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Rattana Than Al Erk 2005
Rattana Than Al Erk 2005
www.elsevier.com/locate/jfoodeng
Abstract
Three indexes, namely colorimetric Hunter parameters (L, a, b and DE), hydroxymethylfurfural (HMF) and brown pigment
formation, were monitored to determine the quality loss of pineapple juice at temperatures ranging from 55 to 95 C. The changes in
a and b values followed rst order kinetics while DE tted well to a combined model which described both non-enzymatic browning
reaction and destruction of carotenoid pigment. For browning indexes, HMF and brown pigment formation increased linearly with
heating time and could be explained using zero order reaction kinetics. The results suggested that processing temperature had a
signicant eect on the color change of pineapple juice. The dependence of the rate constant on temperature was represented by an
Arrhenius equation.
2004 Elsevier Ltd. All rights reserved.
could be used as a guideline for designing thermal pro- measured and total color dierences were calculated
cesses to reduce the quality degradation of the products. from L, a and b values.
2.1. Preparation of pineapple juice The following assays were performed using the
methods as mentioned in Cohen et al. (1998). 5 ml of
Fresh Smooth Cayenne pineapples were obtained 95% ethyl alcohol was added to 5 ml of pineapple juice
from a local market. After rinsing the fruit in tap water, sample. The mixture was centrifuged at 1000g for 15
the shell and core were removed using a stainless steel min. The supernatant of the centrifuged sample was
knife. The esh was cut into small pieces and the juice separated into two portions. One was taken to measure
was extracted using a hydraulic machine (Sakaya Model the absorbency at 420 nm for the non-enzymatic
4104, Thailand) to extract the juice. Total soluble solid browning index. To determine the HMF content, 2 ml
(TSS) and pH value of the juice were determined in the of the other portion was introduced into a 16 ml screw
ranges of 12.214.2 Brix and 3.744.00, respectively. cap tube. 2 ml of 12% w/w trichloroacetic acid (TCA;
The prepared juice was then kept at 4 C until used. Sigma, Germany) and 2 ml of 0.025 M thiobabituric
acid (TBA; Carlo Erba, Italy) were subsequently added
2.2. Thermal treatment and mixed thoroughly. The tubes with sample were then
placed in the water bath (Memmert Model W 600,
A series of thin wall glass tubes (length 30 cm; inner Denmark) at 40 C (0.5 C). After incubating for 50
diameter 5 mm; wall thickness 2 mm) were lled with 8 min, the tubes were cooled immediately using tap water
ml of pineapple juice. The tubes (lled with the juice) and the absorbency was measured at 443 nm. A cali-
were sealed at both ends and then subjected to heat in a bration curve of HMF (Aldrich, Germany) was utilized
water bath (Memmert Model W 600, Denmark) at 55, to quantify the HMF concentration.
65, 75, 85 and 95 C for 80 min. The come up times for
every condition was less than 1 min. The temperature of 2.5. Experimental design
the juice at the center of a tube was monitored during
the experiments using type T thermocouples to an The experiments were conducted for ve levels of
accuracy of 1 C. The tubes were removed every 10 temperatures (55, 65, 75, 85 and 95 C). A 2-factor
min and immediately cooled in an ice-water bath in factorial design was used in scheduling of the experi-
order to stop the heat accumulation. The control ments with three replicates in each case.
experiments (without heat treatment) were done by the
same procedure, lling 8 ml of pineapple juice into the 2.6. Data analysis
tubes and placing them directly in the ice-water bath.
Color change, non-enzymatic browning index and hy- The results were reported as an average of three
droxymethylfurfural (HMF) of pineapple juice were replicates. Analysis of variance (ANOVA) of the two
determined using a spectrocolorimeter (JUKI Model factors and interactions were applied to the dierent sets
JP7100/C, Japan) and spectrophotometer (Shimadzu of data with a signicant level of 0.05 (a 0:05).
Model UV-2101 PC, Japan), respectively. All experi-
ments were performed in three replicates.
