Journal of Food Engineering 143 (2014) 146–153

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Journal of Food Engineering

journal homepage: www.elsevier.com/locate/jfoodeng

Kinetic modeling of phenolic compound degradation during

drum-drying of apple peel by-products
Carolina Henríquez a,1, Andrés Córdova b,⇑, Sergio Almonacid c, Jorge Saavedra b
a
Centro de Investigación y Desarrollo de Alimentos Funcionales (CIDAF), Universidad de Valparaíso, Gran Bretaña 1093, Valparaíso 2360102, Chile
b
DATACHEM Agrofood: Grupo de Quimiometría Aplicada en Agroalimentos, Escuela de Ingeniería de Alimentos, Pontificia Universidad Católica de Valparaíso,
Waddington 716 Playa Ancha, Valparaíso 2360100, Chile
c
Departamento de Ingeniería Química y Ambiental, Universidad Federico Santa María, Valparaíso, Chile

a r t i c l e i n f o a b s t r a c t

Article history: The apple peel, a by-product of apple processing, has a high total phenolic content (TPC); however, these
Received 19 March 2014 compounds can be highly thermosensitive and unstable. Therefore, the aim of this study was to
Received in revised form 24 June 2014 determine the degradation kinetics of the TPC in apple peels during drum-drying as a stabilization and
Accepted 28 June 2014
recovery method. Apple peels (Granny Smith) were dried at 110, 120, 130 or 140 °C for 250 s with a con-
Available online 9 July 2014
stant drum clearance (0.2 mm). TPC degradation exhibited first-order kinetics and their retentions at the
end of the process were 73.13% at 110 °C, 57.28% at 120 °C, 43.40% at 130 °C and 21.10% at 140 °C. Finally,
Keywords:
empirical models were significantly fitted to predict the TPC as the apple peels reached a certain level of
Apple-peel
Kinetic
dehydration, which may be useful from the processing standpoint and validate the use of drum-drying as
Degradation a process tool for the recovery of apple industrial wastes.
Phenolic compounds Ó 2014 Elsevier Ltd. All rights reserved.
Drum-drying

1. Introduction
Apples are a significant part of the human diet because they are
one of the most extensively produced and consumed fruits world-
wide due its availability on the market for the whole year (Vinson
et al., 2001; Brat et al., 2006; Lamperi et al., 2008). They are also a
rich source of phytochemicals, mainly phenolic compounds such as
flavonoids and phenolic acids, and also possess a high antioxidant
capacity (Boyer and Liu, 2004; Wu et al., 2004; Khanizadeh et al.,
2008). Several reports have indicated that apple peels potentially
contain more concentrated antioxidants and a higher antioxidant
capacity than the pulp fraction or the whole fruit (Wolfe et al.,
2003; Khanizadeh et al., 2008; Henríquez et al., 2010a; Manzoor
Abbreviations: ds, dry solids (g) or dry matter; Xe, equilibrium moisture content
of dehydrated material (g water/g ds); X0, initial moisture content (g water/g ds); Xt,
moisture content at any time (g water/g ds); Dwe, effective moisture diffusion (m2/
s); L, thickness of the slab (m); Do, pre-exponential factor for effective diffusion; ḱ,
drying rate; GAE, gallic acid equivalents (mg); TPC, total phenolic content (mg GAE/
ds); Yratio, dimensionless moisture content variation; t, drying time (seconds); k,
reaction rate constant (s1); k0, pre-exponential constant; Ea, activation energy (kJ/
mol); R, universal gas constant; T, absolute temperature (K); C, quality attribute or
concentration of a nutrient at time t; n, kinetic order reaction.
⇑ Corresponding author. Tel.: +56 32 2274220.
E-mail addresses: maria.henriquez@uv.cl (C. Henríquez), andres.cordova@ucv.cl
(A. Córdova).
1
Principal author. Tel.: +56 32 2508418.
et al., 2012; Karaman et al., 2013). The peel fraction is a by-product
generated from the dried apple manufacturing process. Industri-
ally, apples are peeled mechanically, and the peels are typically
used as compost or in the production of juice. Only in Chile, it is
estimated that approximately 9000 tons of peel could be generated
during one year as a result of apple processing (Henríquez et al.,
2010b).
Four scientific reports have described the development of pow-
dered products from apple peels (Bomben et al., 1971; Wolfe and
Liu, 2003; Rupasinghe et al., 2008; Henríquez et al., 2010b).
Bomben et al. (1971) developed this ingredient to enhance the fla-
vor in apple pie, but the authors did not focus on its antioxidant
components.
In the other hand, fruit drying is a very ancient practice and one
of the most important methods to extend their shelf life and to
minimize the handling/distribution of raw materials with a high
moisture content (Simal et al., 2000; Kwok et al., 2004;
Zielinskaa and Markowski, 2010). The main objective of drying is
the removal of water to a level at which microbial spoilage and
deterioration reactions are minimized. However, drying causes
physical, structural, chemical and biological changes that can affect
quality attributes, such as the texture, color, flavor and nutritional
value, and particularly the contents of nutrients and phytochemi-
cals, which are relatively unstable to heat (Nicoli et al., 1999;
Kwok et al., 2004; Chang et al., 2006; Vega-Gálvez et al., 2009). This

