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LWT 40 (2007) 300306

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Color degradation kinetics of pineapple puree during thermal processing

Benjar Chutintrasria, Athapol Noomhormb,
a

Faculty of Science, Food Technology Department, Ramkhamhaeng University, Bangkok 10240, Thailand
Food Engineering and Bioprocess Technology, School of Environment, Resources and Development, Asian Institute of Technology, Pathumthani,
Klongluang 12120, Thailand

Received 26 May 2005; received in revised form 26 October 2005; accepted 14 November 2005

Abstract
Improvement of color, as a quality attribute of processed pineapple puree, has been made possible by the increase in knowledge of
kinetic of color change. The kinetics of color degradation of pineapple puree were investigated during heat treatment at 70110 1C in
order to cover the temperature range that used in preheat and sterilization of commercial aseptic pineapple puree. Color changes
associated with heat-treated puree were monitored using Hunter colorimeter (L, a, b, total color differenceDE) and Browning index
(A420). The changes in L and b values tted well to the rst-order kinetic model while DE, a value, and Browning index followed the zeroorder kinetic. The dependence of the rate constant on temperature was represented by an Arrhenius equation. The results suggested that
DE and lightness, based on activation energy, were the most sensitive measures of color change at temperature range 7090 and
95110 1C, respectively.
r 2005 Swiss Society of Food Science and Technology. Published by Elsevier Ltd. All rights reserved.
Keywords: Activation energy; Lightness; Browning index; Hunter color parameters; Total color difference; Thermal treatment

1. Introduction
Pineapple is an important tropical fruit (Bartholomew,
Paul, & Rohrbach, 2002), particularly as processed
products. Of these, pineapple puree, derived from crushing
those portions of the fruit not otherwise used for solidpacked pineapple products and thermally processing in
cans or aseptic packs, is marketed as a high value added
product at a premium price. During processing, deterioration reaction contribute to the formation of a brown
pigment that is undesirable with respect to color, avor
and market value. Knowledge of the kinetics of color
degradation in other fruit has contributed to minimizing
undesirable color changes and maximizing color retention
(Kessler & Fink, 1986; Lund, 1975; Rhim, Nunes, Jones,
& Swartzel, 1989a; Wells & Singh, 1988).
Typically, color is measured by light absorbance at a
wavelength specic, being 420 nm, for the fruit under
study (Nagy, Lee, Rouseff, & Lin, 1990; Toribio & Lozano,
Corresponding author. Tel.: +66 2 524 5476; fax: +66 2 524 6200.

E-mail address: athapol@ait.ac.th (A. Noomhorm).

1986; Wong & Stanton, 1992) as well as by the Hunter

parameters (L, a, and b) and total color difference (DE)
(Ahmed & Shivhare, 2001; Ahmed, Shivhare, & Debnath,
2002a; Ahmed, Shivhare, & Kaur, 2002b; Buera, Chirife,
Resnik, & Wetzler, 1987; Gunawan & Barringer, 2000;
Gupte, El-Bisi, & Francis, 1964; Lozano & Ibarz, 1997;
Petriella, Resnik, Lazano, & Chirife, 1985; Shin &
Bhowmik, 1994; Steet & Tong, 1996; Weemaes, Ooms,
Loey, & Hendrickx, 1999). A decline in lightness has been
associated with browning in fruit (Labuza, Lillemo, &
Taoukis, 1992).
Optimizing thermal processing to improve the product
color requires data on color degradation kinetics (k values)
and temperature dependence that can be described by
activation energy (Ea). First-order and zero-order kinetic
models have been used to evaluate the appearance of
browning (Ibarz & Bermeijo, 1991; Ibarz, Casero, Miguelsanz, & Pagan, 1989b; Stamp & Labuza, 1983). These
kinetic types are expressed by the following equations:
Zero order : C C 0 k0 t,

(1)

First order : C C 0 expk1 t,

(2)

0023-6438/$30.00 r 2005 Swiss Society of Food Science and Technology. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.lwt.2005.11.003

