Journal of Food Composition and Analysis 98 (2021) 103804

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Journal of Food Composition and Analysis

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

Original Research Article

Chemical characterization of tequila maturation process and their

connection with the physicochemical properties of the cask
Walter M. Warren-Vega a, Rocío Fonseca-Aguiñaga b, Linda V. González-Gutiérrez c,
Francisco Carrasco-Marín d, Ana I. Zárate-Guzmán a, Luis A. Romero-Cano a, *
a
Grupo de Investigación en Materiales y Fenómenos de Superficie, Facultad de Ciencias Químicas, Universidad Autónoma de Guadalajara, Av. Patria 1201, C.P. 45129,
Zapopan, Jalisco, Mexico
b
Laboratorio de Isotopía, Consejo Regulador del Tequila A. C., Av. Patria 723, C.P. 45030, Zapopan, Jalisco, Mexico
c
Centro de Investigación y Desarrollo Tecnológico en Electroquímica (CIDETEQ) S.C., Parque Tecnológico Sanfandila, Pedro Escobedo, Querétaro, 760703, Mexico
d
Grupo de Investigación en Materiales de Carbón, Facultad de Ciencias, Universidad de Granada, Av. Fuente Nueva s/n, Granada, C.P. 18071, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: The effect of time in the maturation process of Tequila employing two types of casks was studied: A new (labeled
Tequila maturation as Cask-New) and a medium-toasted cask (15 min at 200 ◦ C) (labeled as Cask-MT). For that purpose, the wood
Kinetic models used in the casks was characterized physicochemically, and its properties were contrasted with the physico­
Polyphenols extraction
chemical characterization of the beverage throughout the maturation time. To understand the kinetic maturation
Thermic treatment
Physicochemical characterization of casks
process, mathematical models were used. The best model that represented the polyphenol (I280) and flavonoid
(I365) extraction was proposed by Minchev & Minkov. The extraction rate constants were: kcask-new,I280 = 0.233
month− 1 vs. kCask-MT,I280 = 0.560 month− 1, and kcask-new,I365 = 0.132 month-1 vs. kCask-MT,I365 = 0.383 month− 1,
explaining that the extraction process is slower in Cask-MT due to textural characteristics of casks, mainly related
to the thermic treatment used in the toasting stage, which collapses the mesoporous structure having mass
transfer limitations. The results obtained allow a better description of the maturation process, a fundamental step
from a food engineering standpoint. The next step in the research should be to validate the proposed model to
improve the final product quality.

1. Introduction (aged): A product which may be enhanced by mellowing, subject to an

According to the Mexican Official regulation NOM-006-SCFI-2012
(Diario Oficial de la Federación, 2012), Tequila is an alcoholic
beverage obtained from the heads of Agave tequilana Weber blue variety.
Two categories of Tequila exist: i) Tequila 100 % agave, which uses 100
% sugars from the Agave tequilana Weber blue variety, and ii) Tequila,
which corresponds to an alcoholic beverage in which 51 % of the sugars
are from the Agave tequilana Weber blue variety, and 49 % of the sugars
come from another source. Likewise, according to the characteristics
acquired in the maturation process, Tequila can be classified into five
classes: i) "Blanco" (Silver): Transparent product not necessary colorless,
without additives, obtained through distillation, whose commercial
alcohol content must be adjusted by dilution with water; ii) "Joven/Oro"
(Gold): Product that results from blending silver Tequila with additives
permitted by the official standard or from the mix of silver Tequila with
aged and/or extra-aged and/or ultra-aged Tequilas; iii) "Reposado"
aging process of at least two months in direct contact with an oak wood
cask; iv) "Añejo" (Extra-aged): Product which may be enhanced by
mellowing in the aging process at least one year in wood or oak re­
cipients with V ≤ 600 L; v) "Extra añejo" (Ultra aged): Product which may
be enhanced by mellowing in the aging process at least three years in
wood or oak recipients with V ≤ 600 L.
The maturation process involves a few physicochemical changes that
substantially impact the aroma, taste, structure, and stability profiles,
affecting the balance of the final product (Ayala-Magdaleno, 2019).
Tequila changes occur during the maturation process as a result of: (1)
Reduction of higher alcohols due to the carbon present in the wood
casks, that act as an adsorbent agent, smoothing the final product; (2)
Extraction of complex compounds from the wood, giving a particular
color and taste; (3) Reactions between some substances present in Te­
quila, resulting in new components; and (4) Oxidation of chemical
compounds present in Tequila and those extracted from the wood

* Corresponding author.
E-mail address: luis.cano@edu.uag.mx (L.A. Romero-Cano).