http://dx.doi.org/10.1016/j.jfoodeng.2014.06.037
0260-8774/Ó 2014 Elsevier Ltd. All rights reserved.
 C. Henríquez et al. / Journal of Food Engineering 143 (2014) 146–153
implies that the stability of antioxidants during the processing of
fruits and vegetables is an important issue that should be consid-
ered. In fact, in a long-term drying process, apple peels undergo
changes that affect their antioxidant properties. The concentration
of polyphenols declines during drying due to the following: (1)
enzymatic or non-enzymatic degradation; (2) formation of insolu-
ble oxidation compounds; (3) production of polymers; and (4)
decomposition of thermolabile compounds (Larrauri et al., 1997;
Obied et al., 2009).
The drum dryer is an economical industrial device commonly
used in the production of a variety of foods, such as powdered
milk, precooked cereals, applesauce, fruit purees, baby foods
and dry soup mixtures, among others (Kostoglou and
Karapantasios, 2003; Pua et al., 2007). The main advantages of
drum-drying include a high drying rate, an economical usage of
heat (60–90% energy efficiency) and the need for few operational
steps, which make it one of the least expensive methods of dry-
ing (Tang et al., 2003; Pua et al., 2010). In addition, this type of
drying is suitable for many heat-sensitive products because the
exposure to high temperature is limited to a few seconds (Pua
et al., 2007).
Because drying is a complex process involving heat and
mass-transfer phenomena (Garau et al., 2006), it is useful to use
mathematical equations for kinetic simulations of the water trans-
fer occurring during this operation as a function of the drying con-
ditions employed to control and optimize the process (Vega-Gálvez
et al., 2008). Thus, kinetic models that describe the destruction
rates of phenolic compounds and their dependence on the process-
ing temperature and time are important tools for defining the ideal
conditions for minimizing the loss of the antioxidant properties of
different types of products. Because little information has been
reported on this topic, the objective of this study was to determine
the degradation kinetics of the phenolic compounds in apple peels
during drum-drying at different temperatures and times of treat-
ment to determine the stability of these compounds throughout
the process, in order to evaluate such new alternatives for the
recovery of apple industrial wastes.
2. Theoretical background
2.1. Drying kinetics and effective diffusivity
The global moisture (X(t)) of a thin layer of food (2 mm thick)
can been represented in a first-order kinetic model (Krokida
et al., 2003). In this sense, Ficḱs second law can be used to interpret
the experimental drying data because moisture diffusion is one of
the main transport phenomena that describes the falling-rate dry-
ing period. In this model, the dependent variable is the moisture
ratio, which relates the gradient of the sample’s moisture content
in real time to both the initial and equilibrium moisture content
(Vega-Gálvez et al., 2010). Thus, is possible to define the Y-ratio
as a dimensionless moisture variation, as follows (Eq. (1)):
X wt  X we
Y¼
X 0  X we
where Xwt is the moisture content at any time (g water/g dry matter
or dry solids (ds)), X0 is the initial moisture content (g water/g ds),
and Xwe is the equilibrium moisture content (g water/g ds). For the
drum-dryer system, Xwe may be equivalent to mf, which is the mois-
ture content (g water/g ds) of a completely dried sample (a mini-
mum) reached at the respective temperature for conductive
drying kinetics (Karapantsios, 2006). For slab geometry, and assum-
ing constant moisture diffusivity, zero volume change, negligible
external resistance and an isothermal process, the mathematical
solution is given by (Eq. (2)):
147
 
