International Journal of Food Science and Technology 2020, 55, 201–210 201

Original article
Thermal degradation kinetics of carotenoids, vitamin C and
provitamin A in tree tomato juice

Luis Eduardo Ord

on~ez-Santos1* & Jader Mart
ınez-Gir
on2
1 Facultad de Ingenier
ıa y Administraci

on, Departamento de Ingenier
ıa, Universidad Nacional de Colombia-Sede Palmira, Carrera 32 N
12-00, Palmira, Colombia
2 Sede Palmira, Universidad del Valle, Campus La Carbonera-Zamorano, 2704760,Palmira, Colombia
(Received 17 March 2019; Accepted in revised form 4 June 2019)

Summary In this research, the influence of temperature on the degradation of carotenoids, vitamin C and provita-
min A in tree tomato juice was studied at 70, 80 and 90 °C. The thermal processing significantly reduced
(P < 0.001) the concentration of the bioactive compounds, and the thermal degradation in the evaluated
phytochemicals fit a kinetic first order, with the following activation energies (Ea, kJ mol
1): a-carotene
(69.75), b-carotene (59.50), provitamin A (51.67), zeaxanthin (43.66), vitamin C (41.27), lycopene (18.84)
and b-cryptoxanthin (18.23). The kinetic study and thermodynamic analysis of the tree tomato juice
showed that the degree of thermoresistance in the phytonutrients responded in the following order:
b-cryptoxanthin > lycopene > vitamin C > zeaxanthin > provitamin A > b-carotene > a-carotene. This
study benefits engineering processes interested in the design and optimisation of thermal processes aimed
at preserving the nutritional quality of tree tomato juice.
Keywords Activation enthalpy, activation entropy, ascorbic acid, exotic fruit, retinol.

(2013) report in this fruit levels of carotenoids and

Introduction
World sales of fruit juice reached 38.47 million litres
in 2015 (Kamiloglu, 2019). This high consumption of
fruit juice is encouraged by increased awareness in
markets that the consumption of healthy products
reduces the incidence of diseases and promotes a better
quality of life (Curi et al., 2017). In addition, there is
strong interest in the juice industry to offer exotic bev-
erages that are rich in micronutrients, have new fla-
vours and satisfy the growing demand for exotic fruit
juices (Ord
on~ez-Santos et al., 2017). An important
alternative for the current need for healthy, nutritious
and exotic juices is the tree tomato (Solanum betaceum
Cav), a highly valued fruit in the regional markets of
Colombia, Ecuador and New Zealand that is con-
sumed fresh in salads and processed in juice (Espin
et al., 2016). The tree tomato, also known as tamarillo,
has significant levels of micronutrients, such as carote-
noids, vitamin C, vitamin A and bioactive compounds
associated with the reduction of the incidence of dis-
eases such as cancer, cardiovascular diseases, cataracts
and macular degeneration (de Rosso & Mercadante,
2007; Mertz et al., 2009; Mertz et al., 2010). Lim
*Correspondent: E-mail: leordonezs@unal.edu.co
vitamin C of 4.4 and 25 to 30 mg/100 g, respectively.
The demand for exotic juices and bioactive compounds
found in this fruit make it a promising product with a
significant agroindustrial potential, which can diversify
the production of fruit locally, as well as in other areas
of the world (Espin et al., 2016).
The thermal treatments used in the juice processing
industry conserve, extend shelf life and guarantee sta-
bility for up to 18 months in these types of products
(Achir et al., 2016; Peron et al., 2017). However, the
thermal processing of fruit juice can degrade micronu-
trients such as carotenoids, vitamin C and vitamin A.
In fruit juice, the degradation phenomena of these
micronutrients are complex because different factors,
such as temperature, dissolved oxygen, pH and expo-
sure to light, among others, affect the degradation of
these bioactive compounds (Zepka et al., 2009). The
kinetics of thermal degradation of carotenoids and
vitamin C in fruit juice has been addressed in some
studies, such as in the one conducted by Dhuique-
Mayer et al. (2007), who described changes in b-caro-
tene, b-cryptoxanthin and vitamin C with first-order
kinetics in orange juice thermally processed at 75–
100 °C. Zepka et al. (2009) studied the degradation of
b-carotene and b-cryptoxanthin with first-order