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B. Chutintrasri, A. Noomhorm / LWT 40 (2007) 300306

where C is the measured color scale value, or a combination of the color scale values, C0 is the initial C, t is the
heating time, k0 is the zero-order kinetic constant and k1 is
the rst-order kinetic constant.
The Arrhenius equation to relate the dependence of the
rate constant with temperature is represented by



Ea
k k0 exp

,
(3)
RT
where k0 is the pre-exponential factor (min
1), Ea is
activation energy (kJ/mol), R is the gas constant (8.314 J/
mol K) and T is absolute temperature (K).
Color degradation kinetics is specic to each fruit
product and processing procedure. Only limited researches
were reported on quality degradation kinetics of pineapple
products during heating at temperatures lower than 100 1C.
Fontana, Howard, Criddle, Hansen, and Wilhelmsen
(1993) reported the effects of additional components, i.e.
sugar and organic acids on the quality deterioration
kinetics of pineapple juice concentrate at 6080 1C while
Rattanathanalerk, Chiewchan, and Srichumpoung (2005)
presented thermal effect on the quality loss of pineapple
juice at 5595 1C.
Despite the nutritional value and economic importance
of pineapple puree, color change and reaction kinetics
during thermal processing have not been described. The
objective of the present study was to evaluate color changes
for the purpose of gathering data of kinetic parameters
(rate constant, k and activation energy, Ea) of color
degradation in pineapple puree during thermal processing
using Hunter color parameter values and, in the liquid
fraction of the puree, by measuring the Browning index.
Temperature range of 70110 1C with 5 1C interval were
selected in order to cover the temperature range that used
in preheat and sterilization of commercial aseptic pineapple
puree processing.
2. Materials and methods
2.1. Preparation of pineapple puree
The pineapple puree sample (40 kg) was obtained from a
commercial plant in Rayong Province, Thailand. The puree
(0.050.15 mm size) was sampled from the same production
lot after size reduction (Comitrol processor, Urshel, USA)
prior to thermal treatment and kept in industrial plastic
bags with metalized plastic layer on the outside (Scholle
#800465) at
20 1C until used in experiments. The
physicalchemical characteristic of pineapple puree used
in experiments is presented in Table 1.
2.2. Thermal treatment
The inuence of temperature on color was examined
between 70 and 110 1C at intervals of 5 1C and at each
temperature for exposure times of up to 500 min over the
lower range, 7090 1C and 100 min over the higher range of

301

Table 1
Characteristic of pineapple puree raw material
Parameter

Value

Total soluble solid (1Brix)

Total acidity (g citric acid/100 g)
pH
% Pulp
L
a
b

1570.00a
0.6370.07
3.7270.04
68.6772.31
53.3770.96

4.3370.28
22.5970.19

Mean(n 3)7standard deviation.

95110 1C due to rapid change in color. The thermal

treatment of puree was carried out in 3 cm diameter and
12 cm high glass asks with screw caps and with 100 g
sample each according to Lozano and Ibarz (1997). Puree
was exposed to temperatures of 7090 1C in a water bath
(70.1 1C)(Memmert Model W 600, Denmark) and to
higher temperatures in a thermostatic silicone oil bath
(70.1 1C) and periodically agitated to ensure uniform
temperature throughout the bulk of the sample. The
temperature of the puree at the center of the ask was
monitored during the experiments using type T thermocouples to an accuracy of 71 1C. After puree attained the
desired temperature, replicate samples (n 3) were examined at intervals of 100 and 20 min at the lower and higher
temperatures range, respectively. Immediately after samples were heated to the experimental temperature for the
prescribed time, they were cooled in an ice-water bath in
order to stop the heat accumulation. The control experiments (without heat treatment) was done by the same
procedure, lling 100 g of pineapple puree into the asks
and placing them directly in the ice-water bath. Color
change that accompanied heating was assessed with a
Hunter Lab D25-PC2 colorimeter (Hunter Laboratory,
Reston, VA, USA) and measurements of L, a, and b. Each
parameter was measured prior to and after heat treatment.
Browning index values were measured on the liquid
fraction of puree. The experiments were performed in
triplicate for all parameters analysed.
2.3. Color measurement
Objective color measurement was made using a Hunter
Lab D25-PC2 colorimeter (Hunter Associates Laboratory
Inc., Reston, VA, USA) based on three-color co-ordinates,
namely L, a and b. The instrument (451/01 geometry, D25
optical sensor, 101 observer) was calibrated with black and
white reference tiles (L 92:8; a
0:8; b 0:1). A glass
cell containing the heat-treated puree was placed above the
light source and post-processing L, a, b values were
recorded. Color measurements were taken in triplicate
and average values were taken for calculation.
The color degradation of pineapple puree can also be
expressed as a single numerical value DE. This value denes

