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Innovative Food Science and Emerging Technologies 52 (2019) 8–16

Contents lists available at ScienceDirect

Innovative Food Science and Emerging Technologies


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

Dehydration of salmon (Atlantic salmon), beef, and apple (Granny Smith) T


using Refractance window™: Effect on diffusion behavior, texture, and color
changes

S. Francoa, A. Jaquesa, M. Pintoa, M. Fardellaa, P. Valenciaa, H. Núñeza, C. Ramíreza,b, ,
R. Simpsona,b
a
Departamento de Ingeniería Química y Ambiental, Universidad Técnica Federico Santa María, P.O. Box 110-V, Valparaíso, Chile
b
Alimentos y Salud (CREAS) Conicyt-Regional GORE Valparaíso Project R17A10001, Avenida Universidad 330, Curauma, Valparaíso, Chile

A R T I C LE I N FO A B S T R A C T

Keywords: The aim of this research was to study the use of Refractance window™ (RW™) in the dehydration of salmon
Refractance window™ (Atlantic salmon), beef (lean), and apples (Granny Smith) through the analysis of the effective diffusivity de-
Fick's second law termined through the Fick's model and the anomalous model.
Anomalous diffusion Salmon, beef, and apple slices were dried at 55 and 95 °C, using either a conventional drying process or RW™.
Color change
Water activity (aw) was measured periodically by drying, and the effective diffusion (Deff) was measured using
Food matrices
Fick's second law and an anomalous model. Color changes (ΔE) and firmness were also measured.
The results showed that mass transfer in salmon and beef was not improved by RW™. In contrast, in apple
slices dehydrated using RW™, the Deff and processing times were significantly (p < 0.05) affected, reflecting a
reduced drying time required to attain an aw of 0.6.
RW™ is a powerful tool that allows for the dehydration of fruit using temperatures of 95 °C and provides a
50% reduction in drying time.

1. Introduction production of meat and yoghurt powders (Raghavi, Moses, &


Anadharamakrishnan, 2018; Tontul, Ergin, Eroğlu, Küçükçetin, &
Consumers around the world are demanding products with high Topuz, 2018). However, the use of RW™ dehydration for fish, beef, or
nutritional value and quality, that do not require the addition of che- apple slices has not been studied yet. The concentration of juices
mical compounds or intensive treatments to extend shelf life. The food (strawberry, blueberry, mango, and pomegranate) and purees (carrot,
industry has been investigating innovative technologies to meet this tomato, asparagus, and paprika) using RW™ has been investigated, and
increasing demand. One of the most common processes used to extend has resulted in the common conclusion that thermally sensitive com-
the shelf life of food materials is dehydration, whose main objective is pounds such as bioactive compounds are maintained through this
to prevent microorganism spoilage and biochemical reactions that process (Abonyi et al., 2002; Baeghbali, Niakousari, & Farahnaky,
could affect the quality of the products by significantly reducing water 2016; Bernaert, Van Droogenbroeck, Van Pamel, & De Ruyck, 2018;
activity (Ortiz et al., 2013; Simpson et al., 2015). Caparino et al., 2012; Caparino, Sablani, Tang, Syamaladevi, & Nindo,
Refractance window™ (RW™) is a technology patented by Magoon 2013; Castoldi, Zotarelli, Durigon, Carciofi, & Laurindo, 2015; Celli,
(1986) and developed by MCD Technologies Inc. (Tacoma, Washington, Khattab, Ghanem, & Brooks, 2016; Kaur, Saha, Kumari, & Datta, 2017;
USA). It is known for its ability to provide higher quality of dehydrated Nindo et al., 2003; Nindo & Tang, 2007; Trivedia, D'costa, Shitut, &
foods compared with the conventional drying process (i.e. a convection Srivastav, 2017). Other studies have shown that RW™ allows for a
oven). Thus, RW™ improves color, flavor, vitamin retention, and anti- 50 min reduction in the drying time of tomato slices dehydrated at 90 °C
oxidant retention (Nindo, Sun, Wang, Tang, & Powers, 2003; Ortiz- compared with hot-air drying. Also, this process significantly improves
Jerez, Gulati, Datta, & Ochoa-Martínez, 2015; Pavan, Schmidt, & Feng, some of the physical and chemical properties of foods such as color and
2012). Several studies have reported the use of the RW™ technique for polyphenol content (Abbasid, Niakousari, & Yasini Ardekani, 2015).
juice concentration, fruit and vegetable dehydration, and even for the Tontul et al. (2018) compared the RW™ dehydration of yoghurt with a


Corresponding author at: Departamento de Ingeniería Química y Ambiental, Universidad Técnica Federico Santa María, P.O. Box 110-V, Valparaíso, Chile.
E-mail address: cristian.ramirez@usm.cl (C. Ramírez).

