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Original article The mathematical modelling of the osmotic dehydration of shark fillets at different brine temperatures
Saheeda Mujaffar & Clement K. Sankat*
Department of Mechanical Engineering, Faculty of Engineering, The University of the West Indies, St Augustine, Trinidad and Tobago, West Indies (Received 1 July 2004; Accepted in revised form 11 May 2005)

Summary

The eect of brine temperature (20, 30, 40 and 50 C) on the osmotic drying behaviour of shark slabs (10 5 1 cm) in saturated (100) brine was investigated. The parameters investigated were weight reduction, water loss, salt gain and water activity. Salt uptake and moisture data were analysed using various mathematical solutions based on Ficks Law of Diusion and the eective diusion coecients were predicted after considering the process variables. The expressions presented by Azuara et al. (1992), based on the model presented by Crank (1975), were successfully used to predict the equilibrium point and to calculate diusion coecients at not only the initial stages of dehydration, but also at dierent times during the osmotic process.
Diusion coecient, Ficks Law, mass transfer, salting.

Keywords

Introduction

The salting of sh is essentially an osmotic dehydration process. It involves two major mass transfer ows: water ow out of the sh and a simultaneous transfer of salt into the sh. In order to have a comprehensive overview of the salting process and to design an optimum-salting regime, it is rst necessary to investigate the mass transfer changes (salt uptake and water removal), which occur during the process, as well as to describe and predict these changes via mathematical modelling. While the literature abounds with information on general salting and drying techniques, as well as numerous works concerning important chemical, nutritional and microbiological aspects, fewer articles have been dedicated to the scientic study of the process and the basic mechanisms involved in the production of dried salted sh. Most of the studies on the salting and drying of sh have involved the splitting of sh followed by dry or
*Correspondent: Fax: +1 868 662 4414; e-mail: clem@uwi.tt doi:10.1111/j.1365-2621.2005.01086.x
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wet salting and sun drying. Where salting and drying variables are considered, they are done from the perspective of how quickly the process is completed or the overall quality. There are very few reports on the calculation of drying rate constants and diusion coecients for the processes of salt uptake and water loss (WL) during the osmotic dehydration of sh. The main body of knowledge that is referenced is based upon the early work of researchers such as Beatty & Fougere (1957); Jason (1958); Burgess et al. (1967); Del Valle & Nickerson (1967a,b,1968); Zugarramurdi & Lupin (1976,1977,1980) for temperate sh and later reviews by Wheaton & Lawson (1985) and Ismail & Wooton (1992). More recent studies include the work of Berhimpon et al. (1991) who investigated the process requirements for the salting of whole, split or lleted (with skin on) Yellowtail sh, Deumier et al. (1997), who described and experimentally checked a system for continuous determination of mass transfers based on the loss of buoyancy during the brining of whole herring, and MedinaVivanco et al. (1998) who investigated the salting

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behaviour of lleted Tilapia (without skin). Barat et al. (2002) investigated the eect of increasing brine concentration in the cod-salting process (using de-boned cod llets) with a view to increasing process yield. This study was undertaken to investigate and mathematically model the osmotic dehydration of locally available Shark (Carcharhinus leucas, Muller and Henle). Shark is underutilized as fresh sh and therefore available and relatively inexpensive. Shark is an ideal sh model because it can be lleted to give many small llets of uniform size. Additionally, reports indicate that salted sh produced from shark and other species with white or light-coloured esh is similar in appearance to the costly imported salted cod, with comparable protein and fat contents (IDC, 1986). The specic objectives of this study were: 1 To determine the effect of immersion time and brine temperature on WL and salt gain (SG) in shark slabs during osmotic dehydration. 2 To mathematically model mass transfer during osmotic dehydration using various transient solutions to Ficks Law and to calculate the diffusion coefcients for SG and moisture loss for the osmotic process using these models.
Theoretical considerations

amount solute entering/water leaving the sample at equilibrium; D, diffusion coefcient for solute/ water ow; L, half-thickness of slab; t, time. Based on this model (Crank, 1975) and Azuara et al. (1992) presented an expression from which the diusion coecient can be calculated at dierent times during the osmotic process, not just only for the initial stages of dehydration:   2 pL2 St X1 model D 2 1 St X1 experimental 4t where S is the constant related to the rate of WL/ SG; X model, theoretical equilibrium value for WL/SG; X experimental, experimental equilibrium value for WL/SG. The theoretical equilibrium value (X model), and the constant, S, are estimated using the experimental data (Xt) and linear regression: t 1 t : Xt SX1 model X1 model 3