doi:10.1111/ijfs.14263
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kinetics in cashew juice subjected to a heat treatment
of 60–90 °C. Vieira, Mokochinski, and Sawaya (2016)
reported on first-order kinetics for thermal degrada-
tion in vitamin C during a pasteurisation process at
between 50 and 90 °C for orange juice. In another
study, Dhakal et al. (2018) recorded the first-order
kinetics of thermal degradation of vitamin C during
the thermal processing of pineapple juice at 75–95 °C.
Despite these works, other experiments are required
to obtain more information on the reaction kinetics of
bioactive compounds during thermal treatments in
matrices of exotic food with agroindustrial potential;
among these food matrices, the tree tomato has a
worldwide interest for its appreciated organoleptic
characteristics and its important source of bioactive
compounds (Rosso and Mercadante 2007; Mertz
et al., 2009; Mertz et al., 2010; Acosta-Quezada et al.,
2015); however, there is no evidence in the scientific lit-
erature that reports on the effect of thermal treatments
on micronutrients such as carotenoids, vitamin C and
provitamin A present in tree tomato juice. In this
regard, studies are required to increase the levels of
retention of these micronutrients after thermal process-
ing in tree tomato juice; for this, it is necessary to per-
form experiments to determine the kinetic parameters
of the compounds of interest, including the constant
reaction rate, as a function of the process temperature,
as previously indicated by Dhuique-Mayer et al.
(2007). This information would be valuable for the
processing industries of this fruit, since it would allow
the standardisation, the design and the optimisation of
the thermal processes that allow a greater conservation
of the nutritional quality of the juice of this exotic
fruit. Therefore, the objective of this research was to
study the influence of temperature on the degradation
of carotenoids, vitamin C and provitamin A in tree
tomato juice at 70, 80 and 90 °C.
Materials and methods
Chemical
The ethanol, hexane and ascorbic acid were purchased
from Merck, the Folin–Ciocalteu reagent was pur-
chased from Sigma-Aldrich, and the trichloroacetic
acid was purchased from JT Baker.
Preparation of the tree tomato juice
Ripe tree tomato fruits (Solanum betaceum Cav.), yel-
low pulp cultivar, were acquired in a local market in
the city of Palmira, Valle del Cauca, Colombia. They
were taken directly to the Laboratory of Fruit and
Vegetable Technology of the Universidad Nacional de
Colombia, Palmira, for the respective processing. In
the laboratory, the fruits were washed with tap water
International Journal of Food Science and Technology 2020

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and disinfected with a 100 ppm hypochlorite solution
for 10 min. Afterwards, the peduncle was removed,
peeled and cut manually into slices (0.70 9 4.20 cm),
and the slices were blanched in a water bath at 85 °C
for one minute immediately followed by cooling with
water at 4 °C for 1 min. This time–temperature combi-
nation was established in experiments preliminary to
the inactivation of the enzyme peroxidase in the sam-
ples, using the methodology previously described by
Behera et al. (2017). The blanched fruits were crushed
and sieved in a commercial juice extractor; the result-
ing juice was mixed with distilled water that was
refrigerated at 4 °C at a 1 : 1 ratio and centrifuged for
10 min at 1476 x g. After centrifugation, the
supernatant was recovered and the sediment was dis-
carded, which was stored at 4 °C without any additive
or thermal preservation treatment before the thermal
processing. Following the protocols of AOAC (1990),
physicochemical analyses of the pH, titratable acidity
(% citric acid) and total soluble solids (°Brix) were
carried out in the centrifuged juice samples.
Thermal treatments
Aliquots of the centrifuged tree tomato juice, 10 mL,
were distributed in sealed glass tubes and heated to 70,
80 and 90 °C in a water bath for 0, 15, 30, 45 and
60 min. After each heat treatment, the tubes were
immediately cooled with water at 4 °C. The treatments
were performed under dark conditions, the tempera-
ture of the process was controlled with a digital ther-
mocouple, and each treatment was carried out in
triplicate. All samples were immediately taken for the
determination of carotenoids, provitamin A and vita-
min C, as described below.
Determination of the concentration of carotenoids and
provitamin A
The extraction and quantification of the carotenoids
and provitamin A were performed according to the
previously published study of Ordo~ nez-Santos et al.
(2017). The absorbance of each solution in the hexane
phase was read at 450, 444, 451 and 472 nm,
respectively, against hexane as the target in a spec-
trophotometer (Genesys 20 UV-Vis spectrophotome-
ter, Thermo Electron Scientific Instruments LLC,
Madison, WI, USES). The content of carotenoids in
the samples was determined with an extinction coeffi-
cient (E% 1cm Þ in hexane b-carotene (2560), a-carotene
(2800), b-cryptoxanthin (2460), zeaxanthin (2480) and
lycopene (3540), previously published by Hart and
Scott (1995). The provitamin A (retinol equivalent
activity, RAE) was estimated using the conversion fac-
tors 1 lg of retinol equivalent to 12 lg of b-carotene
and 24 lg of a-carotene and b-cryptoxanthin. The
© 2019 Institute of Food Science and Technology