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302

the magnitude of the total color difference. The DE value is

expressed by the following equation:
q
DE L0
L2 a0
a2 b0
b2 ,

of the reaction rate constant. In all cases, data ttings were

considered signicant to a probability level of 95%.

where L0, a0 and b0 represented the reading at time zero,

and L, a and b represented the instantaneous individual
readings during thermal treatment.
Browning index values were measured on the liquid
fraction of puree. Owing to the characteristics of the puree
it was necessary to carry out a clarication of the previous
samples in order to determine absorbance at 420 nm.
Clarication of the liquid portion of the puree was
performed according to Garza, Ibarz, Pagan, and Giner
(1999). Briey, bentonite (10 g) was added to the sample
(100 g), centrifuged (15,300g, 20 min) in a Centrikon T-324
centrifuge (Kontron instrument, Italy) and the supernatant
ltered (45 mm pore). Browning index value was equated
directly to light absorbance of the ltrate, measured at
420 nm using UV/VIS spectrophotometer (Jenway 6450,
UK).

3.1. Kinetics of color change during heating

2.4. Data processing

In order to nd the kinetic model that ts the obtained
experimental data points, the two-step method was used
(Arabshahi & Lund, 1985). Experimental data for the
different parameters were tted to different kinetic models
and processed using SPSS version 10.5 software. Linear
ttings were applied, in the rst step, for zero- and rstorder kinetics for each isothermal experiment to calculate
the corresponding reaction rate constant. Correlation
coefcient and standard error values were used as the
basis to select the best linear tting for the entire
temperature range. In the second step, the Arrhenius
equation was used to describe the temperature dependence

3. Results and discussion

The results obtained were presented in terms of L/L0,

a/a0, b/b0, A420 =A0420 and DE/DE0 where L0, a0, b0, DE0
and A0420 represented the initial values once the sample
temperature had reached the set temperature. The plots
between relative Hunter parameters, Browning index and
treatment time at different temperatures are shown in
Figs. 1, 2 and 4.
3.1.1. Color parameter L
Pineapple puree clearly darkened with temperature and
time. Indeed, after ln transformation, nal lightness relative to initial declined linearly and signicantly (Po0:05)
with time at each treatment temperature between 70 and
110 1C (Fig. 1(a) and (b)). All regressions explained 495%
of the variation in lightness with the standard error values
of less than 0.002. This relationship followed the rst-order
kinetic reaction and it was consistent with previous works
for grape juice (Rhim et al., 1989a; Rhim, Nunes, Jones, &
Swartzel, 1989b), double concentrated tomato paste
(Barreiro, Milano, & Sandoval, 1997), apple pulp, peach
pulp and plum pulp (Lozano & Ibarz, 1997), peach puree
(Garza et al., 1999) and pear puree (Ibarz, Pagan, & Garza,
1999).
3.1.2. Color parameter b
The relative visual yellow color (b values) decreased
during heat treatment under various conditions as shown
in Fig. 1(c) and (d). It was observed that the rst-order
kinetic model tted well to parameter b. In all cases a

100

L/L0

100

L/L0

70C
75C
80C
85C
90C

10
0
(a)

100
200
300
400
Treatment time (min)

10

500

0
(b)

20
40
60
80
Treatment time (min)

100

100

10

b/b0

b/b0

100

70C
75C
80C
85C
90C

1
0
(c)

95C
100C
105C
110C

100
200
300
400
Treatment time (min)

10

95C
100C
105C
110C

500

0
(d)

20
40
60
80
Treatment time (min)

100

Fig. 1. Semi-logarithmic plots of color changes in pineapple puree: (a, b) Hunter L value, (c,d) Hunter b value.

