Accepted Manuscript

Title: Valorization of grape pomace: Drying behavior and

ultrasound extraction of phenolics

Author: Athanasia M. Goula Konstantinos Thymiatis

Kyriakos Kaderides

PII: S0960-3085(16)30068-2
DOI: http://dx.doi.org/doi:10.1016/j.fbp.2016.06.016
Reference: FBP 738

To appear in: Food and Bioproducts Processing

Received date: 5-4-2016

Revised date: 8-6-2016
Accepted date: 28-6-2016

Please cite this article as: Goula, A.M., Thymiatis, K., Kaderides, K.,Valorization
of grape pomace: Drying behavior and ultrasound extraction of phenolics, Food and
Bioproducts Processing (2016), http://dx.doi.org/10.1016/j.fbp.2016.06.016

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Valorization of grape pomace: Drying behavior and ultrasound extraction
of phenolics

Athanasia M. Goula*, Konstantinos Thymiatis, Kyriakos Kaderides

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Department of Food Science and Technology, School of Agriculture, Forestry and Natural

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Environment, Aristotle University, 541 24 Thessaloniki, Greece
*
Corresponding author. Tel.: +30 2310 991658; fax: +30 2310 991658.

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E-mail address: athgou@agro.auth.gr (A.M. Goula)

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Abstract
The wine industry generates huge amounts of grape pomace as an industrial waste. Recently,

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there has been much interest in the phenolic compounds of grape pomace, because of their
health benefits, such as antioxidant activity, acting as free radical scavengers, and inhibition
of lipoprotein oxidation. Thus, the objective of this work is to optimize a new method for
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grape pomace application in food industries based on the ultrasound-assisted extraction of
phenolics compounds. Dehydration of grape pomace is the first step before extraction. Thus,
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another subject of this work is to study the drying behavior of this winery by-product and the
kinetics of total phenolics degradation during the drying process. Drying (moisture vs time)
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data were obtained on slabs of grape pomace in an air dryer operating at 60-85 oC. The
effective diffusivity was determined using the method of slopes of the drying curve taking
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into account the effect of moisture content on diffusivity. The combined effect of moisture
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content and temperature on effective diffusivity was expressed by an empirical model. In

addition, each moisture loss curve was fit to empirical simplified drying models. Finally, the
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effects of solvent type, extraction temperature, solvent/solid ratio, amplitude level, and pulse
duration/pulse interval ratio on the yield of phenolics extraction were studied.

Keywords: diffusivity; drying curve; grape pomace; phenolics; ultrasound-assisted extraction

1. Introduction
Grape pomace is the winery waste originated during the production of must by pressing
whole grapes. Nine million tons of this waste are produced per year in the world, which

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constitutes about 20% w/w of the total grapes used for wine production (Teixeira et al., 2014).
Grape pomace constitutes a source of phenolic compounds. Its phenolic content mainly
include anthocyanins (e.g., malvidin, peonidin), flavan-3-ols (e.g., catechin,
proanthocyanidins), flavonols (e.g., quercetin, myricetin), stilbenes, and phenolic acids
(Negro, Tommasi, & Miceli, 2003; Makris, Boskou, & Andrikopoulos, 2007). Based on its

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polyphenolic content, several studies have reported its high antioxidant activity (Boussetta,

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Lanoisellé, Bedel-Cloutour, & Vorobiev, 2009; Rockenbach et al., 2011a; Rockenbach,
Gonzaga, Rizelio, Gonçalves, Genovese, & Fett, 2011b). Therefore, the recovery of phenolic

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compounds from grape pomace is of great importance, not only because of their significant
properties, but also because it could exploit a large amount of the wine industry wastes, which

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are mainly used today as cattle feed or for soil conditioning or they are trucked away to
disposal sites (Louli, Ragoussis, & Magoulas, 2004).

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Grape pomace is highly perishable due to its high moisture content and water activity.
The pomace could be frozen until required, but large volumes are involved here and an extract
would need to be prepared from the pomace, or it would need to be dried in any event before
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use in value-added or functional food product formulations (Vashisth, Singh, & Pegg, 2011).
Thus, dehydration of wet grape pomace is a first step before developing further applications.
According to Milczarek, Dai, Otoni, and McHugh (2011), the high moisture content of grape
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pomace makes it costly to transport in its original wet form and must be reduced to about 5-
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8% (wet basis) to extract. Drosou, Kyriakopoulou, Bimpilas, Tsimogiannis, and Krokida

(2015) reported that dried grape pomace extracted with water exhibited higher yield than the
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wet pomace, since drying causes breakage and destruction of cell walls and consequently
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large cavities and intercellular spaces are formed allowing to the cellular substances to be
easily extracted. Hartley, Morrison, Himmelsbach, and Borneman (1990) suggested that
because phenolic acids are mainly bonded to carbohydrate and proteinaceous moieties, during
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drying their release might occur due to breakdown of cellular constituents and covalent bonds.
Therefore, the released polyphenolic constituents become more amenable for extraction.
Several researchers have described the advantages of mathematical models to develop a
better understanding of controlling the parameters of a drying process (Perez & Schmalko,
2009). Thin layer drying models have found wide application among mathematical models
and these kinds of models have three categories. While theoretical thin layer models take into
account internal resistance to moisture transfer, semi-theoretical and empirical models
consider external resistance to moisture transfer between product and heated air (Akgun &
Doymaz, 2005). Numerous studies have investigated the drying kinetics of different

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Page 2 of 45
agricultural products in order to determine the water diffusivity coefficient and the suitable
mathematical model of the specific drying process. As far as the grape pomace is concerned,
limited research has been achieved with regard to its drying behavior (Sui, Yang, Ye, Li, &
Wang, 2014; Drosou et al., 2015).
Drying of grape pomace can result in significant degradation of the polyphenolics and

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also affect antioxidant and free-radical scavenging capacities (Vashisth et al., 2011).

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Generally, the problem of chemical conversions during drying is extremely complicated. The
rate constants of the reactions depend on temperature, concentration of the reactants and

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concentration of water (water activity) (Sokhansanj & Jayas, 1995). The influence of the
water activity is important but insufficiently understood. Although various oxidation reactions

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show a minimum rate of reaction at a certain water activity (Pan, Zhao, & Hu, 1999), in
general, chemical reactions are slower as the water activity decreases (Karel, 1979). However,

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limited research has been achieved with regard to the phenolics involvement in product
quality changes during grape pomace drying (Khanal, Howard, & Prior, 2010; Vashisth et al.,
2011; Tseng & Zhao, 2012).
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Several studies have been published in the past to extract phenolic compounds from
grape pomace. Grape pomace phenolics can be extracted with various extraction methods,
such as normal stirring, Soxhlet extraction, microwave-assisted extraction, supercritical fluid
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extraction, and accelerated solvent extraction (Ahn, Grün, & Mustapha, 2004; Louli,
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Ragoussis, & Magoulas, 2004; Fang & Bhandari, 2010; Marqués, della Porta, Reverchon,
Renuncio, & Mainar, 2013; Rajha et al., 2014). Shortcomings of existing extraction
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technologies, like increased consumption of energy, high extraction time, possible