https://doi.org/10.1016/j.jfca.2021.103804
Received 27 August 2020; Received in revised form 29 December 2020; Accepted 4 January 2021
Available online 13 January 2021
0889-1575/© 2021 Elsevier Inc. All rights reserved.
W.M. Warren-Vega et al.
(Cedeño, 1995).
Although there is information that helps to understand the matura­
tion mechanism of different alcoholic beverages, such as some research
works for fruit brandies and different red wines (Dippong et al., 2020,
2019), there is still no scientific information that describes the phe­
nomenon of Aged Tequila. Until now, most of the studies published
focus on the characterization of the final product, showing a decrease in
the concentration of higher alcohols and an increase of acids, esters, and
aldehydes (Cedeño Cruz and Alvarez-Jacobs, 1999). Also, the effects of
volatile compounds have been evaluated (López-Ramírez et al., 2013),
and the impact of white oak casks (regenerated and recycled) on the
sensory properties of the final product has even been studied (Agui­
lar-Méndez et al., 2017). In the maturation process, close attention has
been given to study the impact of active compounds and its concentra­
tions in the aroma of Tequila (González-Robles and Cook, 2016), as well
as an analysis in the profile of minor volatile compounds along the
maturation process of Tequila in new oak casks (Martín-del-Campo
et al., 2019). However, at the moment, there are no published studies
that show the effect of the physicochemical properties of the barrels
used (texture and surface chemistry) with time in the maturation pro­
cess. During this process, there are critical stages that must be estab­
lished based on the physicochemical parameters that the beverage
acquires, such as tonality, color, and changes in the isotopic ratios of
carbon 13 and oxygen 18 due to the migration of aromatic compounds
present in the cask used during the process, as it has been studied for
other types of spirits (Coelho et al., 2021; Vivas et al., 2020). A strategy
to study and understand these phenomena is based on kinetic mathe­
matic models; once the models are established, the optimization, design,
simulation, and control of industrial projects is simplified, contributing
to better use of time and energy (Amendola et al., 2010; Sant’Anna et al.,
2012).
The present study aims to present a rigorous evaluation of kinetic
models to describe the extraction of polyphenols and flavonoids through
the tequila maturation process to determine the best model that repre­
sents the extraction of these components in casks. Besides, the results
obtained were contrasted with the physicochemical characterization of
the casks to determine the critical stages of the maturation process.
2. Materials and methods
2.1. Samples
A batch of Silver Tequila (100 % agave, 55 % ethanol v/v) from the
Cienega, Jalisco-Mexico, was used. The maturation process was carried
out in French oak casks (230 L) in the company’s warehouse (temper­
ature ≈ 18 ± 5 ◦ C, relative humidity ≈ 50 ± 5%, and darkness). A first
sub-sample was placed in two casks without any treatment, which was
labeled as Cask-New. A second sub-sample was placed in two casks,
which received a medium toast at 200 ◦ C for 15 min labeled as Cask-MT.
All the studies carried out in this investigation were verified by Consejo
Regulador de Tequila A. C. (CRT, for its acronym in Spanish) to ensure
the authenticity of the beverage.
The sampling was carried out every four weeks for 12 months. The
collection and sampling were carried out in collaboration with the CRT
through its isotopic laboratory. To guarantee the sample’s representa­
tiveness, qualified personnel carried out sampling following the NOM-
006-SCFI-2012 Standard (Diario Oficial de la Federación, 2012). The
samples analyzed were made up of equal portions, extracted from each
cask, so that a total volume of approximately 3 L was obtained.
Before starting the maturation process, an initial sample of the Silver
Tequila was taken as a control to be considered as an initial time (t = 0).
All samples were analyzed in triplicate, mean and standard deviations
were reported.
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Journal of Food Composition and Analysis 98 (2021) 103804
2.2. Physicochemical characterization of the wood casks
Once the tequila maturation process was completed, small wood
samples were obtained from the casks used. These were obtained from
two different areas with which the Tequila had contact. The samples
obtained were pulverized and homogenized to obtain a representative
sample useful for the casks’ physicochemical characterization.
The specific surface area (SBET) of the woods used in the casks con­
struction was studied by obtaining the nitrogen adsorption-desorption
isotherms at − 196 ◦ C in a QUADRASORB-SI (Quantachrome Ins). For
this, approximately 0.1 g of sample was introduced into a 9 mm bulb and
degassed under high vacuum (10− 6 bar) at 110 ◦ C for 12 h. Subse­
quently, the isotherms were obtained using nitrogen (99.999 %) sup­
plied by Air Liquide (Paris, France).
Morphology and elemental analysis of the materials were studied by
Scanning Electron Microscopy coupled with Energy Dispersive X-Ray
(SEM-EDAX) employing a microscope JEOL model JSM-6510LEDS.
High-resolution images were obtained in SEI mode (Secondary Electron
Image) working at 15 kV with a working distance of WD8mm.
Additionally, functional groups present in the cask woods were
studied, obtaining the FTIR spectrum of the materials at the region
4000− 400 cm− 1 using a spectrophotometer Thermo Scientific, Nicolet,
iS5 FT-IR equipped with an ATR module.
The surface chemistry of the woods was investigated by X-ray
photoelectron spectroscopy (XPS) (ESCA 5701 of Physical Electronics).
The experimental data was obtained with a monochromatic Kα X-ray
source (1486.71 eV) working at 150 W, 15 kV, and 10 mA and a base
pressure of 3 × 10− 8 Torr in the analytical chamber. For the wide scan
spectra, an energy range of 0− 1100 eV with step energy of 80 eV and a
step size of 1 eV was used. Once the peaks were examined, high-
resolution scans were performed with step energy of 40 eV and a step
size of 0.05 eV. Each spectral region of interest was scanned several
times to achieve good signal-to-noise ratios. In order to obtain the
number of components, the position of each peak, peak areas, and the
resultant spectra after background signal correction were fitted to the
Lorentz and Gauss curves (Voigt profile). Peak assignments were made
according to the literature.
2.3. Physicochemical characterization of Tequila
2.3.1. Alcoholic content
Alcoholic content expressed as % ethanol (v/v) at 20 ◦ C was
measured by a densitometer DMA-48 (Anton Paar) in samples obtained
directly from casks.
2.3.2. Determination of the isotopic ratios of carbon 13 (δ13C) and oxygen
18 (δ18O)
The sample preparation consisted of a distillation process described
in the OIV-OENO-426-2011 in Automatic Distillation Control System
(ADCS). The distillation consisted of collecting the distillate of the
ethanol-water azeotrope (78 ◦ C) in an automatic system with a Cadiot
column. The ethanol-water azeotrope is completely recovered, the
alcohol content for distillate must be >92 % m/m, and the distillation
yield must be higher than 96 % to avoid the isotope fractionation. After,
the alcohol obtained was analyzed by GC/C/IRMS for the isotopic ratio
of carbon (δ13C) and GC/HTC/IRMS for the isotopic ratio of oxygen
(δ18O). To determine the isotopic ratios, a gas chromatograph (Thermo
Scientific, model Trace 1310) was used; after the chromatographic
separation, the samples were introduced in a mass spectrometer with
isotopic ratios (Thermo Scientific, Model Delta V Plus). The operating
conditions of the GC/C/IRMS and GC/HTC/IRMS are presented in the
supplementary material (Table Sup.1). All samples were analyzed in
triplicate. The methodology described above has been previously re­
ported in detail (Fonseca-Aguiñaga et al., 2020).
W.M. Warren-Vega et al. Journal of Food Composition and Analysis 98 (2021) 103804