8 Dwe p2 t
Y¼ exp ð2Þ
p2 4L2
where Dwe is the effective moisture diffusion (m2/s) and L is the
thickness of the slab. In addition, the diffusivity dependence on
the temperature can be represented by an Arrhenius equation, as
follows (Eq. (3)):
Dwe ¼ Do expðEa =RTÞ ð3Þ
Finally, the experimental moisture ratio values versus the dry-
ing time were fitted using some of the models most commonly
used to explain the drying kinetics of foods (Table 1), where k1,
k2, k3, k4, k5, k6, k7, k8, k9 are the drying kinetic constants (s1),
and n2, n3, n4, n5, n6, n7, n8, n9 and b are correlation parameters.
2.2. Phenolic compound degradation
The kinetics of food quality loss can be represented by the fol-
lowing equation (Eq. (11)):
dC
¼ k  Cn ð11Þ
dt
A search of the literature suggested that changes in the quality
attributes of food products generally obey zero-, first- and second-
order kinetics (Jensen and Risbo, 2007; Palazón et al., 2009; van
Boekel, 2008). Therefore, these types of kinetics and their respec-
tive pseudo orders were used in the analyses (Saavedra et al.,
2013).
The rate constant (k) of the reaction depends on the tempera-
ture (Goula et al., 2006). Kirca and Cemeroğlu (2003), Kaymak-
Ertekin and Gedik (2005), Goula et al. (2006) and Di Scalaa and
Crapiste (2008) described the temperature dependence of the reac-
tion constant for phenolic compound degradation using the follow-
ing simple Arrhenius equation (Eq. (12)):
 
