USE OF ION EXCHANGE RESINS FOR TARTRATE WINE ...

- 223 -J. Int. Sci. Vigne Vin, 2006, 40, n°4, 223-246

©Vigne et Vin Publications Internationales (Bordeaux, France)*Corresponding author:[email protected]

USE OF ION EXCHANGE RESINSFOR TARTRATE WINE STABILIZATION

UTILISATION DE RÉSINES ÉCHANGEUSES D'IONS POUR LA STABILISATION TARTRIQUE DES VINS

Helena MIRA1, Patrícia LEITE1,2,3, J. M. RICARDO-DA-SILVA2* and A. S. CURVELO-GARCIA3

1: Escola Superior Agrária de Santarém, Apartado 310, 2001-904 Santarém, Portugal2: Universidade Técnica de Lisboa, Instituto Superior de Agronomia, Laboratório Ferreira

Lapa (Sector de Enologia), Tapada da Ajuda, 1349-017 Lisboa Codex, Portugal3: INIAP, Estação Vitivinícola Nacional, Quinta da Almoínha,

2565-191 Dois Portos, Portugal

Abstract: The application of the cation exchange and double cation-anion exchange resins, regarding the wine tartrate stabili-zation, without previous treatment of wine by cold has been studied as well as their influence in phenolic, mineral and organicacid composition. The R1 resin was used in Mg2+, Na+ and H+ form, the R2 resin was always used in H+ form, and the R3 wasused in OH- form. The eluted wine was assembled with untreated wine to obtain stable wine. The R2 resin showed to bemore efficient to enhance the tartrate stabilization than R1 in Mg2+ form; however in H+ form, the behaviour of both resins wasquite similar. The tartrate stabilization results to double cation anion exchange were similar to the results obtained with cationexchange.

Résumé : L'utilisation de résines échangeuses d'ions pour la stabilisation tartrique des vins, sans préalable traitement par le froid,a été comparée avec le traditionnel traitement par le froid. Deux résines échangeuses de cations (R1 et R2) et une échangeused'anions (R3) ont été utilisées pour la stabilisation tartrique de vins portugais de la région Ribatejo (Portugal). La résine R1 aété utilisée sous la forme de magnésium, sodium et hydrogène, la résine R2 a toujours été utilisée sous la forme d'hydrogène,tandis que la résine R3 a été préparée sous forme OH-. On a étudié aussi l'influence de l'échange cationique et le double échangecationique-anionique sur la composition phénolique, métallique et en acides organiques des vins. Initialement, l'étude a comparé différentes solutions de régénération, en ce qui concerne leur influence sur la composition desvins. Si les résines sont régénérées en cycle acide, les cations K+ et Ca2+ du vin sont replacées par les cations H+ avec diminu-tion du pH et augmentation de l'acidité totale. Le vin traité avec la résine R1 sous forme sodium a présenté un grand enrichis-sement du vin en ce cation. La résine R1 en forme magnésium a montré une affinité plus faible pour le potassium quand oncompare avec la même résine sous la forme sodium ou hydrogène, la résine R2 a présenté une affinité similaire à la résineR1-H. La couleur et les composés phénoliques ont diminué dans la phase initiale de passage du vin sur la colonne de résine,avec une accentuation plus marquée dans le double échange.Après le traitement par les résines échangeuses d'ions, le vin est assemblé avec un certain pourcentage de vin non traité pourobtenir un vin stable. On a fait des assemblages de 5 %, 10 %, 15 % et 25 % de vin traité, le vin témoin (0 %) et le vin après pas-sage total par la résine (100 %) ont été aussi analysés. La résine R2 a présenté une plus grande efficacité pour la stabilisationtartrique que la résine R1 sous forme Mg2+; toutefois la résine R1 sous forme H+ est aussi efficace que la résine R2. Ledouble échange cation-anion n'a pas présenté des résultats plus intéressants que l'échange cationique seul. Les vins résultants de l'assemblage ont présenté une légère diminution des composés phénoliques, plus importante dans le doubleéchange, due à la rétention dans la structure des deux résines. Le groupe des anthocyanines monoglucosides a montré uneplus grande réduction qui les autres groupes, suite à l'utilisation des résines.Les dégustateurs n'ont pas trouvé de différences significatives entre le vin témoin et les vins traités avec les résines échangeusesde cations. La technologie des résines échangeuses de cations, avec les résines en cycle acide est un procédé intéressant et alternatif pourla stabilisation tartrique des vins en respectant les limitations imposées par le Code International Œnologique (OIV).