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signicant (Po0:05) linear regression with the coefcient

of determination values (R2) ranged between 0.984 and
0.994 was obtained while the standard error values were
less than 0.002 for all case. Similar results for the order of
reaction were found by other authors in double concentrated tomato paste (Barreiro et al., 1997), peach puree
(Garza et al., 1999), mango puree (Ahmed et al., 2002b)
and pineapple juice (Rattanathanalerk et al., 2005). The
rate constant increased with the higher heating temperatures (Table 2). This could be explained by the assumption
that high temperature accelerated the carotenoid isomerization which led to the loss of yellowness (Chen, Peng, &
Chen, 1995; Singleton, Gortner, & Young, 1961).

3.1.3. Color parameter a

Fig. 2(a) and (b) shows an increase in relative a values
during heat treatment under various conditions. Zeroorder kinetic model described adequately the degradation

303

of Hunter a values of pineapple puree over the entire

temperature range. The coefcient of determination values
(R2) ranged between 0.961 and 0.988, while the standard
error values were less than 0.003 for all case.
The pineapple puree color trend in the plane a and b
(Fig. 3) shows a decrease in the b values and an increase in
a values with treatment time which is accentuated when the
treatment temperature increases. When the temperature
increased the color variation showed a clearer tendency,
describing a shift from the yellow to red hues.

3.1.4. Total color difference (DE)

Total color difference (DE) increases with time and
treatment temperature (Fig. 2(c) and (d)). In this current
study, it was observed that the zero-order kinetic model
tted well to DE. In all cases a signicant (Po0:05) linear
regression with the coefcient of determination values (R2)
ranged between 0.958 and 0.991 was obtained while the

Table 2
Rates of color change in response to treatment time were described as zero and rst-order reaction kinetics depending on the specic parameter
Temp. (1C)

L
k1  103 (min
1)

a
k0  103 (min
1)

B
k1  103 (min
1)

DE
k0  102(min
1)

Browning Index
k0  103(min
1)

70
75
80
85
90
95
100
105
110

0.0670.01
0.0970.00
0.1470.02
0.1570.02
0.2370.02
0.4370.01
0.7570.01
1.6070.80
2.1070.40

0.3470.01
0.3570.02
0.4970.05
0.5270.04
0.6770.02
1.3570.90
1.8170.10
3.3370.30
4.2570.40

0.3070.01
0.5070.02
0.6070.01
0.9070.02
1.0070.10
1.4070.50
2.1070.30
2.5070.10
6.1070.50

0.8770.02
1.3670.40
2.0770.70
3.4070.40
4.1270.50
4.1970.10
5.7870.50
11.0870.20
12.9070.50

0.0470.00
0.0770.00
0.0970.00
0.1070.05
0.2070.02
0.8070.04
1.1070.50
1.5070.30
2.0070.10

3.5
3
2.5
2
1.5
1
0.5
0

a-a0

20

200 300 400 500

Treatment time (min)

600
(b)

70C
75C
80C
85C
90C

15
10
5
0
-5

2
0

100

(a)

(c)

95C
100C
105C
110C

1
0

TCD

70C
75C
80C
85C
90C

TCD

a-a0

Color change in the range green to red, a, total color difference, DE, and Browning Index, A420 are given as zero-order reaction rates while, lightness, L,
and color in the range yellow to blue, b, are given as rst-order reaction rates. All regressions had R2 values 40.95.

100

200 300 400 500

Treatment time (min)

600

-1

16
14
12
10
8
6
4
2
0

40
60
80
100
Treatment time (min)

120

40
60
80
100
Treatment time (min)

120

95C
100C
105C
110C

0
(d)

20

20

Fig. 2. Zero-order kinetic plots of color changes in pineapple puree: (a, b) Hunter a value; (c,d) total color difference (DE).