https://doi.org/10.1016/j.ifset.2018.12.001
Received 25 June 2018; Received in revised form 28 November 2018; Accepted 2 December 2018
Available online 11 December 2018
1466-8564/ © 2018 Elsevier Ltd. All rights reserved.
S. Franco et al. Innovative Food Science and Emerging Technologies 52 (2019) 8–16

freeze-drying process and found that the physical properties obtained fractional calculus, which can be applied to give a phenomenological
using RW™ were better than those obtained through freeze drying. representation of these drying processes with non-Fickean diffusion
However, the levels of bacteria present in the yoghurt were significantly processes. Basically, the fractional calculus model applied to diffusional
reduced by the RW™ method compared to freeze drying. process contains a parameter termed the “fractional order” α, which
The dehydration of animal tissues, such as beef or fish, using the defines that the dehydration process has a sub-diffusive (0 < α < 1)
RW™ technique, has been less reported. Rostami, Dehnad, Jafari, and or super-diffusive mechanism (α > 1) in comparison to Fick's second
Tavakoli (2017) performed a dehydration of meat powder with RW™, law (α = 1). Simpson et al. (2015) and Ramírez et al. (2017) have de-
concluding that the optimal temperature conditions to get a product monstrated that α value has a relationship with the microstructure of
with desirable physical, rheological, microbial, and sensory properties the food material. For example, the application of a moderate electric
was 100 °C (sample thickness of 2 mm). field in the apple osmotic dehydration produces an electroporation
Dehydration through the RW™ technique usually uses hot water at a phenomenon. This produces a more open structure, with clearer paths
temperature of around 90 °C as an energy source and an infrared for solute diffusion, thereby changing the diffusion process. As a result,
transparent plastic film (Mylar™), as a drying contact-surface (Abonyi the fractional order of time (α) decreased from 1.35 (without electro-
et al., 2002; Nindo et al., 2003; Ochoa-Martínez, Quintero, Ayala, & poration) to close to 1 (with electroporation), representing a transition
Ortiz, 2012). When there is no product to be dehydrated, energy to Fick's diffusion in the latter case (Simpson et al., 2015). It is worth
transfer through the radiation mechanism is slow; however, if there is a noting that through fractional calculus Simpson, Ramírez, Nuñez,
fresh product (with a high moisture content), the amount of energy Jaques, and Almonacid (2017) established that the well-known Page's
transferred by the radiation mechanism increases, allowing the food to model can be obtained from fractional calculus, which can be con-
be dehydrated in a short time; this is known as RW™ (Ortiz-Jerez et al., sidered as the first phenomenological approach of Page's model and
2015). validates the power of fractional calculus as a tool to model mass
The food materials can be pre-treated in various ways to improve transfer phenomena beyond Fickean behavior.
mass transfer during the drying process. Freezing and thawing (F-T) can Nowadays, dehydrated products from beef meat (beef jerky) or
be used as pre-treatment to enhance the mass transfer rate because apple (apple chips) are commonly found in the market place. The de-
there is damage to the food microstructure, and furthermore water hydration processes used to create these products are salting, hot-air
movement through the cell membrane and wall is facilitated. Ramírez, drying, or freeze drying. Considering the advantages of RW™ reported
Troncoso, Muñoz, and Aguilera (2011) have evaluated the effect of F-T over the last years, exploring the production of dehydrated salmon,
as a pre-treatment for the dehydration of apple samples, and the results beef, (beef jerky), and apple foods through RW™ appears to be an in-
demonstrated that there was an increase in the mass transfer rate teresting opportunity.
compared with other pre-treatments such as compression or immersion The aim of this research was to study the application of Refractance
in boiling water, due to the formation of extracellular spaces, inter- window™ (RW™), compared with a conventional drying method for the
cellular channels, and new pathways in the apple structure. On the dehydration of salmon (Atlantic salmon), beef (lean), and apples
other hand, freezing-thawing has been used in muscle-based foods such (Granny Smith) through an analysis of the effective diffusivity (obtained
as fish and beef to extend their shelf life and this treatment damages the by either Fick's law or an anomalous model based on fractional calculus
food microstructure (Cheng, Sun, Han, & Zeng, 2014). For example, in tool), processing time, and quality of the final products.
salmon tissue, previous research has reported that a slow F-T treatment
(between −5 and −20 °C with a freezing rate of 0.5–1.0 °C/min) pro-
duces large extracellular gaps and cell wall rupture because the ice 2. Materials and methods
crystals formed are bigger when compared to a faster F-T treatment
(freezing temperature between −30 and −80 °C with a freezing rate of 2.1. Materials
−20 °C/min), so this can be considered as an advantage when the
process is used as a pre-treatment (Alizadeh, Chapleau, de-Lamballerie, Salmon (Atlantic salmon), beef (lean), and apples (Granny Smith)
& Le-Lebail, 2007, 2009; Faridnia et al., 2015; Hughes, Oiseth, Purslow, were acquired from a local market in the city of Valparaíso, Chile, and
& Warner, 2014; O'Dowd, Arimi, Noci, Cronin, & Lyng, 2013; Vieira, were immediately transferred to the laboratory and stored at 4 °C. The
Diaz, Martinez, & Garcia-Cachan, 2009). three types of tissues were cut into slab shape pieces of
Fick's second law, and its solution proposed by Crank (1975), have 50 × 35 × 5 mm. For apples, the cut samples were immediately im-
been widely used to give a phenomenological representation of the mersed in a 1% w/w ascorbic acid solution and a 2% w/w citric acid
dehydration process. It has been used for several kinds of tissues and for solution to prevent enzymatic browning.
different drying methods. For example, it has been used in fish samples The weights of the resulting samples of salmon, beef, and apples
dried using hot air (Djendoubi, Boudhrioua, Bonazzi, & Kechaou, 2009; ranged between 10.382 ± 0.663 g, 9.944 ± 1.243 g, and
Ortiz et al., 2013; Vega-Gálvez et al., 2011), by osmotic dehydration 6.070 ± 0.508 g, respectively.
(Gallart-Jornet et al., 2007; Uribe et al., 2011), and by sun dehydration For the salmon and beef tissues, the initial moisture content was
(Jain & Pathare, 2007); in beef dried through hot-air dehydration 0.78 g of water/g of sample and 0.77 g of water/g of sample, respec-
(Trujillo, Wiangkaew, & Pham, 2007) and osmotic dehydration tively. Both were determined according to the Association of Official
(Dimakopoulou-Papazoglou & Katsanidis, 2016); and in apple samples Analytical Chemist by drying at 105 °C for 24 h (AOAC, 1996). For the
dried by hot-air dehydration (Ramírez et al., 2011; Ramírez, Astorga, apple tissue, the initial moisture was 0.90 g of water/g of sample and
Nuñez, Jaques, & Simpson, 2017), by osmotic dehydration (Simpson was determined according to the Association of Official Analytical
et al., 2015), and by freeze dehydration (Ben Haj Said, Bellagha, & Chemist by drying fresh apple at 60 °C under vacuum conditions for
Allaf, 2015). However, independently of the dehydration, these kinds of 24 h until the samples reached a constant weight (AOAC, 2000).
tissues are not well represented by Fick's second law because there are
several phenomena that are not included in this model, such as
shrinkage, volume changes, moisture loss, and protein denaturation; 2.2. Freezing-thawing pre-treatment
these can produce water movement that can be faster or slower than
predicted by Fick's second law. Faster or slower diffusion movements The freezing-thawing pre-treatment of the salmon, beef, and apple
than predicted by Fick's second law are known as anomalous diffusion samples was carried out in a freezer (General Electric, RGE1436, USA)
(Simpson, Jaques, Nuñez, Ramirez, & Almonacid, 2013). at −5 °C for 48 h. Following this, the thawing process was carried out at
Simpson et al. (2013) has proposed a mathematical tool based on 5 °C, 24 h before the drying process.