Keywords : tartrate stabilization, cation exchanger, anion exchanger, wineMots clés : stabilisation tartrique, résines échangeuses d'ions, vin

- 224 -J. Int. Sci. Vigne Vin, 2006, 40, n°4, 223-246©Vigne et Vin Publications Internationales (Bordeaux, France)

Helena MIRA et al.

INTRODUCTION

The tartrate precipitation in wines is one of the mainoenological problems. This natural phenomenon occursduring winemaking and can be observed some monthsafter bottling in untreated wine, according to its evolu-tion. The occurrence of tartrate salt crystals (potassiumhydrogen tartrate - KHT and calcium tartrate - CaT) inbottles, with dramatic consequences in the final aspect ofthe wine, makes tartrate wine stabilization imperativebefore bottling. Preventive solutions of tartrate precipi-tation range from physic and chemical treatments to sub-tractive and additive processes, like cold stabilization(BLOUIN et al., 1979; BURNETT, 1982; SERRANOet al., 1983; MAUJEAN, 1994; MINGUEZ andHERNÁNDEZ, 1998), electrodialysis (ESCUDIER etal., 1985; MOUTOUNET et al., 1997; CAMEIRA-DOS-SANTOS et al., 2000), ion-exchange (AUSTERWEIL,1953, 1955; DAL CIN, 1984; RANKINE, 1985;MOURGUES, 1993; BENITEZ et al., 2002a), and usingprotective colloids like yeast mannoproteins (LUBBERSet al., 1993; MOINE-LEDOUX et al., 1997; FEUILLATand CHARPENTIER, 1998; MOINE-LEDOUX andDUBOURDIEU, 2002a, b) or metatartric acid(WUCHERPFENNIG, 1973; COLAGRANDE, 2002).

Since the middle of last century, the ion exchangetechnology has been used for tartrate wine stabilization,wine acidification and elimination of metals such as iron,copper and lead (AUSTERWEIL, 1953, 1955;IONESCU, 1969; DAL CIN, 1984; RANKINE, 1985;BONORDEN et al., 1986; LEE, 1991; MOURGUES,1993; WEINAND and DEDARDEL, 1994;HERNÁNDEZ and MÍNGUEZ, 1997; PALACIOS etal., 2001a, b; WALKER et al., 2002; BENITEZ et al.,2002a, b).

According to their polar groups, ion exchange resinsare categorised as strong and weak acid cation exchan-gers or strong and weak anion exchangers. The activegroup of cation exchange resins is usually sulphonic-acid(-SO3H), or a carboxylic acid (CAPUTI, 1994; OIV,1995). The active radical of anion exchangers is a qua-ternary ammonium or tertiary amine salt.

RANKINE (1985) and MOURGUES (1993) repor-ted that the wine can be stabilized by ion exchange inthree different ways: a) by replacing potassium and cal-cium with cation of the cation exchange resin; b) by repla-cing the tartrate anion with hydroxyl or other anion in ananion exchange resin and c) by replacing potassium andcalcium, and tartrate, by hydrogen and hydroxyl in a cationand anion exchange resins, exchanging the potassiumhydrogen tartrate and the calcium tartrate for water.