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degradation of bioactive compounds, and high consumption of harmful chemicals, have

forced the food and chemical industries to find new separation ‘‘green’’ techniques, such as
ultrasound extraction (Chemat, Huma, & Khan, 2011). Extraction enhancement by ultrasound
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has been attributed to the cavitation, which generates high shear forces and microbubbles that
enhances surface erosion, fragmentation, and mass transfer (Awad, Moharram, Shaltout,
Asker, & Youssef, 2012). In recent years, ultrasonic irradiation has been used to recover
phenolic compounds from different plant food materials and their by-products, such as green
tea, wheat bran, jatoba bark, arecanut, Stevia Rebaudiana Bertoni, citrus peel, black
chokeberry waste, coconut shell, orange peel, onion waste, and olive mill wastewater (Xia,
Shi, & Wan, 2006; Rodrigues & Pinto, 2007; Rodrigues, Pinto, & Fernandes, 2008; Wang,
Sun, Cao, Tian, & Li, 2008; Ma, Chen, Liu, & Ye, 2009; Khan, Abert-Vian, Fabiano-Tixier,
Dangles, & Chemat, 2010; Jerman-Klen & Mozetic-Vodopivec, 2011; Galanakis, Markouli,

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Page 3 of 45
& Gekas, 2013; Jang, Asnin, Nile, Keum, Kim, & Park, 2013; Veggi, Martinez, & Meireles,
2013; Galvan D’Alessandro, Dimitrov, Vauchel, & Nikov, 2014; Barba, Grimi, & Vorobiev,
2015). However, limited research has been achieved with regard to the ultrasound-assisted
extraction of phenolics from grape pomace (Corrales, Toepfl, Butz, Knorr, & Tauscher, 2008;
Delgado-Torre, Ferreiro-Vera, Priego-Capote, Pérez-Juan, & Luque de Castro, 2012; Drosou

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et al., 2015). In addition, the multitude of process dimensions which present themselves when

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they are combined with conventional process variables such as temperature, time, solid/liquid
ratios should be further studied in order to optimize the whole process for a future industrial

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implementation.
One objective of this work was to study the phenomena governing the diffusion process

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during grape pomace drying, determining the effects of process parameters on diffusivity and
expressing these effects with empirical models. These models can be used to control or

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optimize the variables of grape pomace drying process, which is a first step before developing
further applications of this important food industry waste. Another objective of this work was
to study the kinetics of total phenolics degradation during the drying process. In addition, the
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ultrasound-assisted extraction of phenolics from grape pomace was optimized.

2. Materials and Methods

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2.1. Plant material

Agiorgitiko (Vitis vinifera) grape pomace, harvested in 2013, was kindly provided from
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Epanomi region (North Greece) after red vinification. The pressed pomace was received
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containing 81.7 ± 1.4% moisture content and immediately stored at −30 oC to avoid
enzymatic degradation of the polyphenols until further use.
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2.2. Drying of grape pomace

Flat grape pomace (slabs) was prepared in 30 cm × 19 cm dishes. The pomace samples
were spread in the dishes applying light pressure to form slabs of uniform thickness of about 6
mm. The drying experiments were performed at temperatures of 60, 65, 70, 75, 80, and 85 oC
in a tray dryer with an air velocity of 1.2 m/s. The drying data were obtained by periodic
weighing of the samples with a balance (PCB 1000-2, KERN & Sohn GmbH, Germany),
placed on the top of the dryer. The initial moisture content was determined by the vacuum
oven method at 70 oC for 24 h. Dried pomace samples were drawn periodically and analyzed

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Page 4 of 45
for total phenolics. Grape pomace drying and thermal degradation kinetics were replicated
twice at the six product temperatures.

2.3. Extraction of phenolics from grape pomace

Grape pomace was dried at 60 °C for 20 h and kept at −30 °C until use. The pomace

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was ground in a laboratory mill (Type A10, Janke and Kunkel, IKA Labortechnik, Germany)

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immediately prior to extraction. A 130 W of maximum nominal output power, 20 kHz of
frequency VCX-130 Sonics and Materials (Danbury, CT, USA) sonicator equipped with a Ti–

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Al–V sonoprobe (13 mm) was used for ultrasound-assisted extraction in pulsed mode. The
solvents used were ethanol, water, 50% aqueous ethanol, 70% aqueous ethanol, and 70%

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aqueous methanol. A sample of powdered grape pomace was mixed with 200 mL solvent to
produce different solvent/pomace ratios. During the extraction process, the sample container

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was held in a thermostat-controlled water bath and two T-type thermocouples were immersed
into the extraction solution. The temperature was kept constant by periodical adding of ice in
the bath. The extracts were collected at 4, 10, 20, 30, 40, and 60 min. The resulting extracts
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were evaporated using a rotary evaporator (Rotovapor R114, Waterbath B480, Büchi, Flawil,
Switzerland) to approximately 40 mL final volume.
The extraction temperature (T), the solvent/pomace ratio (LP), the amplitude level (A),
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and the pulse duration/pulse interval ratio (PUL) were varied between 20 and 40 oC, 8/1 and
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24/1 mL/g, 20 and 60%, and 5/15 and 2/1, respectively. These factors were optimized using
response surface methodology. A central composite design was applied to determine the
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effects of the above parameters on extraction yield. The effects were studied at five
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experimental levels –a, –1, 0, +1, and +a, where a = 2n/4 and n is the number of variables.
Extraction yield, Y (mg GAE/g of dry pomace), was defined as the ratio of the total
weight of gallic acid equivalents extracted to the dry pomace sample weight.
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2.4. Total phenolics measurement

The total phenolic content of grape pomace extracts was determined according to the
Folin-Ciocalteu method (Kim, Jeong, & Lee, 2003). Briefly, 0.2 mL of the extract was added
to a 25 mL volumetric flask and additional distilled water was added to make a final volume
of 10 mL. A reagent blank was prepared using distilled water. Folin-Ciocalteu phenol reagent
(0.5 mL) was added to the mixture and shaken vigorously. After 5 min, 5 mL of 5% Na2CO3
solution was added with mixing. The solution was immediately diluted to 25 mL with
distilled water, mixed thoroughly and then allowed to stand for 90 min. The absorbance was

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Page 5 of 45
measured at 750 nm versus the prepared blank. The total phenolic content of the sample was
expressed as gallic acid equivalents (GAE) mg/mL.

2.5. Modeling
2.5.1. Kinetic models of drying

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The drying air velocity was 1.2 m/s, which was reported as an adequate air velocity to

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assume an internal mass transfer prevails (Mulet et al., 1999). Thus, the transport of water can
be described by the Fick’s second law for unsteady state diffusion without taking into

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consideration the external mass transfer (Karathanos, Villalobos, & Saravacos, 1990). If the
moisture movement by thermal gradient within the thin slab is neglected, the moisture transfer

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can be considered as an one-dimensional diffusion process in the upward direction from the
bottom of the sample towards the top surface (Celma, Rojas, & Lopez-Rodríguez, 2008).