Table 1 UV–vis spectroscopy. This information was used to evaluate the

Mathematical models tested to predict tequila maturation kinetics. extraction kinetics during maturation and obtain a mathematical model
Model Equation Kinetic parameters References that describes the process. The determination of I280 was obtained from
the measurement of absorbance at 280 nm because this is attributable to
Weibull- C = C0 exp⁡ (kt ) n C, is the concentration at (Amendola
type determinate time t, C0 is et al., 2010) the characteristic benzene nucleus that all polyphenols compounds have
the concentration a t = 0, (Zamora, 2003). The I365 was obtained from the absorbance measure­
k is the constant of ment at 365 nm (Andrés-Lacueva et al., 1997), which corresponds to the
velocity and n is order of band I of flavonoids in the B ring.
reaction.
Two-rate C = a[1 − exp(− bt) (Cacace and
Mathematic models that have been applied in recent research are
Ct∞ is the concentration of
] + c[1 − exp(− dt)] equilibrium extract, Cd∞ is Mazza, Weibull-type, two rates, Swelling/diffusion, Sorption/desorption, Min­
the concentration of the 2003) chev & Minkov (Table 1). The mathematical considerations on which
extract in equilibrium due the proposed kinetic models are based are presented in the Supple­
to diffusion, kd is the mentary Material.
kinetic constant due to
The maturation kinetics were studied by fitting the experimental
diffusion mechanism.
data to the mathematical models previously described. Statistical anal­
Swelling/ Ct∞ t Ct∞ is the concentration of (Linares
diffusion
C =
t1/2 + t
+
equilibrium extract, Cd∞ is et al., 2010) ysis was performed using the STATISTICA 10 software (StatSoft, USA)
Model Cd∞ [1 − exp(− kd t)] the concentration of the through a non-linear regression test using the Levenberg-Marquard
extract in equilibrium due method. All correlations were established at least at a 95 % signifi­
to diffusion, kd is the cance level (p < 0.05).
kinetic constant due to
diffusion mechanism.
t
2.3.5. Chromatographic analysis
Sorption/ K1 and K2 correspond to (Peleg,
C = The determination of aldehydes, methanol, esters, and higher alco­
desorption K1 + K2 t the constants of velocity 1988)
related to the extraction hols was carried out by the chromatographic method shown by the
process. official Mexican standard NMX-V-005-NORMEX-2013 (Diario Oficial de
Minchev & C = α − βexp(− kt) α is the saturation (Balyan la Federación, 2013). Briefly, gas chromatographic analyses were car­
Minkov concentration, β is a et al., 2019)
constant of the model y k
ried out using a gas chromatograph Agilent 7890 (Agilent Technologies,
is the constant rate. USA) equipped with a flame ionization detector. The column used was
an Agilent J&W DB-WAX UI (30 m x0.25 mm, 0.25 μm). The chro­
matographic conditions were as follows: 40 ◦ C for 4 min, increased at 5
2.3.3. FTIR and UV–vis analysis ◦
C/min to 100 ◦ C, then 10 ◦ C/min to 220 ◦ C, and maintained at this
To carry out FTIR and UV–vis analyzes, samples obtained directly temperature until a 10 min run was completed. A sample volume of 0.5
from the casks without any type of pre-treatment were used. FTIR μL was automatically injected using helium as carrier gas at a flow rate
spectrum of the beverages was taken at the region 4000− 400 cm− 1 of 0.7 mL min− 1. Injector and detector temperatures were maintained at
using a spectrophotometer Thermo Scientific, Nicolet, iS5 FT-IR equipped 220 ◦ C and 250 ◦ C, respectively.
with an ATR module. Additionally, UV–vis spectra were collected using Quantitative data were obtained by interpolating peak areas using
a spectrophotometer UV-1800 SHIMADZU. Absorbance data were calibration plots built from the analysis of solutions containing a known
collected at 0.1 nm intervals between 200 and 800 nm. For all cases, the amount of the analytes mentioned above.
spectrophotometric analysis was referenced against a solution of 55 %
vol. ethanol: water. 3. Results and discussion
According to this, from the UV–vis spectroscopy, it is possible to
determine the changes that Tequila undergoes during the maturation 3.1. Physicochemical characterization of casks
process; in order to study this process, the next parameters were deter­
mined: i) color intensity, ii) tonality, and iii) the percentage of yellow Elemental analysis of the casks was realized by energy-dispersive X-
color. The calculations were according to the methodology proposed by ray spectroscopy (EDX); results obtained are shown in Table 2. The main
Glories (1984), from the following equations: elements are oxygen and carbon; due to lignocellulose, polyphenols, and
Color intensity = Abs(420 nm) + Abs(520 nm) + Abs(620 nm) (1) flavonoids present in the wood, traces of aluminum and nitrogen
attributable to the materials’ origins can be observed too. Besides, it is
Tonality = Abs(420 nm) /Abs(520 nm) (2) important to highlight the presence of copper in the samples, maybe
because wood can act as an adsorbent material retaining this metal,
yellow color (%) = (Abs(420 nm) /Color intensity) × 100 (3) which is present in the beverage due to the use of copper stills during the
distillation process (Casas, 2006; Christoph and Bauer-Christoph, 2007).
2.3.4. Mathematical models tested to describe maturation kinetics Therefore, the high concentration of oxygenated groups in the cask
Tequila is a complex hydroalcoholic mixture. Different studies have wood act as binding sites (Sciban and Klasnja, 2004; Šćiban and Klašnja,
identified more than 30 phenolic compounds present in the beverage, as 2004), reducing the presence of this metal in the final product. Finally,
well as a large number of flavonoids, which increase in concentration the slight increase in the percentage of oxygen in the Cask-MT sample
during the maturation process. A strategy to evaluate all these compo­ can be attributed to the thermal treatment since it has been carried out
nents present throughout the process is by determining the Total Poly­ in an oxidizing atmosphere (air).
phenol Index (I280) and the Total Flavonoid Index (I365) employing Fig. 1a shows the SEM micrographs of cask wood samples used in this

Table 2
Physicochemical and textural characterization of the woods (casks used).
Samples C O N Cu Al SBET Vmeso V0.95
weight % weight % weight % weight % weight % m2 g− 1
cm3 g− 1
cm3 g− 1

Cask-New 53.95 40.98 3.25 1.33 0.49 1.83 0.0030 0.0032

Cask-MT 51.95 45.33 1.72 1.18 0.02 0.81 0.0012 0.0014

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W.M. Warren-Vega et al. Journal of Food Composition and Analysis 98 (2021) 103804

Fig. 1. a) SEM micrographs of the holes and a tangential section of the woods used: 1) and 2) Cask-New, 3 y 4) Cask-MT; b) FTIR spectrums of: ∆Cask-New,
Cask-MT.

