Ciência Téc. Vitiv. 34(2) 91-101.

2019

THE EFFECT OF CATION EXCHANGE RESIN TREATMENT OF GRAPE MUST ON

THE CHEMICAL AND SENSORY CHARACTERISTICS OF BASE WINES FOR
SPARKLING WINE

EFEITO DO TRATAMENTO COM RESINA DE TROCA CATIÓNICA NO MOSTO DE UVA SOBRE AS

CARACTERÍSTICAS QUÍMICAS E SENSORIAIS DOS VINHOS BASE PARA ESPUMANTE

Bruno Cisilotto, 1,2*, Simone Bertazzo Rossato1, Evandro Ficagna 1, Luísa Carolina Wetzstein1, Angelo Gava1,
Gisele Mion Gugel 1, Ana Paula Longaray Delamare2, Sergio Echeverrigaray2

1
Federal Institute of Education, Science and Technology of Rio Grande do Sul–Bento Gonçalves Campus, Brazil.
2
Institute of Biotechnology, University of Caxias do Sul, 95001-970 Caxias do Sul, RS, Brazil.

* Corresponding author: Tel: +55(54)981141369, email: [email protected]

(Received 10.08.2019. Accepted 29.10.2019)

SUMMARY

Ion exchange resins are polymers with high physical and chemical stability, which, upon activation, acquire positive charge (H+) ions which
interchange with existing cations during musts or wines treatment. The chemical composition of the grape must, and wines are highly affected by
said modifications. This study aimed to evaluate the impact of the cationic resin treatments on the physicochemical and organoleptic
characteristics of base white wines for sparkling wine production. Thus for, Chardonnay must was exposed to a cation exchange resin specific for
oenological usage, and fermented to obtain wines. Resulting wines included an untreated control sample with pH 3.15 and treated samples with
pH 3.08, 3.02 and 2.97. Physicochemical and volatile compounds analyses as well as quantitative sensory evaluations were conducted. The results
showed that, on the scenarios tested, treatments with cationic resins before fermentation resulted in wine with higher oxidative stability, with
significative variation on the concentration of several volatile compounds that influenced organoleptic perceptions.

RESUMO

As resinas de troca iónica são polímeros com alta estabilidade física e química, que, após a ativação, adquirem íons de carga positiva (H+) que se
intercambiam com cátions existentes nos mostos ou vinhos durante o tratamento. A composição química dos mostos e dos vinhos são altamente
afetadas por estas modificações. O objetivo deste estudo foi avaliar o impacto da técnica acima mencionada sobre as características químicas e
organolépticas dos vinhos brancos base para espumantes. Para tanto, mosto Chardonnay foi exposto a resina de troca catiônica para uso enológico,
e fermentado para obtenção de vinhos. Os tratamentos incluíram um controle não tratado com pH 3,15 e amostras tratadas com pH modificado
para 3,08, 3,02 e 2,97. Foram realizadas análises físico-químicas, medições de cor e compostos voláteis, bem como uma análise sensorial
quantitativa. Este estudo mostrou que, nos cenários testados, os tratamentos com resinas catiônicas antes da fermentação resultaram em vinhos
com maior estabilidade oxidativa, variação significativa na concentração de diversos compostos voláteis, influenciando as percepções
organolépticas.

Key words: wine, cation exchange resin, total acidity, pH, aroma compounds, sensory characteristics.
Palavras-chave: vinho, resina de troca catiônica, acidez total, pH, compostos do aroma, características sensoriais.

gustatory balance and increase stability (Blouin and

INTRODUCTION
Peynaud, 2006). Techniques of pH and acidity
The acidity of grape must and wines are currently control, such as qualitative separation of the must
controlled for several reasons, mainly to guarantee during pressing phase, addition of organic acids,

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Article available at https://www.ctv-jve-journal.org or https://doi.org/10.1051/ctv/20193402091