The expression presented by Azuara et al. (1992) was tested using previously reported data on the osmotic treatment of apple, pineapple and beef. Medina-Vivanco et al. (1998) used the regression equation to determine equilibrium salt content (SC) in tilapia.
Materials and methods

The mathematical models used to describe mass transfer during osmotic dehydration are usually based upon various solutions to Ficks Law of Diusion. The solution given by Crank (1975) has been applied to the osmotic dehydration of fruits and vegetables (Hawkes & Flink, 1978; Favetto et al., 1981; Magee et al., 1983) but has also been used to describe salt uptake of sliced and whole sh (Del Valle & Nickerson, 1967b; Zugarramurdi & Lupin, 1977; Medina-Vivanco et al., 1998). The solution applies to unsteady one-dimensional transfer between a plane sheet and a well-stirred solution with a constant surface concentration, that is, innite or semi-innite medium. Rate constants and diusion coecients for the initial stages of the process are determined from plots of Xt/X vs. t1/2: Xt Kt1=2 X1 1

Sample preparation Shark was obtained from a local supplier. Upon capture, sh were cleaned, gutted and skinned before being split in half and lleted along the direction of the muscle bres (Riley, 1973). The layer of dark, subepidermal esh was trimmed. The llets were transported to the Processing Laboratory (University of the West Indies, St Augustine, Trinidad) in an iced box, where they were immediately cut into smaller pieces of the required size (10 5 cm). These pieces were then carefully placed in reclosable plastic freezer bags and stored overnight at )30 C in a chest type home freezer. The following day, llets were allowed to thaw partially to allow for easy cutting and accurately cut to the desired thickness (1 cm) using a Hobart food slicer (Model 1612E; Hobart Corporation, Troy, OH, USA).

where K 2(D/pL2)1/2, Xt is the amount solute entering/water leaving the sample at time t; X,