results were expressed in mg L
1 for carotenoids and
lg RAE/L for provitamin A.
Determination of the vitamin C concentration
The vitamin C in the samples was determined follow-
ing the protocol proposed by Jagota and Dani (1982).
An aliquot of 0.2 mL of the sample was mixed in a
test tube with 0.8 mL of a 10% (w/v) trichloroacetic
acid solution, and the tubes were placed in an ice bath
for 5 min. Then, 0.5 mL of the solution was diluted
with 2 mL of ultra pure water and, subsequently,
200 lL of a 1 : 10 dilution of Folin–Ciocalteu reagent
was added. The solution was brought to rest for
10 min at room temperature. After 10 min, the absor-
bance was read at 760 nm against the respective target
using a spectrophotometer (Genesys 20 UV-Vis spec-
trophotometer, Thermo Electron Scientific Instruments
LLC, Madison, WI, USA). The concentration of vita-
min C (mg of ascorbic acid/100 mL of juice) in the
samples was calculated from a calibration line pre-
pared with a standard solution of ascorbic acid (6–
125 lg mL
1, R2 = 0.9860).
Determination of the kinetic parameters
According to Dhuique-Mayer et al. (2007), the thermal
degradation of micronutrients is commonly expressed
with a first-order reaction, as described by eqn 1:
Ct ¼ C0 e
kt
where C0 and Ct are the concentration of the micronu-
trient of interest at time 0 and t, k is the rate of con-
stant degradation (min
1), and t is the time period of
the heat treatment (min).
The decimal reduction time (D, min), the half-life
time (t0.5, min), the temperature coefficient (Q10) and
the thermal resistance coefficient (z, °C) in each of the
evaluated bioactive compounds were calculated with
eqns 2–5, as described by Toledo (1999).
D ¼ lnð10Þ=k
t0:5 ¼ lnð2Þ=k
10=ðT2
T1 Þ
Q10 ¼ k2 =k1
ln 10
z ¼ 10
ln Q10
Determination thermodynamic parameters
Determination of the thermodynamic parameters
The thermodynamic parameters of the degradation of
the evaluated phytochemical compounds included the
activation energy (Ea), activation enthalpy (DH),
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inactivation free energy (DG) and activation entropy
(DS). These parameters were determined with eqns 6–
9, as established by Martynnenko and Chen (2016).
k ¼ k0 eð
Ea=RTÞ ð6Þ
DH ¼ Ea
R  T ð7Þ
DG ¼
R  T  lnðk  h=kB TÞ ð8Þ
DS ¼ ðDH
DGÞ=T ð9Þ

1
where k0 corresponds to the frequency factor (min ),
Ea is the activation energy of Arrhenius (kJ mol
1), R
is the universal constant of gases (8.314 J mol
1 °K),
T is the absolute temperature in °K, h is Plank’s con-
stant (6.6262 9 10
34 J s
1), and kB es la constante de
Bolstzmann’s (1.3806 9 10
23 J K
1).
Statistical analyses
The thermal treatments were performed in triplicate,
and the response variables are expressed as mean
value  standard deviation. One-way analysis of vari-
ance (ANOVA) was carried out using SPSS for Windows
v.25, and P < 0.05 was applied to determine the level
of significance. The thermal degradation of the bioac-
tive compounds was analysed through a regression
analysis using MS Excel software (version 10, Micro-
soft Corporation, Redmond, WA, USA). The correla-
tion coefficients (R2) were calculated to determine the
ð1Þ goodness of the fit. All treatments were made in tripli-
cate.
Results and discussion
Kinetics of the thermal degradation in the carotenoids,
vitamin C and provitamin A
The physicochemical characterisation of tree tomato
juice are presented in Table 1. pH and soluble solids
are lower than those recorded by Falguera et al.
ð2Þ (2012) in tree tomato juice. The studies carried out by
Mertz et al. (2009) and Mertz et al. (2010) in fruits
ð3Þ and tree tomato nectar also report significant concen-
trations of b-cryptoxanthin, zeaxanthin and b-caro-
ð4Þ tene. Concentration values of vitamin C agree to those
registered by Ordo~nez et al. (2009) in fruits and tree
ð5Þ tomato juice. Thermal processing significantly affects
(P < 0.001) the concentration of carotenoids in tree
tomato juice, and these bioactive compounds are
reduced with the increase in temperature and process-
ing time. Figure 1a-e shows the increase in the rate of
constant degradation of carotenoids found in tree
tomato juice with the increase in the intensity of the
thermal treatment; in all cases, the correlation coeffi-
cient was R2 > 0.90, evidencing that the first-order
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Table 1 Characterisation of tree tomato juice used for kinetic
study
Property
pH
Titratable acidity
Soluble solids (°Brix)
Carotenoids (mg L
1)
b-Carotene
a-Carotene
b-Cryptoxanthin
Zeaxanthin
Lycopene
Vitamin C (mg/100 mL)
Provitamin A (lg RAE/L)
kinetics of degradation can explain the changes in the
concentration of carotenoids in tree tomato juice after
thermal processing.
The degradation of carotenoids during thermal pro-
cessing has also been reported by Bozkir et al. (2015),
Achir et al. (2016) and Rodr
ıguez-Roque et al. (2016)
in orange juice and by Mertz et al. (2010) in tree
tomato nectar. Sharma et al. (2008) stated that carote-
noid pigments, with strongly unsaturated structures,
are susceptible to oxidation, isomerisation and other
chemical modifications during processing and storage
of fruit juices. First-order kinetics of thermal degrada-
tion in carotenoids have been reported by other
researchers: Dhuique-Mayer et al. (2007) on the ther-
mal degradation of b-carotene and b-cryptoxanthin in
orange juice during thermal processing between 75 and
100 °C; Sharma et al. (2008) for lycopene in water-
melon juice processed thermally between 50 and
90 °C; and Xiao et al. (2018) in the kinetics of thermal
gradation of solutions of b-carotene, b-cryptoxanthin
and zeaxanthin between 25 and 45 °C. Table 2 shows
the kinetic parameters of carotenoids in tree tomato
juice; the rate of constant degradation of carotenoids
(k, min
1) was higher in a-carotene, followed by b-car-
otene, zeaxanthin, lycopene and b-cryptoxanthin. The
values of D (min), t0.5 (min) and Q10 (Table 1) con-
firmed different levels of thermal sensitivity among the
carotenoids found in tree tomato juice; the thermal
degradation rates were higher in a-carotene, followed
by b-carotene, zeaxanthin, lycopene and b-cryptoxan-
thin. The highest z value (°C) was in b-cryptoxanthin
and lycopene, indicating that these two pigments had
the highest level of thermoresistance of the evaluated
carotenoids in the temperature range of 70–90 °C
(Table 2). The values of D and t0.5 in the pigments b-
carotene, b-cryptoxanthin and zeaxanthin were lower
than those reported Xiao et al. (2018); Dhuique-Mayer
et al. (2007) reported values of D in orange juice that
exceeded those obtained in the present study, but z
values lower than those recorded for the tree tomato
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juice. The high variation of the results is mainly due to
the differences in the thermal treatments applied in
each of the study matrices and in the type of research
Media values
matrix. Researchers such as Murador et al. (2014)
3.59  0.02 have confirmed that the plant variety affects the cellu-
0.90  0.01 lar structure of the carotenoids since these pigments
4.73  0.05 are linked to the different proteins that form lipid dro-
plets or crystalline structures, allowing the release or
2.87  0.07 retention of carotenoids. Rickman et al. (2007)