Ea
k ¼ k0 exp  ð12Þ
RT
where k = rate constant, k0 = frequency factor, Ea = activation
energy, R = universal gas constant and T = absolute temperature.
3. Materials and methods
3.1. Experimental
To determine the model’s parameters, a set of experiments
were designed:
3.1.1. Apple peel
The peel of Granny Smith apples was used as the raw material
because this variety presents a high phenolic content (Henríquez
et al., 2010a). Peels were collected from a Chilean commercial
dried-apple manufacturer, the SURFRUT Company (Romeral,
Chile). Immediately after peeling, the peels (pieces of approxi-
mately 5  5 mm, with some attached pulp) were packed into
ð1Þ polyethylene bags, frozen, transported to the laboratory and stored
in a freezer chamber at 20 °C until use.
3.1.2. Pre-processing conditioning
Thirty minutes before the experiments began, 100 g of frozen
apple peels was mixed with 60 mL of distilled water and ground
using a Waring blender (51 BL 32, Torrington, CT, USA) for 5 min
at high speed.
3.1.3. Drying conditions
The drying experiments were conducted in a pilot-scale double
drum dryer (Model ADD, Food and Chemical Equip. Inc., Buffalo,
148 C. Henríquez et al. / Journal of Food Engineering 143 (2014) 146–153
Table 1
Mathematical models applied for drying curves of apple peel.
Equation Model name
(4) Newton
(5) Henderson-Pabis
(6) Page
(7) Two-term
(8) Logarithmic
(9) Modified page
(10) Midilli–Kucuk
New York, USA). The dryer consisted of two hollow cylinders of
equal diameters rotating very close together in opposite directions,
heated internally by saturated steam. A drum dryer produces indi-
rect heat transfer through a solid surface. The drums were 30 cm in
diameter and 46 cm long. The material to be dried was fed into the
wedge-shaped space between the drums and was then divided into
two films (one on each drum). After a residence time of contact
with the heated surface, the dried material was removed using a
scraper blade that spanned the entire width of each drum
(Kostoglou and Karapantasios, 2003; Pua et al., 2007, 2010).
Fig. 1 shows a schematic representation of a double drum dryer.
The drying experiments were conducted at atmospheric
pressure at 110, 120, 130 and 140 °C; the time of the thermal treat-
ment (based on the rotation speed of the drums) ranged from 300
to 15 s (at 0.10 and 7.5 rpm, respectively), with samples taken
every 15 s. The drum clearance was maintained at 0.2 mm. All
the experimental conditions were done in triplicate. The drums’
temperature during drying was maintained using a superficial
thermocouple. Immediately after drying, the apple peels were
placed in high-density polyethylene (HDPE) plastic bags and
sealed. The samples were stored at room temperature until
evaluation.
3.2. Methods
All of the reagents and solvents were analytical-grade chemicals
purchased from Merck (Darmstadt, Germany) or Sigma Chemical
Co. (St Louis, MO, USA). The analytical methods here applied for
raw matter and apple peel ingredients are described below:
3.2.1. The moisture content
The moisture content was determined gravimetrically based on
the weight difference before and after the sample was heated in an
oven at 70 °C for 16 h. The moisture content was expressed on a
dry basis (n = 3) (g water/g ds) (AOAC, 2006).
Fig. 1. Schematic representation of a double drum dryer.
Model References
Y = exp (k1t) ÓCallaghan et al. (1971)
Y = n2 exp (k2t) Henderson and Pabis (1969)
Y ¼ expðk3 t n3 Þ Page (1949)
Y = n4 exp(k4t) + n5 exp(k5t) Sharaf-Eldeen et al. (1980)
Y = n6 exp(k6t) + n7 Yagcioglu et al. (1999)
n
Y ¼ expððk8 tÞ 8 Þ Overhults et al. (1973)
Y = n9 exp (k9t) + bt Midilli et al. (2002)
3.2.2. The total phenolic content (TPC)
The total phenolic content (TPC) was determined using a color-
imetric method proposed by Singleton and Rossi (1965). The
method involves the reduction of the Folin–Ciocalteu reagent by
the phenolic compounds, with the concomitant formation of a blue
complex. The extracts were prepared by mixing 20 g of fresh apple
peel or 4 g of dry apple peel with 90 mL of the extraction solvent
(70:30 acetone:water). This mixture was homogenized for 1 min
using an Ultra Turrax homogenizer (GLH-02, Omni International,
Kennesaw, GA, USA), and the extracts were shaken in a water bath
at 20 °C for 60 min. Three samples (1.5 mL) were centrifuged at
2500g for 15 min, and the supernatants were used for analysis.
An aliquot of 0.50 mL of the extract was mixed with 3.0 mL of dis-
tilled water and 0.25 mL of Folin–Ciocalteu reagent.
Immediately after this, 0.75 mL of saturated sodium carbonate
and 0.95 mL of distilled water were added. The mixture was incu-
bated for 30 min at 37 °C, and the absorbance at 765 nm was read
using a UV–Vis spectrophotometer (Unicam Hekio a, Cambridge,
UK). The value was compared to those of a standard curve prepared
using gallic acid (Sigma Chemical Co, St Louis, MO, USA) solution.
The total phenolic content was expressed as milligrams of gallic
acid equivalents per gram of dry mass (mg GAE/g ds). The analyses
were performed in triplicate. The percentage of retention of pheno-
lic compounds was calculated through comparing the content of
total phenolics in the raw matter (fresh apple peel) and dry apple
peels (ingredient).
3.3. Statistical analysis
All results were expressed as mean ± SD of three replicates for
each experimental condition and observation evaluated. Kinetic
models for the phenolic compound degradation were obtained by
solving Eq. (11) for different kinetic orders (n = 0, n = 1, n = 2) and
adjusting the experimental data via a least-square fitting proce-
dure. The same fitting procedure was applied for the drying kinet-
ics modeling using Eqs. (4)–(10). The quality of the experimental
data of all the models was evaluated using the root mean square
error (RMSE) (Eq. (13)), where Ze is the experimental data and Zc
is the predicted or calculated value:
" #12
1X N
RMSE ¼ ðZ e  Z c Þ2 ð13Þ
N i¼1
In addition, all of the kinetic models (both for drying and TPC
degradation) were evaluated using ANOVA regressions (a = 0.05)
by plotting the experimental data against calculated values. The
