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Instituto Universitario de Ingeniera de Alimentos para el Desarrollo, Universidad Politcnica de Valencia, Camino de Vera s/n, 46022 Valencia, Spain
Department of Food Science, Alma Mater Studiorum, University of Bologna, Piazza Goidanich 60, 47521 Cesena (FC), Italy
a r t i c l e
i n f o
Article history:
Received 25 August 2010
Received in revised form 22 March 2011
Accepted 26 March 2011
Available online 31 March 2011
Keywords:
Osmotic dehydration
Thermodynamics
Mass transfer
Enthalpyentropy compensation
Kiwifruit
a b s t r a c t
Osmotic dehydration experiments of kiwifruit (Actinidiadeliciosa cv Hayward) were carried out in order to
apply a nonlinear irreversible thermodynamic model. Samples were immersed into 65% (w/w) sucrose
aqueous solution at 30 C during 5, 10, 15, 20, 30, 45, 60, 90, 120, 180, 250, 320, 400, 720, 1440 min. Some
physicalchemical parameters were measured in fresh, treated and reposed (24 h at 30 C) samples. It
was possible to apply the enthalpyentropy compensation coupled to a nonlinear thermodynamic model,
obtaining the apparent bulk modulus and explaining the elastic answer of the tissue throughout the
osmotic process. The osmotic dehydration also produces losses in the native compounds of kiwifruit such
as citric acid and Calcium and Potassium.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
Osmotic treatment is a dehydration technique usually used in
fruits and vegetables, which produces a reduction in food water
activity and therefore allows storing the foods for longer periods
improving the stability and quality of products. Osmotic
dehydration consists on the introduction of foods in a low water
activity solution in order to induce water outows and inows of
external solutes (Ferrando and Spiess, 2001). This treatment
depresses the food water activity and improves the biochemical
and microbiological stability. The structure of plant tissue can be
considered as one of the main factors for understanding the
osmotic dehydration process (Mavroudis et al., 1998). Osmotic
dehydration in a biological system involves complex mass transfer
phenomena simultaneously (chemical and also mechanical) producing physical and structural changes. These changes were
described for isolated cells by Segu et al. (2010) and thermodynamically quantied in apple tissue by Castro-Girldez et al.
(2011).
Kiwifruit is a biological system constituted by three distinct
tissue types, namely outer pericarp, inner pericarp and core. The
core is composed by spherical/ellipsoidal cells (0.1 and 0.2
mm diameter), whereas the outer pericarp is composed by large
cells (0.50.8 mm diameter) dispersed in a matrix of smaller cells
(0.10.2 mm diameter) (Hallett et al., 1992). The inner pericarp
Corresponding author. Tel.: +34 96 387 9832; fax: +34 96 387 7369.
E-mail address: pedsu@tal.upv.es (P.J. Fito).
0260-8774/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2011.03.029
dS a dH b
600
Nomenclature
aj
G
Gj
Jj
Lj
Mr
M
n
P
R
A
S
H
T
t
V
x
z
The objectives of this work are to quantify the effect of the osmotic dehydration treatment in the kiwifruit structure for short
treatment times in a system with a fast mechanical response,
and to develop a methodology for calculating the phenomenological coefcient by applying the compensation theory.
2. Material and methods
Sucrose solution (65% w/w, 30 C), prepared with commercial
sugar and distilled water, was used as osmotic agent. Before the
experiment, kiwifruits (Actinidiadeliciosa cv Hayward) with the
same size and ripeness were bought from a local supermarket
and kept refrigerated until use. The kiwifruits were cut with a calimeter in half slices (1 cm thickness) and the core was eliminated.
There were prepared 47 samples which were immersed in a vessel
containing the osmotic solution with continuous stirring. The relation between the fruit and the solution was of 1:20 (w/w) to avoid
changes in the solution during the process. The system was maintained at 30 C in a constant-temperature chamber. To prevent
evaporation the vessel was covered with a sheet of plastic wrap.
Preliminary kinetic studies were done at the same working conditions in order to select the osmotic dehydration times. These results show that, in the rst minutes of treatment, some structural
changes occur affecting the rest of treatment. Therefore, the selected times for the present study were: 5, 10, 15, 20, 30, 45, 60,
90, 120, 180, 250, 320, 400, 720, 1440 min. Six samples were used
at each dehydration time.
A ow-diagram of the experimental procedure is presented in
Fig. 1.