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Besides, provided that moisture cannot be transferred through the sample tray, the lower slab
surface was assumed to be the symmetry axis.
The method of slopes was applied to estimate the effective moisture diffusivity at
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various moisture contents. The experimental drying curve (logMR vs t) was compared to the

theoretical diffusion curve (MR vs Fourier number, Fo) ( Fo  Dt / L2 ), where

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X  Xe
MR  is the fractional moisture ratio, X0 is the initial moisture content, X is the
X0  Xe
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mean moisture content at time t, Xe is the equilibrium moisture content, D is the moisture
diffusivity, and L is the slab thickness. The slopes of the experimental curve (dMR/dt)exp and
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the theoretical curve (dMR/dt)th were estimated at a given moisture ratio using numerical
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differentiation (Goula, Chasekioglou, & Lazarides, 2015). The effective moisture diffusivity
(Deff) at a given moisture ratio MR (or moisture content X) was estimated from Eq. (1)
(Karathanos et al., 1990; Babalis & Belessiotis, 2004):
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 
Deff  dMR / dt exp / dMR / dFo th  L2 (1)

Each moisture loss (MR vs t) curve was fit to ten simplified drying models given in
Table 1. In addition, the dependence of the best descriptive model constants on drying
temperature was expressed by an appropriate type of model (linear, power, exponential,
Arrhenius, logarithmic, or polynomial).

2.5.2. Kinetic model of phenolics degradation during drying

The kinetic models representative of total phenolics degradation during drying were

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obtained using a dynamic test approach. The dynamic method for determining decay kinetics
requires the acquisition of moisture, temperature and quality factor concentration during the
actual process. The degradation achieved is the common and indistinguishable effect of both
temperature and moisture integrated in time (Goula & Adamopoulos, 2010).
An empirical first-order kinetic model was used for degradation kinetics of total

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phenolics (Koca, Burdurlu, & Karadeniz, 2007; Lavelli, Zanoni, Zaniboni, 2007):

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dC
  k C (2)
dt

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where C is the concentration of total phenolics (mg/g dry solids) at time t (min) and k is the
reaction rate constant (min–1), which is a function of temperature and moisture content (Pan,

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Zhao, & Hu, 1999; Erenturk, Gulaboglu, & Gultekin, 2005):
k  kT  k X (3)

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 Ε 
kT  k 0  exp  a  (4)
 R T 

k X  A1  A2  X  A3  X 2 (5)
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where k0 is the so called frequency factor (min–1), Εa is the activation energy (kJ/mol), X is the
pomace moisture content (g/g dry solids), and A1, A2, and A3 are constants.
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Let us divide the drying time into n intervals, where Ti and Xi are the mean values of
temperature and moisture content in the relevant interval. Calculating the reaction rate
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constants k1, k2,…., kn from the mathematical model (3), the concentration of the lycopene
corresponding to the time tn can be given as (Goula et al., 2006):
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 n 
C n  C 0  exp   k i Δt i 
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(6)
 1 
where C0 is the initial phenolics concentration.
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2.6. Statistical analysis

The parameters of the models were estimated by non-linear regression. To evaluate the
goodness of each approach fit, three criteria were used: the coefficient of determination, R2,
the root mean square error (RMSE), and the reduced chi-square (χ2).
The extraction data were analyzed using the statistical software MINITAB (Release
13.32). Regression analysis was used to fit a full second order polynomial, reduced second
order polynomials, and linear models to the data of the response variable. F values for all
reduced and linear models with an R2 > 0.70 were calculated to determine if the models could

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Page 7 of 45
be used in place of full second order polynomials to predict the response of a variable to the
independent variables. The reason that a subset of variables rather than a full set would be
used is because the subset model may actually estimate the regression coefficients and predict
future responses with smaller variance than the full model using all predictors. Typically, R2
always increases with the size of the subset. Therefore, R2 is most useful when comparing

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models of the same size. The square root of mean square error (S) and the Mallows’ Cp

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statistic (Cp) can be used as comparison criteria to compare models with different numbers of
predictors. A good model should have a high R2, a small S , and a Mallows’ Cp statistic close

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to the number of predictors contained in the model (Goula, 2013).

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3. Results and discussion

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3.1. Drying of grape pomace
The drying curves obtained are of the form depicted in Fig. 1. The initial moisture
content of grape pomace was about 81.7% (wet basis) and the drying times to a moisture
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content of about 4.5% (wet basis) were about 1560, 1170, 950, 710, 420, 300 min at 60, 65,
70, 75, 80, and 85 oC, respectively. Temperature had a great impact on drying rate, so that the
drying time almost doubled from 75 to 60 oC. This is due to the increase of the air heat supply
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rate to the product and to the acceleration of water migration inside the pomace. Drying rate
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decreased continuously with time and it is obvious that the drying occurred mostly in the
falling rate period. That means that the controlling resistance to mass transfer was internal
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diffusion of moisture. Similar findings were for apple purees, carrots, figs, sultanas, bananas,
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kiwifruits, green pepper, and olive pomace (Karathanos & Belessiotis, 1997; Maskan, 2000;
Maskan, 2001).
To confirm that slow diffusion in the grape pomace was limiting the drying rate, the
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dimensionless Biot mass number, Bi, which is the ratio of external to internal mass transfer,
was calculated:
Bi  k  L / Deff (7)

where k is the convective mass transfer coefficient, Deff is the diffusivity, and L is the slab
thickness.
To calculate the Bi, it was firstly necessary to obtain k, which was calculated by the
analogy of Sherwood (Vazquez et al., 1999). The obtained value of k, about 0.18 m/s,

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Page 8 of 45
afforded a Bi > 100, confirming that diffusion within the pomace is the factor limiting the rate
of drying.
In addition, it was found that the falling rate period had two distinct phases. Similar
results were also observed by Göğüş and Maskan (1999; 2006) and Maskan and Göğüş (1998)
for mulberry, okra, and solid waste of olive oil processing. From the logarithmic drying

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curves, the average D values were obtained for each case (Fig. 2) considering only first falling

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rate periods. According to Göğüş and Maskan (2006), the development of cracks in the
second falling rate period lead to a non diffusional migration.

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The method of slopes (Fig. 2) yielded indicative values of the effective moisture
diffusivity (Deff), assuming that the diffusion equation could be applied to sections of the

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drying curve. The Deff values obtained by the method of slopes varied considerably with
moisture content. According to Babalis and Belessiotis (2004), the values of the effective

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moisture diffusivity obtained by the method of slopes, if compared with the accurate ones
obtained solving Fick’s unsteady diffusion, and using iterative techniques, are similar in
materials where liquid diffusion is predominant.
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As it can be drawn from Fig. 3, moisture diffusivity decreased as the moisture content
increased. A similar trend was found during drying of mint leaves (Ozbek & Dadali, 2007),
bamboo shoot slices (Bal, Kar, Satya, & Naik, 2010), and hydrated granular Amioca
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(Karathanos et al., 1990). On the contrary, an opposite effect was reported during drying of
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Amioca (high-amylopectin) starch gels (Karathanos et al., 1990) and olive mill waste solids
(Goula, Chasekioglou, & Lazarides, 2015). This indicates that other factors also affect the
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diffusivity such as the complex matrix of foods and this variation may be attributed to the fact
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that those materials had low porosity hindering the transfer of water vapor within the samples.
The effect of moisture content on diffusivity depends on the type of material. In gelatinized
starch, a gradual decrease of Deff as moisture content is reduced may be due to the lower
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mobility of water molecules in the compact polymer structure. However, diffusivity increases
as the moisture content of granular materials decreases, evidently due to the formation of
pores and channels. In general, the pore structure and distribution of food materials affect
moisture diffusivity, which increases with increasing porosity. The usual way of relating
moisture diffusivity with bulk porosity is by evaluating diffusivity as a function of moisture
content while porosity and temperature can then by incorporated by regression analysis of the
experimental data using a suitable structural model.
The moisture content dependence of the diffusivity can be introduced in the Arrhenius
equation by considering either the activation energy or the Arrhenius factor as an empirical