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Osmotic medium Saturated brine, made from food-grade sodium chloride (NaCl) dissolved in distilled water, was used as the osmotic medium. Saturated brine contains 26.5% salt (w/v) and has a specic gravity of 1.19 at 15 C (Gould & Gould, 1988). At ambient tropical temperatures, this corresponds to approximately 360 g of salt in 1 L solution (Clucas, 1981). The specic gravity of the brine was checked using a hydrometer (Woolf Thermo-Hydrometer SPGR; American Beverage and Supply Company, Indianapolis, IN, USA) and brine saturation was maintained by suspending a ne nylon mesh containing solid salt in the solution [United Nations Development Fund for Women (UNIFEM), 1988]. A total of 10 L of brine was used for each osmotic run. The weight:volume ratio of solution to samples was at least 20:1, to avoid signicant dilution of the medium (by the absorbed salt) and subsequent decrease in the (osmotic) driving force during the process (Lazarides & Mavroudis, 1996). Experimental design The brine solution and the samples were contained in temperature-controlled (0.1 C) stainless-steel water-baths with water circulators and digital temperature display (BlueM Constant Temperature Water-bath, Model WB1110A; Asheville, NC, USA). Solutions were constantly circulated at a ow rate of 200 mL s)1. This improved mass transfer allowed for closer control of the brine (Lazarides et al., 1995). Osmotic trials were done at four brine temperatures: 20, 30 (ambient), 40 and 50 C. It is recognized that temperatures of 40 C and 50 C may not be of practical importance to sh osmotic dehydration because of microbial contamination. However there is potential application at these temperatures for other products such as fruits and vegetables. Temperatures above 50 C were not used as this is the temperature reported as the upper limit beyond which cooking of sh esh occurs (FAO, 1981). Use of low temperatures (below 20 C) increases the viscosity of the osmotic medium and prohibits thorough mixing and satisfactory mass transfer of brine (Lazarides et al., 1995). To facilitate osmotic dehydration at 20 C, the water-bath was placed
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in a refrigerated room (1.77 2.36 2.29 m) set at 20 C (1.5 C). Experimental treatment The experiments were designed to investigate the eect of brine temperature (20, 30, 40, 50 C) on the salting of shark llets (10 5 1 cm) in saturated brine. Saturated brine (360 g L)1) was used throughout because preliminary experiments revealed that spoilage occurred when slabs were immersed in a 210 g L)1 salt solution (60% saturation) at all temperatures. Slabs immersed in a 270 g L)1 salt solution (80% saturation) at 20 C were shown to reabsorb water after an initial loss while the mass transfer changes at 30 50 C were generally similar to those that occurred in slabs in a saturated solution (36% w/v). Therefore, as a matter of convenience the saturated solution was chosen for osmotic trials as the salt concentration in saturated brine is easier to maintain. Sampling procedure Each osmotic trial consisted of placing the shark slabs (10 5 1 cm) in 100brine at a xed temperature for a maximum immersion time of 32 h. At the start of the experiment, sh samples were immersed completely in the brine. At specied time intervals, samples were removed from the solution and weight, moisture content (MC), SC and water activity measured. For weight measurement, the same ve samples were used throughout each osmotic trial. These samples were separated from the other slabs using a ne nylon mesh. For moisture and salt analysis, duplicate samples were quickly rinsed with water to remove any surface salt and excess moisture blotted o using household tissue paper (Favetto et al., 1981; Heng et al., 1990; Lazarides et al., 1997). For water activity determination, duplicate samples were removed from the solution and excess moisture blotted o before measurement. Analytical methods and calculations Two important mass transfers occur during the osmotic process: water ow out of the sample into the surrounding medium and solute transfer from

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the medium into the sample. To consider the changing solute content during the osmotic process, moisture and SC data were expressed on a non-salt dry matter basis. Non-salt dry matter was calculated as the sample weight minus the weight of water and the weight of absorbed salt (Del Valle & Nickerson, 1967a,b; Zugarramurdi & Lupin, 1980; Favetto et al., 1981; Berhimpon et al., 1991): Non-salt dry matter Sample weight (g) Water (g) Absorbed salt (g) 4

1981). SC was expressed as the weight of salt in the sample on a non-salt dry weight basis (g NaCl g DM)1): SC NaClt : DM 8

Salt gain (SG), which represents the total amount of salt absorbed by the slabs from the beginning of the process up to that sampling interval, was also expressed on a non-salt dry matter basis (g NaCl g DM)1): SG NaClt NaCl0 : DM 9

Del Valle & Nickerson (1967a) noted that expressing moisture and salt data on a non-salt solids basis instead of the total solids basis is preferable as this is the only parameter that remains constant during the process as loss of soluble material is small. Favetto et al. (1981) added that for an osmotic process, the non-solute dry matter is a measure of the true dry matter of the sample. Sample weight in grams (g) was measured using an Ohaus Galaxy (110) Analytical Balance (Ohaus Scale Corporation, New Jersey, NJ, USA). Weight reduction (WR) was calculated as the change from the original fresh weight (FWt ) FW0) and expressed on an initial non-salt dry matter basis (g g DM)1): WR FWt FW0 : DM 5

The salt : water ratio (S/W) was calculated as SC divided by the MC of the sample: S=W SC : MC 10

Water activity (aw) was measured using a water activity meter (Rotronic Hygroskop DT; Rotronic Instrument Corp., Huntington, VA, USA) and calculated as the equilibrium relative humidity divided by 100 (Labuza et al., 1976; Gould & Gould, 1988). Statistical analysis Data analysis consisted of simple regression analysis using Microsoft Excel 97 to examine the data for good t. Further regression analysis and anova were carried out by using Genstat Statistical Software (Lawes Agricultural Trust, 1996).
Results and discussion