Three samples per osmotic treatment time were reposed at
30 C for 24 h, on Decagon containers, closed with paralm, in order to eliminate the concentration proles in samples.
Mass, volume and surface water activity were analyzed for each
fresh, treated and reposed samples. Representative fresh samples
were used to determine the initial moisture, sugar content (Brix),
citric acid content, cation content and Cryo-SEM. Moisture and sugar content (Brix) were measured for each reposed sample. The
other three samples per time were used for the cation analysis, citric acid content and Cryo-SEM.
At each osmotic time, an aliquot of sucrose solution was also taken from the vessel. Water activity and Brix of the solution were
measured at each time.
F
l
F
force (N)
displaced distance (m)
molecular force (N/mol)
Greek alphabet
chemical potential of the specie j (J/mol)
l0j
chemical potential of reference of the specie j (J/mol)
m
specic volume (L/mol)
D
variation of a variable
g
apparent bulk modulus
lj
Subscript
0
24
LP
max
s
w
t
and superscript
initial time
time 24 h after the treatment
liquid phase
maximum
sucrose
water
time (min)
601
Fig. 1. Diagram of the experimental procedure. Cryo-SEM was made in fresh and treated samples until 60 min of treatment.
(0.2 kPa), applied for 3 min, with an ionization current of 2 mA. The
observation in the scanning electron microscope was carried out at
15 kV, at a working distance of 15 mm and a temperature 6130 C.
3. Results and discussion
The osmotic dehydration operation with 65Brix solution produces compression and relaxation phenomena (Fito and Chiralt,
1997). These mechanisms could be observed by analyzing the mass
and volume variations. Fig. 2 shows the overall mass variation,
water loss and sucrose gain through the osmotic treatment. In
the gure, the decrease in total mass is explained by the high water
losses while the sucrose mass increases during the osmotic treatment. In Fig. 3, the volume variation is observed; it is possible to
appreciate the overall decrease in volume through the osmotic
treatment. The half slice of kiwifruit can be divided in two zones
(see Fig. 4c), zone A represents the external zone composed by
homogeneous reservoir cells explained in the introduction; and
zone B represents the internal part of the tissue, where the reservoir and vascular cells are combined in radial way. These two zones
show different directions in the mechanical tension, during the
contraction and expansion.
Fig. 2. Evolution of overall mass (), water mass (j) and sucrose mass (N) variation through the osmotic treatment.
602
shows the tissue with the extracellular space lled with liquid.
Afterwards, until 15 min of treatment, the fruit suffers expansions,
recovering 93% of the initial volume, recovering the zone A; Fig. 5c
shows the membrane/wall system intact, thus the expansion must
be a response of the tissue to the rst fast contraction. At 20 min of
treatment, the fruit again is contracted strongly (32% of the initial
volume), disappearing again the zone A and contracting the zone B.
After this time, the expansion/contraction phenomena are less
marked and, at long osmotic times, the fruit is completely retracted
(Fig. 4a) and zone B is absolutely contracted. It is important to
highlight that although the fruit suffers important expansions at
the beginning of the treatment, it is dehydrating and losing overall
weight (Fig. 2).
Second expansion occurs at 30 min, as shows Fig. 4b, recovering
no more than 5% of volume; Fig. 6a and b, show Cryo-SEM pictures
of samples treated 30 min and gures c and d show Cryo-SEM pictures of samples treated 45 min. All pictures show an initial plasmolysis so incipient. Therefore the second expansion must be
also an elastic response to the second fast contraction.
The water and solute uxes promoted in the osmotic treatment
can be estimate with the mass variation, the process time and the
variation of the samples surface (Eqs. (2) and (3)):
DM w M o
Dt A Mrw
DM s M o
Js
Dt A Mrs
Jw
2
3
Fig. 4. Kiwifruit deformation through the osmotic dehydration; (a) pictures of fresh and treated kiwifruit at different treatment times; (b) volume variation curve at short
treatment times and (c) detail of the zones of the kiwi tissue with the sense of the deformations.
603
Fig. 5. Cryo-SEM pictures at different treatment times; (a) fresh kiwi at 350; (b) treated sample at 5 min, at 1000 and (c) treated sample at 15 min, at 200.
the relationship between the moisture in dry basis and the surface
water activity of the treated, reposed samples and data from pure
solutions of water and sucrose (Starzak and Mathlouthi, 2006). In
this gure it is possible to observe that the reposed samples maintain the same relationship surface water activity/moisture as the
pure sucrose solution at different concentrations. Therefore, the
water and sucrose concentrations are homogeneous in the reposed
samples because moisture is an average value of the whole sample
and the water activity is just the surface value. Thus, the concentration proles through the tissue are negligible. The surface water
Fig. 6. Cryo-SEM pictures at different treatment times; (a) treated sample at 30 min, at 1000; (b) treated sample at 30 min, at 500; (c) treated sample at 45 min, at 500
and (d) treated sample at 45 min, at 500.