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S. Franco et al. Innovative Food Science and Emerging Technologies 52 (2019) 8–16

Fig. 1. Experimental setup of the Refractance window™ system.

2 2
2.3. Drying processes ∞ ⎛ −(2i − 1) π Deff t ⎞
W − We 8 1 ⎜ 4L2 ⎟
MRt = t = 2 ∑ e⎝ ⎠
2.3.1. Conventional drying W0 − We π i=1
(2i − 1)2 (1)
The conventional drying of the salmon, beef, and apple slices was
where W(t) is the moisture content at any time t (g water/g dry basis),
performed in a convection oven at 55 °C and 95 °C (MEMMERT, HCP-
We is the moisture content at equilibrium (g water/g dry basis), and W0
108, Germany) until a constant weight was attained.
is the initial moisture content (g water/g dry basis). The value of We
was obtained by checking the asymptotic value of the moisture profile.
For a long time (MR < 0.6), Eq. (1) could be simplified into Eq. (2),
2.3.2. Refractance window™ drying
using only the first term of the series:
Fig. 1 shows a schematic representation of the experimental setup
2
for RW™. This experimental setup consisted of a thermos-regulated bath ⎛ −Deff π t ⎞
with a 60 L capacity (MERMMERT, WNB22 model, Germany) filled 8 ⎜ 4L 2 ⎟
MRt = 2 e⎝ ⎠
with distilled water at a temperature of either 55 ± 0.5 °C or π (2)
95 ± 0.5 °C. These temperatures were chosen based on preliminary where Deff is the effective moisture diffusion coefficient (m2/s), t is the
tests. A plastic film sheet (MYLAR™, polyethylene terephthalate) of drying time (s), and L is the half-thickness of the slice (m).
2 mm thickness was placed in contact with the water in the thermo-
regulated bath allowing for a drying surface of 150 × 470 mm2. A
2.4.2. Anomalous diffusion model
distance of 4 cm between the thermoregulated bath boundaries and the
Traditionally diffusion is represented by the Fick's laws of diffusion.
MYLAR™ sheet was used to purge air bubbles produced as a result of
These are well known to describe molecular transport processes.
heating. An automatic water level control system was used to keep a
However, their applicability is restricted to homogeneous, isotropic,
permanent contact between the water and the MYLAR™ sheet. The
media. In the case of biological materials, the presence of preferential
samples were put on the Mylar™ without turning them during the ex-
paths could produce a deviation in traditional diffusion. This is referred
periment, and at each sampling time a sample was removed for weight
to as anomalous diffusion (Klafter & Sokolov, 2005). This requires that
and water activity measurements.
alternative models be used to deal with this deviation from traditional
diffusion.
Simpson et al. (2013) have implemented an anomalous diffusion
2.3.3. Data collection from the drying processes
model for some food matrices based on a fractional calculus approach.
During the conventional and RW™ drying processes, weight changes
Fractional calculus is an extension of traditional calculus, where the
were measured with a precision of ± 0.001 g using a digital balance
order of differentiation can be different than an integer. This can re-
(Precisa Gravimetric AG, XB620M model, Switzerland) and water ac-
present diffusion processes where the diffusant does not have a
tivity was determined using a 4T AQUALab (Decagon Devices Inc.
homogeneous media and has a high diffusion path. This model is given
Pullman, Washington, USA). Both measures were recorded along with
by Eq. (3):
the drying time. Drying experiments were performed in triplicate
(n = 3) and the results were expressed as the mean ± standard de- ∂αW ∂ βW
= Deff
viation. ∂t α ∂x β (3)

where W corresponds to the food water concentration (g water/g dry


basis), Deff corresponds to the effective diffusion coefficient (m2/sα),
2.4. Mathematical models
where α is related to the anomalous waiting times between jumps, and
the fractional differentiation order β is related to the anomalous jump
2.4.1. Fick's second law
lengths.
From the analytical solution of Fick's second law proposed by Crank
It has been demonstrated that in food matrices, the space compo-
(1975) and experimental considerations, the following assumptions
nent converges to 2, and the temporal component has a fractional order
were considered: a) the tissue sheet is considered as an infinite slab, b)
(Simpson et al., 2013). Thus, Eq. (3) can be represented according to:
the ambient temperature is constant, c) the diffusion coefficient is
constant, and d) other diffusion mechanisms and shrinkage of the ∂αW ∂ 2W
= Deff
sample are neglected. The model is given by Eq. (1). ∂t α ∂x 2 (4)

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S. Franco et al. Innovative Food Science and Emerging Technologies 52 (2019) 8–16

Fig. 2. Drying curves for the control and pre-treated samples dehydrated using conventional drying and RW™ drying methods at 55 and 95 °C for: A) salmon, B) beef,
and C) apple.