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Page 9 of 45
function of moisture. However, empirical equation with functions concerning the
discrimination of the moisture and temperature effects can be also used. In this work, the
combined effect of moisture content (X in % wb) and temperature (T in K) on effective
diffusivity was expressed by the following equation:

Deff  1.018  10 39  X 0.44  T 11.94 (R2 = 0.996) (8)

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Thin-layer drying models have found wide application due to their ease of use and lack

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of required data, such as phenomenological and coupling coefficients, as in complex
theoretical models (Goula et al., 2015). Nonlinear regression was used to obtain the constants

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of the selected empirical models (Table 2). The highest values of R2 and lowest values of
RMSE and χ2 were chosen for goodness of fit (Table 2). Generally, R2, RMSE, and χ2 values

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were varied between 0.981 and 0.999, 2.58 × 10–3 and 62.47 × 10–3, and 0.72 × 10–5 and 41.19
× 10–4, respectively.

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The Midilli model was the best descriptive model as shown in Table 2. Fig. 4 includes
the comparison of predicted and experimental values of moisture ratio change for the Midilli
model. This observation is similar to that reported by Sui et al. (2014), Togrul (2005), Puente-
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Díaz, Ah-Hen, Vega-Gálvez, Lemus-Mondacace, and di Scalaf (2013), and Goula et al.
(2015), for wine grape pomace, apple slices, Murta berries, and olive mill wastes. On the
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contrary, Togrul and Pehlivan (2003), Sacilik Elicin, and Unal (2006), Wang, Sun, Liao,
Chen, Zhao, and Wu (2007), Doymaz (2008), and Mohammadi, Rafiee, Keyhani, and Emam-
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Djomeh (2009) showed that the logarithmic model could describe the drying behavior of a
quantity of biological materials more accurately than the other thin-layer models, whereas
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other researchers (Tan, Miyamoto, Ishibashi, Matsuda, & Satow, 2001; Falade & Solademi,
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2010) reported that the Page model is the best descriptive model.
The effect of drying temperature T (in K) on Midilli model constants can be expressed
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by Eqs. (9)-(12).

a  7  10 6  T 3  6.9  10 3  T 2  238.97  10 2  T  275.38 (R2 = 0.965) (9)

b  2  10 7  T 3  3  10 4  T 2  8.68  10 2  T  10.028 (R2 = 0.935) (10)

n  2  10 4  T 3  1.76  10 1  T 2  60.804  T  7000 (R2 = 0.915) (11)

ln k  1012  T 3  1010 T 2  3  10 7  T 1  28569 (R2 = 0.895) (12)

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Page 10 of 45
3.2. Phenolics degradation during drying of grape pomace
The total phenolics content in grape pomace during each drying experiment is shown
in Fig. 5. The phenolics content of unprocessed grape pomace was about 165 mg GAE/g of
dry solids, whereas final phenolic content has decreased by 87.0, 87.5, 91.4, 93.2, 94.6, and
95.4%, after drying at 60, 65, 70, 75, 80, and 85 oC, respectively. As can be observed, higher

t
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temperatures caused more loss of phenolic substance. A similar observation was reported by
Silva, Pinedo, and Kieckbusch (2005), who found that during drying of camu camu slices,

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even considering that in order to attain the same final moisture content, samples dried at
higher temperatures were exposed for a shorter period to hot air, raising the drying

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temperature increased the loss of ascorbic acid. On the contrary, Erenturk, Gulaboglu, and
Gultekin (2005) and Bejar, Ghanem, Mihoubi, Kechaou, and Mihoubialso (2011), who

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studied the hot air drying of rosehip fruits and orange peels and leaves, observed maximum
content of total phenolics during drying at high temperatures, due to the shorter time
necessary to attain the specific moisture content, whereas at low temperatures the longer time
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of exposure to hot air, even at lower temperature, led to less phenolics content. Senevirathne
et al. (2010) dried citrus press-cakes at five temperatures (40, 50, 60, 70, and 80 oC) and
found the dried products had the most total phenolic content at 70 oC.
d

Polyphenolics are heat labile and prolonged heat treatment causes irreversible
te

chemical changes to such compounds (Lin, Durance, & Scaman, 1998; Mejia-Meza et al.,
2008). Drying of grape pomace at high temperatures can result in significant degradation of
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the polyphenolics and also affect antioxidant and free-radical scavenging capacities (Larrauri,
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Rupérez, & Saura-Calixto, 1997; Larrauri, Sánchez-Moreno, & Saura-Calixto, 1998).

Julkunen-Tiitto and Sorsa (2001) reported the destruction of flavanoids and tannins (i.e.,
polymeric forms of flavanoids) as a result of drying treatments. These authors also noted that
Ac

during decomposition glycosides formed the corresponding aglycones. Several researchers

have reported that when temperatures below 70 oC are employed during drying, the integrity
of fruit polyphenolics is retained. Nindo, Sun, Wang, Tang, and Powers (2003) observed that
at 60 oC by heated air or a microwave spouted bed drying method, most phenolic compounds
were preserved. In their study on the effect of drying temperature on red grape pomace,
Larrauri et al. (1997) also concluded that a dehydration temperature of 60 oC resulted in no
significant changes in the endogenous polyphenolics relative to freeze dried pomace.
According to Khanal et al. (2010), although total anthocyanin contents in both grape and
blueberry pomace were slightly reduced by drying at 40 oC, it was not statistically significant.

11
Page 11 of 45
A significant overall drop in total anthocyanin content occurred with increasing drying
temperature from 40 to 125 oC, but without a significant drop from 40 to 60 oC in both types
of pomace. However, when the temperature increased from 60 to 125 oC, a sharp reduction in
total anthocyanin contents occurred in both grape and blueberry pomace. The reduction was
more drastic in grape, which declined by about 70% from its original level. De Ancos, Ibañez,

t
Reglero, and Cano (2000) suggested that anthocyanin and other polyphenolics compounds

ip
may degrade depending upon many factors other than just heat treatment. These included the
activity of polyphenol oxidase, organic acid content, sugar concentration, and pH. During

cr
long thermal treatments, polyphenol oxidase can cause a marked reduction in the phenolic
constituents, and hence measured total phenolics content values.