Fig. 2. Deconvolution of high-resolution XP spectra corresponding to: a) C1s region Cask-MT b) O1s region Cask-MT c) C1s region of Cask-New d) O1s region
Cask-New.

study. For Cask-New (images a1 and a2), a typical wood characteristic in

its structure is observed, has hollow spaces inside the individual’s fibers Table 3
Binding energies (eV) of the regions C1s and O1s of woods used in the con­
that are interconnected between them (Fromm et al., 2003; Vasubabua
struction of casks.
et al., 2016). Instead, Cask-MT (images a3 and a4) show morphological
alterations caused by the thermic treatment during the toasting process Samples C1s eV Peak % %C O1s eV Peak % %O O/C ratio

because the wood’s existing channels are contracted. In order to study 284.51 43 531.60 7 30
the porosity of the materials, nitrogen physisorption analysis was per­ Cask-New
286.25 51
70
532.71 93
0.3185
287.95 4
formed at − 196 ◦ C to obtain BET surface area (SBET), mesoporous vol­
289.16 2
ume (Vmeso), and total pore volume (V0.95) shown in Table 1. Through 284.51 47 531.60 10 28
these results, it is possible to quantify the morphological alterations of 286.12 45 532.71 90
Cask-MT 72 0.2860
the materials; it can be observed that wood of Cask-New presents SBET = 287.75 5
1.83 m2 g− 1, and for Cask-MT, this value is reduced by half after the 289.05 3

thermic treatment SBET = 0.81 m2 g-1, which can be associated to the

contraction of channels, reduced exactly in the same proportion (Vmeso,
3 -1 3 -1
Cask-New = 0.0032 cm g vs. Vmeso, Cask-MT = 0.0014 cm g ).
Characterization of functional groups present in the woods was

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W.M. Warren-Vega et al. Journal of Food Composition and Analysis 98 (2021) 103804

Fig. 3. Isotopic ratios: a) δ13CVPDB and b) δ18OVSMOW for the samples: Cask-New, Cask-MT.