Moisture content was determined by an ovendrying method (FAO, 1981). Samples were dried for 24 h at 105 C in a Gallenkamp Size One BS Oven (Loughborough, England, UK). MC was expressed on a non-salt dry weight basis (g H2O g DM)1): H2 Ot MC : 6 DM Water loss (WL), which represents the total amount of moisture lost by the slabs from the beginning of the process up to that sampling interval, was also expressed on a non-salt dry matter basis (g H2O g DM)1): WL H2 O0 H2 Ot : DM 7

Quality changes Slabs immersed in 100brine at 20 and 30 C had a good colour, odour and texture. Increasing the brine temperature to 40 C resulted in shrinkage and discolouration of slabs. A cooking eect was observed at 50 C, whereby slabs became translucent in colour and developed the aroma of cooked sh. While the use of high temperatures can increase the rate of osmotic dehydration, high temperatures may result in undesirable changes in the food piece. For example, in the osmotic treatment of apple chips using a sugar solution, the rate of dehydration increases as temperature

Salt (NaCl) content of the llets was determined titrimetrically using silver nitrate solution (FAO,

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increases from 22 to 40 C (Ponting et al., 1966). However, enzymatic browning and avour deterioration occur above 49 C. Similarly for sh, the higher the temperature, up to a certain limit, the quicker the salt uptake (Burgess et al., 1967; Clucas & Sutclie, 1981). However, at higher temperatures, spoilage and protein denaturation become the limiting factors for sh and meat. Doe et al. (1982) reported that changes in cod esh occur when it is heated to 31.5 C. At this temperature some of the tissue water become less strongly bound to protein and appears as free uid. At about 43 C, the sh esh becomes somewhat more translucent followed by an increase in opacity because of the precipitation of thermally denatured sarcoplasmic proteins, which begins at about 45 C. It is therefore usually safer to keep sh cool during salting. Ordinarily, in the tropics, the process is, for convenience, at room temperature (Burgess et al., 1967). Weight reduction Weight reduction in shark slabs was calculated from the weight data using eqn 5. WR was signicantly aected by immersion time and brine temperature (P 0.001). All slabs showed an increase in WR (Fig. 1) and increasing brine temperature increased the weight loss. This means that the higher the temperature, the higher the reduction in weight for the 24 h of dehydration.

Weight loss values after 24 h of dehydration averaged 0.18, 0.36, 0.54 and 0.95 g g DM)1 for slabs dehydrated at 20, 30, 40 and 50 C, respectively. Moisture content and water loss The MC of shark slabs was calculated on a dry matter basis using eqn 6. MC was signicantly aected by immersion time and brine temperature (P 0.001). All slabs showed a decrease in MC (Fig. 2). MC values declined rapidly during the rst 2 h of dehydration and more gradually after. The higher the temperature, the more rapid the initial decline in MC. Initial moisture values averaged 2.76 g H2O g DM)1 (73.4% wb). Values after 4 h of dehydration averaged 2.18, 2.06, 1.87 and 1.70 g H2O g DM)1 for slabs dehydrated at 20, 30, 40 and 50 C, respectively. When calculated on a fresh weight basis (wb), this corresponds to 60.5, 58.0, 57.0 and 55.9% (wb) moisture. Water loss in shark slabs calculated from moisture data (eqn 7) was signicantly aected by immersion time and brine temperature (P 0.001). This value represents the total amount of moisture that has been lost by the slabs from the beginning of the process up to the sampling time. All slabs showed a noticeable increase in WL during the rst 4 h of dehydration,
2.8 2.6

1.0

20C

MC (g H2O g DM1)

2.4 2.2 2.0 1.8 1.6 1.4

30C 40C 50C

0.8

WR (g g DM1)

0.6

20C 30C 40C 50C

0.4

0.2

0.0 0 4 8 12 16 20 24

Time (h)
Figure 1 Effect of brine temperature on the weight reduction (WR) of shark slabs (10 5 1 cm) immersed in 100brine. SEM 0.0536.