The cation exchangers in sodium, magnesium andhydrogen forms may be used to remove the K+ and Ca2+

from the wine (RIBÉREAU-GAYON et al., 1977; RAN-KINE, 1985; MOURGUES, 1993). In the past, the mostcommon was the use of the cation resins in sodium form(RIBÉREAU-GAYON and PEYNAUD, 1966; TAM-BORINI and MAGRO, 1970; RANKINE, 1985).Nevertheless, their use has decreased greatly because thewine stayed much enriched in sodium content. If the cationresin is in hydrogen form, the exchange of cations ofthe wine by H+ ions of the resin will originate a veryimportant decrease in pH. To avoid the considerabledecrease in the wine pH after treatment, MOURGUES(1993) suggested treating only one fraction of the wine,or using a resin in the mixed forms. In order to avoid alarge acidification or an excessive increase in sodiumcontent, we can also use the resin in the magnesium form.Another possibility to prevent the tartrate wine precipi-tation and minimize the decrease of the wine pH is, infact, a double cation-anion exchange, however this pro-cess could be very drastic, and involves excessive,although temporary, important variations in the pH of thewine (RIBÉREAU-GAYON et al., 1977). Nevertheless,the anion exchanger can have negative effects in the phy-sicochemical composition and sensory characteristics ofthe wine (BONORDEN et al., 1986; RIBÉREAU-GAYON et al., 1998).

Although the use of the cation and anion exchangershas been authorized in some countries as the United Statesand Australia; in Europe, the use of the ion exchange resinis only accepted by the Office International de la Vigneet du Vin (OIV) for tartrate stabilization with cationexchangers in acid cycle (OIV, 1995).

The prescriptions of OIV (1998) for tartrate stabili-zation by treatment with cation exchangers are the follo-wing: the treatment must be limited to the elimination ofthe excess cations, the wine will be initially cold treatedand only the minimum fraction of wine necessary forobtaining stability will be treated with cation exchangers;the treatment will be performed using cation exchangeresins regenerated in the acid cycle; the whole processwill be placed under the responsibility of an enologistor a specialist technician; the resins shall comply with theprescriptions of the International Oenological Codex andshall not lead to excessive modifications of the physico-chemical composition and sensory characteristics of thewine.

The limitations for the treatment using cation exchangeresin reported by OIV (1995) are the subsequent: the treat-ment does not alter the character of the wine; does notreduce the colour of the wine to less than the one normallycontained in such wines; it does not reduce the metalliccation concentration in the wine to less than 300 mg/L; itdoes not reduce the pH of the wine to less than 3.0; andthe pH reducing does not exceed 0.3 unit of pH; the resin

does not impart to the wine any substances or characte-ristics which do not normally exist in the wine.

When using ion exchange resins for wine tartaric sta-bilization purposes, enologists usually perform previousslight cold treatment, as also recommended by OIV (OIV,1998). So, the aim of this study was the use of the cationexchange and double cation-anion exchange, regardingtartrate wine stabilization, nevertheless without previouscold treatment; and it compares its results with those ofthe wine submitted only to cold treatment. The effects ofthis technology in some oenological characteristics of thewine, as the phenolic, mineral and organic acid compo-sition were evaluated. Also, we have studied the influenceof the different operational conditions (type of resin anddifferent regenerating solutions) of the ion exchange resinsfor tartrate wine stabilization, in some oenological cha-racteristics of wines.

MATERIAL AND METHODS

I - WINES

The white wines used in this study were prepared usinggrapes of Fernão Pires vine variety (Vitis vinifera L.) andthe red wines using grapes of the Castelão vine variety(Vitis vinifera L.). The grapes were harvested in 2001(white wine and red wine A) and 2002 (white wine andred wine B) at the Ribatejo region (Portugal). The wineshave been selected by their degree of tartaric instability,determined with a Boulton test (BOULTON, 1982) modi-fied by VIALATTE (1984). The alcohol content (%, v/v)of the wines was the following: white wine A (11.9), whitewine B (11.3), red wine A (12.8) and red wine B (11.3).

II - ION EXCHANGE RESINS

Two strong cation exchange resins were used, R1(Amberlite SR-1L Na) and R2 (Amberlite FPC-23 H)(Rohm and Haas), both are constituted by a matrix ofpolystyrene reticulate with divinylbenzene, and with sul-fonic functional groups. R1 is a gel type while R2 is amacroporous resin, with a high percentage of divinyl-benzene. One anion exchanger was used, R3 (AmberliteIRA-410 Cl), which is a strong basic resin type II, withpolystyrene matrix.