3. Results and discussion
2.3. Color measurement
3.1. Color change of pineapple juice during heat treatment
Color changes of pineapple juice were analyzed by
measuring the transmittance using a spectrocolorimeter. The color degradation of pineapple juice as aected
2 North skylight was used as the light source. The by thermal processing was investigated using Hunter
spectrocolorimeter was calibrated against distilled water parameters (L, a and b). The enzymatic browning reac-
(L 100, a 0, b 0) before the measurement tion was neglected in this study as the enzymes causing
(according to the equipment instruction manual). A browning were susceptible to heat, at temperatures of
glass cuvette (3.5 4 1.5 cm3 ) containing heat-treated >50 (Martinez & Whitaker, 1995). Therefore, non-
juice was placed in the cell transmittance specimen enzymatic browning and pigment destruction were
compartment. The lid of the compartment was closed considered as the major causes of color change in
and the analysis was then conducted. Three Hunter pineapple juice.
parameters, namely L (lightness), a (redness and The results obtained were presented in terms of L=L0 ,
greenness) and b (yellowness and blueness) were a=a0 and b=b0 when L0 , a0 and b0 represented the initial
M. Rattanathanalerk et al. / Journal of Food Engineering 66 (2005) 259265 261
values once the sample temperature had reached the set 4.50
E
2.00
1.50
1.00
1.04 0.50
1.02 0.00
1.00 0 10 20 30 40 50 60 70 80 90
0.98 Heating time (min)
0.96
L/L0
Table 1
Kinetic parameters for color change of pineapple juice
Parameter Kinetic model T (C) k0 (min1 ) 103 k1 (min1 ) 103 R2
a=a0 n1 55 0.50 0.980
65 0.83 0.950
75 1.41 0.962
85 1.79 0.992
95 2.40 0.972
b=b0 n1 55 0.52 0.958
65 0.91 0.996
75 1.40 0.987
85 1.87 0.990
95 2.40 0.985
DE Combined 55 28.73 25.31 0.963
65 69.72 31.64 0.968
75 81.03 31.34 0.996
85 132.31 46.39 0.991
95 219.47 59.96 0.982
increased with the higher heating temperatures. This an important driving force behind the changes in the
could be explained by the assumption that high tem- color of heated samples. The results suggested that the
perature accelerated the carotenoid isomerization which change in DE was inuenced by both non-enzymatic
led to the loss of yellowness (Chen, Peng, & Chen, 1995; browning and pigment destruction. The combined
Singleton, Gortner, & Young, 1961). model was applied to describe the phenomena which
Previous studies of the color change during heat occurred during heating of pineapple juice.
treatment showed similar results. Avila and Silva (1999) The combined model was used widely to explain the
examined the color degradation of peach puree as af- color change in many fruit products (Avila & Silva,
fected by heat treatment. Peach puree became darker, 1999; Garza et al., 1999; Ibarz et al., 1999; Lozano &
corresponding to a decrease in L value and an increase in Ibarz, 1997) and was proposed as a two-stage mecha-
a value, with increasing temperature. Moreover, the loss nism (Ibarz et al., 1999). The rst stage is color forma-
of yellowness was also expressed by a decrease in the b tion due to the Maillard reaction which follows a zero
value. They concluded that the major causes of color order kinetics k0 . The second stage is destruction of
change were due to carotenoid degradation and non- natural fruit pigments which follow rst order kinetics
enzymatic browning (Maillard). k1 . The combined kinetic model is shown in Eq. (2):
To describe the total color of pineapple juice, the
C Kc Kc C0 expk1 t 2
combination of parameters L, a and b, were determined
in terms of total color dierence (DE). DE of pineapple Substituting C with DE and DE at initial time is zero
juice sample was calculated using Eq. (1): (C0 0), Eq. (2) becomes
2 2 2 1=2
DE DL Da Db 1 DE Kc 1 expk1 t 3
The plot between the total color dierence of pine- where Kc k0 =k1 .
apple juice and time is shown in Fig. 4. The results In this work, the results showed that the two reac-
showed that DE increased signicantly at higher heating tions occurred at a higher rate as temperature increased.