criteria for selecting the best fitting of models were: the highest
values of F-ratios and the percentage of variability explained (R2
adjust), as well as the lowest RMSE value. The computations and
adjustments were performed using Statgraphics Centurion XV
(Statpoint Inc., USA, 2005) and Excel 2003 software (Microsoft,
USA, 2009).
 C. Henríquez et al. / Journal of Food Engineering 143 (2014) 146–153
4. Results and discussion
4.1. Experimental data for the drying kinetics
The experiments were satisfactorily reproducible (coefficient of
variation <10%). The initial moisture content in the samples was
9.67 ± 0.23 g water/g ds (the s value). The apple peel drying kinet-
ics, expressed in terms of the Y-ratio, for all of the temperatures
used (110, 120, 130 and 140 °C) are shown in Fig. 2. As expected,
the drying rate increased with the increase of the temperature in
the drum-dryer. This could be observed by a rapid linear decrease
of moisture content during the first drying period (120 s at 110 °C,
75 s at 120 °C, 60 s at 130 °C and 30 s at 140 °C). The drying time
was defined as the time (s) required to remove water from a fresh
apple peel slurry until the minimum average dimensionless mois-
ture content value reached 0.018 (equivalent to 0.02 g moisture/g
sample), which was 60 s at 140 °C, whereas at 130, 120 and
110 °C, the drying times were 81.5 s, 124 s and 203 s, respectively.
These values are lower than those reported by Karapantsios (2006),
wherein the drying times ranged from 600 s to 750 s in a drum-
dryer system at operation temperatures ranging from 120 °C to
150 °C, which were applied to thin pre-gelatinized starch films
with a thickness that varied between 0.5 mm and 4 mm. Notably,
in that study, the temperature profiles showed that the prelimin-
ary heating system required an average of up to 300 s to reach
the chosen temperature, and therefore, during this time, the prod-
uct was in contact with the walls of the drum, extending the resi-
dence time and the conductive heating of the product. However, in
the present study, the thickness of the samples and the processing
temperature were kept constant. In this sense, if the drying curves
of the pre-gelatinized starch (data not shown) with the elimination
of the pre-heating time of the system are compared with those pre-
sented in Fig. 2, they result quite similar. Furthermore, all of these
curves had the same shape as those obtained using a convective
drying process, which demonstrate that this is a rapid rate
decrease in the moisture content followed by a slow prolonged
decrease to a stable level (this last period is called the falling-rate
period). This behavior validates the use of Fick’s second law. In
contrast, Karapantsios (2006) tested different sample thicknesses,
and as expected, for the thicker films, the drying rate was lower,
which was more evident when the temperature was increased.
The effective moisture diffusivity values at the different drying
temperatures were 2.75  108 ± 1.95  109 m2/s at 110 °C,
5.12  108 ± 3.62  109 m2/s at 120 °C, 7.95  108 ± 5.62 -
 109 m2/s at 130 °C and 1.03  107 ± 7.34  109 m2/s at
Fig. 2. Drying kinetics of apple peel: Experimental data for the moisture contents of
apple peels dried in a drum dryer at 110, 120, 130 and 140 °C.
149
140 °C. These values are higher than those reported in apple fruit
tissues subjected to a hot-air drying process, where the air temper-
ature is generally used in a range between 50 °C and 80 °C (Krokida
et al., 2003; Kaymak-Ertekin and Gedik, 2005; Vega-Gálvez et al.,
2010). Vega-Gálvez et al. (2012) reported effective diffusivity val-
ues of 3.22  109–1.5  108 m2/s for apples dried at 40–80 °C
with 1.5 m/s of air velocity, whereas Velić et al. (2004) reported
values of 1.7–4.4  1010 m2/s in samples dried at 60 °C with air
velocities from 0.64 to 2.75 m/s. In both of those studies, the peels
were removed and only the pulp tissues were used, at a sample
thickness of 5 mm. In addition, the drying time was several min-
utes, whereas in the present research, the sample thickness was
2 mm and the heat was transferred by conduction at higher tem-
peratures. The effective moisture diffusivity of different biomateri-
als varies according to their structure, the drying temperature and
their moisture content. Furthermore, previous studies demon-
strated the physical changes in the food caused by the convective
drying process (Lozano et al., 1980; Leonardo and Dermeval,
2004; Doymaz, 2005), which could explain the greater moisture
diffusivity reported here.
The natural logarithm of effective diffusivity (LN Dwe) as a func-
tion of the reciprocal of absolute temperature is plotted in Fig. 3
The results demonstrate a good relationship according to the
Arrhenius linearized equation (R2 = 0.976). From this relationship,
the activation energy for Dwe was estimated to be 60.98 ± 7.73 kJ/
mol.
4.2. Mathematical modeling of the drying kinetics
The results of using the seven mathematical models selected
for modeling the drying kinetics are summarized in Table 2.
Regression analysis of the Y-ratios of the experimental data
against those of each model showed a significant relationship
in all of the cases (ANOVA p 6 0.05). This relationship is also
demonstrated by the high values of the F-ratio and the percent-
age of variability explained by the model (R2 adjust) and low
RMSE values (in this order of importance). Comparing the statis-
tical values showed that the Two-terms model had the best
goodness of fit at 110 °C. At 120 °C the best fitting was for the
Page model, whereas at 130 °C, the Midilli–Kucuk model had
the best goodness of fit but with very similar statistical fitting
values than those reported by the Two-terms model. At 140 °C
the Logarithm model had the best fit. In addition, the drying
kinetic constants (ḱ) were quite similar at each temperature.
According to Muller (2007), Page’s equation is the most conve-
nient mathematical model for thin-layer drying kinetics and has
been widely used in drying studies.
Fig. 3. Linearized Arrhenius plot for the effective diffusivity of moisture.
150 C. Henríquez et al. / Journal of Food Engineering 143 (2014) 146–153