control of malolactic fermentation and ion exchange residual sugar, total acidity, pH and volatile acidity
resins usage have been studied, tested and discussed are considered extremely relevant from both gustatory
(Togores, 2018). and aromatic characteristics (Ribéreau-Gayon et al.,
2007), but their specific effect is still controversial.
Grape must pH is considered an important indicator
Despite the consensus on the influence of pH and
of the wine quality. On white wines intended for the
acidity on the aroma compounds of wines, few
production of sparkling wines, low pH values are
studies show a clear relation between these factors.
considered to increase freshness, vivacity, and
Lambrechts and Pretorious (2000), among other
brightness by interfering with redox reactions.
authors, pointed out that esters produced during
Moreover, low pH values also increase the physical
alcoholic fermentation are responsible for fruity and
stability and fining of base wines, improving
floral aromas of wines, some of which are the most
clarification (Moreno and Peinado, 2012).
important aromatic attributes of white wines. Liu et
Cationic resins for oenological purpose directed to al. (2015) showed significant differences of yeast
increase wine acidity have become a technical option response to must pH, and an increase of acetic acid
since 2012, when the International Organization of production on lower pH. Esters are produced by
Vine and Wine (OIV) foreseen their usage in grape enzymatic and chemical esterification, and the acid
must and wines to increase of the real and total catalyzed esterification is modified under lower pH
acidity, resulting in pH reduction, tartaric acid (Marais, 1978; Edwards et al., 1985). However,
stabilization, and wine durability (OIV, 2018). conflicting results were reported by Patrianakou and
Roussis (2013) who pointed the effects of lower pH
Oenological ion exchange resins are typically
on Fe II ions kidnapping, and the consequent
constituted by a matrix of cross-linked polystyrene reduction of several esters during wine storage.
and divinylbenzene. These materials are referred as
resins due to the tridimensional porous matrix that The number of cations present in the musts may have
support the “exchanging” groups. The resins are a significant influence on fermentations, and
obtained by condensation and polymerization, consequently in the final aromatic composition of the
resulting in a polystyrene matrix with high wine. According to Walker (2004), metal ions may
thermoplastic and physical stability, commercialized impact on yeast growth and enzymatic activities
as 0.3 to 1.2 mm microspheres (Mira et al., 2004, during fermentation, influencing various parameters
2006). Upon activation with H+ ions by acid mineral such as the conversion rate of sugar to ethanol, yeast
washing (typically a sulfuric acid solution), the resins biomass production, cell viability and stress tolerance,
act directly, exchanging the H+ ions with cations, foam production and yeast flocculation, among
mainly K+ and Ca+ present in the grape must or others. Moreover, many cations act as cofactors for
wine. This ionic stoichiometric exchange liberates enzymes and their availability can influence the
causes a decrease in pH and an increase in total production of several metabolites.
acidity (AEB-group, 2013).
Additionally, to classical chemical analysis and
Although licensed for winemaking since 2012, the volatile compounds and color evaluation, a sensory
scientific information about the effect of cationic analysis is valuable to support the physical and
resins treatment of grape musts or the resulting wines chemical analyses, through which is possible to verify
is scarce. Some works have been done on red and any connection from visual to olfactory and gustatory
white wines (Mira et al., 2004; Bruijn et al., 2009; evaluations detected during tasting. According to
Lasanta et al., 2013; Cabrita et al., 2014; Ibeas et al., Bailetti et al. (2019), the descriptive analysis (DA) is
2015) showing important effect on several the most well-known and widely used method of
physicochemical characteristics of wines, but there sensory analysis, in which a trained panel is used to
are not reports on the treatment of grape must for the identify qualitative and quantitative sensory
production of base wines for sparkling wines characteristics of a product and to punctuate their
production, a class of white wines with very peculiar intensities of a set of attributes. Thus, descriptive
characteristics such as higher acidity, lower alcohol analysis still stands as the most comprehensive,
content and lower aromatic intensity. flexible and useful sensory method, providing
detailed information of a given product (Murray et
Total acidity, pH and volatile acidity are a constant
al., 2001).
concern of oenologists in the production of wines,
especially the base wines intended for sparkling In this context, the present work aimed to evaluate the
wines. The main reason to such interest is the sensory physicochemical characteristics, the volatile
influence of acidity on final products. Indeed, in composition, and the organoleptic attributes of base
professional sensory analysis, alcohol strength, wines for sparkling wines production obtained from