Then, the solution for anomalous diffusion model is shown in Eq. (5) 2.5.2. Firmness
∞ 2
To characterize the texture of the dehydrated samples, firmness was
8 1 (2i − 1) π ⎞ α ⎞
MRt =
π2
∑ (2i − 1)2 Eα ⎛−Deff ⎛ ⎜
2L
t ⎟ measured according to Ortiz et al. (2013) with some modifications. This
i=1 ⎝ ⎝ ⎠ ⎠ (5) physical property was measured using a texture analyzer (Brookfield,
CT, USA). For salmon and beef samples, a column formed by 10 slices
where Eα corresponds to a Mittag-Leffler function (Simpson et al.,
(salmon final height = 43 ± 1 mm; beef meat final height = 30 ±
2013). Considering the long drying time, the Eq. (5) can be simplified
1 mm) was used to perform a puncture test using a puncture probe of
to:
2 mm diameter, adjusted with a trigger force of 0.1 N at a test speed of
8 π 2 1.7 mm/s until 40% of the sample height was attained.
MRt = Eα ⎛−Deff ⎛ ⎞ t α ⎞
⎜ ⎟

π 2
⎝ ⎝ 2L ⎠ ⎠ (6) For apple samples, the test was performed using a puncture probe of
5 mm diameter with a trigger force of 0.1 N and a test speed of 1.0 mm/
If the parameter over time, α, converges to a unit value, the Mittag- s and the maximal force attained at 50% of the distance of five dehy-
Leffler function converges to the exponential function. Thus, if the long drated slices (apple final height = 24 ± 1 mm) was obtained (Huang,
drying time conditions are met, Eq. (6) can be represented by Eq. (7) Zhang, Wang, Mujumdar, & Sun, 2012; Velickova, Winkelhausen, &
(Ramírez et al., 2017; Simpson et al., 2013, 2015, 2017): Kuzmanova, 2014). The test was conducted in triplicate. The mean
2 value of firmness for each treatment was then calculated and expressed
8 ⎛−Deff ( 2πL )
⎜ t α ⎞⎟
MRt = e⎝ ⎠ in N/mm.
π2 (7)

The α value indicates that the transport mechanism dominates the


2.6. Statistical analysis
mass transfer process. Then, if 0 < α < 1, the diffusion mechanisms
can be assumed to be sub-diffusive, while the mechanisms can be
Tests of the significance of the results were performed using an
considered to be super-diffusive for α > 1. If α converges to the unit
analysis of variance (ANOVA) and Duncan's multiple range tests with a
value, the anomalous diffusion model tends to Fick's second law.
significance of 95% using STATGRAPHIC Centurion XVI software
(Statistical Graphic Corporation, version 16.0.07, Rockville, MD, USA).
2.5. Quality attributes

2.5.1. Color change measurements (ΔE) 3. Results and discussion


Color parameters were measured using a colorimeter (Minolta, CR-
400 model, Tokyo, Japan) equipped with illuminant D65 and based on 3.1. Drying analysis of conventional and RW™
the CIELab color space after white standard calibration. ΔE was cal-
culated with the three CIELab parameters: lightness (L*), greenness- The drying curves for the control and pre-treated samples of the
redness (a*), and blueness-yellowness (b*). ΔE was obtained between three kinds of tissues dried using conventional and RW™ drying
the fresh and dried samples according to Eq. (8) (Gnanasekharan, methods and performed at 55 °C and 95 °C, are shown in Fig. 2A
Shewfelt, & Chinn, 1992). The color measurement was carried out when (salmon), Fig. 2B (beef), and Fig. 2C (apple).
the samples achieved a water activity below 0.6. As was expected for these three kinds of tissues, it was possible to
observe a significant difference in drying time when the drying tem-
ΔE = ΔL2 + Δa2 + Δb2 (8) perature was changed from 55 to 95 °C for both drying methods. For

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S. Franco et al. Innovative Food Science and Emerging Technologies 52 (2019) 8–16

Table 1
Effective diffusion coefficient obtained from Fick's second law for the conventional and RW™ drying processes used to dry control and pre-treated samples of salmon,
beef, and apple at 55 °C and 95 °C.
Drying temperature °C Conventional drying Refractance windows™

Control Pre-treated Control Pre-treated

Deff (10−10 m2/s) SSE R2 Deff (10−10 m2/s) SSE R2 Deff (10−10 m2/s) SSE R2 Deff (10−10 m2/s) SSE R2

Salmon tissue
55 1.37 ± 0.03a 0.011 0.958 1.64 ± 0.06a 0.0016 0.993 1.43 ± 0.04a 0.0042 0.971 1.24 ± 0.11a 0.006 0.999
95 3.54 ± 0.31b 0.003 0.980 3.58 ± 0.48b 0.006 0.978 2.96 ± 0.38c 0.008 0.981 3.09 ± 0.28b,c 0.006 0.997