temperatures and prolonged processing times. It was Kc represents the relation between kinetic constants, k0
also observed that the rst portion of the curves exhib- (color formation) and k1 (pigment destruction). Kc val-
ited steeper slopes as the heating temperature increased. ues greater than 1 indicated that the Maillard reaction
It means that higher temperature accelerated the predominated over pigment destruction. Moreover, the
chemical reactions and most of the color change oc- higher the temperature, the higher the value of Kc . This
curred during the early heating period. To describe the suggested that reaction rates were strongly dependent on
reactions closely, the juice samples may be taken more processing temperatures.
frequently at higher heating temperatures. Many studies of the color changes during heat
In this current study, the change in DE did not t treatment of fruit puree demonstrated similar nding.
simple zero or rst order kinetic models. Color changes Ibarz et al. (1999) found that a combined model could
of pineapple juice may be the result of more than one be used to describe the change of DE in pear puree. The
reaction and these reactions may not occur simulta- Maillard reaction was found to be dominant rather than
neously at one temperature. Therefore, temperature was pigment destruction. Garza et al. (1999) implied that DE
M. Rattanathanalerk et al. / Journal of Food Engineering 66 (2005) 259265 263
Table 2
Arrhenius equation parameters for the dierent variables of pineapple juice
Variable Kinetic model K0 Ea (kJ/mol) R2
2
a=a0 n1 11.46 10 39.788 0.983
b=b0 n1 9.67 102 39.201 0.978
DE Combined; n 0 1.12 105 47.336 0.962
HMT / HMT o
perature could be described using the Arrhenius rela- 1.60
Table 3
Kinetic parameters for HMF evolution and brown pigment formation of pineapple juice
Parameter Kinetic model T (C) k0 (min1 ) 103 R2
HMF=HMF0 n0 55 3.80 0.971
65 5.07 0.992
75 6.76 0.982
85 9.14 0.989
95 12.26 0.990
A420 =A0420 n0 55 0.10 0.973
65 0.19 0.956
75 0.31 0.973
85 0.41 0.988
95 0.56 0.982
264 M. Rattanathanalerk et al. / Journal of Food Engineering 66 (2005) 259265
Table 4
Arrhenius parameters for the dierent variables of pineapple juice
Variable Kinetic model K0 Ea (kJ/mol) R2
HMF=HMF0 n0 179.182 29.401 0.998
A420 =A0420 n0 724.95 42.794 0.977
temperature. This indicated that HMF was formed at a to 95 C. The changes in Hunter parameters a and b
higher rate at elevated temperatures and subsequently followed rst order kinetics while the change in para-
this phenomenon aected brown pigment formation. meter L could not be tted to any simple relationship.
Several works studied the Maillard reaction in Total color dierence DE could be described using a
aqueous systems containing glucose and amino acid combined model which included the eect of both non-
(Carabasa-Giribet & Ibarz-Ribas, 2000; Gogus, Bo- enzymatic browning and pigment destruction. The
zkurt, & Eren, 1998; Reyes, Poocharoen, & Wrolstad, changes of 5-hydroxymethylfurfural (HMF) and brown
1982). Garza et al. (1999) reported that the HMF con- pigment formation were chosen to demonstrate the non-
tent increased with treatment time. This increase oc- enzymatic browning reaction occurring during the study
curred from with disappearance of the sucrose due to and were found to follow zero order kinetics. The results
Maillard reaction and sucrose hydrolysis increased with suggested that processing temperatures strongly inu-
treatment temperature. Pineapple juice typically con- enced the reaction rate. The Arrhenius model could be
tains sucrose, glucose and fructose (C amara, Dez, & used to describe the temperature dependence of the
Torija, 1995) which are the substrates of the Maillard reaction rate constant for all parameters considered. A
reaction. When the temperature increased, the sucrose in study of quality loss in terms of sugars and amino acids,
the juice was easily hydrolyzed and more glucose and the substrates of the Maillard reaction, together with
fructose were formed, and thus increased the substrates carotenoid destruction as aected by heat treatment is
of the Maillard reaction. Moreover, the high tempera- recommended for future work.
ture accelerated the reaction which is shown by the in-
crease in rate constant values.
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