Table 2
Drying kinetic parameters for the fitted drying models.

Drying temperature (°C) k1 (s1) RSME R2 adjust (%) F-ratio

Newton
110 0.0158 ± 0.0004 0.0499 99.89 14696.4
120 0.0301 ± 0.0007 0.0128 99.94 266883.05
130 0.0550 ± 0.0012 0.0140 95.74 361.2
140 0.0772 ± 0.0042 0.0037 96.85 494.17

Drying temperature (°C) k2 (s1) n2 RSME R2 adjust (%) F-ratio

Henderson-Pabis
110 0.0171 ± 0.0008 1.0840 ± 0.0535 0.0366 99.87 12910.2
120 0.0309 ± 0.0007 1.0303 ± 0.0119 0.0097 99.99 400000.01
130 0.0548 ± 0.0010 0.9948 ± 0.0112 0.0136 95.82 367.98
140 0.0783 ± 0.0034 1.0211 ± 0.0235 0.007 97.11 538.83

Drying temperature (°C) k3 (s1) n3 RSME R2 adjust (%) F-ratio

Page
110 0.0072 ± 0.0035 1.2691 ± 0.1647 0.0167 99.96 46378.6
120 0.0281 ± 0.0086 1.0235 ± 0.0508 0.0073 99.99 161300.2
130 0.0615 ± 0.0186 0.9622 ± 0.0986 0.0136 95.56 345.45
140 0.0673 ± 0.0253 1.0645 ± 0.1266 0.0096 98.45 1020.5

Drying temperature (°C) n4 k4 (s1) n5 k5 (s1) RSME R2 adjust (%) F-ratio

Two-terms
110 1.0715 ± 0.1611 0.0017 ± 0.0024 0.0708 ± 0.0143 0.2426 ± 0.0330 0.0033 99.97 77,439
120 0.9824 ± 0.0219 0.0316 ± 0.0008 9.76  105 ± 0.0009 0.0219 ± 0.0047 0.0002 99.94 33,568
130 1.2917 ± 0.0007 0.0780 ± 0.0014 10.2890 ± 0.0015 0.0705 ± 0.0107 0.0178 99.58 3856
140 0.1413 ± 0.0853 0.2300 ± 0.0840 0.8588 ± 0.0965 0.0485 ± 0.0166 0.00023 97.98 778.65

Drying temperature (°C) n6 k6 (s1) n7 RSME R2 adjust (%) F-ratio

Logarithm
110 1.0310 ± 0.0685 0.0158 ± 0.0006 0.0105 ± 0.0096 0.0009 97.62 658.24
120 0.9825 ± 0.0319 0.0315 ± 0.0010 1.0901 ± 0.0035 1.77  107 98.95 33127.98
130 1.0570 ± 0.0358 0.0365 ± 0.0086 0.0159 ± 0.0019 0.0376 98.07 813.59
140 0.9929 ± 0.0277 0.0552 ± 0.0126 0.0024 ± 0.0002 0.0061 99.93 24046.81