Beef
55 1.50 ± 0.20a 0.013 0.963 1.82 ± 0.22a 0.006 0.962 1.25 ± 0.09a 0.0059 0.967 1.41 ± 0.04a 0.011 0.985
95 4.66 ± 0.56b 0.011 0.934 5.34 ± 0.12c 0.005 0.918 3.86 ± 0.14d 0.025 0.954 3.62 ± 0.43b 0.018 0.947

Apple tissue
55 0.61 ± 0.06a 0.039 0.987 0.77 ± 0.09a 0.054 0.960 2.65 ± 0.4a 0.01 0.987 1.25 ± 0.16a 0.004 0.999
95 4.57 ± 0.29b 0.017 0.973 7.32 ± 0.45c 0.003 0.991 14.3 ± 2.80d 0.002 0.954 14.06 ± 0.90d 0.007 0.987

Different superscripts in the same row and column indicate that the mean values differ significantly (p < 0.05).

example, a drying time of 21 h at 55 °C for the control and pre-treated drying time compared with conventional drying. For example, for RW™
samples was required to achieve an MR of 0.1 for both the conventional at 55 °C, the drying time required to achieve MR = 0.1 was 5 h, whereas
and RW™ drying of salmon tissue, whereas at 95 °C, the drying time was only 1 h was required at 95 °C.
close to 7 h for both methods. These results are in accordance with Based on the processing time required to get an aw value of 0.6,
other fish drying studies (Corzo & Bracho, 2007; Djendoubi et al., 2009; salmon slices dried by the conventional drying method required a
Jain & Pathare, 2007; Ortiz et al., 2013; Vega-Gálvez et al., 2011). processing time of 15 h at 55 °C, and 3 h for samples dried at 95 °C.
However, based on the drying curves obtained for the drying methods When the samples were dried by the RW™ method the processing time
at 55 and 95 °C, salmon tissue did not show an enhancement in the mass was 14 h at 55 °C, and 4 h at 95 °C. In the case of beef slices dried with
transfer rate between control and pre-treated samples, or in a com- the conventional method, the processing time was 17 h at 55 °C, and 5 h
parison of both the conventional and RW™ drying methods. at 95 °C, whereas the times for RW™ were 17 h at 55 °C, and 9 h at 95 °C.
The time for beef drying (Fig. 2B) varied when the temperature was The results demonstrate that for both salmon and beef, the time needed
increased from 55 to 95 °C. For example, conventional drying of control to get a water activity value of 0.6 was not reduced by using RW™.
and pre-treated samples at 55 °C required 12 h to achieve an MR of 0.1, For apple tissue, the process times for conventionally dried samples
whereas the drying time was reduced to 4 h for both the control and were 14 h at 55 °C and 3 h at 95 °C. The time required to attain an aw of
pre-treated samples at 95 °C. In the case of the RW™ there were not 0.6 using RW™, was however significantly lower, being 3 h at 55 °C and
differences with respect to the conventional drying method. Similar to 1.5 h at 95 °C. When the sample was pre-treated and dried at 95 °C, the
salmon tissue, the beef samples did not show an enhanced mass transfer time was reduced to 0.5 h.
between the control and pre-treated experiments or by using RW™. Previous studies have reported that the net isosteric heat at low
Previous studies have reported that there is no significant difference moisture levels increased up to 35 kJ mol−1 for apple tissue (Kaymak-
(p > 0.05) between the control and pre-treated samples in a cooking Ertekin & Gedik, 2004), whereas for fish and beef muscle it increased
loss test because the water loss that occurs during cooking corresponds up to 70–75 kJ mol−1 (Djendoubi et al., 2009; Hadrich, Boudhrioua, &
to constitutive water from melting fat during thermal treatment Kechaou, 2008; Iglesias & Chirife, 1976). Specifically, apple tissue re-
(Faridnia et al., 2015; Leygonie, Britz, & Hoffman, 2012; Vieira et al., quires half the amount of energy to remove water molecules that had
2009). Another key factor is treatment temperature. Temperature in- some form of interaction with the tissue, such as through dipole-dipole
duced protein denaturation modifies the isoelectric point of muscle or ion-dipole interactions (Fennema, Damodaran, & Parkin, 2017). In
(Delgado & Sun, 2002; Vieira et al., 2009) and causes shrinkage of the contrast, salmon and beef have highly polar or active sites that inhibit
muscle fibers (Hughes et al., 2014) affecting their water binding ca- water movement and its migration (Delgado & Sun, 2002; Iglesias &
pacity. Therefore, pre-treatment could damage beef tissue, but unlike Chirife, 1976).
the temperature used during drying this was not an important factor. Clearly, RW™ is a drying technique that is more suitable for vege-
Apple samples showed a significant increase in mass transfer when tables than for muscle-based foods such as fish and meat. The main
the samples were pre-treated or when RW™ was used. For example, for reason for this could be attributed to water content, which is higher in
the control and pre-treated samples conventionally dried at 55 °C, a apple (approximately 90%), whereas the water content in muscle-based
processing time of 12.5 h was needed to achieve an MR of 0.1, but only foods was 76% for salmon and 78% for meat.
3 h was required at 95 °C. In the case of pre-treated samples, the time
required at 55 °C was close to 12.5 h, and it was approximately 2 h at
95 °C. As observed in Fig. 2C, there were no significant differences in 3.2. Mathematical modeling of water diffusion in the conventional and
drying time between control and pre-treated samples when the drying RW™ drying processes
temperature was 55 °C; however, there were differences at 95 °C,
especially during the first 2 h of drying. Other workers such as Ramírez The effective diffusion coefficient (Deff) was obtained by fitting the
et al. (2011) have reported that freezing-thawing pre-treatment im- drying data for salmon, beef, and apple slices dried using either con-
proves the mass transfer rate, which was not observed in the present ventional drying or RW™ at 55 and 95 °C, to Fick's second law (Table 1).
work, and could be attributed to the conventional drying being per- According to the data in Table 1, Deff was increased as the temperature
formed in a convection oven in our study, whereas in the Ramirez study increased from 55 to 95 °C for both the control and pre-treated samples
it was performed in a hot-air drying tunnel, where the air current is an dried either conventionally or with RW™.
important factor during drying. The results obtained for apple tissue In general, the values of Deff ranged from between
dried with RW™ showed that that there was an important reduction in 0.61 × 10−10 m2/s for apple dried at 55 °C using the conventional
method, to 14.3 × 10−10 m2/s for apple dried at 95 °C using the RW™