realized by infrared spectroscopy. FTIR spectrums are shown in Fig. 1b. treatment of the wood of Cask-MT and it can be associated with the
Both casks have the appearance of the same bands; in the regions of evaporation of volatile compounds initially present in the wood or the
1800 to 900 cm− 1, 1592 to 1260 cm− 1, 1056 to 1030 cm-1, and 897 formation of volatile byproducts due to thermic degradation.
cm− 1, which are representative of lignin and cellulose present in the It is important to highlight that the characterization by XPS is a
samples. Likewise, there is a signal at 1457 cm− 1 related to the defor­ surface technique (around 3 nm deep); due to these, the %O values are
mation of C–H bonds in the pyran ring, which is found because of the different from those obtained by EDX (0.5–1 μm deep).
polyphenols and flavonoids (Traoré et al., 2016).
Finally, the characterization of surface chemistry was investigated
3.2. Physicochemical characterization of tequila samples
using X-ray photoelectron spectroscopy (XPS). Fig. 2 and Table 3 exhibit
the results obtained after the deconvolution of spectrums in high reso­
The results obtain for the determination of δ13C and δ18O are shown
lution corresponding to C1s and O1s regions. Deconvolution of spectrums
in Fig. 3. From δ13C results, it is possible to determine the type of plant
in C1s region was realized, separating it into four components: C1, C2, C3,
used as a sugar source during the fermentation step. According to Puente
and C4, according to previous studies for lignocellulosic materials
et al. (2004) depending on the photosynthetic process to fix atmospheric
(Kamdem et al., 1991; Nguila-Inariet al., 2006; Nzokou and Kamdem,
CO2, plants are classified into three groups: i) C3 plants that use the
2005). C1 peak is centered at 284.51 eV, corresponding to C–C asnd/or
Calvin cycle, whose values of δ13C have been reported in a range of -22
CH– bonds in reason of lignin and wood extracts. C2 peak localized at
to -33‰; ii) C4 plants, that follow the Hatch Slack cycle, whose values of
286.12 ± 0.13 eV, attributed to C–O bonds no carbonyl groups, derived
δ13C are within a range of -10 to -20‰; iii) CAM plants (Crassulacean
from cellulose. C3 peak at 287.75 ± 0.2 eV represents C– – O or OCO––.
Acid Metabolism) which have a δ13C in a range of -12 to -30‰, of this
Finally, the C4 peak at 289.05 ± 0.11 eV corresponds to O–CO– – bonds.
group, the species that fix CO2 at night stand out, which have a carbon
In the case of region O1s, it was deconvoluted into two peaks centered at
delta close to 13‰ very similar to the experimental results obtained in
531.60 y 532.71 eV (Kamdem et al., 1991; Nguila-Inari et al., 2006;
the range between -12.0 to 13.5 ‰, these values can be related to the
Nzokou and Kamdem, 2005). The first peak is assigned to C– – O bonds,
species of Agave tequilana Weber blue variety used in the process of
while the second one is for C–O bonds. Previously, it has been reported
sugar’s fermentation (Aguilar-Cisneros et al., 2002; Fonseca-Aguiñaga
that the first peak can be attributed to lignin and its extracts, while the
et al., 2020).
second peak is related to cellulose and hemicellulose in the structure of
On the other hand, results of δ18OVSMOW analysis are in the range
the wood (Kamdem et al., 1991; Nguila-Inari et al., 2006; Nzokou and
+23.6 to +24.7‰ (average = +24.17‰) for the Cask-New and +22.13
Kamdem, 2005).
to +24.34‰ (average = +23.13‰) for the Cask-MT. These values are
Mathematic analysis of the XPS study shows more contribution in C1
higher and positive than the ones previously reported for tequila silver
and C2 peaks, and O/C relation of approximately 0.3, which explain that
class 100 % agave, which are between +14.0 to +26.0 % (average =
woods are essentially composed of lignin (Johansson, 2002; Nguila-Inari
+21.1‰) in 2018 (Fonseca-Aguiñaga et al., 2020). This isotopic
et al., 2006). According to this, it is concluded that molecules with C–C