Drying temperature (°C) n8 k8 (s1) RSME R2 adjust (%) F-ratio

Modified page
110 1.0120 ± 0.0245 0.0134 ± 0.0040 0.0250 97.61 655.33
120 0.9899 ± 0.0316 0.0291 ± 0.0051 0.0188 99.83 9909.97
130 0.9998 ± 0.0227 0.0316 ± 0.0019 0.0498 97.52 631.62
140 1.0012 ± 0.0097 0.0551 ± 0.0040 0.0066 99.93 23,928

Drying temperature (°C) n9 k9 (s1) b RSME R2 adjust (%) F-ratio

Midilli–Kuck
110 1.0224 ± 0.0598 0.0160 ± 0.0008 3.7245 ± 0.0003 0.0102 97.57 645.91
120 0.9825 ± 0.0307 0.0315 ± 0.0068 5.2537 ± 0.0001 7.65  106 99.96 40704.9
130 1.0430 ± 0.0246 0.0370 ± 0.0070 5.20  105 ± 2.58  105 0.0390 99.92 22740.03
140 0.9949 ± 0.0260 0.0548 ± 0.0130 6.86  106 ± 5.86  106 0.0068 99.96 769.81

rized as follows: (a) at 110 °C the degradation of TPC is fast in

4.3. Experimental data for the behavior of the phenolic compounds
Fig. 4 shows the average TPC measured in fresh apple peels and
in apple peels dried at 110 °C, 120 °C, 130 °C or 140 °C until
reaching approximately 0.02 g moisture/g sample. Although there
are a few experimental points that are not properly adjusted to
the respective models, in terms of overall development of the phe-
nomenon, first-order kinetics (n = 1) could be significantly fitted
for all of the temperatures (p 6 0.05), as shown by the continuous
lines. This situation may be due to the natural variability of the
degradation phenomenon, as well as variability due to the content
of phenolic compounds in the treated samples. In addition, Fig. 4
also shows the first period of drying which corresponded to the
rapid linear decrease of moisture stated above. In this sense, the
TPC degradation at the four drying temperatures can be summa-
the first 15 s, but then is constantly decreasing over the vast major-
ity of the time, (b) at 120 °C this behavior is more pronounced and
extends even beyond the first drying period, to reach a stage where
degradation is found to be marginal, around the 200 s. This situa-
tion can also be observed at 130 °C, but at a higher rate and (c)
at 140 °C the degradation of TPC is dramatic at an early stage,
not only in terms of speed, but also to the concentration obtained
at the end of the operation, regardless the drying period. The rela-
tionship between TPC and the moisture content at any time of the
process are discussed in Section 4.4.
The TPC in fresh apple peels was 35.74 ± 3.09 mg GAE/g ds. This
value is 3.3- and 3.7-fold higher than those reported by Łata (2007)
and Drogoudi et al. (2008), respectively. These differences may be
due to the complexity of these compounds, different growing
 C. Henríquez et al. / Journal of Food Engineering 143 (2014) 146–153
Fig. 4. TPC thermal degradation kinetics in fresh apple peels dried at 110, 120, 130
and 140 °C. The continuous lines represent the fitted model (first-order kinetics) for
each temperature.
conditions and/or the methods of extraction and analysis used. The
TPC of dried apples ranged from 7.54 to 26.14 mg GAE/g ds,
depending on the drying temperature. Table 3 shows that when
lower temperatures and longer times of residence were utilized,
the retention of the TPC was higher. Thus, at 110 °C, approximately
73.13% of the phenolic compounds present in the fresh apple peel
were retained at the end of the process (t = 240 s). Therefore, if the
desired goal is to obtain a low-moisture product, the use of high
temperatures, such as 130 °C and 140 °C, allows shorter drying
times and reduces the exposure of the product, but a lower TPC
is reached. A suitable dehydration method is one that decreases
the moisture content and water activity (aw) while maintaining
the nutritional value, achieves the required amount of product in
a reasonable time and minimizes the operating costs (Bangay
et al., 2003). Based on these criteria, lower temperatures may pro-
vide suitable conditions for processing apple peels using a drum-
dryer system. For comparison, at 140 °C, a drying time of 60 s
allowed the retention of 54.11% of the TPC, whereas at 110 °C,
75.93% of these compounds were retained during 203 s of process-
ing (drying time).
4.4. Mathematical models of the degradation of phenolic compounds
The results described above imply that the kinetics of degrada-
tion were different in each situation. The degradation phenomena
were accelerated with the use of higher temperatures/shorter
times compared with the utilization of lower temperatures/higher
times. Since the loss increases with the duration and intensity of