1.80 0.02
reported that b-carotene is the most sensitive carote-
2.20  0.05
3.61  0.10
noid and lycopene is the least sensitive to isomerisa-
1.26  0.07
tion during thermal processes, which agrees with our
39.48  1.06 results. V
asquez-Caicedo et al. (2007) observed the for-
406.01  5.15 mation of 13-cis-b-carotene and 9-cis-b-carotene dur-
ing the degradation of b-carotene in mango nectar
pasteurisation treatments at 90 °C. Achir et al. (2010)
stated that, during thermal processing of palm oil
between 120 and 180 °C, b-carotene was degraded,
mainly in 13-cis-b-carotene and 9-cis-b-carotene. Mertz
et al. (2010) observed the formation of 13-cis-b-caro-
tene, 5,6-epoxy-b-cryptoxanthin and zeaxanthin esters
during the degradation of b-carotene, b-cryptoxanthin
and zeaxanthin, respectively, in tree tomato nectar
thermally treated at temperatures of 80 and 90 °C. Lee
and Chen (2002) reported on the formation of 5-cis-,
9-cis-, 13-cis- and 15-cis isomers during the thermal
degradation of lycopene at 50 °C.
The concentration of vitamin C and provitamin A
in the tree tomato juice was also significantly affected
(P < 0.001) by the thermal treatments; these vitamins
are reduced with the increase in the temperature and
the processing time. The degradation of vitamin C and
provitamin A in tree tomato juice strongly fits first-
order kinetics. At all evaluated temperatures, a corre-
lation coefficient of R2 > 0.93 is shown in Fig. 1f–g;
therefore, the first-order kinetics of degradation could
explain the changes in the concentration of these vita-
mins in the tree tomato juice after thermal treatments.
The reduction of vitamin C during heat processing has
also been reported in orange juice (Dhuique-Mayer
et al., 2007), tree tomato nectar (Mertz et al. 2010)
and pineapple juice (Dhakal et al., 2018). The reduc-
tion of provitamin A during thermal processing has
been reported in apple juice (Su
arez-Jacobo et al.,
2011) and bovine milk (Liu et al. 2018). Santos & Silva
(2008) report that the oxidative degradation of ascor-
bic acid can be catalysed by temperature, and this
micronutrient is oxidised to dehydroascorbic acid, fol-
lowed by hydrolysis and further oxidation. Other stud-
ies have confirmed that the degradation of vitamin C
in fruit derivatives fits first-order kinetics: Dhuique-
Mayer et al. (2007) in orange juice in a temperature
range of 75 and 100 °C, and Dhakal et al. (2018) in
pineapple juice at a temperature of 75–95 °C. Liu
et al. (2018) also reported that the thermal degradation
of provitamin A in bovine milk can be explained by
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β-Carotene α-Carotene
1.00
(a) 1.50 (b) y = –0.0118x + 0.6199
1.00 0.50
y = –0.0133x + 1.0444 R² = 0.9884
0.50 R² = 0.9899 0.00
0 10 20 30 40 50 60 70
–0.50
Ln (Ct)