δ18OVSMOW enrichment can be explained by the oxidation reactions that
and CO– bonds are the most abundant on the material’s external sur­
the beverage undergoes during the maturation process. During the
face. The analysis indicates that C1 peak increase concerning the
maturation, ethanol is oxidized, forming acetaldehyde, which begins to
reduction of O/C ratio (≈10 %), which is clearly related to the thermic
accumulate in the beverage, triggering polyphenol oxidation such as

Fig. 4. a) FTIR spectra, and b) UV–vis spectra for the samples: time zero (silver Tequila), 12 months Cask-New, 12 months Cask-MT.

5
W.M. Warren-Vega et al.
Fig. 5. UV–vis characterization of 12 months maturation kinetics of Tequila: a) Color intensity, b) Tonality, c) Yellow color (%); and d) Alcoholic content. Samples:
Cask-New, Cask-MT.
anthocyanins and flavonoids affecting color and aroma (Oliveira et al.,
2011). After that, the acetaldehyde is oxidized to form acetic acid which
it combines with ethanol to form ethyl acetate (Miller, 2019).
The results obtained by FTIR are shown in Fig. 4. All the spectra
obtained showed the same behavior. As proof of this, Fig. 4a shows the
FTIR spectra for t = 0 and t = 12 months. Three characteristics signals
that determine the presence of ethanol were observed: 2990 cm− 1, 1100
cm-1, and 850 cm− 1, attributable to stretching of C–H, CO– bonds and
vibration of O–H bond respectively (Debebe et al., 2017); also, there is
a wide signal in the 3500 to 3200 cm− 1 range, attributable to the vi­
bration of the O–H bond that may be due to water, alcohols and/or
phenolic compounds present in Tequila. It is also important to highlight
the absorption band at 1640 cm− 1, which is due to the stretching of C– –C
bonds corresponding mainly to aromatic compounds (flavonoids)
(Basalekou et al., 2017). Besides, there is an extension in the region 1200
to 950 cm− 1 attributable to ketones, esters, and alcohols. From this
analysis, a characterization of the beverage’s matrix was made; how­
ever, significative changes were not observed with respect to maturation
time. To strengthen the beverage characterization, ultraviolet-visible
spectroscopy studies were carried out to determine organic com­
pounds that impact on its physicochemical profile.
Fig. 6. 12 months maturation kinetics study of Tequila using UV–vis spectroscopy employing a) Cask-New b) Cask-MT.
6
Journal of Food Composition and Analysis 98 (2021) 103804
Fig. 4b shows the UV–vis spectra of the sample at t = 0 and t = 12
months. A signal at 280 nm was observed in the samples, and it is about
the characteristic benzene nucleus of all polyphenolic compounds
(Zamora, 2003). There is an absorbance increment in the region of
320–420 nm for all samples that have been in contact with the wood of
the cask; in this region two important bands can be distinguished, the
first one, from 320 to 360 nm, is related to the hydroxycinnamic acid
and flavonol groups, the second, at 420 nm, is attributed to anthocya­
nins. These compounds are extracted from the casks during the process
(Luis Aleixandre-Tudo and du Toit, 2019).
The results for color intensity, tonality, and yellow color (%) are
shown in Fig. 5. For both casks studied, there is a drastic increase in the
beverage tonality during the maturation process since the first month.
From the sixth month, the parameters stabilized (Fig. 5a, b, and c),
which explain that color is related to free species, like flavonoids, that
are now in contact with the Tequila, additionally, due to the high con­
centrations of oxygen there is a promotion of oxidation in molecules
generating an increase in color, which is reflected in the tonality and
percentage of the characteristic yellow color (Gambuti et al., 2018;
Glories, 1984). Finally, Fig. 5d shows the evolution of alcoholic
beverage content during the maturation process, noting that there are no
W.M. Warren-Vega et al. Journal of Food Composition and Analysis 98 (2021) 103804

