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DOI 10.1007M1947-011-0649-9
ORIGINAL PAPER
Springer
CIELab color parameters (L*, a*, and b*) with the adsorption
time was studied, obtaining results that match the kinetic
adsorption model proposed.
Keywords Adsorption . Kinetics model . Discoloration . Resin.
Apple juice. Browning
Notation
A Absorbance (dimensionless)
A0 Initial absorbance (dimensionless)
C
Resin concentration in the juice (grams resin/gram
juice)
Z
Adsorption efficiency (%)
m
Adsorbate concentration on resin surface (grams
melanoidins/gram resin) S Adsorbate
concentration in the juice
(grams melanoidins/gram juice) m0 Maximum
concentration of adsorbate retained in the
juice (grams melanoidins/gram resin) Kads Equilibrium
adsorption constant (Langmuir model,
grams juice/gram resin) KF Equilibrium adsorption
constant (Freundlich model,
grams juice/gram resin) n
Constant of adsorption
equilibrium (Freundlich
model, dimensionless) t
Adsorption time (hours)
ka Kinetic constant of the adsorption stage (grams
juice/gram resin second) kd Kinetic constant of the
desorption stage (per second) K
Equilibrium constant of
dynamic adsorptiondesorption process (grams juice/gram resin) mm
Adsorbate concentration on resin surface in equilibrium
conditions (grams melanoidins/gram resin) L* CIELab
color parameter (dimensionless) a*
CIELab color parameter
(dimensionless)
b* CIELab color parameter (dimensionless) L0 Initial value
of CIELab L* parameter
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Introduction
Two of the most important stability problems during the
processing of fruit juices are browning and turbid appearance. In
the case of apple juices, the main reason for these changes is the
oxidation of polyphenolic substances (Constenla and Lozano
1995;Fernndez de Simn et al. 1992;Falguera et al. 2011).
Browning is one of the most important processes of
deterioration that occurs in fruit juices during processing and
storage (Toribio and Lozano 1984), and consists of the
appearance of colored reaction products. There are two kinds of
browning: enzymatic browning and non-enzymatic browning
(Shahidi and Naczk 1995). Enzymatic browning is caused by the
action of polyphenol oxidase over phenolic substrates, resulting
in melanins. Non-enzymatic browning is caused by the reaction
between the reducing sugars and the free amino acids that result
in melanoidins. Both melanins and melanoidins are colored
products that confer the juice a dark color.
Different methods are currently used to reduce browning and
the possible turbidity. Turbidity treatment usually takes place
prior to the pasteurization process, and its utility is not to avoid
browning but to allow the reduction of colored compounds
(melanins and/or melanoidins) once they have been undesirably
produced during storage and/or thermal treatment. One of the
methods used to remove the color of juices is flocculation and
later sedimentation through the use of gelatine and bentonite
(Gokmen et al. 2001). This method has the disadvantage of
obstructing the pores of the membranes used in the clarification
stage. A method also used in the clarification of apple juices by
ultrafiltration is adsorption through polyvinylpolypyrrolidone
(PVPP; Gokmen et al. 2001;Humset al. 1980), but PVPP has the
inconvenience of being expensive and hard to recover. Another
method that can be used is the photochemical destruction of
these compounds (Ibarz et al. 2005), although it is expensive
and the products of the reaction are not known and could be
toxic. The adsorption method with cheaper and easier-to-recover
adsorbents is an alternative to remove the colored compounds
causing the turbidity that appears in juices (Carabasa et al. 1998;
Fisher and Hofsommer 1992; Qiu et al. 2007). The adsorbent
that meets these requirements is activated carbon, and it is
widely used with good results. If its particle size is very small, it
makes it hard to remove and able to contaminate the juice. If the
size is bigger, the price is much higher. There are other
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1 + KadsS
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(3)
AH
AS
ln Kads
R
AG =-RT ln K d
(Van't Hoff's equation)
(6)
a s
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0,5 OC
0,400
0.CO3
Fig. 1 Evolution of adsorption efficiency (Z) with resin/juice ratios at different temperatures
process as two-staged, one of adsorption and another of
desorption, both of them being first-order kinetic stages
(Langmuir 1918). This model has the disadvantages that it is
necessary to know the equilibrium constant in order to calculate
the equation parameters and the desorption constant cannot be
measured independently. To work out this inconvenience, an
approximate geometric model has been developed (Kuan et al.
2000; Qiu et al. 2007)to calculate the two constants.
Ibarz et al. (2008) developed an equation to describe the
variation with time of the adsorbate contents (colored solute) in
the resin:
For each resin/juice ratio, seven samples were prepared, one for
each time: 0.5, 1, 2, 3, 4, 5, and 6 h. After the corresponding time
of adsorption, these samples were filtered through a 0.45 -|j.m
membrane filter prior to the measurement of absorbance values at
420 nm and
and
measuringthe CIELabcolor parameters (L*
b*). In the CIELab color space, L* stands for luminance, a* is the
red-green axis, and b* corresponds to the blue-yellow axis. In this
a so
0,12
a
60 50
-
u
C
20
0,200
0,300
Absorbante at 4Z0 nm
0,16
O50!C 3S*C
20K
O50S
C
35?C
X 20'C
0.100
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dm ~d7
(7)
,-ti-
0,06
15
OS0C
1,5
20
A35SC
X205C
3,5 3
m = K(1 - e-kdt)
If 2,5
0'
....a::-**
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(9)
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-4
-3,5
-3
-2,5
-2
-1,5
-1
-0,5
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Table 1 Parameters for Langmuir
and Freundlich isotherms
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Langmuir model
Freundlich model
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adsS
l+KBdBS
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-k?Sn
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T (C)
20 35 50
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mo
R2
KF
23.752.32
7.951.84
0.9834
27.653.93
0.430.08
0.9593
37.261.09
8.700.61
0.9988
46.495.04
0.460.06
0.9826
81.988.82
3.790.48
0.9836
86.2510.01
0.610.15
0.9470
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data processing. All the fittings and the estimates were calculated
at a 95% significant level. All experiments and analysis were
carried out in triplicate.
a 24-h time frame; thus, the 24-h period is adequate for this
experiment.