Ln (Ct)
0.00
0 10 20 30 40 50 60 70
–0.50 –1.00
y = –0.0198x + 1.0112 y = –0.0253x + 0.7326
–1.00 –1.50
R² = 0.9937 R² = 0.9184
–1.50 y = –0.0421x + 1.1537 –2.00 y = –0.0453x + 0.8435
–2.00 R² = 0.9177 R² = 0.9390
–2.50
Time (min) Time (min)
70 °C 80 °C 90 °C
70 °C 80 °C 90 °C

β-Cryptoxanthin Zeaxanthin
1.00 2.00
(c) (d)
1.50
0.50
y = –0.0195x + 0.817 1.00 y = –0.0158x + 1.3169
0.00 R² = 0.9893 0.50 R² = 0.9713
Ln (Ct)

Ln (Ct)
0 10 20 30 40 50 60 70 y = –0.0244x + 1.2848
0.00
–0.50 y = –0.0244x + 0.8353 0 10 20 30 40 50 60 R² = 0.9806
70
R² = 0.9353 –0.50
–1.00 –1.00
y = –0.0277x + 0.8772
R² = 0.9107 y = –0.0367x + 1.3838
–1.50 –1.50
Time (min) R² = 0.9620
Time (min)

70 °C 80 °C 90 °C 70 °C 80 °C 90 °C

Lycopene Vitamin C
1.00
(e) (f) 4.00
0.50 3.50
0.00 3.00 y = –0.0224x + 3.7041
0 10 20 30 40 50 60 70 R² = 0.9672
–0.50 2.50
Ln (Ct)

Ln (Ct)

y = –0.0305x + 0.3392 2.00

–1.00
R² = 0.9615
–1.50 1.50 y = –0.037x + 3.6709
1.00 R² = 0.9365
–2.00 y = –0.0357x + 0.4045
R² = 0.9622 0.50 y = –0.0496x + 3.641
–2.50 y = –0.0439x + 0.3333
R² = 0.9889 0.00 R² = 0.9544
–3.00 0 10 20 30 40 50 60 70
Time (min)
Time (min)
70 °C 80 °C 90 °C
70 °C 80 °C 90 °C

Provitamin A
(g) 6.50
6.00 y = –0.0142x + 6.0107
5.50 R² = 0.9945
Ln (Ct)

5.00
4.50 y = –0.0216x + 6.0163
4.00 R² = 0.9895
3.50 y = –0.0381x + 6.1202
R² = 0.9303
3.00
0 10 20 30 40 50 60 70
Time (min)
70 °C 80 °C 90 °C

Figure 1 Thermal degradation kinetics of bioactive compounds in tree tomato juice. b-carotene (a), a-carotene (b), b-cryptoxanthin (c), zeaxan-
thin (d), lycopene (e), vitamin C (f) and provitamin A (g). Each point represents the average of three repetitions per thermal treatment.

first-order kinetics in a temperature range between 70 by Dhuique-Mayer et al. (2007) in orange juice and
and 90 °C. Table 2 lists the kinetic parameters of vita- Dhakal et al. (2018) in pineapple juice; on the other
min C and provitamin A in the tree tomato juice; the hand, the D (min) and t0.5 (min) values were lower
values of k (min
1), D (min), t0.5 (min) and Q10 con- than those reported by these researchers. The z value
firm that these micronutrients are thermolabile com- (°C) of vitamin C in the tree tomato juice indicates
pounds in tree tomato juice. The k values (min
1) in that this bioactive compound is more thermoresistant
vitamin C in this study are higher than those recorded than a-carotene, b-carotene, provitamin A and

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Table 2 Kinetic parameters obtained for bioactive compounds degradation in tree tomato juice between 70 and 90 °C

Bioactive compounds T (°C) k (min
1) D (min) t (0,5) (min) Q10 (70–90 °C) z (°C)

b-Carotene 70 0.0133 173.13 52.12 1.78 39.97

80 0.0198 116.29 35.01
90 0.0421 54.69 16.46
a-Carotene 70 0.0118 195.13 58.74 1.96 34.23
80 0.0253 91.01 27.40
90 0.0453 50.83 15.30
b-Cryptoxanthin 70 0.0195 118.08 35.55 1.19 131.19
80 0.0244 94.37 28.41
90 0.0277 83.13 25.02
Zeaxanthin 70 0.0158 145.73 43.87 1.52 54.64
80 0.0244 94.37 28.41
90 0.0367 62.74 18.89
Lycopene 70 0.0305 75.49 22.73 1.20 126.45
80 0.0357 64.50 19.42
90 0.0439 52.45 15.79
Vitamin C 70 0.0224 102.79 30.94 1.49 57.93
80 0.0370 62.23 18.73
90 0.0496 46.42 13.97
Provitamin A 70 0.0142 162.15 48.813 1.64 46.66
80 0.0220 104.66 31.51
90 0.0381 60.44 18.19