Fig. 7. Approach of experimental data to models of Minchev & Minkov (dotted line) and Weibull-type (continuous line). a) Total Polyphenols Index (I280) and b)
Flavonoids Index (I365). Samples: Cask-New, Cask-MT.

Table 4
Kinetic parameters for the studied models to describe the extraction of polyphenols and flavonoids.
Weibull-type Model

Cask Total Polyphenols Index (I280) Total Flavonoids Index (I365)

C0 k n R C0 k n R

New 1.35 0.51 0.320 0.971 0.0012 5.22 0.102 0.985

MT 1.48 0.70 0.163 0.959 0.0010 6.01 0.546 0.920

Two-rate Model

Cask Total Polyphenols Index (I280) Total Flavonoids Index (I365)

A B C D R A B C D R

New 2.849 0.249 1.327 2.994 0.856 12.951 0.289 14.051 0.277 0.995
MT 2.526 0.556 1.529 15.875 0.796 0.481 0.368 0.469 0.368 0.971

Swelling/diffusion Model

Cask Total Polyphenols Index (I280) Total Flavonoids Index (I365)

C∞ W t1/2 d kd R C∞ W t1/2 d kd R
3
New 2.22 1.72 3.28 0.05 13.88 0.854 0.5*10− 1.08 18.15 0.02 0.13 0.994
MT 1.80 13.83 0.99 2.36 0.71 0.802 0.029 4.16 4.51 0.14 0.36 0.971

Sorption/desorption Model

Cask Total Polyphenols Index (I280) Total Flavonoids Index (I365)

k1 k2 R k1 k2 R

New 0.368 0.219 0.850 5.501 0.523 0.993

MT 0.150 0.230 0.788 2.347 0.823 0.958

Minchev & Minkov

Cask Total Polyphenols Index (I280) Total Flavonoids Index (I365)

α β k R α β k R
(I280) (I280) (months− 1) (I365) (I365) (months− 1)

New 4.21 2.82 0.233 0.991 1.267 1.256 0.132 0.994

MT 4.05 2.54 0.560 0.990 0.947 0.980 0.383 0.971

significant changes, in which it is possible to conclude that these phe­
nomena are not affected by possible ethanol evaporation.
The change of the band located in the range of 352–385 nm over time
is shown in Fig. 6. It is observed that from the beginning of the matu­
ration process, the intensity of the signals increase for both casks stud­
ied, which evidence the physicochemical exchange between the
compounds present in the surface of the cask with the Tequila, indi­
cating that there is an extraction of wood compounds granting the yel­
lowing characteristic of aged beverages. To describe the processes,
experimental data for I280 and I365 were fitted to different non-linear
kinetic models (Fig. 7).
Table 3 shows the kinetic parameters obtained from all the mathe­
matical models tested. It is observed that the best model that describes
the phenomenon of extraction is the Minchev & Minkov equation,
related to the processes of Total Polyphenols Index and Flavonoids
Index, explaining an extraction process limited by diffusion.
Comparing the results shown in Table 4, it stands out that for the best
fit model, Minchev & Minkov, the constant of velocity increases more
than double comparing both casks studied: kcask-new,I280 = 0.233
month− 1 vs. kCask-MT,I280 = 0.560 month− 1, kcask-new,I365 = 0.132 month-
1
vs. kCask-MT,I365 = 0.383 month− 1, therefore explaining that the
extraction process of polyphenols and flavonoids is slower in Cask-MT.
This phenomenon can be attributed to the textural characteristics of
woods used in the fabrication of the casks. As observed in the charac­
terization results, the thermic treatment during the toasting process
collapses the mesoporous volume by half; thus, the extraction to Cask-
MT is slower due to mass transfer limitations since the alcohol solu­
tion must spread in the new texture. It is important to note that although
the maturation kinetics is slower once the cask has been lightly toasted,
saturation is achieved at the same time as when using a new cask
without modifications.
Finally, the characterization of Tequila by gas chromatography