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304

30

0.12

25

0.1

Hunter b values

70C
20
15
10
5

-5

-4

-3

-2

0
-1
0
Hunter a values

A420

70C
75C
80C
85C
90C

75C

0.08

80C

0.06

85C

0.04

90C

0.02
0

3.2. Effects of temperature on the rate constant

Effect of temperature on color degradation rate constants is shown in Table 3. Dependence of the rate constant
on temperature obeyed the Arrhenius relationship
(R2 40:90) (Eq. (3)). The computed values of the activation energy (Ea) and frequency factor (k0) are reported in
Table 3. Most of the color parameters tended to show
much higher Ea values at the high temperature range.
Higher activation energy signied greater heat sensitiveness
of visual color degradation during thermal processing.
Table 4 shows the comparison of Ea of color parameters
of pineapple puree with various fruit products. Comparing

500

600

95C

A420

0.2

3.1.5. Browning index (A420)

The change in the relative absorbancy at 420 nm
A420 =A0420 which related to brown pigment formation
was adequately described by zero-order kinetic model
(Fig. 4(a) and (b)). In all cases a signicant (Po0:05) linear
regression with R2 between 0.973 and 0.990 was obtained
while the standard error values were less than 0.002.
Similar results for the order of reaction were found by
other authors in pear juice concentrate (Beveridge &
Harrison, 1984), in apple juice (Cohen, Birk, Mannheim,
& Saguy, 1998) and in pear puree (Ibarz et al., 1999).
Table 2 illustrates rates of color change in response to
treatment time as zero- and rst-order reaction kinetics
depending on the specic parameter. The clear increase in
the kinetic constants with treatment temperature can be
observed, i.e. the rate constant for L value, k1 at 70 1C,
0.06  10
3 min
1 increased to 2.30  10
3 min
1 at 110 1C.
Similarly all other kinetic constants increased with
temperature. The evident increase of the kinetic constants
with the treatment temperature conrmed that nonenzymatic browning is favored by the increase in treatment
temperature.

200
300
400
Treatment time (min)

0.25

Fig. 3. Change in b versus a parameters during heating of pineapple puree

at 7090 1C.

standard error values were less than 0.002. The same order
of reaction was found by Flora (1976) and Rhim et al.
(1989b) in grape juice, by Pagliarini, Vernile, and Peri
(1990) in milk and by Barreiro et al. (1997) in double
concentrated tomato paste.

100

(a)

100C
105C

0.15

110C
0.1
0.05
0
0

(b)

20

40
60
80
Treatment time (min)

100

120

Fig. 4. Zero-order kinetic plots of color changes in pineapple puree: (a)

Browning index at 7090 1C, and (b) Browning index at 95110 1C.

to pineapple juice, the Ea for Hunter a of pineapple puree

was almost identical to that found for pineapple juice while
the Ea for Hunter b and total color difference (DE) was
about 37% and 43% higher than that found for pineapple
juice (Rattanathanalerk et al., 2005). This indicated that
both Hunter b and total color difference of pineapple
puree were more sensitive to the change of temperature
(7090 1C) than pineapple juice. This could be due to
pineapple puree contain more pulp than pineapple juice.
Comparing to other fruit products, the results showed
that the Ea for lightness for pineapple puree in the
temperature range of 70 and 90 1C was almost identical
to that found for apple and plum pulp (Lozano & Ibarz,
1997) and about 40% higher than that found for double
concentrated tomato paste and peach pulp (Barreiro et al.,
1997; Lozano & Ibarz, 1997). Over the higher temperature
range (95110 1C), the Ea for lightness for pineapple was
slightly above that for peach puree (Avila & Silva, 1999).
Activation energy for other measures of color compared
favorably with those for other fruit. Some fruit exhibited
high activation energy for one parameter but less for
another reecting differences in their sensitivity to temperature. Pear puree (Ibarz et al., 1999) had a higher Ea
value over the lower temperature range for yellowness
(b value), but lower value for DE and the Browning Index
compared to pineapple puree. Similarly, the Browning
Index for peach puree at low temperatures was above that
for pineapple puree (Garza et al., 1999) while that for
yellowness was similar to pineapple puree at higher
temperatures (Avila & Silva, 1999). Double concentrated