us
Fig. 6 presents the adjustment of the empirical dependence approach model to the
experimental data of total phenolics retention during each drying experiment. Estimated

an
parameters for the model are presented in Table 3. To evaluate the goodness of fit of the
model, linear regression and paired t-test were applied. The slope and the intercept of
predicted values versus experimental values are not significantly different (p = 0.05) from the
M
theoretical values 1.00 and 0.00, respectively, whereas applying paired t-test the calculated t
values were found lower than the theoretical t values (p = 0.05). Therefore, the null
hypothesis was retained: the empirical dependence approach model is suitable for modeling
d

the degradation of total phenolics during drying of grape pomace.

te

3.3. Ultrasound extraction of phenolics from grape pomace

p

In all experiments, the extraction yield increased with ultrasonic time, especially from 2
ce

to 10 min and slowly from 10 to 60 min. Thus, the efficient extraction period for achieving
maximum yield of grape pomace phenolics was about 10 min. A similar behavior found by
many researchers during ultrasound-assisted extraction and was attributed to the fact that the
Ac

ultrasonic waves affect the mass transfer rate mainly in the solvent penetration stage (Zhang,
Wang, Li, Jiao, Chen, & Mao, 2008). In addition, Kaderides, Goula, and Adamopoulos (2015)
reported that as cell walls ruptured, impurities suspend in the extract, lowering the solvent’s
permeability into cell structures, whereas target components re-adsorb into the ruptured tissue
particles due to their relatively large specific surface areas, lowering yields of peel phenolics.
However, Jerman, Trebše, and Vodopivec (2010) found that the extraction yield of olive
phenolics was low for the first 4 min of ultrasound application. This difference may be
attributed to the level of ultrasonic power applied, since Jerman et al. (2010) accomplished

12
Page 12 of 45
their experiments in an ultrasonic bath, which actually supplies lower ultrasonic intensities
than probe systems.
The direct ultrasound-assisted extraction of phenolics had a maximum yield of 9.57 mg
GAE/g of dry pomace at extraction time of 10 min. Many researchers extracted phenolic
compounds of grape pomace using different extraction methods (Soxhlet, normal stirring,

t
pressurized water extraction, high voltage electrical discharges (HVED)) and reported much

ip
longer extraction times (up to 100 times) to achieve lower or similar extraction yields. The
industrial batch extraction of polyphenols from grape pomace is performed for about 20 h at

cr
50–60 oC. Boussetta, Vorobiev, Deloison, Pochez, Falcimaigne-Cordin, and Lanoisellé (2011)
optimised the electrically assisted extraction in order to obtain grape pomace extracts with

us
high polyphenols content and reported that the most efficient extraction (28 mg GAE/g dry
pomace) was an HVED pre-treatment followed by a diffusion with 30% ethanol in water at 60
o

an
C for 30 min. Thus, ultrasounds increased extraction yield, but mainly shortened the
treatment time. Improved yields may be explained in terms of cavitational effects caused by
the application of high-intensity ultrasound. According to Chemat et al. (2011), a cavitation
M
bubble can be generated close to the plant material surface, then during a compression cycle,
this bubble collapse and a microjet directed toward the plant matrix is created.
According to Aliakbarian, Fathi, Perego, and Dehghani (2012), total phenolic content of
d

grape pomace obtained by subcritical water extraction at optimized conditions and at

te

extraction time of 130 min was 31.69 mg GAE/g dry pomace, whereas Brahim, Gambier, and
Brosse (2014) reported that microwave-assisted extraction (MAE) for 20 min achieved a yield
p

of about 8 mg GAE/g dry pomace. However, subcritical water extraction and MAE present
ce

the following drawbacks: additional filtration or centrifugation is necessary to remove the

solid residue after the process; the efficiency can be poor when the target compounds or
solvents are nonpolar, or when they are volatile; and the use of high temperatures can lead to
Ac

degradation of heat-sensitive bioactive compounds (Kaderides et al., 2015).

González-Centeno, Knoerzer, Sabarez, Simal, and Rosselló (2014) studied the
extraction of antioxidants from grape pomace using indirect ultrasound-assisted extraction
and reported that the phenolic yield under the optimum conditions was 0.32 mg GAE/g
pomace at extraction time of 25 min. However, in that study the effects of extraction
temperature, solvent type, and solvent/pomace ratio were not taken into account. González-
Centeno, Comas-Serra, Femenia, Rosselló, and Simal (2015) studied the extraction kinetics of
phenolics from grape pomace at different temperatures with mechanical stirring and with
acoustic assistance (direct ultrasounds) and found that the greatest quality attributes were

13
Page 13 of 45
obtained after 1 h of acoustic extraction at 50 oC. Specifically, the total phenolic content of
the extracts was around 3.3-fold higher (7.7 mg GAE/ g dry pomace) than in conventional
extraction at 20 oC. However, the effects of processing factors on the yield of ultrasound-
assisted extraction have not been studied.
Methanol, ethanol or acetone and their mixtures in water are so far the most

t
commonly used solvents in the extraction of phenolic compounds from the plant materials

ip
(Liu & Yao, 2007). Methanol has been generally found to be more efficient in extraction of
lower molecular weight polyphenols, while the higher molecular weight flavanols are better

cr
extracted with aqueous acetone (Guyot, Marnet, & Drilleau, 2001). However, the toxicity
associated to this solvent restricts its use to analytical procedures. In this regard, ethanol has

us
been studied as a more environmentally friendly solvent, recognized as safe according to the
European Food Safety Authority (EFSA) and FAO/WHO Expert Committee on Food

an
Additives. The comparison of the suitability of the distinct methods assayed so far shows that
hydroalcoholic solutions provides quite high yield of total extracts, although they are not
highly selective for the distinct classes of phenolics present in the residues (Lapornik, Prošek,
M
Golc Wondra, 2005; Spigno & de Faveri, 2007; Karvela, Makris, Kalogeropoulos, &
Karathanos, 2009; Agustin-Salazar, Medina-Juárez, Soto-Valdez, & Manzanares-López,
2014). Concerning the comparison between distinct solvents, recently, the effect of solvent
d

systems (MeOH and EtOH) on the efficiency of the extraction of total phenolic compounds,
te

total flavonoids, and individual phenolics, as well as on the antioxidant capacity of the
extracts obtained from grape pomace, and its constituents (peduncle, skin, and seed) has been
p

further investigated (Agustin-Salazar et al., 2014).

ce

In this work, the ability of different solvents in extracting phenolic compounds from
grape pomace was compared. Fig. 7 is the main effect plot for solvent type, which was found
to have a significant effect (p < 0.05) on total phenolic yield. The yield was increased in the
Ac

following order of solvents: water < ethanol < 70% aqueous methanol < 70% aqueous ethanol
< 50% aqueous ethanol. Mixture of ethanol and water was found more efficient in extracting
phenolic constituents than compared to mono-component solvent system. This observation is
similar to that reported by other researchers (Spigno, Tramelli, & De Faveri, 2007; Uma, Ho,
& Aida, 2010). Addition of a small quantity of water in organic solvents usually creates a
more polar medium, which facilitates the extraction of polyphenols. Lapornik, Prošek, &
Wondra (2005) reported that ethanol/water and methanol/water extracts (both at ratio 7:3 v/v)
of grape pomace had seven times higher values than water extracts, with 12 h generally being
the appropriate time of extraction. Extraction of phenolics from wheat bran requires 80%