7
W.M. Warren-Vega et al.
Fig. 8. Chromatographic characterization of 12 months maturation kinetics of Tequila: a) Aldehydes, b) Methanol, c) Higher Alcohols, d) Esters. Samples:
New, Cask-MT.
(determination of aldehydes, methanol, esters, and higher alcohols) is
shown in Fig. 8. In the case of methanol and higher alcohols, there are no
significant changes during the maturation process; slight variations
observed can be associated with experimental error finding the mean of
data in 227.24 and 436.88 mg/100 mL A.A. (Anhydrous Alcohol),
respectively. The linear behaviour can be explained due to the previous
process that beverages suffer, such as fermentation, in which the syn­
thesis of higher alcohols occurs because of sugars present in the cooked
heads of Agave tequilana Weber blue variety. This information is
corroborated by previous studies in which these components decrease or
stay in equilibrium during the maturation process, as the wood cask
works as an adsorbent agent and chemical oxidation also occur due to
the presence of oxygen diffusion (Cedeño Cruz and Alvarez-Jacobs,
1999; Cedeño, 1995).
On the other hand, for both casks, aldehydes and esters show an
increment during the maturation process. In the case of aldehydes, the
increase is very slight, whereas the concentration of esters increases in a
similar way to that observed in Fig. 8a. At the beginning of the matu­
ration process (t = 0), esters concentration is low (8.75 mg/100 mL A.
A.); this can be attributed to fermentation products, such as ethyl ace­
tate, ethyl lactate, and isoamyl acetate. Later, as maturation time passed,
there is an exponential increase until equilibrium is reached in the fifth
month. The previous effect can be described as the generation of esters
associated with the extraction of polyphenols and flavonols; once these
have migrated from the wood to the beverage, an oxidation reaction
occurs due to the amount of oxygen that is incorporated into the
distillate through the wood of the cask (Zhang et al., 2015). An
approximation of the incorporated oxygen during the maturation pro­
cess is 2− 5 mL/L/ year (due to the space between staves), 2− 4
mL/L/year (due to the operations of emptying and filling), 40
mL/L/year (due to samplings), and 15− 25 mL/L/year (due to poor
sealing of casks) for a cask of 225 L (Ayala-Magdaleno, 2019).
4. Conclusions
From the characterization and description studies of the maturation
kinetics of Tequila, it was possible to determine the critical stages of the
8
Journal of Food Composition and Analysis 98 (2021) 103804
Cask-
maturation process. These are: (i) The thermal treatment of the cask
impacts the time in which the migration of aromatic compounds from
the wood reaches an equilibrium. This effect is because toasting con­
tracts the channels of the wood, causing impediments to mass transfer.
(ii) Data obtained from the isotopic ratios of Carbon 13 and Oxygen 18
showed that this could be considered an additional parameter in eval­
uating the authenticity of aged tequilas since the isotopic enrichment of
δ18OVSMOW is attributed to extraction of polyphenols and flavonoids
during the maturation process.
CRediT authorship contribution statement
Walter M. Warren-Vega: Conceptualization, Formal analysis,
Investigation, Validation, Writing - original draft. Rocío Fonseca-
Aguiñaga: Conceptualization, Resources, Methodology, Formal anal­
ysis, Writing - original draft. Linda V. González-Gutiérrez: Resources,
Writing - original draft, Formal analysis. Francisco Carrasco-Marín:
Resources, Formal analysis. Ana I. Zárate-Guzmán: Validation, Formal
analysis, Writing - original draft, Writing - review & editing. Luis A.
Romero-Cano: Conceptualization, Resources, Methodology, Supervi­
sion, Formal analysis, Writing - original draft, Writing - review & edit­
ing, Project administration.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgments
The authors thanks to the members of the Isotopy Subcommittee of
the Tequila Regulatory Council (CRT) for the support received for taking
and collecting samples, as well as for their constructive comments
during the meetings. And to the Centro de Investigación para el Desar­
rollo Industrial (CIDI – UAG). WMWV thanks to the Universidad
Autónoma de Guadalajara for the scholarship received for the comple­
tion of undergraduate studies.
W.M. Warren-Vega et al.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jfca.2021.103804.
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