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S. Franco et al. Innovative Food Science and Emerging Technologies 52 (2019) 8–16

Effective diffusion and time coefficients obtained from an anomalous model based on fractional calculus for the conventional and RW™ processes used to dry control and pre-treated samples of salmon, beef, and apple at
method. In more specific terms, the Deff for salmon ranged from be-

0.999
0.995

0.963
0.968

0.999
0.898
tween 1.37 × 10−10 and 3.58 × 10−10 m2/s, representing the values

R2
control samples using conventional drying at 55 °C and 95 °C, respec-

0.0002
0.0006

0.0001
0.0028
0.009
0.004
tively. For beef, the Deff ranged from between 1.25 and

SSE
5.34 × 10−10 m2/s, representing values for the control samples dried at
55 °C using RW™ and samples that were pre-treated and dried at 95 °C

0.73 ± 0.05

0.82 ± 0.10

0.74 ± 0.01
using a conventional method, respectively. The values obtained within
an order of magnitude of range reported in the literature for salmon and
beef drying (Ortiz et al., 2013; Trujillo et al., 2007). For apple, the
α

values ranged from 0.61 × 10−10 m2/s to 14.3 × 10−10 m2/s, re-
Deff (10−10 m2/sα)

14.97 ± 0.11e
1.86 ± 0.19d
3.98 ± 0.40b

2.04 ± 0.61a
5.06 ± 0.85c
presenting samples obtained using conventional drying at 55 °C and
1.93 ± 0.1a

RW™ at 95 °C, respectively. The Deff obtained are in concordance with


Pre-treated

those obtained by Ramírez et al. (2011, 2017) and Simpson et al.


(2015).
Focusing on the Deff values obtained using conventional drying, the
0.987
0.981

0.971
0.988

0.980
0.95

results showed that for salmon and beef, pre-treatment did not have a
R2

significant effect on Deff. However, for apple tissue, especially at 95 °C


(the Deff values for 55 °C increased from 0.61 to 0.77 × 10−10 m2/s,
0.004
0.003

0.017
0.005

0.003
0.003
SSE

which was not significant), there was a significant increase the Deff
comparing the control (4.75 × 10−10 m2/s) with the pre-treated sample
0.85 ± 0.14

0.57 ± 0.09

1.23 ± 0.40

(7.32 × 10−10 m2/s), which is in agreement with the literature. In the


case of pre-treatment, studies have been performed to determine the
effect of freezing on salmon tissue, and it has been reported that with a
Refractance windows™

slow freezing process over a range of −5 to −20 °C, ice crystals are
Deff (10−10 m2/sα)

mainly formed in the extracellular space and cannot rupture cell walls
15.30 ± 2.70e
3.83 ± 0.82b

2.88 ± 1.15d
1.95 ± 0.48a

2.59 ± 0.15a
4.98 ± 0.60c

(Alizadeh et al., 2007, 2009; Kaale & Eikevik, 2013). Another factor
that could affect mass transfer is the content and distribution of fat and
Control

oil, due to the energetic interactions that can occur between water
molecules and polar sites present in fats and oils (Alizadeh et al., 2009;
Djendoubi et al., 2009; Hadrich et al., 2008). Moreover, a freezing-
0.995
0.978

0.993
0.880

0.940
0.985

thawing pre-treatment produces a high degree of structural damage


R2

Different superscripts in the same row and column indicate that the mean values differ significantly (p < 0.05).

because apple tissue has a rigid cell wall, unlike salmon and beef muscle
0.002
0.002

0.045
0.006
0.0018
0.0033

which have an elastic structure and so the freezing-thawing effect is


SSE

minimized (Smith, 2011).


Analyzing the values of Deff obtained for RW™, the first thing that
1.04 ± 0.05

0.86 ± 0.03

1.34 ± 0.12

can be observed in Table 1 is that for both the salmon and beef samples,
the application of RW™ on control and pre-treated samples did result in
any significant changes compared with the Deff values obtained using
α

conventional drying. For example, at 95 °C, for the control salmon


Deff (10−10 m2/sα)

samples dried conventionally, the Deff was 3.54 × 10−10 m2/s, whereas
6.40 ± 0.30b
2.09 ± 0.08a

0.32 ± 0.10a
7.16 ± 0.73c
3.18 ± 0.1b
1.54 ± 0.1a

the Deff value was 3.09 × 10−10 m2/s for RW™ drying. However, in the
Pre-treated

case of apple dried by the RW™ method, the Deff values increased sig-
nificantly with respect to conventional drying. At the same temperature
of 95 °C, the Deff for the control apple sample dried conventionally was
0.61 × 10−10 m2/s, whereas this value increased to 14.3 × 10−10 m2/s
0.958
0.980