92
‘Chardonnay’ musts treated with a commercial cation phosphate, yeast autolysate and thiamine (Laffort,
exchange resin. These results will help oenologists to Bordeaux, France), and 15 g/hL of Microcol Alpha
decide pre-fermentative treatments to obtain a desired bentonite (Laffort, France) were added, in order to
product. reduce the risk of stuck fermentation and a to clarify
the wine, respectively. After fermentation the wines
were subjected to tartaric stabilization (15 days at
MATERIAL AND METHODS 0°C), and then bottled and stored at 18°C for
subsequent analyzes. The treatments comprised of a
Grape must control sample with pH 3.15, named ST (Standard or
For the experiment, juice of the variety ‘Chardonnay’ Control Treatment), and treated samples with pH 3.08
was obtained by pressing the whole clusters with a (TR1), pH 3.02 (TR2) and pH 2.97 (TR3). It is
pneumatic press PPC 9 (Enoveneta SPA, Italy). After important to emphasize that this is within the pH used
extraction, the juice was treated in the following in Brazilian base wines for sparkling production.
order: enzymatic treatment with pectinase ZIMOPEC Given five months after the end of the alcoholic
PML (3 ml/hL) (Perdomini-IOC SpA, Italy), addition fermentation, the wines were analyzed for their
of sulfur dioxide (50 mg/L SO2), and two hours after physicochemical characteristics, volatile compounds,
the enzyme addition, the juice was clarified with and sensory analysis. Moreover, color evolution was
silica Xiles 40 (70 ml/hL) (Perdomini-IOC SPA, monitored during nine months with three months
Italy) and gelatin Gecoll (10 g/hL) (LAFFORT, intervals.
France). Finally, the juice was cooled to 12 ºC for
Physicochemical analyses
static decantation. After 10 hours the lees were
separated (debourbage), and the juices were divided Alcohol strength (ethanol) was determined by
into 5.5 L volumes for resin treatment. distillation and measurement of the distillate density
at 20°C in hydrostatic balance (Gibertini, Italy). The
Ion exchange resin alcohol was expressed by volume-volume percentage
The cation exchange resins (pH-Stab) and the sulfuric (% v/v). The total dry extract was obtained by the
acid activator (ACID +) used in the present study densimetric method using hydrostatic balance
were acquired from AEB Latin American (Gibertini, Italy), and reducing substances were
Biochemistry S.A. (Brazil). The cationic resin (pH- measured by Fehling test (AOAC, 1995).
Stab) is a styrene-divinylbenzene copolymer matrix The determination of pH were performed with a
with sulfonic functional groups, commercialized as benchtop pH meter MPA210 (Tecnopon, Brazil)
microbeads with 0.3 to 1.2 mm. According with the (MAPA, 2013), and total acidity was determined by
manufacturer, a gram of the resin can interchange 1.4 neutralization of titratable acids using a NaOH
meq of H+. The doses, application mode, washing solution (Portaria nº 76/1986, 1986). The levels of
procedure and resin regeneration followed the tartaric acid were evaluated by Wineflow enzymatic
manufacturer’s recommendation.
kit (Gibertini, Italy). The separation of the volatile
Ion exchange system and experiments acids occurred by steam distillation in Super DEE
(Gibertini, Italy) and quantified by titration (Portaria
To perform the ionic exchange between the resins and nº 76/1986). Volatile acidity was expressed as g/L of
the juice on a pilot scale, an experimental glass device acetic acid.
was developed in cylindrical format, with volumetric
capacity of 600 mL with a Teflon valve, and a porous Total phenolic compounds was determined by the
disc filter type that retains the resin. The juice was Folin-Ciocalteau colorimetric method (Rockenbach et
passed, and refluxed by the resin column, as many al., 2008), and the results were expressed as mg/L of
times to obtain the desired pH reduction. When the gallic acid. Total polyphenols index was determined
must attained the desired pH it was separated into a by absorbance at 280 nm using an UV/VIS T92
container with a volume of 4.4 L for fermentation. spectrophotometer (PG Instruments, England),
The container volumes were all adjusted by weight according with Ribéreau-Gayon et al. (2007), and
with a precision scale. All treatments were made in free and total sulfur dioxide were quantified using an
triplicate. automatic titrator (Quick, Gibertini Italy). The two
parameters were expressed in mg/L of sulfur dioxide.
Subsequently, all samples were submitted to
controlled alcoholic fermentation with selected yeast Color intensity of wines was determined by
Saccharomyces cerevisiae (20 g/hL) Zimaflore X5 absorbance at 420 nm, and expressed as optical
(Laffort, France). After 48 hours of fermentation, density units (Ribéreau-Gayon et al., 2007). The
nutrient Nutristart 30 g/hL, containing diammonium chromatic characteristics of wines were determined