14
Page 14 of 45
aqueous ethanol (Verma, Hucl, & Chibbar, 2008) and according to Kalpana, Lal, Kusuma,
and Khanna (2008), 50% aqueous ethanol was more efficient than pure or 50% aqueous
methanol and acetone for the extraction of phenolics from Potentilla atrosanguinea. In
contrast, the highest extraction yields of phenolics from Vitis vinifera wastes and sunflower
meal were achieved with methanol and 80% aqueous acetone, respectively (Taha et al., 2011).

t
These differences could be due to the properties of the phenolic components of the plants

ip
concerned (Kaderides et al., 2015).
Fig. 8 presents the effect of the process variables on extraction yield. Increasing

cr
extraction temperature from 20 to 35 oC, extraction yield increased, whereas an opposite trend
was observed when T increased from 35 to 40 oC. The first effect agrees with those previously

us
found in the literature, since it is widely recognized that temperature enhances mass transfer
by the improvement of the extraction rate. This can be explained by the effect of temperature

an
on the vapor pressure, surface tension, and viscosity of the liquid medium, which facilitates
mass transfer (Ahmad-Qasem, Cánovas, Barrajón-Catalán, Micol, Cárcel, & García-Pérez,
2013). In addition, the increase in the extraction yield may be linked to the increased ease
M
with which solvent diffuses into cells and the enhancement of desorption and solubility at
high temperatures (Esclápez, García-Pérez, Mulet, & Cárcel, 2011). However, at temperatures
higher than 35 oC, the vapor pressure was higher and more bubbles were created, but they
d

collapsed with less intensity due to a smaller pressure difference between inside and outside
te

of bubbles (Hromádková, Kováčiková, & Ebringerová, 1999; Zhang et al., 2008). Another
reason may be that the bubbles may be so easily collapsed at higher temperature, thus
p

reducing the intensity of the mass transfer enhancement (Zhang et al., 2008). This pattern of
ce

temperature effect is similar to that reported by many researhers. Zhang, Yang, Zhao, and
Wang (2009), Jerman et al. (2010), and Kaderides et al. (2015) reported an increase in
extraction yield at temperatures of up to 45 °C during extraction of olive phenolic
Ac

compounds, epimedin from fresh leaves of Epimedium, and pomegranate peel phenolics,
respectively. However, Zhang, He, and Hu (2011), who studied the extraction of flavonoids
from Prunella vulgaris L., found that extraction yields increased as the temperature increased
from 60 to 80 °C. This controversy surrounding the influence of temperature in antioxidant
extraction processes may be attributed to the fact that the introduction of a given amount of
ultrasound energy into the medium could also contribute to mask the effect of temperature
(Ahmad-Qasem et al., 2013).
The extraction yield improved with increased amplitude level (A) up to values around
40% (Fig. 8). This effect may be due to the fact that the acoustic energy transmitted into the

15
Page 15 of 45
medium is directly related to the extension of the ultrasonic effects (Ahmad-Qasem et al.,
2013). The more the ultrasonic power applied, the greater the cavitation intensity. Cavitation
makes it easier for the solvent to penetrate into thematrix and eases interface transport,
increasing the extraction efficiency of compounds present in the sample. According to Zu et
al. (2012), who extracted carnosic acid and rosmarinic acid from Rosmarinus officinalis, the

t
higher the ultrasound power was, the more solvent could enter cells and the more target

ip
compounds could permeate cell membranes, which suggested that increasing ultrasound
power could enhance compounds yield. Due to the presence of the hard cell walls, which are

cr
not so permeable, the large increase in ultrasonic power resulted in a moderate rise in yield
(Kaderides et al., 2015). However, for amplitude levels above 40%, the increase in A led to a

us
small decrease in yield, possibly due to degradation of the plant material. Similar explanation
was also reported to support the effect of ultrasonic power on the extraction of

an
polysaccharides from longan fruit pericarp (Yang, Zhao, Shi, Yang, & Jiang, 2008). A
different explanation was proposed by Maran and Priya (2015), who reported that although
the violent shock wave and high-speed jet generated by the ultrasound provoke the swelling
M
of the materials and enlargement of the pores in the materials, beyond the ultrasonic power of
90 W could cause an increase in bubble numbers in solvent during cavitation, which might
reduce the efficiency of the ultrasound energy transmitted into the medium and diminished
d

the extraction yield

te

As far as the ratio of solvent/pomace (LP) is concerned, in general a high solvent

content may cause complex procedures and unnecessary wastage and increase the energy
p

consumption during recycling, while a low solvent content may lead to incomplete extraction.
ce

As it can be seen in Fig. 8, the extraction yield increased with increasing the ratio of up to
values around 18/1 mL/g. Higher solvent/solid ratio resulted in larger concentration gradient
during the diffusion from solid into the solution and, thus, in higher phenolics concentration
Ac

in the extract. Qu, Pan, and Ma (2010) and Kaderides et al. (2015) also reported this effect of
solvent/sample ratio on the extraction yield of antioxidants from pomegranate marc and peels,
respectively. However, with further increase in liquid-to-solid ratio, a decrease in total
phenolics content was observed. A similar observation was reported by Prasad et al. (2011),
Zu et al. (2012), and Kaderides et al. (2015), who found the maximum extraction yield of total
phenolics from pomegranate and Mangifera pajang peels and of carnosic acid and rosmarinic
acid from Rosmarinus officinalis at solvent/solids ratios of 31/1, 20/1, and 33/1, respectively.
According to Maran and Priya (2015), who studied the ultrasound-assisted extraction of
pigments from Amarantus, an increase in solvent/solids ratio up to 18/1 enhances the contact

16
Page 16 of 45
area between material and solvent and lower the concentration and viscosity of the extraction
solvent, but the intensity of cavitation falls down with an increase in the viscosity of the
medium as the formation of cavitation requires the negative pressure in the rarefaction region
of wave function to overcome the natural cohesive forces.
As far as the effect of pulse duration/pulse interval ratio is concerned, an optimal

t
combination of duration and interval is critical for reducing the overall processing time and

ip
energy. As it can be seen in Fig. 8, the extraction yield increased with decreased ratio, since a
long interval indicates a long total processing time, which allow sufficient time for

cr
completing the mass transfer. A similar trend was reported by Pan, Qu, Ma, Atungulu, &
McHugh (2012), Goula (2013), and Kalamara, Goula, and Adamopoulos (2015). However,

us
further decrease in pulse duration/pulse interval ratio had an opposite effect due to the
possible degradation of plant material (Kaderides et al., 2015).

an
The regression coefficients were calculated and the data was fitted to a second-order
polynomial equation. The response (Y), extraction yield, can be expressed in terms of the
regression Eq. (13):
M
Y  42.3  1.49  T  0.846  A  1.36  LP  0.0162  T 2  0.00642  A 2
(13)
 0.0417  LP 2  0.0104  T  A
The coefficient of determination, R2, was 0.872, indicating that 87.2% of the total
d

variability in the response could be explained by the specific model, whereas an adjusted R2
te

value of 0.858 revealed that there was a good agreement between experimental and predicted
values of extraction yield. The model F-value was 14.97, corresponding to a p-value of less
p

than 0.01, which, along with the p-value for lack of fit (0.536), indicated that the model fit the
ce

experimental data accurately. According to the ANOVA analysis of the optimization study,
the amplitude level, the quadrate of solvent/pomace ratio, and the interaction of temperature
and amplitude level significantly influence the extraction yield (p < 0.05).
Ac

The generated by the MINITAB software desirability profile for optimum extraction
yield indicates that the maximum desirability level of 1.0 (on a scale of 0–1) can be achieved
with an extraction temperature of 34.5 oC, a solvent/solid ratio of 18.6/1 mL/g, an amplitude
level of 39%, and a pulse duration/pulse interval ratio of 8/6. Under these optimized
conditions, the predicted value for extraction yield was 9.93 mg GAE/g dry pomace, whereas
the observed experimental value was found 10.14 mg mg GAE/g dry pomace.

