according to an Arrhenius type relationship: A = A0 exp Ea RT (7 )

RESULTS AND DISCUSSION Some rehydration curves of B edulis mushrooms at different temperatures are shown in Fig 3. It can be observed that the higher the temperature, the higher the initial absorption water rate. The equilibrium water

where A matches up with the reciprocal of the Peleg constant k1 , the reciprocal of the Weibull scale parameter and the effective diffusivity,14,17,18 Ea is like an activation energy (kJ mol1 ) and R is the universal gas constant (8.31439 J K1 mol1 ). Assessment of the rehydration ability Lewicki27 proposed three indices to characterize rehydration: the water absorption capacity (WAC), which gives information about the ability of the material to absorb water with respect to the water loss during dehydration and may be calculated as follows: WAC = Mr (1 sr ) Md (1 sd ) M0 (1 s0 ) Md (1 sd ) (8 )
Figure 3. Rehydration experimental data of Boletus edulis.

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content (We ) also increased with temperature, except for the highest considered temperature, 70 C. Empirical models for rehydration: Peleg and Weibull According to the methodology previously described, the parameters of both empirical models were estimated at different temperatures from equations (1) and (3). Unlike the drying process, in the rehydration one We cannot be measured independently because many changes can occur at long soaking times, it being difcult to establish when equilibrium is attained. Hence, We was considered as an additional parameter to be identied in the Weibull model.16,17,29 Tables 1 and 2 show the identied coefcients of Pelegs and Weibulls models at each temperature. All VAR values were equal to or higher than 99.4% except at 25 C for the Peleg model (98.3%). The MRE were equal or lower than 5.54% for the Peleg model and equal to or lower than 1.89 for the Weibull model. Equilibrium water content tended to increase along with temperature up to 60 C, and then decreased at 70 C. The values obtained from both models followed the same tendency, as can be observed in Tables 1 and 2. The agreement between the models was quite good for We estimated at different temperatures. The gures obtained are grouped into three sets. We at 70 C was statistically signicant different from the values at 50 and 60 C in the Peleg model and at 60 C in the Weibull model. The kinetic parameters of both models (k1 and , respectively) increased with temperature. The values for the Peleg k1 constant were similar to the gures found by Sanju an et al 14 for broccoli stems and slightly higher than the gures found by Garc a-Pascual et al 13 for Morchella esculenta, another wild edible mushroom.
Table 1. Identied parameters of the Peleg model

Table 3. Parameters of the Arrhenius relationship (condence intervals, = 0.05)

Model

Pre-exponential factor

Ea (kJ mol1 ) 21.1 16.8 18.5 14.4 19.8

Peleg k0 = 3.47 102 s (kg ms) (kg H2 O)1 Weibull 0 = 5.64 101 s Average

Temperature ( C) 25 30 40 50 60 70

We (kg H2 O kg1 dm) 2.9a 3.1ab 3.4bc 3.5c 3.7c 3.2ab

k1 (skg dm kg1 H2 O) 143 186 141 834 71 71

k2 (kg dm kg1 H2 O) 0.35a 0.33ab 0.30bc 0.29c 0.27c 0.32ab

Different letters in each column denote signicance at p < 0.05. Table 2. Identied parameters of the Weibull model

The values of the Weibull scale parameter, , were one order of magnitude lower than the gures obtained by Machado et al 17 in ready-to-eat breakfast cereal. Owing to the meaning given by different authors,13,16,17 the reciprocals of k1 and could be compared with the effective diffusion coefcient of diffusion models. Both kinetic coefcients were tted to the Arrhenius equation. As seen in Table 3, where the values obtained for the activation energy (Ea ) are shown, the condence intervals are quite large, being an indicator of the experimental difculties as well as differences in raw material. The values attained at 70 C were not considered when estimating Ea . The values estimated in this work through Pelegs and Weibulls equations are of the same order of magnitude as those obtained by other authors for dif a-Pascual et al 13 ferent dried products.17,18,30,31 Garc 1 obtained an Ea value of 31.6 kJ mol for rehydrated M. esculenta samples. The difference between both mushrooms may lie in the fact that B edulis has a more uniform and spongy structure than M esculenta, and water can penetrate more freely. The Weibull shape parameter ranged between 0.54 and 0.64. However, there were no statistically signicant temperature differences. As a consequence, the shape parameter could be considered constant for this product. These values are, according to the results of Cunha23 and Machado et al ,16 in the range of values of mass transfer processes where the internal resistance prevails. Finally, the Peleg constant k2 tended to decrease as the rehydration temperature increased, following the opposite trend to the equilibrium water content (We ), with the same statistically signicant differences among several temperatures found in the We , as shown in Table 1. At 70 C the value of k2 rose, and the estimated We decreased, since the k2 Peleg constant allows us to estimate the equilibrium water content through equation (2). The effect of temperature on We and k2 will be considered later. Diffusion models for rehydration Table 4 shows the effective diffusion and We coefcients identied from equation (5). The values of We were similar to those obtained with the empirical models, with data grouped in three statistically signicant different sets. By tting the values of De with the Arrhenius equation, the Ea obtained was 16.2 kJ mol1 (condence interval = 8.9); this value is similar to those obtained with Pelegs and Weibulls models. However, the accuracy attained in the estimations was not satisfactory, and not only were the nal
J Sci Food Agric 85:13971404 (2005)