93
with a KONICA MINOLTA colorimeter CR-400 labeled “little” at the left end and “high” at the right
(Tokyo, Japan). The measured parameters were: L* end. Data were collected and analyzed manually by
which represents lightness (L* = 0 being black and measurement of the lines as recommended by
L* = 100 being white); a* and b* being coordinates Dutcosky (2007).
of colors responsible for the chromaticity (+a* being
Statistical analysis
red and –a* being green, +b* being yellow and –b*
being blue), coordinates of CIELab color space, the The results obtained in the physicochemical and
value of chroma C* = (a*2 + b*2)1/2 and hue angle h* sensory analyses were submitted to an analysis of
= tg-1(b*/a*). Data was transmitted through a variance (two-way ANOVA) followed by a mean
computer with CR 400 Utility software. comparison by the Tukey test at 95% probability
(p<0.05). The results of the sensory analysis were
Analysis of volatile compounds
presented in a radar chart. Statistical analyses were
Determinations of ethanal, ethyl acetate, 1-propanol, achieved by Graphpad Prism®, ASSISTAT and
2-methyl-1-propanol, 2-methyl-1-butanol and 3- Microsoft Excel software.
methyl-1-butanol content were performed
simultaneously as well as those of the fatty acid
content, esters, volatile acids, acetates and 2- RESULTS AND DISCUSSION
phenylethanol. All determinations were performed by
gas chromatography with flame ionization detector Physicochemical characteristics of wines obtained
(GC-FID), according to the procedure described by from musts treated by cation exchange resins are
Webber et al. (2014). Chromatographic analyses were shown in Table I. As expected, total acidity was
conducted in a Agilent Plus 6890 series higher on wines obtained from treated musts (Table I)
chromatograph (Santa Clara, CA, USA), with a and showed a significant negative correlation with pH
capillary column HP Innowax (30 m x 0.25 mm x (r=-0.9736). Although non-significant tartaric acid
concentration showed a direct relation with resin
0.25 µm). The compounds were identified by
comparison of their retention times with authentic treatment intensity as verifying by the high negative
standards from Sigma-Aldrich (St Louis, USA), and correlation between pH and tartaric acid (r=-0.8322)
Moreover, a positive correlation between total acidity
their concentration determined with a calibration
curve prepared for each standard with seven and tartaric acid (r=0.364) was also evident. The
concentration values. The evaluations were conducted relations observed between pH, total acidity and
tartaric acid concentration are the result of the
in triplicate, and the results were expressed in mg/L.
exchange of hydrogen ions of activated resin with the
Sensory analysis cations of must salts, mainly potassium and calcium
tartrate, releasing tartaric acid. This exchange results
Sensory analysis occurred five months after the end
in a reduction of pH and an increase in total acidity
of the wine fermentation. It was attended by 13
(AEB-group, 2013). Mira et al. (2006), Cabrita et al.
experienced oenologists in sparkling wines tasting,
(2014), Ibeas et al. (2015), and Ponce et al. (2018)
who act in the official Brazilian wine sector panel.
showed that the treatment of red and white wines with
The tasters were not informed about the experiment to
cation exchange resin results in lower pH, and higher
avoid tendencies. The quantitative descriptive
total acidity. Ponce et al. (2018) evaluated ion
analysis method (Quantitative Descriptive Analysis –
exchange resins applied in wines with several
QDA) followed the standards of ABNT NBR ISO
varieties of white and red grapes, on a laboratory and
13299 (2017). Briefly, the attributes and definitions of
industrial scale, and showed that a significant
the references used in the sensory analysis were
reduction of the concentrations of Ca, K, Na, Mg, Cu,
predefined with the tasting participants, and included:
Mn, Fe and Zn after treatment with resins. Similar
color intensity; white fruits, floral, citric fruits, and
results were obtained by Palacios et al. (2001) after
herbaceous aroma; acidity and bitterness. The
the passage of sherry wines by the resin, and Tamasi
samples were tasted in insulated booths under
et al. (2018) using two types of resin on sweet and
artificial lighting with white led lamps. The wines
dessert wines. Moreover, several authors (Cabrita et
were presented with a randomized block design in 40
al., 2014, Ibeas et al., 2015, Ponce et al., 2018)
mL aliquots in ISO glass, encoded with three digits.
pointed out that the reduction of cations concentration
Three repetitions (triplicates) were performed with a
after cationic resin-treated wines resulted in higher
15 minute interval between each section (four wines
tartaric stability by an increase of tartaric acid and a
in each section). The wine tasting temperature was
consequent reduction on tartaric salts.
controlled at 12 °C. The intensity of each attribute
was rated using a 10 cm unstructured line scale

94
 TABLE I
Physicochemical characteristics of wines obtained from musts treated by cation exchange resin
Características físico-químicas dos vinhos obtidos a partir de mostos tratados com resina de troca catiônica

Effect of cation ST TR1 TR2 TR3

Analytical parameters exchange
treatment (pH 3.15) (pH 3.08) (pH 3.02) (pH 2.97)