zeaxanthin, but it is more thermolabile than lycopene
and b-cryptoxanthin (Table 2). Dhuique-Mayer et al.
(2007) reported a value close to that recorded in the
present study in orange juice (z = 64 °C, between 75
and 100 °C).
These kinetic parameters of thermal degradation can
be useful to understand, predict and control the losses
of carotenoid pigments, vitamin C and provitamin A
in tree tomato juice during thermal processing. For
example, the values of k, D, z, t0.5 and Q10 obtained in
each of the molecules offer information on the thermal
stability that would allow to estimate the losses of
these micronutrients and design thermal treatments
that allow to preserve the highest levels of retention of
these important bioactive compounds in the study
matrix, processes that would benefit consumers and
processors of such important exotic fruits.
Thermodynamic analysis of the carotenoids, vitamin C
and provitamin A
Figur 2a-b shows that the rate of constant degradation
(k) of the bioactive compounds analysed in the tree
tomato juice in the temperature range of 70 to 90 °C
was affected by the temperature and fit the Arrhenius
model (R2 > 0.95). The energy activation (Ea) in the
tree tomato juice during the thermal treatments was
higher in a-carotene, followed by b-carotene, provita-
min A, zeaxanthin, vitamin C, lycopene and b-cryptox-
anthin (Table 3). The results are consistent with those
reported by Aparicio-Ruiz et al. (2011), who indicated
that high values of Ea imply higher thermal sensitivity
of bioactive compounds since they require small tem-
perature changes for their degradation. Other studies
differ from our results for Ea: Aparicio-Ruiz et al.
(2011) who reported on b-carotene (14.30–
14.77 kJ mol
1) and b-cryptoxanthin (15.15–
16.60 kJ mol
1) in a temperature range of 60–20 °C;
Mitra et al. (2017) who reported on b-cryptoxanthin
(13.27 kJ mol
1) in a temperature range of 25–80 °C;
and Xiao et al. (2018) who reported values of b-
carotene of 8.63 kJ mol
1, b-cryptoxanthin of
33.90 kJ mol
1 and zeaxanthin of 65.55 kJ mol
1 in
pure carotenoid solutions in a temperature range of
25–45 °C. For the vitamin C, the values of Ea in the
present study are close to those previously reported by
Dhuique-Mayer et al. (2007) for orange juice
(Ea = 35.90 kJ mol
1) in a temperature range of 75
and 100 °C. Dhakal et al. (2018) reported a lower
value in pineapple juice than that in our study
(Ea = 22.02 kJ mol
1), in a temperature range between
75 and 95 °C. For provitamin A, the Ea was consistent
with that reported by Liu et al. (2018)
(52.26 kJ mol
1) in bovine milk in a temperature
range of 70 and 90 °C.
Table 3 shows the values for the activation enthalpy
(DH), inactivation free energy (DG) and activation
entropy (DS) in the degradation of the carotenoids,
vitamin C and provitamin A at each studied tempera-
ture. Vikram et al. (2005) observed that DH is the min-
imum energy necessary for the reaction of reactants
and the strength of the bonds that are destroyed and
formed during the associated state transition. Mercali
et al. (2013) stated that DG is the difference between

International Journal of Food Science and Technology 2020 © 2019 Institute of Food Science and Technology

n
Thermal degradation kinetics juice L. E. Ordo ~ ez-Santos and J. Mart
ınez-Giro

n 207

1/T (°K–1)
–2.8
(a) 0.0027 0.00275 0.0028 0.00285 0.0029 0.00295
–3
–3.2
–3.4 y = –2265.7x + 3.1028
y² = 0.9911
–3.6

Ln (k)
y = –2192.2x + 2.4654
–3.8 y² = 0.9799
–4 y = –5251.2x + 11.156
y² = 1
–4.2 y = –7156.7x + 16.473
–4.4 y² = 0.9632
y = –8390x + 20.033
–4.6 R² = 0.9963
β-Carotene α-carotene β-Cryptoxanthin Zeaxanthin Lycopene

1/T (°K–1)
(b) –2.5
0.0027 0.00275 0.0028 0.00285 0.0029 0.00295
–3

y = –4964x + 10.697
–3.5 R² = 0.9821
Ln(k)

Figure 2 Arrhenius plot for the degradation

of bioactive compounds in tree tomato juice. –4
b-carotene, a-carotene, b-cryptoxanthin,
zeaxanthin and lycopene (a), and vitamin C –4.5
and provitamin A (b), during thermal pro- y = –6214.4x + 13.821
cessing. Each point represents the average of R² = 0.995
three repetitions. [Colour figure can be –5
viewed at wileyonlinelibrary.com] Vitamin C Provitamin A

Table 3 Thermodynamic parameters obtained for bioactive compounds degradation in tree tomato juice between 70 and 90 °C