0.920
0.937

0.987
0.993

when the samples were dried using the RW™ method. Based on the data
R2

obtained for the control and pre-treated samples dried using RW™, we
0.010
0.003

0.013
0.006

0.006
0.001

can conclude that pre-treatment did not have a significant effect on


SSE

improving the mass rate transfer. This result could be attributed to the
0.89 ± 0.03

0.76 ± 0.13

1.86 ± 0.03

fact that for RW™, the main aspect that controls the drying process is
the water content rather than food structure. This can be a key aspect
when comparing Deff or drying times obtained from muscle tissues dried
under using the conventional method or samples dried using the RW™
α
Conventional drying

method; for both muscle tissues, the water content was below 0.8 g
Deff (10−10 m2/sα)

5.43 ± 0.01b,c
3.85 ± 0.41b

3.01 ± 0.27b
1.60 ± 0.10a

2.07 ± 0.68a

0.14 ± 0.02a

water/g of sample, and no significant differences were observed be-


tween the two drying methods.
In addition, Fick's second law was shown to be a good approxima-
Control

tion for the three tissues studied, salmon, beef meat, and apple, because
R2 was within a range of 0.918 to 0.999, as well as for control and pre-
Drying temperature °C

treated samples dried using either the conventional and RW™ methods
at 55 and 95 °C. However, our experience has demonstrated that in
55 °C and 95 °C.

order to improve data fitting and also to include a phenomenological


Salmon tissue
55
95

55
95

55
95
Apple tissue

description of the process, the anomalous diffusion model can provide a


more adequate representation of the drying process in food materials.
Table 2

Beef

Accordingly, the drying data for salmon, beef, and apple slices were
fitted to the anomalous diffusion model, and the effective diffusion

13
S. Franco et al. Innovative Food Science and Emerging Technologies 52 (2019) 8–16

coefficient (Deff) and α parameter were obtained and analyzed differences. For samples dehydrated using RW™, there were no sig-
(Table 2). nificant differences between the control and pre-treated samples at the
The results showed that in general, both salmon and beef tissues, same temperature. In general, the behavior of ΔE was similar for con-
dried using either the conventional or RW™ methods, had a sub-diffu- ventional drying and RW™ drying.
sive mechanism (α < 1) and tended to have Fickean behavior for the For the beef slices, the ΔE values were higher than those obtained
control and pre-treated samples. For example, for salmon samples dried for salmon tissue, showing a range of data of 20.41 ± 0.92 obtained
using the conventional method, the α value was 0.89 ± 0.03 for the for the control samples dehydrated at 95 °C using RW™ to
control and 1.04 ± 0.05 for the pre-treated samples (fractional order 27.06 ± 1.47 for samples dehydrated at 95 °C using the conventional
time was not significantly different of 1 with a 95% degree of con- method. For samples dehydrated using conventional drying, the main
fidence), which correspond to a sub-diffusive and Fickean mechanism, differences in color were obtained at 95 °C for the control and pre-
respectively. treated samples. In the case of the RW™ method, the control samples
In case of RW™, the α values were 0.85 ± 0.14 for the control and had a lower ΔE value than samples dried using conventional drying,
0.73 ± 0.05 for the pre-treated samples. This sub-diffusive behavior having ΔE values between 20.41 and 22.70. For the pre-treated sam-
could be explained by damage to the fish matrix, which produces a ples, the values were higher, being in the range of 24.39 to 25.81,
leakage of fat and oil that can affect water mobility due to an energetic which could be caused by the structural damage that facilitates he-
interaction (Alizadeh et al., 2009; Djendoubi et al., 2009). moglobin oxidation and browning. It is worth noting that the lowest ΔE
In the case beef samples dried using either the conventional or RW™ values were obtained in samples dehydrated using RW™, which could
methods, the behavior of the diffusive mechanism was similar to that be considered to be an advantage for this drying technology.
obtained for salmon slices. The α values was approximately For apples, the drying process performed using RW™ clearly showed
0.57 ± 0.09 for the control samples dried using RW™ and 0.86 ± 0.03 a better result in terms of ΔE when compared with the conventional
for the pre-treated samples dried using conventional drying. drying process, especially at 95 °C. For example, for the RW™ method
Apple tissue, unlike the salmon and beef samples, showed a super- the ΔE values were not significantly different at 55 or 95 °C, with values
diffusive mechanism, but in some cases also had clear Fickean behavior. of ΔE of 14.60 ± 1.52 and 14.84 ± 0.98, respectively. For the pre-
For example, for conventional drying, the control samples had an α treated samples, the values of ΔE were higher, but not significantly
value of 1.86 ± 0.03, which is similar to the value reported by different at both temperatures. For the conventional drying method,
Simpson et al. (2015) for osmotic dehydration. In contrast, the pre- both the temperature and pre-treatment were determinant for the ΔE
treated samples had an α value of 1.34 ± 0.12. For the pre-treated values, being higher when the temperature was increased, and when
samples, the lowest value of α could be explained by damage to the the samples were pre-treated.
apple cell walls, changing their microstructure and turning the diffusion The results obtained are in accordance with other investigations
mechanism close to Fickean behavior instead of anomalous diffusion examining drying using the RW™ method, because this technique al-
(Simpson et al., 2015). For RW™, it was shown that the mechanism was lows for the dehydration of fruits at temperatures higher than 55 °C,
super diffusive for the control samples (α = 1.23 ± 0.4), and sub-dif- over a short period of time, with the same damage or impact on the
fusive for the pre-treated samples (α = 0.74 ± 0.01), which could be final quality at different temperature levels (Abonyi et al., 2002;
explained by microstructural changes in the sample due to pre-treat- Caparino et al., 2012; Nindo & Tang, 2007; Pavan et al., 2012).
ment.
3.3.2. Firmness
3.3. Quality of salmon, beef, and apple dehydrated using the conventional Firmness (N/mm) values obtained from the puncture test for control
and RW™ methods and pre-treated salmon, beef, and apple slices are shown in Table 4. The
results showed that in general firmness was highly dependent on the
3.3.1. Color change (ΔE) kind of sample and the drying method. For example, for salmon tissue,
The ΔE values for the control and pre-treated salmon, beef, and the range of firmness was from 0.08 N/mm for pre-treated samples
apple samples dehydrated at 55 °C and 95 °C using the conventional and dehydrated at 95 °C using RW™ to 0.38 N/mm for samples con-
RW™ methods, are presented in Table 3. For salmon slices, the data ventionally dehydrated at 55 °C. Based on Table 4, the higher firmness
showed that for the conventional drying process, ΔE was not sig- values were obtained in conventionally dehydrated samples, whereas
nificantly affected by pre-treatment at the same temperature. For ex- for RW™, the firmness values were lower, which could be related to the
ample, at 55 °C, ΔE was 14.85 ± 1.99 for the control and fact that the samples were observed to be more brittle following de-
16.45 ± 2.36 for the pre-treated sample. However, the temperature hydration with RW™ compared with conventional drying. Additionally,
had a significant effect on ΔE, especially for the control samples. For at the highest temperature a large muscle separation around the con-
example, for the control samples, ΔE was increased from 14.85 ± 1.99 nective tissue was observed which reduced the penetration force. For
to 17.45 ± 2.33 when the temperature increased from 55 to 95 °C. In example, for the control samples dried using conventional drying, the
the case of the pre-treated samples, ΔE did not show any significant firmness was 0.38 N/mm, and 0.29 N/mm when the samples were