Volatile acidity (g/L) n.s. 0.35 ±0.09 0.36 ±0.03 0.36 ±0.02 0.39 ±0.05
Alcoholic strength (v/v %) n.s. 10.23 ±0.08 10.36 ±0.09 10.37 ±0.09 10.23 ±0.09
Reducing substances (g/L) n.s. 1.48 ±0.07 1.41 ±0.02 1.38 ±0.02 1.4 ±0.02
Dry extract (g/L) n.s. 20.6 ±0.1 20.5 ±0.1 20.63 ±0.3 20.9 ± 0.4
TP Index (A 280 nm) n.s. 4.42 ±0.07 4.22 ±0.16 4.16 ±0.02 4.24 ±0.14
Folin-Ciocalteau Index (mg/L) n.s. 147 ±12 136 ±7 133 ±6 139 ± 7
Free SO2 (mg/L) n.s. 7.3 ±.,40 7.4 ±0,51 7.1 ±0.49 7.2 ±0.14
Combined SO2 (mg/L) n.s. 30.06 ±2.94 33.8 ±3.96 32.6 ±4.55 35.63 ±7.28
Total SO2 (mg/L) n.s. 37.36 ±2.54 41.06 ±3.97 40.06 ±4.18 43.73 ±7.25
pH ** 3.15 ±0.01 a 3.08 ±0.01 b 3.02 ±0.01 c 2.97 ±0.01 d
Total acidity (g/L) ** 9.1 ±0.1 d 9.4 ±0.1 c 9.8 ±0.1 b 10.4 ±0.1 a
Tartaric acid (g/L) * 2.45 ±0.06 b 2.45 ±0.17 b 2.57 ±0.08 b 3.03 ±0.10 a
L* n.s. 75.16 ±0.07 75.39 ±0.09 75.53 ±0.15 75.55 ±0.12
a* n.s. -2.09 ±0.04 -2.07 ±0.03 -2.03 ±0.01 -2.05 ±0.03
b* * 6.3 ±0.2 a 5.6 ±0.2 b 5.2 ±0.4 b 5.2 ±0.1 b
C* * 6.62 ±0.15 a 5.98 ±0.15 b 5.61 ±0.41 b 5.56 ±0.10 b
h* * 108.40 ±0.63 b 110.32 ±0.73 ab 111.33 ±1.44 a 111.65 ±0.65 a
A 420 nm ** 0.086 ±0.006 a 0.074 ±0.002 bc 0.073 ±0.004 bc 0.070 ±0.003 c
Mean values ± standard deviation followed by different letters are significantly different according to the Tukey’s test; n.s. –
non-significant; * significant (p<0.05); ** very significant (p<0.01); Volatile Acidity (expressed as acetic acid); Total Acidity
(expressed as tartaric acid); TP Index = Total Polyphenols Index (expressed as absorbance at 280 nm); Folin-Ciocalteau Index
(expressed in mg/L of gallic acid). CIELab color (L* = lightness; a* = green-red compound; b* = blue-yellow compound; C* =
color chromaticity; h* = hue angle); A 420 nm = absorbance at 420 nm.

As observed in Table I, base wines obtained from the emphasize that in the present work, ‘Chardonnay’
control and resin treated musts did not exhibit must, the most important component of base wines
significant differences in volatile acidity, alcoholic for sparkling wines production, was used to evaluate
content, reducing sugars, dry extract, and sulfur the effect of cation exchange resins.
dioxide (SO2), indicating no influence of the cation
Color is one of the most important visual properties
exchange resin treatments on these parameters.
of wines and provides considerable information about
Moreover, wines did not differ in their polyphenol
their quality. Color is a visual sensation perceived
content (Total Polyphenol Index and Folin-Ciocalteau
from the refraction or reflection of light on the
Index), corroborating the results obtained by Bruijn et
surface of objects. The evaluation of the chromatic
al. (2009) using ion exchange resins on white wines.
characteristics of base wines obtained by the
Conversely, Mira et al. (2004), Cabrita et al. (2014),
alcoholic fermentation of control and cationic resin-
Lasanta et al. (2013), and Ibeas et al. (2015) reported
treated musts are shown in Table I. The lightness (L*)
a decrease in polyphenols, tannins, and/or
and red/green color component (a*) were not
anthocyanins of wines that had passed through ionic
significantly (p≥0.05) affected by resin treatments,
resins. Conflicting results may be associated with the
and as expected, a* values were negatives, indicating
use of different types of wines, resins and treatment
a green tonality. Conversely, cationic resin treatments
intensity, but point out the need for additional studies
showed a significant decrease of blue/yellow color
to elucidate the effect of resins on polyphenols and
component (b*), and chroma (C*), and an increase of
assist winemakers' decisions. It is important to