Bioactive compounds T (°C) Ea (kJ mol
1) DH (kJ mol) DG (kJ mol
1) DS (J mol
1 °K)

b-Carotene 70 59.50 56.95 108.23
149.46

80 56.86 110.30
151.32
90 56.78 111.23
149.94
a-Carotene 70 69.75 67.20 108.57
120.57
80 67.12 109.58
120.25
90 67.03 111.01
121.10
b-Cryptoxanthin 70 18.23 15.67 107.14
266.56
80 15.59 109.69
266.46
90 15.51 112.50
267.08
Zeaxanthin 70 43.66 41.10 107.74
194.19
80 41.02 109.69
194.44
90 40.94 111.65
194.71
Lycopene 70 18.84 16.28 105.87
261.06
80 16.20 108.57
261.57
90 16.12 111.11
261.57
Vitamin C 70 41.27 38.72 106.75
198.25
80 38.63 108.47
197.74
90 38.55 110.74
198.78
Provitamin A 70 51.67 49.11 108.05
171.74
80 49.03 109.99
172.63
90 48.95 111.53
172.35

© 2019 Institute of Food Science and Technology International Journal of Food Science and Technology 2020
208
n
Thermal degradation kinetics juice L. E. Ordo ~ ez-Santos and J. Mart
ınez-Giro
the energy of the activated state and the reactants.
Vikram et al. (2005) reported that DS is associated
with the number of molecules with adequate energy
that can actually react. Positive values in the kinetic
parameter DH indicate that the degradation of carote-
noids, vitamin C and provitamin A is an endothermic
process, and the reduction of DH with the increase in
temperature shows that the maximum energy limit to
destroy the bonds is lower at higher temperatures
(Martynenko, and Chen 2016; Peron et al., 2017).
The DH values of the carotenoids surpassed the val-
ues previously reported by Aparicio-Ruiz et al. (2011)
for b-carotene (12.92–13.83 kJ mol
1) and b-cryptox-
anthin (12.42–14.58 kJ mol
1) in a working tempera-
ture range of 60–120 °C and by Xiao et al. (2018) for
b-carotene (6.07 kJ mol
1), b-cryptoxanthin
(31.34 kJ mol ) and zeaxanthin (62.69 kJ mol
1) in a

1
temperature range of 25–45 °C. Vikram et al. (2005)
recorded values of DH (37.03 kJ mol
1) in vitamin C
during the thermal processing of orange juice in a tem-
perature range of 50–90 °C that are in agreement with
those obtained in the present research, while Vieira
et al. (2016) reported lower values of DH in vitamin C
during the pasteurisation of orange juice (17.99–
18.33 kJ mol
1) in a temperature range of 50–90 °C.
It was observed that DH has a behaviour similar to
that of Ea, where b-cryptoxanthin is the most stable
bioactive compound, while a-carotene was the least
stable in the tree tomato juice. This behaviour agrees
with those recorded by Aparicio-Ruiz et al. (2011) and
Xiao et al. (2018) in xanthophylls versus carotenes.
In all the studied temperatures, positive values were
observed for DG in the phytonutrients studied in the
present study (Table 2), which indicates that the degra-
dation of these micronutrients in the tree tomato juice
is not a spontaneous process; in addition, close values
were recorded in the evaluated temperature range (70–
90 °C), suggesting that the temperature similarly
affects the rate of degradation of carotenoids, vitamin
C and provitamin A. Positive DG values were also
reported by Aparicio-Ruiz et al. (2011) for b-cryptox-
anthin (27.38–27.84 kJ mol
1) and b-carotene (27.65–
27.80 kJ mol
1) in olive oil, and by Vieira et al. (2016)
for vitamin C in orange juice (79.56–87.15 kJ mol
1);
however, these values are lower than those recorded in
the present study.
The DS values in the studied bioactive compounds
had negative values during the thermal treatments; the
micronutrient with the highest negative value was b-
cryptoxanthin, followed by lycopene, vitamin C, zeax-
anthin, provitamin A, b-carotene and a-carotene
(Table 2). This confirms the sequence of the degree of
thermoresistance in the phytonutrients found in tree
tomato juice as b-cryptoxanthin > lycopene > vitamin
C > zeaxanthin > provitamin A > b-carotene > a-car-
otene, indicating that greater energy is required in the
International Journal of Food Science and Technology 2020