III - ION EXCHANGE SYSTEM AND EXPERI-MENTS

The experiments have been carried out using appro-priate resin columns with of 20 cm or 50 cm height and2.5 cm internal diameter (Bio-Rad) and with a reservoirat the top. A peristaltic pump Masterflex, model 7550-62(Cole-Parmer Instrument Company, Chicago-Illinois,USA) was used to control the flow in the columns withfood-grade tubing (Norpene food -A60F, type 14).

The regeneration of the R1 resin was carried out withthree different solutions: NaCl (30 % p/v) (R1-Na), MgCl2(15 % p/v) (R1-Mg) and HCl (30 % v/v) (R1-H), the R2resin was regenerated with HCl solution (30 % v/v) andthe R3 resin with NaOH solution (30 % p/v). The rege-neration phase of the cation exchange resins was carriedout with percolation of ten bedvolumes (liquidvolume/resin volume) of the solution through the exchan-gers' column. The anion resin was regenerated in immer-sion using ten bedvolumes of NaOH solution, the mixturewas agitated during 75 minutes in an automatic agitator.

1) Experiments with cation exchangers

To evaluate the influence of the cation exchangers inthe wine composition and the breakthrough point for thecations we are studying (potassium, calcium, sodium,magnesium, iron and copper), the wine previously fil-tered, passed through a column of polymerized resin, anddifferent samples of the effluent were collected at regu-lar intervals. In these fractions, some oenological para-meters were measured.

In the second part, the exchanged wine was mixed indifferent proportions (5 %, 10 %, 15 % and 25 %) withthe untreated wine. The control wine (represented at 0 %),and the eluted wine (represented at 100 %) were also ana-lysed. In each lot, we have performed the analytical deter-minations. The control wines were subjected to a coldtreatment; thus, the wines were refrigerated at 0 ºC (thelowest temperature available in our experimental condi-tions) and kept at this temperature for 4 weeks. The assayswere performed in duplicate.

2) Experiments with anion exchanger

To evaluate the effect of the anion resin in the mainwine characteristics, different samples of eluted winewere collected at regular intervals and some parameterswere measured, as in the cation experiments.

3) Experiments with cation and anion exchangers

As in the previous experiments, the wine passedthrough the resins, first in cation resin and after that inanion resin; different samples of the effluent wine werecollected at regular intervals, and some oenological para-meters were measured.

In the second part, the exchanged wine passed pre-viously through a cation resin and next an anion resinwas mixed in different proportions (5 %, 10 %, 15 % and25 %) with the original wine. The control wine and theeluted wine (represented by 0 % and 100 %, respectively)were also analysed. The assays were performed in dupli-cate.


©Vigne et Vin Publications Internationales (Bordeaux, France)

Ion exchange resins for tartrate wine stabilization

IV - MINERAL COMPOSITION ANALYSIS

The concentration of cations (potassium, calcium,sodium, magnesium, iron and copper) was carried out byflame atomic absorption spectrophotometry (FAAS) usinga Varian Spectra 10/20 (Victoria, Australia), accordingto the official methods of OIV (OIV, 1990). Chloridescontent was determined by potentiometric method (OIV,1990) using a PHM 82 Standard pH meter (RadiometerAnalytical, Lyon, France).

V - COLOUR AND PHENOLIC COMPOUNDSEVALUATION

The total content of the phenolic compounds wasmeasured by the absorbance at 280 nm (RIBÉREAU-GAYON, 1970); tonality is defined as the ratio(A420 nm/A520 nm) and colour intensity as the sum(A420 nm+A520 nm+A620 nm). For the white wine, to mea-sure the wine colour intensity it was used the absorbanceat 420 nm. Colour measurements of the wines were alsoperformed according to the CIELAB 76 method(McLAREN, 1980). Spectral readings-transmittanceevery 10 nm over visible spectrum, 380-770 nm wereperformed with a UV4 Unican Visible Spectrometry(Cambridge, UK), using quartz cells of 1-mm (red wine)or 10-mm (white wine) path length. The software Chroma2.0 colour measurement was used to directly calculatethe CIELAB coordinates. L*, a* and b* values describea tree-dimensional colour space. The vertical axis L* isa measure of lightness, from completely opaque (0) tocompletely transparent (100), whereas on the hue-circlea* is a measure of redness (or -a* of greenness), and b*of yellowness (or -b* of blueness).