604
Fig. 7. Variation of water (d) and sucrose (s) uxes versus time through the treatment.
activity of treated samples is lower than that of the reposed samples; it denotes concentration proles in the kiwifruit tissue and
an important internal transport is driven; only at the end of the
treatment, the treated and the reposed values concur with the pure
solution values; this fact denotes the disappearance of concentration proles in the tissue.
Fig. 9 shows the water ux and the volume variation during the
24 h of repose time. In the gure, two steps can be observed: the
rst one, composed by the samples treated less than 180 min,
Fig. 8. Relationship between the moisture in dry basis and the water activity for samples dehydrated (d), reposed 24 h (s), and sucrose solutions () obtained from Starzak
and Mathlouthi (2006).
605
4
5
6
dS
X
1
PdV Fdl
ldni
T
Castro-Girldez et al. (2011) developed a non-equilibrium thermodynamic model for describing the long time osmotic dehydration through the apoplastic ways in apple tissue. The authors
dened the water chemical potential for a non ionic added solute
and an isotherm system, as follows:
dG
aOS
Js
aOS
s
dlext
RTLn we
w mw dP F w dl RT ln e
dnw
as J w
aw
Fig. 10. Kiwifruit tissue scheme with the simplied phases used in the thermodynamic model (adapted from Castro-Girldez et al., 2010).
dS
aOS J
aOS
RT ln se s RT ln we Fw dl pw dV
dnw
as J w
aw
606
Fig. 11. Scheme of the iteration process developed in order to estimate the phenomenological coefcient.
for apple tissue obtaining the value: Lw = 1.095 105 mol2/J s m2. In
animal tissue, phenomenological coefcient was calculated for pork
meat salting process, Lw = 2.7 105 mol2/J s m2 (Castro-Girldez
et al., 2010).
Fig. 12 shows the relationship between the entropy and enthalpy, resulted from the iteration, where the linear adjust of values
between 10 min to the end of treatment shows a good correlation
coefcient (R2 = 0.9941). It is possible to observe that, throughout
the rst 5 min of treatment, the non consideration of the elongation term in the entropy estimation is not negligible. Using Eq.
(1) and the elongation in the entropy estimation (Eq. (9)), the elongation term can be estimated by using next equation:
dS
aOS J
aOS
RT ln se s RT ln we 1 a F w dl
dnw
as J w
aw
10
Fig. 13 shows the elongation term through the dehydration process, where it is possible to observe the high values of this term
during the lost of turgid pressure throughout the rst minutes of
treatment.
DP
g
DV
Vi
11
The apparent bulk modulus obtained (3.9 MPa) reects the elasticity of wall-membrane system of kiwifruit. This value is similar to
the values of different elastic modulus obtained in other fruits:
1.84 MPa for Golden Delicious apples (De Baerdemaeker et al.,
1982), 39 MPa for different varieties of apple (Rosenfeld et al.,
1992), 5 MPa for an unripe green apples to 0.5 MPa for overripe
fruit (De Baerdemaeker et al., 1982; Duprat et al., 1997), 2.5 MPa
for pineapples (Chen and De Baerdemaeker, 1993), 1.9 MPa for
pears (Chen and De Baerdemaeker, 1993).
Osmotic solution only contains water and sucrose, then the
activity gradient of other native substances present in kiwifruit is
Fig. 13. Evolution of the elongation term through the dehydration process.
Fig. 14. Volume variation as a function of pressure variation throughout the interface.
607
608
4. Conclusions
It is possible to apply the enthalpyentropy compensation coupled to a nonlinear thermodynamic model for determining the
water transport through the apoplastic ways in kiwifruit and to describe the behaviours involved in the osmotic dehydration. The
apparition of concentration proles and the structural changes
was also determined. It is also possible to obtain the apparent bulk
modulus by the mechanical terms estimated in the thermodynamic model, explaining the elastic answer of the tissue throughout the osmotic process. The osmotic dehydration also produces
losses in the native compounds of kiwifruit such as citric acid
and Calcium and Potassium.
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