Temperature 25 30 40 50 60 70

( C)

We (kg H2 O kg1 dm) 3.0a 3.0ab 3.3bc 3.4cd 3.6c 3.1abd

0.5 0.6 0.6 0.6 0.6 0.6

(s) 849 980 854 488 461 419

Different letters in each column denote signicance at p < 0.05.

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Table 4. Estimations of parameters of Boletus edulis samples [equation (5)] Table 5. Parameters using a variable De

Temperature ( C) 104 25 30 40 50 60 70

a 5.1 6.2 5.8 4.9 4.9 4.7

b 1.41 0.97 0.94 1.07 1.01 1.21

Temperature ( C) 25 30 40 50 60 70

We (kg H2 O kg1 dm) 2.8a 2.8ab 3.1bc 3.2c 3.4c 2.9ab

De

L2

(s1 ) 4.9 3.7 4.9 8.1 7.9 9.4

Different letters in each column denote signicance at p < 0.05.

Figure 4. Fit of experimental data considering constant De .

the moisture content.25 From these results, and considering that the product has a spongy structure, it was assumed that an effective diffusivity depending on moisture content would be more realistic. Thus, Ficks second law [equation (4)] was solved numerically, considering an effective diffusion coefcient moisture dependent [equation (6)]. The average values of the We obtained at each temperature with Pelegs model were used in the parameter estimation procedure in order to diminish the number of parameters to be identied. The results obtained with this modied diffusion model are shown in Table 5. Table 5 shows that the diffusion model, taking into account that De varies with the moisture content of the product, allows us to describe the rehydration kinetics of B edulis mushroom properly. The parameters of the model, a and b, did not show a clear relationship with rehydration temperature, as no statistically signicant differences among the values were found. As a consequence, the parameters a and b could be considered as constant. All VAR values were equal or higher than 99.6% and the MRE values equal or lower than 2.81%. Inuence of rehydration temperature on equilibrium moisture content Two effects of rehydration temperature on the We can be observed. The rst one is an increase of We and accordingly a decrease of k2 with temperature. The second one is the abrupt decrease of We in the trials conducted at 70 C. Many authors consider that, when rehydrating, We is a constant parameter for each product, irrespective of temperature. A similar reasoning can be applied to Pelegs parameter k2 , which has been considered by many authors as a characteristic constant for each product, since its temperature dependence is often either null or very low.32 34 Water absorption capacity of biological products is related to the type of material, the ultrastructure and chemical composition of cells. Hence, changes in the chemical or physical structure of the material may promote variations of We linked to the rehydration or soaking temperature in some particular products and/or conditions. In that way, We has been found to be temperature-dependent in some cases.3,12,15,31,35 38 With regard to mushrooms, Pal and Chakraverty,19 and Krokida and MarinosKouris21 found an increase of We along to temperature for P. ostreatus and A. bisporus, respectively.
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Figure 5. Test of the constancy for De .

moisture data of the process often under-estimated, but also the shape of the estimation did not match the estimations, as can be observed in Fig 4. Considering that a constant diffusivity could be the main source of errors leading to a poor t, plotting LnY (Fig 5) vs time can be a way to check if the effective diffusivity varies during rehydration,25 where Y is the dimensionless moisture content. For a long enough time, according to equation (5) a straight line should be obtained. As can be observed in Fig 5, effective diffusivity does not appear to be constant, as the diffusion model [equation (5)] assumes. This variation constitutes a rst check indicating a dependence on other variables, the most likely being
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Equilibrium moisture content at 70 C identied in all the replicates did not follow the general trend and decreased greatly with respect to the other temperatures. To conrm this nding, a new set of rehydration experiments was carried out 22 months later using dried material from the same batch in order to nd out whether this phenomenon was linked to a mathematical artefact or was actually a feature of the B edulis material during the rehydration process at high temperatures. This second set of samples of dried B edulis mushrooms was rehydrated at 45, 50, 60, 70 and 80 C. The Peleg model was used to estimate the We of the samples. This parameter rose with temperature up to 70 C, and it diminished at 80 C (Fig 6). ANOVA showed a non statistically signicant effect of temperature on We . However, the unprotected Fishers LSD test showed a statistically signicant difference at = 0.05 between values at 70 and 80 C. In the rst set of experiments a decrease of We was observed between 60 and 70 C; this difference with the second set could be due to aging or to experimental uncertainties mostly linked to raw material natural variability. Aging could be the most likely explanation because all the values for We were consistently lower in the second set of experiments. These results suggest that there is a change in the physiochemical behaviour of the mushroom tissue at high temperatures. This decrease in the We is only noticeable if the temperature goes beyond a threshold. In B edulis mushrooms this threshold temperature is around 65 and 75 C, at which a reduction of hydrophilic properties of the samples could occur. Abu-Ghannam and McKenna12,30 obtained similar results when they rehydrated blanched beans. These authors observed that We rose with temperature from 20 to 40 C, but it diminished at 60 C. Other authors15,18,31,37 found that We diminished when rehydration temperature increased in broccoli and chickpea samples. In order to elucidate the behaviour of B edulis hyphae rehydrated at 70 C, several micrographs were taken by cryo-SEM microscopy. Figure 7 shows the mushroom tissue rehydrated for 15 min at 20 and 70 C. At 70 C the hyphae were contracted, showing less turgidity than samples rehydrated at
3.8 We (kg H2O kg-1 d.m.) 3.6 3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 20 40 60 Temperature (C) 80 100 1st trials 2nd trials