95
hue angle (h). The reduction of b* and C* values color reduction in resin-treated red wines, attributing
were directly related to pH reduction by must resin this finding to a decrease of total anthocyanins and
treatments, and on TR3 (pH 2.97) wines reached - phenol content. The evolution of wine color over nine
17.67 and -16.01% of the control wine, respectively. months is presented in Figure 1. As can be observed,
initial color intensity was proportional to the cationic
The decrease in yellow color intensity on resin-
resin treatment of musts. Moreover, wines obtained
treated derived wines was confirmed by absorbance at
from TR3 must (pH 2.97) showed lower color,
420 nm (Table I). As b* and C* parameters, the
compared with the control. This result corroborates
reduction of yellow color intensity was proportional
that obtained by Benitez et al. (2002) that showed that
to pH reduction by the cationic resin treatments.
resin-treated white wines exhibit a notably reduced
These results differ from those obtained by Mira et al.
susceptibility to browning. This phenomenon can be
(2006) that did not evidence important color
associated with the very slow phenol oxidation to
modification after treatment of white wines with
quinones reactions at low pH and ion and copper
different cationic ion exchange resins but showed a
depletion (Li et al., 2008; Oliveira et al., 2011).

Figure 1. Evolution of the color (A 420 nm) of wines obtained from control and cationic resin treated musts. Different letters at each time indicate
significant differences by the Tukey's test (p<0.05). A 420 nm = absorbance at 420 nm.
Evolução da cor (A 420nm) de vinhos obtidos a partir de mostos controle e tratados com resina catiônica. Letras distintas em cada tempo
indicam diferenças significativas pelo teste de Tukey (p<0,05). A 420 nm = absorbância a 420 nm.

Low pH affects microbial development and (Zoecklin et al., 1995). This reduction of flavor and
fermentation extending yeast lag phase, reducing aroma has been attributed to the decrease in the
fermentation rate, and increasing the acetic acid and concentration of several volatile compounds (Walker
glycerol concentrations (Liu et al., 2015). Moreover, et al., 2002; Lasanta et al. 2013; Ibeas et al., 2015).
pH stress can also affect enzymatic activities and the
Table II shows the results of the analyses concerning
production and release of volatile compounds from
the concentrations of the volatile compounds on
sugar-bound aroma precursors and fermentative
wines obtained with resin-treated and control musts.
derived volatile compounds that contribute to wine
Only three out of 18 compounds identified exhibited a
aroma. Although not directly related to the present
significant difference between the control and the
study, cationic resin-treated wines are perceived as
resin-treated samples. All these compounds are
less acidic than those treated by tartaric acid addition
classified as acetate esters, and their sum showed a
(Plane et al., 1980), but are generally considered as
reduction dependent on the intensity of the resin
less colored and flavored than non-treated wines
treatments and the pH of the musts.

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 TABLE II
Mean values of volatile compounds concentrations in the wines (mg L-1)
Valores médios de concentração dos compostos voláteis nos vinhos (mg L-1)

Effect of cation ST TR1 TR2 TR3

Treatment exchange
treatment (pH 3.15) (pH 3.08) (pH 3.02) (pH 2.97)

LIGHT COMPOUNDS
Acetaldehyde n.s. 5.64 ±5.64 4.40 ±4.40 5.49 ±5.49 4.10 ±4.10

ALCOHOLS 159.29 166.13 169.35 167.01

1-propanol n.s. 49.0.3 ±6.59 8.74 ± 3.55 46.0 ±7.00 41.14 ±4.19
2-methyl-1-propanol n.s. 17.35 ±1.83 18.96 ±1.15 19.47 ±2.10 19.94 ±1.83
2-methyl-1-butanol n.s. 16.82 ±1.14 17.46 ±1.19 18.58 ±0.91 19.47 ±2.86
3-methyl-1-butanol n.s. 65.93 ±7.69 70.90 ±5.24 73.77 ±4.09 73.67 ±8.90
2-phenylethanol n.s. 6.77 ±1.35 6.91 ±1.51 8.13 ±1.24 9.36 ±4.04
Hexanol n.s. 3.39 ± 0.24 3.16 ±0.15 3.40 ±0.29 3.42 ±0.62
Cis-3-hexan-1-ol ND ND ND ND
Trans-3-hexen-1-ol ND ND ND ND