Adsorption Efficiency
Color Evolution
A consequence of melanoidin adsorption is the discoloration of
the juice. Thus, to know the adsorption kinetics, the evolution of
the L*, a*,and b* CIELab parameters can be studied. The
following equation is used for L* (Carabasa and Ibarz 2000; Ibarz
et al. 1999):
L
(10)
0 +
(L
l - L )(1-e
0
-at
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Fig. 3 Resin adsorption dynamic curves, at 35 C, for three different ratios resin/juice
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ads
AG (kJ/mol)
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^ = ka - kdm $ m
= K(1 - e-kdt)
Ratio (g resin/ g
juice
0.01
0.02
0.03
kd (h-1)
0.450.13
0.580.13
0.690.05
mi = K = kd/kd (g juice/g
resin)
17.351.81
12.710.74
10.360.20
R2
0.9868
0.9894
0.9987
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Table 4 Adjustment parameters of
L* evolution for different
resin/juice ratios at 35 C
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L = L'a + (Li
89.690.42
89.370.66
90.350.76
R2
0.480.18
0.920.32
1.120.48
0.9901
0.9860
0.9778
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Conclusion
The adsorption efficacy does not clearly rise when temperature
increases and rises when the amount of resin used increases.
Considering the technical and economic disadvantages associated
with these optimal conditions, the most reasonable option is to
work with the lowest parameters for both of them that allow
obtaining the desired characteristics of juice coloring.
The adsorption process is spontaneous, exothermic, and not
favored by an increase in temperature.
The values of the kinetic constant of the adsorption stage are
higher than the ones of the desorption stage. Thus, the
concentrations of adsorbed colored compounds in the steady state
are high.
The evolution of the adsorbed concentration values (m)and the
L* parameter values follows an increasing exponential function,
in accordance with the observed adsorption kinetics. The greater
the adsorption, the lighter the juice becomes.
The evolution of the a* and b* parameters shows a color
reduction, which continued for the b* parameter but limited for
the a* parameter, which is globally appreciated as a reduction of
the reddish colors.
References
Achaerandio, I., Gell, C., & Lpez, F. (2002). Continuous vinegar
decolorization with exchange resins. Journal of Food Engineering,
51,311-317.
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Atac, B., & Gokmen, V. (2011). Adsorption of dark colored compounds in
apple juiceEffects of initial soluble solid concentration on adsorption
kinetics and mechanism. Journal of Food Process Engineering, 34, 108124. Augusto P, Falguera V, Cristianini M, Ibarz A (2011). Rheological
behavior of tomato juice: Steady-state shear and time-dependent
modeling. Food and Bioprocess Technology.doi:10.1007/s11947-0100472-8.
Beveridge, T., Franz, K., & Harrison, J. E. (1986). Clarified natural apple
juice: Production and storage stability of juice and concentrate. Journal of
Food Science, 51(2), 414-414. Brouillard, R. (1982). Chemical structure
of anthocyanins. In P. Markakis (Ed.), Anthocyanins as food colors (pp. 1
10). New York: Academic.
Carabasa, M., & Ibarz, A. (2000). Kinetics of colour development in
aqueous glucose systems at high temperatures. Journal of Food
Engineering, 44, 181 -189. Carabasa, M., Ibarz, A., Garza, S., & BarbosaCnovas, G.-V. (1998). Removal of dark compounds from clarified fruit
juices by adsorption processes. Journal of Food Engineering, 37,25-41.
Constenal, D.-T., & Lozano, J.-E. (1995). Effect of ultrafiltration on
concentrated apple juice color and turbidity. International Journal ofFood
Science and Technology, 3,23-30. Falguera, V., Gatius, F., Pagn, J., &
Ibarz, A. (2010). Kinetic analysis ofmelanogenesis by means ofAgaricus
bisporu tyrosinase. Food Research International, 43, 1174-1179. Falguera
V, Snchez-Riao A, Quintero-Cern J, Rivera-Barrero C, MndezArteaga J, Ibarz A (2011). Characterization of polyphenol oxidase activity
in juices from 12 underutilized tropical fruits with high agroindustrial
potential. Food and Bioprocess Technology. doi: 10.1007/s11947-0110521-y. Fernndez de Simn, B., Prez-Ilzarbe, J., Hernndez, T.,
Gmez-Cordovs, C., & Estrella, I. (1992). Importance of phenolic
compounds for the characterization of fruit juices. Journal of
Agricultural and Food Chemistry, 40, 1531-1535. Fischer, K.-P., &
Hofsommer, H.-J. (1992). Application of the
adsorption techniques in the fruit industry. Confructa Studien,
36(3-4), 101-107. Freundlich, H.-M.-F. (1906). Uber die adsorption
in losungen
Zeitschrift fur Physikalische Chemie. Leipzig, 57A, 385-470.
Gokmen, V., Artik, N., Acar, J., Kahraman, N., & Poyrazoglu, E.
(2001). Effect of various clarification treatments on patulin,
phenolic compound and organic acid composition of apple juice.
European Food Research and Technology, 213, 194-199. Gokmen,
V., & Serpen, A. (2002). Equilibrium and kinetic studies on
the adsorption of dark colored compounds from apple juice using
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