12 16 Time (h)

20

24

Figure 2 Effect of brine temperature on the moisture content (MC) changes of shark slabs (10 5 1 cm) immersed in 100brine. SEM 0.093.

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1.4 1.2

0.8

WL (g H2O g DM1)

0.8 0.6 0.4 0.2 0.0 0 4 8 12 16 20 24 20C 30C 40C 50C

SC (g NaCl g DM1)

1.0

0.6

0.4 20C 30C 40C 0.2 50C

0.0 0 4 8 12 16 20 24

Time (h)
Figure 3 Effect of brine temperature on the water loss (WL) of shark slabs (10 5 1 cm) immersed in 100brine. SEM 0.043.

Time (h)
Figure 4 Effect of brine temperature on the salt content (SC) changes of shark slabs (10 5 1 cm) immersed in 100brine. SEM 0.044.

after which WL became more gradual until equilibrium was achieved (Fig. 3). The higher the brine temperature, the greater the WL. Values after 4 h of dehydration averaged 0.58, 0.71, 0.89 and 1.06 g H2O g DM)1 for slabs at 20, 30, 40 and 50 C, respectively. Beyond this time, WL gradually increased and levelled o, with values after 24 h averaging 0.69, 0.80, 0.95 and 1.22 g H2O g DM)1 for slabs dehydrated at 20, 30, 40 and 50 C, respectively. Salt content and salt gain The SC of shark slabs was calculated on a dry matter basis using eqn 8. SC was signicantly aected by immersion time (P 0.001) but not by brine temperature. As shown in Fig. 4, all slabs showed a similar rapid increase in SC during the rst 2 h of dehydration, after which the increase became more gradual. The eect of brine temperature was more apparent beyond the rst 2 h. Further increasing the temperature to 50 C resulted in a decline in salt uptake, probably because of the cooking of the slabs. Values after 4 h of dehydration averaged 0.61, 0.64, 0.63 and 0.53 g NaCl g DM)1 for slabs dehydrated at 20, 30, 40 and 50 C, respectively. When calculated on a wet basis, this corresponds to a SC of between 17% to 19% salt for all slabs.

Salt gain in shark slabs was calculated using the SC data and eqn 9. This value represents the total amount of salt absorbed by the slabs from the beginning of the process up to the sampling time. As the initial SC of the slabs was found to be zero, SG was equivalent to SC. Therefore, SG was also aected by immersion time (P 0.001) but not by brine temperature. SG values after 4 h of dehydration averaged 0.61, 0.64, 0.63 and 0.53 g NaCl g DM)1 for slabs dehydrated at 20, 30, 40 and 50 C, respectively. At 20 C, SG values were similar to WL values. As the immersion temperature increased to 50 C, the slabs showed an increase in WL, while SG values remained stable. An increase in WL rates with increasing temperature without a concomittant rise in solute uptake has been reported by many researchers (Hawkes & Flink, 1978; Islam & Flink, 1982; Raoult-Wack et al., 1989; Lazarides et al., 1995; Lazarides & Mavroudis, 1996). Lazarides et al. (1995) noted that at increased temperatures, high rates of WL during the osmotic dehydration of apples seem to prevent the development of proportionally high rates of counter current sucrose diusion. They added that whenever it is desirable to achieve higher water removal and lower solids gain, a higher process temperature (within allowable limit) should be used.

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Salt:water ratio For all osmotic trials, MC values were higher than SC values, therefore throughout the osmotic trials the S/W (eqn 10) was always less than 1.00. All slabs showed an increase in S/W, but there was no xed pattern of change with increasing brine temperature (Fig. 5). Equilibrium S/Ws for all slabs averaged between 0.27 and 0.37. According to Riley (1973), shark llets can be oven dried after a S/W exceeding 0.30 has been attained in the sh esh. Lazarides et al. (1997) also found that the ratio of water to solids content of apple and potato remained constant or decreased with increasing temperature. Water activity Water activity (aw) reects the active part of MC or the part, which can be exchanged between the product and the environment. It is a measure of the free water in a food, which is available to react chemically or to support the growth of microorganisms during spoilage. Most foods have an aw level in the range of 0.2 for very dry foods to 0.99 for moist fresh foods. Water activity values of slabs immersed in brines at all temperatures were signicantly aected by immersion time

1.00

0.95 20C 0.90 30C 40C

aw

50C 0.85

0.80

0.75 0 4 8 12 16 20 24

Time (h)
Figure 6 Effect of brine temperature on the water activity (aw) of shark slabs (10 5 1 cm) immersed in 100brine. SEM 0.0076.