n
degradation of b-cryptoxanthin and lower energy in
the degradation of other compounds. These results
agree with those expressed by Martynenko and Chen
(2016), who confirmed that negative DS values indicate
that the transition state has less structural freedom
than the reactants. Aparicio-Ruiz et al. (2011) pre-
sented DS values of b-carotene (
205.92 to
197.54 J mol
1 °K) and b-cryptoxanthin (
209.17 to
185.42 J mol
1 °K) close to those recorded in this
study. For vitamin C, Vieira et al. (2016) recorded DS
values (
189.58 to 190.91 J mol
1 °K) that fit those
obtained in the present research during the process of
pasteurisation of orange juice in a temperature range
of 50–90 °C. On the contrary, Vikram et al. (2005)
recorded positive DS values (0.17 J mol
1 °K) in vita-
min C during the thermal processing of orange juice in
a temperature range of 50–90 °C. On the other hand,
despite the structural differences between carotenoids
and vitamin C, it is evident that these micronutrients
were thermally degraded by similar mechanisms, prob-
ably by oxidation reactions, as evidenced by the corre-
lation coefficient of r2 = 0.9992 obtained between
values of (DS) and (DH) (Table 3). Other studies
recorded similar results that show a linear compensa-
tion between the two thermodynamic parameters eval-
uated in the thermal degradation of carotenoids
(Minguez-Mosquera and Jaren-Galan 1995; Henry
et al. 1998). The results of the thermodynamic study
of the bioactive compounds in tree tomato juice
(Table 3) confirm that the kinetic model used in the
present work is thermodynamically possible and would
allow to predict the nutritional changes depending on
the bioactive compounds of interest during the thermal
treatments; therefore, from the engineering point these
results can be used to optimise the thermal processing
depending on the maximum level of retention of caro-
tenoids, vitamin C and provitamin A present in the
derivative of this exotic fruit. These results show that
in the study matrix, b-cryptoxanthin and lycopene are
the most stable bioactive compounds in the evaluated
temperature rank (Table 3).
A possible explanation for the thermal stability of
b-cryptoxanthin in tree tomato juice in the present
study is offered by Xiao et al. (2018) who confirmed
that these carotenoids are more stable at temperatures
since they have hydroxyl groups in their structure that
replaces the conjugated coplanar double bonds, giving
it greater stability against the action of free radicals
generated during thermal treatments. The thermal
resistance of lycopene in the present study was proba-
bly a consequence of the low sensitivity to isomerisa-
tion (Rickman et al., 2007); another explanation for
the stability of lycopene is the possible presence of
other antioxidant compounds, such as tocopherol, and
phenolic compounds that may have acted as protective
agents in the oxidation and isomerisation of lycopene
© 2019 Institute of Food Science and Technology

Thermal degradation kinetics juice L. E. Ordo ~ ez-Santos and J. Mart
ınez-Giro
(Ord
on~ez-Santos et al., 2009). Another explanation for
the stability of this carotenoid is the degradation of
vitamin C during thermal treatments of tree tomato
juice since this degradation may neutralise the free
radicals found in the medium.
Regarding the degradation of the other carotenoid
compounds, Boon et al. (2010), Rodriguez-Amaya
(2016), and Xiao et al. (2018) report that temperature is
a factor that catalyses the isomerisation and oxidation
of carotenoid compounds, its effect is a function of the
intensity of the thermal treatment and the structure of
the carotenoid pigments, and the temperature can gen-
erate chemical reactions that form structures cis-carote-
noids, epoxycarotenoids, apocarotenoids and structures
of low molecular weight (b-ionone, 2-hydroxy-2,6,6-
trimethylcyclohexanone, 2,6,6-trimethylcyclohexanone,
2-hydroxy-2,6,6-trimethylcyclohexane-1-carboxaldehyde,
among others). The degradation of vitamin C during
thermal processing can be explained by the oxidation
processing of ascorbic acid to dehydroascorbic acid,
which is subsequently degraded by irreversible hydroly-
sis to 2,3-diketogulonic acid (Cruz et al., 2008). Brad-
shaw et al. (2011) reported that 2,3-diketogulonic
acid continues the path of degradation where decar-
boxylation, dehydration, readjustment and cyclisation
reactions occur, which end in products such as 3-hy-
droxy-2-pyrone, 2-furoic acid, acetylfuran, 5-methyl-
3,4-dihydroxytetrone and a-dicarbonyl compounds.
Conclusions
In this study, the kinetics of thermal degradation of
carotenoids, vitamin C and vitamin A in tree tomato
juice were evaluated in the temperature range of 70–
90 °C. All of the evaluated phytochemicals in the tree
tomato juice presented first-order kinetic thermal
degradation (R2 > 0.90), and changes in the rate of
constant degradation in each of the micronutrients
could be explained with the Arrhenius model
(R2 > 0.95). b-cryptoxanthin was the most thermoresis-
tant compound, while a-carotene was the most ther-
molabile in the thermally treated tree tomato juice.
The evaluation of the parameters DH, DG and DS con-
firmed that the degradation of the studied micronutri-
ents corresponded to endothermic, non-spontaneous
processes, and the transition state had less structural
freedom than the reagents. This study benefits engi-
neering processes interested in the design and optimi-
sation of thermal processes aimed at preserving the
nutritional quality of tree tomato juice.
Acknowledgment
This research was supported by Universidad Nacional
de Colombia Sede Palmira.
© 2019 Institute of Food Science and Technology

n

n 209
Conflict of interest
Luis Eduardo Ord
on~ez-Santos, Jader Mart
ınez-Gir
on
and others have no conflict of interest for this manu-
script.
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