heating, the time–temperature regime during the process should
be considered in order to retain the content of individual bioactives
(Kwok et al., 2004; Berardini et al., 2005; Henríquez et al., 2010).
This result is reflected by the increase in the kinetic constant (k)
Table 3
Comparison of the TPC retention at the end of the process and at the drying times.
Drying temperature (°C) Values at the end of the process
TPC (mg GAE/g ds) Retention (%)
110 26.14 73.13
120 20.47 57.28
130 15.42 43.40
140 7.54 21.10
151
with the temperature increase. Similar results were reported by
Wolfe et al. (2003) for oven-dried apple peels and by Chantaro
et al. (2008) for carrot peels dried in a tray dryer; however, these
researchers did not fit kinetic models. Table 4 summarizes the
kinetic parameters with their respective fitting degree for first-
order kinetics. In addition, the natural logarithm of (k) as a function
of the absolute reciprocal temperature showed a good relationship
(not shown in plots) (R2 = 0.968) when Eq. (8) was linearized. From
this result, the activation energy was estimated to be
1.026 ± 0.068 kJ/mol.
The moisture content is one of the most important factors in the
degradation of nutrients. As water is removed, the concentration of
the chemicals increases. Moreover, some water-soluble com-
pounds may act as catalysts of the decomposition process. These
catalytic effects are greatly reduced as moisture is removed
because chemical reactions are slower as the water activity
decreases. If more liquid water is present, the volume available
for reactions is greater (Goula et al., 2006).
The decomposition of polyphenols depends on the food matrix
and the processing conditions (Mrkìc et al., 2006). The decrease in
the TPC reported here can be explained by three possible
mechanisms: (1) The release of bound phenolic compounds; (2)
the partial degradation of lignin, which could lead to the release
of phenolic acids; and (3) the thermal degradation of the phenolic
acids or catechins (Larrauri et al., 1997). Whatever the mechanism,
it should be noted that this is the first report of the degradation
dynamics of the TPC during a conductive drying process.
Finally, from a simple non-linear regression between the aver-
age moisture content (expressed in dry mass, as s (Tau)) and the
average TPC, a logarithmic relationship between these attributes
was observed at 110 and 120 °C (Fig. 5a and b), whereas at 130
and 140 °C, the effect of temperature is more evident and a recipro-
cal relationship between s and the TPC was observed (Figs. 5c and
d). All of the models fitted significantly (p 6 0.05). The TPC predic-
tion equations depending on the moisture content, with their
respective degree of fitting, are summarized in Table 5. Thus, by
maintaining constant operating conditions, it is possible to build
empirical models to establish a numeric relationship for predicting
the TPC when a certain level of dehydration is reached. This finding
could be useful from the standpoint of processing development;
however, further studies of the desirable moisture content of dried
apple peel ingredients should be undertaken in the near future.
Knowledge of the kinetics of the TPC degradation in apple peels
is a first step in searching for new foods with healthful properties,
and a validation criterion for the use of drum-drying systems as
tools for stabilizing these compounds, allowing agro-industrial
waste recovery.
Table 4
First-order kinetic parameters fitted for TPC degradation.
Drying temperature (°C) k (s1) RSME R2 adjust (%) F-ratio
110 0.0010 ± 0.0001 0.4620 93.45 213.94
120 0.0020 ± 0.0002 1.6331 92.08 187.11
130 0.0031 ± 0.0003 1.6805 90.07 146.29
140 0.0059 ± 0.0002 1.1458 97.84 726.13
Values at each drying time
Drying time (s) TPC (mg GAE/g ds) Retention (%)
203 27.14 75.85
124 23.63 66.60
81.5 22.49 63.33
60 19.35 54.17
152 C. Henríquez et al. / Journal of Food Engineering 143 (2014) 146–153

Fig. 5. Relationship between s (g water/g dry mater) and the TPC at different drying temperatures. The blue lines correspond to the predicted models, the red lines
correspond to the confidence intervals, and the black lines provide the prediction limits for new observations (one standard deviation from the prediction equation). (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Table 5
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