0.4

0.3

S/W ratio

(P 0.001). All slabs showed decline in water activity (Fig. 6) from an approximate initial value of 1.00, but there was no detectable pattern in the change in aw with brine temperature. Values after 4 h of dehydration averaged 0.849, 0.802, 0.823 and 0.808 for slabs dehydrated at 20, 30, 40 and 50 C, respectively. Doe et al. (1982) noted that the aw of fresh sh is above 0.95 and this can be reduced during salting and drying. With the exception of certain halophilic organisms, bacteria do not generally grow in products with an aw of less than about 0.88, and the growth of most moulds is inhibited below 0.80 (FAO, 1981; Doe et al., 1982). Rate of change in MC and SC According to Lazarides et al. (1995), the rate of moisture removal is a characteristic of prime importance to every dehydration process as it is indicative of process eectiveness and suggests the productive duration of the process. MC data for shark slabs were used to calculate the rate of change in moisture (RateMC). This was done by calculating the dierence in MC (g H2O g DM)1) between consecutive sampling times (t, t + 1), and dividing this value by the time interval (h):

0.2 20C 30C 40C 0.1 50C

0.0 0 4 8 12 16 20 24

Time (h)
Figure 5 Effect of brine temperature on the salt/water ratio (S/W) of shark slabs (10 5 1 cm) immersed in 100brine. SEM 0.013.

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RateMC

MCt MCt1 : t 1 t

11

(a) 3.0
Rate (gH2O g DM1 h1)
2.5 2.0 1.5 1.0 0.5 0.0 0 1

Rate vs. Time

Results of anova revealed that the rate of change in MC (dM/dt) was signicantly aected by immersion time (P 0.001) but not by immersion temperature. A plot of the rate of change in moisture (dM/dt) in shark slabs vs. immersion time as shown in Fig. 7a revealed that rate is highest at the beginning and declines rapidly within the rst hour of dehydration. Generally, during the rst hour, the higher the brine temperature, the higher the drying rate. Drying rates were highest for slabs at 50 C, and lowest for slabs at 20 C. Initial rates of dehydration averaged 0.56, 1.00, 1.74 and 2.83 g H2O g DM)1 h)1 for dehydration at 20, 30, 40 and 50 C, respectively. Beyond 2 h of dehydration, rate changes were negligible regardless of brine temperature and averaged below 0.10 g H2O g DM)1 h)1. The plot of rate of change in moisture (dM/dt) vs. average moisture (M) is given in Fig. 7b. There are no periods of constant water removal and therefore no constant rate period. Rates declined with declining MC (P 0.001). This means that the drying rate of slabs was dependent on the moisture concentration inside the sh muscle. It is generally accepted that mass transfer during osmotic dehydration of fruits is governed by internal diusion, that is, movement under the inuence of a concentration gradient. Where a constant rate of drying does occur, the period is brief and does not exceed tens of seconds (Magee et al., 1983; Lenart, 1992). As also shown by Lenart & Lewicki (1987) for the osmotic dehydration of fruit, the relationship between rate and MC of shark during the falling rate period is rstly exponential in character. However, when the MC falls below a certain critical value, in this case approximately 2.3 g H2O g DM)1, the plot was linear. Salt content data for shark slabs was used to calculate the rate of change in salt (RateSC). This was done by calculating the dierence in SC (g NaCl g DM)1) between consecutive sampling times, and dividing this value by the time interval (h): RateSC SCt SCt1 : t 1 t 12

20C 30C 40C 50C

Time (h)

(b) 3.0
2.5

Rate vs. Moisture content

Rate (gH2O g DM1 h1)

20C 2.0 1.5 1.0 0.5 0.0 1.5 30C 40C 50C

2.0

2.5

3.0

Moisture content (gH2O g DM1)

Figure 7 Effect of brine temperature on the rate of change in moisture content (dM/dt) during the osmotic dehydration of shark slabs (10 5 1 cm) immersed in 100brine.