Table 3
Color changes obtained for control and pre-treated samples of salmon, beef, and apple, dried at 55 °C and 95 °C using conventional and RW™ drying processes.
Color change, ΔE

Conventional drying Refractance Window™

Sample Temperature Control Pre-treated Control Pre-treated

Salmon 55 14.85 ± 1.99a 16.45 ± 2.36b 12.40 ± 1.51c 16.40 ± 1.99b


95 17.45 ± 2.33b 16.95 ± 2.98b 17.33 ± 2.09b 15.88 ± 1.38a,b
Beef 55 26.24 ± 1.33a 21.45 ± 1.88b 22.70 ± 1.40b 25.81 ± 1.11c,d
95 27.06 ± 1.47a 26.12 ± 1.82a,d 20.41 ± 0.92b 24.39 ± 1.92c
Apple 55 14.18 ± 1.91a 22.82 ± 1.63b 14.60 ± 1.52b 19.87 ± 0.87a,c
95 17.12 ± 1.43a 30.36 ± 1.96a 14.84 ± 0.98b 22.27 ± 1.38c

Different superscripts in the same row and column indicate that the mean values differ significantly (p < 0.05).

14
S. Franco et al. Innovative Food Science and Emerging Technologies 52 (2019) 8–16

Table 4
Firmness obtained from a puncture test for control and pre-treated samples of salmon, beef, and apple, dried at 55 °C and 95 °C using conventional and RW™ drying
processes.
Firmness, N/mm

Conventional drying Refractance Window™

Sample Temperature Control Pre-treated Control Pre-treated

a c,i,k e,l
Salmon 55 0.38 ± 0.05 0.26 ± 0.01 0.14 ± 0.02 0.14 ± 0.03g,l
95 0.29 ± 0.01b,i 0.21 ± 0.05d 0.28 ± 0.02f,j 0.08 ± 0.01h
Beef 55 3.27 ± 0.33a 4.12 ± 0.36a 1.70 ± 0.28b 3.80 ± 0.60a
95 4.09 ± 0.06a 3.95 ± 0.06a 7.37 ± 0.57c 7.06 ± 0.46c
Apple 55 0.59 ± 0.01a 0.83 ± 0.06c,h 0.15 ± 0.05e,i 0.47 ± 0.09a,b
95 0.40 ± 0.02b 0.92 ± 0.09d,h 0.19 ± 0.05f,i,j 0.29 ± 0.01g,b,h

Different superscripts in the same row and column indicate that the mean values differ significantly (p < 0.05).

dehydrated at 55 and 95 °C, respectively. For the control samples de- Acknowledgements
hydrated using the RW™ method at 55 °C, the firmness was 0.14 N/mm,
whereas at 95 °C the penetration force increased to 0.21 N/mm. The The authors are grateful for the financial support provided by
difference in this case is due to the presence of connective tissue, which CONICYT through FONDECYT project nos. 1181270 (Ricardo Simpson)
in some cases facilitates probe movement through the sample. and 1160811 (Cristian Ramírez). Also, author Sebastián Franco is
For the beef slices, firmness values (1.70 to 7.37 N/mm) were higher grateful for the financial support provided by Programa de Incentivo a la
than those of salmon or apple tissues. Visually, the beef slices appeared iniciación Científica (PIIC) de la Dirección de Postgrado y Programas de la
to be more intact and had muscle cohesion. As shown in Table 4, the Universidad Técnica Federico Santa María.
firmness values for the control and pre-treated samples dried using
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