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305

Table 3
Arrhenius equation parameters for different studied parameters in pineapple puree
Parameter

Temp. (1C)

Kinetic model

k0 (min
1)

Ea

R2

Lightness
L/L0

7090
95110

n1

5.59  105
1.04  1015

65.2772.49
129.4273.68

0.966
0.975

Redness
a/a0

7090
95110

n0

1.30  103
3.93  1011

36.8573.25
94.9474.47

0.944
0.972

Yellowness
b/b0

7090
95110

n1

9.7  105
4.19  1012

62.1874.20
109.3572.82

0.961
0.904

Total color
Difference
(DE)

7090
95110

n0

5.0  1010
1.05  1012

83.7171.41
94.4172.82

0.987
0.953

Browning
Index
A420 =A0420

7090
95110

n0

3.07  107
1.39  1012

77.9273.80
109.1473.28

0.987
0.953

Table 4
Comparison of Ea of color parameters of pineapple puree with various fruit products
References

Fruit product

Temp. (1C) Time (min)

Ea (kJ/mol)
L

Rhim et al. (1989a, b)

Grape juice

6095

Avila and Silva (1999)

Peach puree

115135

107

109

Lozano and Ibarz (1997)

Apple pulp
Plum pulp
Peach pulp
Double tomato paste

5694
5694
5694
70100

Ibarz et al. (1999)

Pear puree

8098

Garza, Ibarz, Pagan, and

Giner (1999)

Peach puree

8098

0480

Ahmed et al. (2002a, b)

Mango puree

5090

Rattanathanalerk et al.
(2005)

Pineapple juice

Result from this study

Pineapple puree
Pineapple puree

Barreiro, Milano, and

Sandoval (1997)

15700
15700
15700
590

DE

Browning
index

92.8

66.4
67.8
45.1
48.1

85.7

42.6

76.4

102.1

62.5

62.8

110

020

36.3

36.8

5595

080

39.8

39.2

47.4

7090
95110

0500
0100

65.3
129.4

36.7
94.9

62.2
109.4

83.7
94.4

77.9
109.1

tomato paste was below the Ea value for DE of pineapple

puree at the low temperature range and above that for the
yellowness (Barreiro et al., 1997). This could be due to
the differences in composition such as sugar and amino
acid content, pH, acidity and also the temperature range of
the study (Ahmed et al., 2002a; Beveridge & Harrison,
1984).
The results from this study indicated that the most
sensitive parameter for the measurement of color degradation in pineapple puree in response to temperature
treatment during processing was total color difference
(DE) and lightness over the lower and higher temperature

148

ranges, respectively, based on their Ea estimates. Higher Ea

values indicated greater heat sensitivity of DE and L values
than that of other color parameters.
The relationship between ln k and 1/T for total color
difference (DE) in the temperature range of 7090 1C could
be described by
ln k
100691=T a 24:637
n 5; R2 0:988; Pp0:05.

And the relationship between ln k and 1/T for lightness

(L) in the temperature range of 95110 1C could be

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306

described by
ln k
155671=T a 34:578
n 4; R2 0:975; Pp0:05,

where Ta represents absolute temperature (K).

Total color difference and L parameter may therefore be
recommended as an on-line quality control parameter to
monitor processing effects on color change during thermal
processing of pineapple puree.
References
Ahmed, J., & Shivhare, U. S. (2001). Thermal kinetics of color change,
rheology and storage characteristics of garlic puree/paste. Journal of
Food Science, 66, 754757.
Ahmed, J., Shivhare, U. S., & Debnath, S. (2002a). Color degradation and
rheology of green chilli puree during thermal processing. International
Journal of Food Science and Technology, 37, 5764.
Ahmed, J., Shivhare, U. S., & Kaur, M. (2002b). Thermal color
degradation kinetics of mango puree. International Journal of Food
Properties, 5(2), 359366.
Arabshahi, A., & Lund, D. B. (1985). Considerations in calculating kinetic
parameters from experimental data. Journal of Food Process Engineering, 7, 239251.
Avila, I. M. L. B., & Silva, C. L. M. (1999). Modelling kinetics of thermal
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