VOLATILE ACIDS 18.15 19.54 18.55 19.17

Octanoic Acid n.s. 8.62 ±0.83 9.71 ±1.44 8.90 ±1.93 9.53 ±0.77
Decanoic Acid n.s. 7.49 ±0.18 7.52 ±0.39 7.30 ±0.31 7,37 ±0.21
Dodecanoic Acid n.s. 2.03 ±0.29 2.31 ±0.36 2.36 ±0.74 2.27 ±0.55
Isobutyric acid n.s. ND ND ND ND
Butyric Acid n.s. ND ND ND ND
Hexanoic Acid n.s. ND ND ND ND
Isovaleric Acid n.s. ND ND ND ND

ACETATES 33.12 31.26 28.62 22.09

Ethyl Acetate ** 27.06 ±2.77 a 26.01 ±1.84 a 23.66 ±1.70 a 19.98 ±2.17 b
Isoamyl Acetate ** 1.39 ±0.26 a 0.75 ±0.20 b 0.51 ±0.34 bc 0.16 ±0.29 c
Hexyl Acetate ** 2.45 ±0.19 a 2.49 ±0.10 a 2.34 ±0.20 a 0.01 ± 0 b
Butyl Acetate n.s. 2.22 ±0.29 2.01 ±0.11 2.11 ±0.52 1.94 ±0.23
2-phenylethyl Acetate ND ND ND ND

ETHYL ESTERS 8.10 7.65 7.47 7.60

Ethyl Hexanoate n.s. 1.99 ±0.08 1.99 ±0.17 1.97 ±0.08 2.03 ±0.13
Ethyl Octanoate n.s. 5.38 ±0.12 5.33 ±0.25 5.13 ±0.44 5.16 ±0.22
Ethyl Decanoate n.s. 0.73 ±0.49 0.33 ±0.31 0.38 ±0.39 0.41 ±0.46
Ethyl Dodecanoate ND ND ND ND
OTHER 7.17 6.74 7.15 6.40
Hexanal n.s. 2.05 ±0.50 1.68 ±0.25 1.54 ±0.29 1.57 ±0.49
Diethyl Succinate n.s. 5.12 ±0.94 5.06 ±1.35 5.61 ±1.69 4.83 ±0.64
Mean values ± standard deviation followed by different letters are significantly different according to the Tukey’s test;
n.s. – non-significant; ** very significant (p<0.01); ND = Not Detected.

97
Ethyl acetate showed a significant reduction of 26.2% number of volatile compounds. Some of these
in samples under TR3 and exhibited a linear decrease disagreements can be attributed to methodological
depending on the cationic resin treatment and pH of differences, cationic resins and treatments, and pH-
musts (r=0.949). Ethyl acetate accentuates varnish, dependent extraction of volatile compounds used in
nail polish, and somewhat fruity descriptors, and in GC sample preparation. Independently of this, most
excess can contribute negatively to wines of the work involving the treatment of wines with
(Lambrechts and Pretorius, 2000). The concentration cationic resins evidenced a reduction of the aromatic
of ethyl acetate varied from 27.06 mg/L (control) to characteristics of the wines (Benitez et al., 2002,
19.98 mg/L (TR3) all above its threshold 7.5 mg/L Walker et al., 2002, Lasanta et al., 2013, Ibeas et al.,
(Ferreira et al., 2000). 2015, Ponce et al., 2018).
Isoamyl acetate showed the same behavior (r=0.988), Sensory analysis (Figure 2) showed low variations in
but its concentration was significantly lower in all color intensity, confirming the results obtained by
resin-treated wines compared to the control, with a CIELab and A 420 nm. Bitter taste (bitterness), at
reduction of 46.0%, 63.2%, and 88.5%, on TR1, TR2, gustatory analysis, showed no differences among the
and TR3 treatments, respectively. This compound has treated samples, whereas the acidity had significant
banana and pear descriptors with an odor threshold of differences. The sensation of acidity increased as in
0.03 mg/L (Ferreira et al., 2000). The observed the chemical analyses, but only TR3 was statistically
differences in wines fell from 46.4x (control) to 5.3x different from the ST.
(TR3) the odor threshold. Hexyl acetate concentration
At the aroma evaluation, the floral, citrus and
reduced only in the most drastic treatment (TR3), in
herbaceous descriptors did not show statistical
which this compound was almost absent. This
differences. In the case of the white fruit descriptor,
compound has perfume, green and floral descriptors
the ST obtained the highest value and differed from
with an odor threshold of 1.5 mg/L (Ferreira et al.,
all other treatments, which have not differed from
2000).
each other. These results are in agreement with data
The acetates of higher alcohols are among the main found in the analyses of volatile compounds on which
responsible for the fermentation aromas of white analytes such as isoamyl acetate, hexyl acetate and
wines and are synthesized by yeasts through the ethyl acetate, which are described as fruity and
reaction of acetyl-CoA with alcohol catalyzed by flowery, decreased as the treatments became more
alcohol acetyltransferases (Saerens et al., 2008). The intense, coming to disappear in the case of hexyl
lower concentration of acetates of higher alcohols of acetate at TR3. The decrease of these compounds
wines after cationic resin treatments might be probably altered the perception of white fruits in the
explained by the removal of some cations that could olfactory analysis.
have catalytic functions as enzymatic cofactors
As observed by Lasanta et al. (2013) testing red
(Stehlik-Thomas et al., 2004). Moreover, Marais
wines with cationic resin treatment having a pH value
(1978) reported an important decrease of acetate
reduced from 3.8 to 3.5 and 3.3, those wines with
esters concentration in wines obtained by the
reduced pH received better evaluations. The scores
fermentation of acidified grape musts, indicating a
for the intensity of taste and overall appreciation were
possible impact of pH on the production, hydrolysis,
also higher for wines with reduced pH. However, the
and accumulation of this group of compounds. In this
same results were found in the quality of the aroma,
sense, it is important to emphasize that although not
since the wines with cationic resin treatment were not
significant, higher alcohols concentration was higher
the favorites. As analyzed in the present experiment,
on resin-treated wines, except for 1-propanol, and this
Lasanta et al. (2013) also observed a decrease of
increase was directly related to the intensity of resin
esters with fruity aromatic descriptors in the analyses
treatment of grape musts, and inversely correlated
performed.
with must pH and the corresponding acetates in
wines. At the sensory analysis performed by Ibeas et al.
(2015) red wines treated with pH reduction (initial pH
Quantitative variations of aroma compounds have
3.55) that had a reduction of 0.03 presented no
been reported in wines after ion exchange treatment
differences in relation to the control. However, those
(Benitez et al., 2002, Lasanta et al., 2013), but the
with a reduction of 0.1, 0.16, 0.19 and 1.09 were
results are conflicting. Benitez et al. (2002) reported a
evaluated negatively in comparison to the control.
significant reduction of several aromatic compounds,
The evaluation criteria that had a negative impact on
among which acetates, while Lasanta et al. (2013)
the perception of the judges were aromatic finesse,
were able to identify just slight differences in a small
flavor intensity, body, balance, and persistence.