4. Conclusions

17
Page 17 of 45
 A new method for grape pomace application in food industries based on the ultrasound-
assisted extraction of phenolics compounds was optimized. Dehydration of grape pomace is
the first step before extraction. The proposed method meets the terms of green process
definition, since it reduces energy consumption and solvent amount, allows the use of
alternative solvents and renewable natural products, and ensures a safe and high quality

t
extract/product.

ip
Drying kinetics of grape pomace was investigated in an air dryer at different
temperatures. The drying rate increased on increasing the temperature, whereas the drying

cr
occurred mostly in the falling rate period. The slope of the second falling rate line was steeper
than that of the first falling rate line and hence drying rate decreased rapidly during last stages

us
of drying. Experimental data were compared with values predicted by ten thin-layer drying
models. It was evident that the drying rate was better described by the Midilli model, whereas

an
the temperature dependence of the model constants was described by empirical equations. The
method of slopes was applied assuming that the diffusion equation could be applied to
sections of the drying curve. The diffusivity values obtained by this method decreased as the
M
moisture content increased. The combined effect of moisture content and temperature on
effective diffusivity was expressed by an empirical model.
In addition, phenolics content of grape pomace decreased by 87.0-95.4% after drying at
d

60-85 oC and higher temperatures caused more loss of phenolic substance. The retention of
te

phenolics during drying can be described by an empirical dependence approach model, which
is a first-order decay model with an Arrhenius and a polynomial dependency on temperature
p

and water content, respectively.

ce

As far as the ultrasound-assisted extraction process is concerned, only 10 min in

aqueous ethanol (a green environmental solvent) are needed to recover polyphenols from
grape pomace with a high yield (9.57 mg GAE/g of dry pomace), whereas conventional
Ac

extraction procedures need much longer extraction times (up to 100 times). Extraction yield
increased with increasing extraction temperature from 20 to 35 °C, amplitude level up to
values around 40%, solvent/pomace ratio up to values around 18/1 mL/g, and pulse duration/
pulse interval ratio up to values around 8/6.

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 t
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List of Figures
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Fig 1. Drying rate curves of grape pomace at different temperatures.
Fig. 2. Experimental and theoretical drying curves of grape pomace at 85 oC.
Fig. 3. Effective moisture diffusivity during drying of grape pomace.
d

Fig. 4. Experimental and predicted values of moisture ratio change for the Midilli model at
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different drying temperatures.

Fig. 5. Total phenolics retention during drying of grape pomace at 60, 65, 70, 75, 80, and
p

85°C.
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Fig. 6. Experimental and predicted values of total phenolics retention at various times of
grape pomace drying at different temperatures.
Fig. 7. Main effect of solvent type on extraction yield.
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Fig. 8. Effects of extraction temperature (T, °C), solvent/pomace ratio (LP,−), amplitude level
(A, %), and pulse duration/pulse interval ratio (PUL,−) on extraction yield (Y, mg GAE/g dry
pomace).

List of Tables
Table 1. Mathematical models applied to drying of grape pomace (Torrecilla, Aragón, &
Palancar, 2006).
Table 2. Parameters of the mathematical models for drying of grape pomace.

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Table 3. Parameters of the empirical dependence model for total phenolics degradation
during drying of grape pomace.

t
ip
cr
us
an
M
d
p te
ce
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 Ac
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pte
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31
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an
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Valorization of grape pomace: Drying behavior and ultrasound extraction

of phenolics

Highlights

 The drying behavior of grape pomace was studied.

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 The kinetics of phenolics degradation during drying of grape pomace was studied.

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 The ultrasound-assisted extraction of phenolics from grape pomace was studied.
 The effect of different parameters on extraction yield was studied.

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us
an
M
d
p te
ce
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 Table 1. Mathematical models applied to drying of grape pomace (Torrecilla, Aragón, &
Palancar, 2006).
Model Equation
Lewis MR  exp kt 

 

t
Page MR  exp  kt n

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Modified Page MR  exp kt n 
Henderson & Pabis MR  a  exp kt 

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Logarithmic MR  a  exp kt   c
Two term MR  a  exp k1t   b  exp k 2 t 

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Diffusion approach MR  a  exp kt   1  a   exp kbt 
Modified Henderson & Pabis MR  a  exp kt   b  exp gt   c  exp ht 
Wang & Singh MR  1  at  bt 2
 
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Midilli MR  a  exp  kt n  bt
k, n, a, b, c, k1, k2, g, h: model constants
M
d
p te
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 Table 2. Parameters of the mathematical models for drying of grape pomace.

Temperature Statistical parameter

Constant
(°C) R2 χ2 RMSE
Lewis
k (min-1)
60 0.003692 0.993 0.93× 10-3 0.030
65 0.004676 0.991 1.71× 10-3

t
0.040
2.58× 10-3

ip
70 0.005074 0.993 0.049
75 0.005833 0.995 0.80× 10-3 0.027
80 0.006206 0.993 1.27× 10-3 0.034

cr
85 0.007972 0.987 4.12× 10-3 0.062
Average 0.992 1.90× 10-3 0.041
Page

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-1
k (min ) n (-)
60 0.001336 1.193 0.997 1.83× 10-4 0.013
65 0.001043 1.294 0.999 7.21× 10-5 0.008
70 0.000982 1.319 2.63× 10-4

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0.998 0.016
75 0.002455 1.177 0.998 1.21× 10-4 0.011
80 0.001937 1.245 0.999 5.19× 10-5 0.007
85 0.001146 1.398 0.997 3.89× 10-4 0.019
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Average 0.998 1.80× 10-4 0.012
Modified Page
k (min-1) n (-)
60 0.00390 1.193 0.997 1.83 × 10-4 0.013
d

65 0.00495 1.289 0.999 7.17 × 10-5 0.008

70 0.00525 1.319 0.998 2.63 × 10-4 0.016
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75 0.00606 1.177 0.998 1.21 × 10-4 0.011

80 0.00662 1.241 0.999 5.15 × 10-5 0.007
85 0.00789 1.398 0.997 3.89 × 10-4 0.019
p

Average 0.998 1.80 × 10-4 0.012

Henderson & Pabis
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-1
a (-) k (min )
60 1.0334 0.00390 0.991 6.28 × 10-4 0.024
65 1.0521 0.00505 0.988 1.02 × 10-3 0.031
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70 1.0622 0.00551 0.985 1.69 × 10-3 0.040