The rate of change in SC was signicantly aected by immersion time (P 0.001) but not by temperature and was highest during the rst 4 h of dehydration. The rate of change in SC was generally lower than the rate of change in MC, averaging 0.60, 0.67, 0.52 and 0.61 g NaCl g DM)1 h)1 for slabs dehydrated at 20, 30, 40 and 50 C, respectively. High rates of WL and solids gain during the initial stages of dehydration followed by drastically lower rates have been attributed (Lazarides et al., 1995) to the large initial osmotic driving force between the sample and the surrounding hypertonic solution, structural changes such as shrinkage leading to the compaction of the surface layers of the tissue and the decreasing availability of free or loosely bound water leading to the

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progressively slower moisture removal as the process goes on. Rate constants and diffusion coefcients Model no. 1: Crank (1975) When the solution given by Crank (1975) for a well-stirred solution is applied to the WL and SG by shark slabs, the t1/2 law given in eqn 1 can be applied satisfactorily to the linear section of the data which corresponds to the rst 2 h of dehydration (P 0.001). The slopes of these plots are given in Table 1. The higher the temperature of the osmotic treatment, the steeper the slope of the graph and the higher the constant (K). Increasing the brine temperature from 20 to 50 C resulted in an increase in the constant for moisture diusion from 0.3657 to 0.6561 h)0.5, an almost twofold increase. Increasing the brine temperature from 20 to 50 C resulted in a small increase in the constant for salt diusion from 0.5254 to 0.6789 h)0.5. Diusion coecients calculated using these rate constants assuming a (thickness)2 relationship between thickness and rate constant are also given in Table 1. Moisture diusion was found to

increase with increasing brine temperature from 7.29 10)6 to 2.35 10)5 cm2 s)1. Salt diusion showed a smaller increase from 1.50 to 2.51 10)5 cm2 s)1. The activation energy for moisture diusion, estimated using an Arrhenius type equation, was calculated to be 31.7 kJ mol)1. As expected, the data for salt diusion did not t very well and the correlation coecient was very low (r2 0.68). Model no. 2: Azuara et al. (1992) Based on the approach of using Cranks solution for a well-stirred solution, presented by Azuara et al. (1992), the plot of t/WL vs. t based on the straight line equation (eqn 3) was used to generate S-values (intercept) and equilibrium values (slope) that are given in Table 2. All r2-values were >0.99. S-values, which are related to the rate of WL, increased from 0.83 to 1.66 h)1 as brine temperature was increased from 20 to 50 C. The S-value is a measure of the rate of the diusion process, with 1/S being the time taken for half the diusible material to diuse in or out. For example, for WL at 20 C, this corresponds to 1.2 h, while for WL at 50 C, this corresponds to 0.6 h.

Table 1 Constants (K) and diusion coecients (D) obtained using water loss (WL) and salt gain (SG) data and model no. 1 (Crank, 1975) for shark slabs at dierent temperatures

Water loss (WL) K (h)0.5) 0.3657 0.4350 0.5649 0.6567 D (10)5 cm2 s)1) 0.729 1.03 1.74 2.35

Salt gain (SG) K (h)0.5) 0.5254 0.5991 0.5615 0.6789 D (10)5 cm2 s)1) 1.50 1.96 1.72 2.51

Temperature 20 30 40 50 C C C C

r2 0.9688 0.9917 0.9970 0.9993

r2 0.9955 0.9949 0.9926 0.9020

Constant slope of plot WL/WLeqm vs. t (for rst hour of dehydration). WLeqm equilibrium water loss. D (slope)2 (pL2/4), where L 1/2 thickness of slab. r2 determination coefcient.