98
trials where these samples were presented, wines of the aromatic intensity and certain aromas described
treated with ion exchange resin received a lower as fruity should be taken into account as in this study,
rating. The sensory analysis performed in wines as well as in other related ones, this aspect was better
treated with ion exchange suggests that flavor and evaluated in the control wines in both white wines
aroma are impacted by the treatment. The reduction and red wines.

Figure 2. Sensory Analysis - Comparison of the means of the wine’s attributes found by Quantitative Descriptive Analysis – QDA. *** Values
are significantly different (p≤0.05, Tukey test) between ST and treatments TR1, TR2 and TR3. * Values are significantly different (p≤0.05, Tukey
test) between ST and TR3 treatment.
Análise Sensorial - Comparação das médias dos atributos dos vinhos encontrados pela Análise Descritiva Quantitativa - ADQ. *** Os valores do
ST são significativamente diferentes (p≤0,05, teste de Tukey) dos tratamentos TR1, TR2 e TR3. * Os valores do ST são significativamente
diferentes (p≤0,05, teste de Tukey) do tratamento TR3.

CONCLUSIONS isoamyl acetate, and hexyl acetate concentration,

directly proportional to pH reduction by resin
The increase in the concentration of total acidity in treatment. Moreover, the reduction of these
wines with ionic resin treatment was in accordance compounds influenced the olfactory perception in the
with the treatment proposal. The analyses for alcohol sensory analysis, mainly in the grape must treatment
strength, sugars, volatile acidity, dry extract, and total to reduce the pH value by 0.18. The increase of
polyphenols returned no significant differences in the acidity through the resin influenced the taste analysis
levels tested, which show that treatments with ion by changing the same pH value of 0.18.
exchange resins for the grape must have no influences
on such indicators. Wines from resin-treated musts In general, moderate treatments (reduction of the pH
had lower yellow color intensity indices than the value up to 0.13) led to minor changes in the
control treatment, indicating greater oxidation concentration of volatile compounds and in the
stability than the standard treatment. quantitative differences found in the sensory analysis,
maintaining the advantage of increasing the acidity
The cationic resin treated must derived wines and color stability of the wine due to pH reduction.
exhibited a significative decrease in ethyl acetate,

99
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