75 1.0333 0.00613 0.994 5.16 × 10-4 0.022
80 1.0464 0.00668 0.990 7.28 × 10-4 0.026
85 1.0857 0.00875 0.981 2.78 × 10-3 0.051
Average 0.988 1.23 × 10-3 0.032
Logarithmic
a (-) k (min-1) c (-)
60 1.7589 0.00172 -0.756 0.999 1.84 × 10-5 0.004
65 1.7401 0.00224 -0.724 0.999 6.04 × 10-5 0.008
70 1.5459 0.00273 -0.528 0.999 7.83 × 10-5 0.009
75 1.3894 0.00367 -0.381 0.999 5.72 × 10-5 0.007
80 1.6142 0.00331 -0.600 0.999 4.33 × 10-5 0.006
85 1.3647 0.00501 -0.331 0.997 3.42 × 10-4 0.018

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Temperature Statistical parameter
Constant
(°C) R2 χ2 RMSE
Average 0.999 7.32 × 10-4 0.009
Two term
a (-) k1 (min-1) b (-) k2 (min-1)
60 0.51671 0.00390 0.51671 0.00390 0.991 6.28 × 10-4 0.024

t
65 0.52603 0.00505 0.52603 0.00505 0.988 1.02 × 10-3 0.031

ip
70 0.53109 0.00551 0.53109 0.00551 0.985 1.69 × 10-3 0.040
75 0.51667 0.00613 0.51667 0.00613 0.994 5.16 × 10-4 0.022
80 0.52321 0.00668 0.52321 0.00668 0.990 7.28 × 10-4 0.026

cr
85 0.54287 0.00875 0.54287 0.00875 0.981 2.79 × 10-3 0.051
Average 0.988 1.23 × 10-3 0.032
Diffusion approach

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a (-) k (min-1) b (-)
60 3.9815 0.00622 1.1999 0.998 1.44 × 10-4 0.012
65 3.9910 0.00838 1.2399 0.999 6.83 × 10-5 0.008

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70 17.4491 0.00974 1.0461 0.997 2.77 × 10-4 0.016
75 17.4482 0.01015 1.0361 0.999 1.02 × 10-4 0.010
80 6.7337 0.01136 1.1175 0.999 4.01 × 10-5 0.006
85 6.7357 0.01475 1.1445 0.996 5.35 × 10-4 0.023
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Average 0.998 1.95 × 10-4 0.012
Modified Henderson & Pabis
-1
a (-) k (min ) b (-) g (-) c (-) h (-)
60 0.44828 0.00390 0.13687 0.00390 0.44828 0.00390 0.991 6.28 × 10-4 0.024
d

65 0.45622 0.00505 0.14510 0.00505 0.45074 0.00505 0.988 1.02 × 10-3 0.031
70 0.47561 0.00551 0.11097 0.00551 0.47561 0.00551 0.985 1.69 × 10-3 0.040
te

75 0.46736 0.00613 0.09863 0.00614 0.46736 0.00613 0.994 5.16 × 10-4 0.022
80 0.49255 0.00668 0.06136 0.00669 0.49252 0.00668 0.990 7.28 × 10-4 0.026
85 0.39463 0.00875 0.29649 0.00875 0.39463 0.00875 0.981 2.79 × 10-3 0.051
p

Average 0.988 1.23 × 10-3 0.032

Wang & Singh
ce

a (-) b (-)
60 -0.00294 0,0000019 0.999 2.55 × 10-5 0.005
65 -0.00294 0.0000001 0.990 1.06 × 10-3 0.032
Ac

70 -0.00384 0.0000034 0.999 8.06 × 10-5 0.009

75 -0.00384 0.0000014 0.990 1.26 × 10-3 0.034
80 -0.00494 0.0000055 0.990 6.38 × 10-5 0.008
85 -0.00583 0.0000082 0.999 2.10 × 10-4 0.014
Average 0.996 4.50 × 10-4 0.017
Midilli
-1
a (-) k (min ) n (-) b (-)
60 1.00615 0.002753 0.96422 -0.000734 0.9998 1.50 × 10-5 0.004
65 1.00102 0.001504 1.18771 -0.000313 0.9999 1.15 × 10-5 0.003
70 0.99881 0.001663 1.17540 -0.000352 0.9997 2.91 × 10-5 0.005
75 1.00342 0.003569 1.06121 -0.000447 0.9993 5.04 × 10-5 0.007
80 0.99954 0.002369 1.17125 -0.000374 0.9999 7.21 × 10-6 0.003
85 0.98965 0.001546 1.30818 -0.000245 0.9994 7.69 × 10-5 0.009

35
Page 35 of 45
Temperature Statistical parameter
Constant
(°C) R2 χ2 RMSE
Average 0.9997 1.50 × 10-4 0.005

t
ip
cr
us
an
M
d
te
p
ce
Ac

36
Page 36 of 45
Table 3. Parameters of the empirical dependence model for total phenolics degradation
during drying of grape pomace.
Parameter Value R2 SSE
-1 –5 –5
ko (min ) 483.77∙10 ± 4.17∙10 0.909 0.037
Ea (kJ/mol) 19.39 ± 0.14

t
A1 1127.50 ± 5.39

ip
A2 730.77 ± 3.74
A3 60.83 ± 0.27

cr
us
an
M
d
p te
ce
Ac

37
Page 37 of 45
Figure 1

90
80
60
70
65
X (% wet basis)

60
70
50
75
40 80
30 85

t
ip
20
10

cr
0
0 200 400 600 800 1000 1200
t (min)

us
Fig 1. Drying rate curves of grape pomace at different temperatures.
an
M
ed
pt
ce
Ac

Page 38 of 45
Figure 2

t
ip
cr
us
an
Fig. 2. Experimental and theoretical drying curves of grape pomace at 85 oC.
M
ed
pt
ce
Ac

Page 39 of 45
Figure 3

t
ip
cr
us
Fig. 3. Effective moisture diffusivity during drying of grape pomace.
an
M
ed
pt
ce
Ac

Page 40 of 45
Figure 4

t
ip
cr
us
Fig. 4. Experimental and predicted values of moisture ratio change for the Midilli
an
model at different drying temperatures.
M
ed
pt
ce
Ac

Page 41 of 45
Figure 5

t
ip
cr
us
Fig. 5. Total phenolics retention during drying of grape pomace at 60, 65, 70, 75, 80,
and 85°C.
an
M
ed
pt
ce
Ac

Page 42 of 45
Figure 6

t
ip
cr
us
Fig. 6. Experimental and predicted values of total phenolics retention at various times
of grape pomace drying at different temperatures.
an
M
ed
pt
ce
Ac

Page 43 of 45
Figure 7

t
ip
cr
us
an
Fig. 7. Main effect of solvent type on extraction yield.
M
ed
pt
ce
Ac

Page 44 of 45
Figure 8

t
ip
cr
us
an
M

Fig. 8. Effects of extraction temperature (T, °C), solvent/pomace ratio (LP,−),

ed

amplitude level (A, %), and pulse duration/pulse interval ratio (PUL,−) on extraction
yield (Y, mg GAE/g dry pomace).
pt
ce
Ac

Page 45 of 45