Figure 7. Cryo-SEM micrographs of rehydrated Boletus edulis at 22 C (a) and at 70 C (b) showing hyphae (arrows) and intercellular spaces (asterisks).

22 C, which implies less water absorbed by the sample. The origin of that behaviour could be the damage of the product structure at high temperatures, which hinders the absorption of water by the product. That implies the breakdown of the hyphae together with the denaturation of proteins and the loss of soluble solids. Thus, the process must be a complex set of phenomena, whose effect is the low moisture absorption at high temperatures. Some authors have pointed out for rehydration the relevance of changes in proteins and polysaccharides in the We .7,39,40 Assessment of Boletus edulis rehydration ability Table 6 shows the average values of the three indices proposed by Lewicki.27 There were statistically signicant differences only in the WAC, in a trend similar to that observed for We . Rehydrated samples of B edulis absorbed around 5565% of the fresh product water, and retained an average of 45.4% of soluble solids of the initial dry weight (DHC). Finally, the index that assesses the RA reached an average value of 27.1%. These values are indicative of the damage suffered by the product during drying and rehydration. It is generally accepted that the degree of rehydration is dependent on the
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Figure 6. We (Peleg model) for the Boletus edulis rehydration trials.

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Table 6. Rehydration indices for Boletus edulis mushroom (%)

Temperature ( C) 25 30 40 50 60 70

WAC (%) 56.5a 55.4a 61.3abc 62.5bc 66.5c 57.9a

DHC (%) 46.1 47.6 45.5 44.0 42.4 46.7

RA (%) 26.0 26.3 27.8 27.3 28.2 27.1

ACKNOWLEDGEMENTS The authors acknowledge the support from the CICYT and from the FEDER, reference 1FD970196-C02-02. In addition, the support of the Servicio de Microscop a Electronica of the Universidad Polit ecnica de Valencia is a acknowledged.

REFERENCES
Different letters in each column denote signicance at p < 0.05.

degree of cellular and structural disruption suffered during drying, which leads to loss of integrity, dense structure of collapsed and shrunken capillaries with reduced hydrophilic properties, as reected by the inability to imbibe sufcient water to rehydrate fully.21 Lewicki27 and Lewicki et al 41 applied these indices to several dried products, such as potato, apple, parsley and tomato. The WAC of B edulis reached a value between that of potato (42.5%) and parsley (86.4%). The index DHC was similar to parsley (50.2%) and tomato (51%). Finally, the RA of B edulis was lower than in potato (37.9%) and parsley (43.4%) and higher than in apple (10.1%) and tomato (18.3%). Most authors simply assess the rehydration comparing the mass of the product after rehydration with the initial mass or the dry matter content.7,9,20,21 Thus, it is not possible to compare those data with the gures obtained in the present work. On the other hand, and as a consequence, it could be interesting to use the soaking water for cooking in order to recover the soluble solids lost. It is also worth pointing that, in large-scale rehydration of dried vegetables, the remaining liquid could be an interesting source of some valuable substances, such as vitamins, minerals, sugars or proteins, and its recovery could also eliminate an environmental impact as well as increase the value of such residues.

CONCLUSIONS Mathematical models are a proper way to describe the soaking process of B edulis mushroom at different temperatures. The kinetic parameters of Pelegs and Weibulls models were inuenced by temperature, in the way that an Arrhenius type equation could describe the relationship between them and the rehydration temperature. The average activation energy obtained was 19.2 kJ mol1 . In the diffusion equation, an effective diffusion coefcient dependent on moisture content was identied. The We increased with temperature up to 60 C, and then diminished. This constitutes an indication of the highest temperature advisable for the soaking process. The shift in the water absorption trend appears to be at a threshold temperature of around 6575 C. The samples of B edulis absorbed around 5565% of the fresh product moisture; they lost more than 50% of the initial solids, and the index that assesses the rehydration ability reached a value similar to other vegetable products.
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