Table 2 S-values (calculated from intercept) and theoretical equilibrium values (calculated from slope) obtained using model no. 2 (Azuara et al., 1992) for shark slabs at dierent temperatures

Water loss (WL) S-value (h)1) 0.83 1.05 1.92 1.66 WL model (g H2O g DM)1) 0.7 0.8 1.0 1.3

Salt gain (SG) S-value (h)1) 1.44 1.74 1.54 2.22 SG model (g NaCl g DM)1) 0.7 0.7 0.7 0.7

Temperature 20 30 40 50 C C C C

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The diusion coecients for WL in shark slabs were calculated at dierent times during the osmotic process according to eqn 2 and are given in Figs 8 and 9. Diusivities were signicantly aected by immersion time (P 0.001) but not by brine temperature. Generally values were highest approximately after 1 h of dehydration, then declined rapidly during the rst 4 h, after which the decline was more gradual. The diusion coecients for WL increased as brine temperature increased. As shown in Fig. 8, water diusivity values for the rst hour of dehydration averaged 0.90, 1.55, 2.25 and 2.31 10)5 cm2 s)1 for dehydration at 20, 30, 40 and 50 C, respectively. The results were found to compare favourably with the results of model no. 1, which was applicable only to the initial stages of dehydration. The advantage of using this approach is therefore the ability to calculate diusivities for the entire duration of the osmotic treatment and not just the initial stages. Values after 24 h of dehydration were lower and averaged 0.17, 0.23, 0.23 and 0.24 10)5 cm2 s)1 at 20, 30, 40 and 50 C, respectively. Average diusion coecients for WL for the 24 h of dehydration were 0.54, 0.90, 1.34 and 1.35 10)5 cm2 s)1 at 20, 30, 40 and 50 C, respectively. As shown in Fig. 9, there were no marked changes in salt diusion as brine temperature

3.5

3.0 20C 2.5 30C 40C 50C 2.0

D (105 cm2 s1)

1.5

1.0

0.5

0.0 0 2 4 6 8 10 12

Time (h)
Figure 9 Diffusion coefcients (D) for salt gain in shark slabs calculated using model no. 2 (Azuara et al., 1992).

3.0

2.5

20C 30C

2.0

40C 50C

D (105 cm2 s1)

1.5

increased from 20 to 40 C, but values increased as the temperature was increased further to 50 C. Salt diusivity values for the rst hour of dehydration averaged 2.12, 2.07, 1.95 and 2.59 10)5 cm2 s)1 at 20, 30, 40 and 50 C, respectively. Again, these results were found to compare favourably with the results of model no. 1. Average diusion coecients for SG for the entire process (24 h) were 1.23, 1.22, 1.13 and 1.29 10)5 cm2 s)1 for slabs at 20, 30, 40 and 50 C, respectively. Azuara et al. (1992) modelled data of Favetto et al. (1981) for the salting of beef and noted that the diusion coecient was not constant for the duration of the diusion process. At 85 C, Dvalues decreased from an initial value of 4.0 1.5 10)5 cm2 s)1 in 3 h. At 30 C, D-values increased from an initial value of 0.5 1.0 10)5 cm2 s)1 in 3 h.
Conclusions

1.0

0.5

0.0 0 2 4 6 8 10 12

Time (h)
Figure 8 Diffusion coefcients (D) for water loss in shark slabs calculated using model no. 2 (Azuara et al., 1992).

Brine temperature has a pronounced eect on the osmotic dehydration of small shark slabs (10 5 1 cm). Salting can be successfully achieved at 20 and 30 C. Dehydration at higher temperatures (above 40 C) resulted in undesirable changes such as shrinkage, discolouration and cooking. For slabs at all temperatures, the greatest

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change in weight, MC, SC and water activity occurred during the rst 4 h of immersion. During this time the higher the temperature, the greater the reduction in weight and the decline in MC. Mass transfer during osmotic dehydration of shark slabs occurred in the falling rate period. The expressions presented by Azuara et al. (1992), based on the model presented by Crank (1975), were successfully used to predict the equilibrium point and to calculate diusion coecients during the osmotic process. This model allows for the calculation of moisture and salt diusivities at intervals during the osmotic treatment and not just the initial stages.
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