To red wine, the total pigments were estimated usingthe method of SOMERS and EVANS (1977); polyme-ric pigment index was determined by a method propo-sed by GLORIES (1978) and total anthocyanins evaluatedaccording to the method of RIBÉREAU-GAYON andSTONESTREET (1965). The data of each measurementare the average of duplicate samples.

VI - ACID COMPOSITION ANALYSIS

Organic acids (tartaric, malic, citric, lactic and shiki-mic acid) were analysed by high performance liquid chro-matography using a method described by TUSSEAU andBENOIT (1986a, b). Two columns with reverse phaseLichrospher 100 RP 8 (Merck, Darmastadt, Germany)(particle size 5 µm, 250 x 4 mm) were used. Detectionwas made with a UVIS 206 PHD (KONIK Instruments,Barcelona, Spain) set at 210 nm, and the peak areas weredetermined with Konikchrom 5.2 software.

pH, titrable and volatile acidity were determined byFourier Transform Infrared Spectrometry - FTIR(WineScan FT120, Foss, Slangerupgade, Denmark)


Helena MIRA et al.

Tabl

e I

- Evo

lutio

n of

cat

ions

and

chl

orid

e an

ion

cont

ent i

n th

e el

uted

whi

te a

nd re

d w

ine

A, u

sing

R1

resi

n in

Na+

form

(R1-

Na)

or

in M

g2+

form

(R1-

Mg)

Evo

lutio

n de

la c

once

ntra

tion

des

catio

ns e

t d'a

nion

chl

orur

e da

ns le

s vi

ns b

lanc

et r

ouge

A, a

près

l'ut

ilisa

tion

de la

rés

ine

R1

sous

form

e N

a+(R

1-N

a)

ou s

ous

form

e M

g2+

(R1-

Mg)

Leg

end:

nd

- no

t de

tect

ed;

R1-

Na

catio

n ex

chan

ge r

esin

in

sodi

um f

orm

; R

1-M

g ca

tion

exch

ange

res

in i

n m

agne

sium

for

m;

bv-

bedv

olum

es;

resi

n vo

lum

e =

50

mL

; fl

ow =

2.7

ml.m

in-1

(MOREIRA et al., 2002a, b), and the wine pH was alsodetermined by a potentiometric method (OIV, 1990).

VII - WINE TARTRATE STABILITY EVALUA-TION

Tartrate stability evaluation was done using twomethods: the mini-contact method, which was reportedby BOULTON (1982) and modified by VIALATTE(1984) and the determination of the temperature of satu-ration in wines (WURDIG et al., 1982; MAUJEAN etal., 1985) optimised by CAMEIRA-DOS-SANTOS etal. (2002). By the mini-contact method, the wine stabi-lity assessment is based on the difference between initialconductivity (Ci) and final conductivity (Cf). Generally,if such difference is less than 5 % of the original value,the wine is stable; otherwise the wine is instable. In whatconcerns the saturation temperature (Tsat), according toMAUJEAN et al. (1985) white wines are considered stableif Tsat is below 12 ºC-13 ºC, what means there isn't therisk of tartrate crystals precipitation.

The conductivimeter used to perform the Boultonmethod was a 220 model, Denver Instrument Company(Colorado, USA). The determination of the temperatureof saturation requires the measurement of the wine conduc-tivity by increasing the temperature at a constant rate; aCrison micro CM 2201 conductivity meter (Barcelona,Spain) was used to measure the values of conductivityand temperature. These values were registered by a per-sonal computer by means of RS232 port using acquisi-tion data software written by CAMEIRA-DOS-SANTOSet al. (2002). The wine was cooled to near 0 ºC and thenheated at predetermined heating rate up to 30 ºC. Thesame procedure was done with the wine containing 4 g/LKHT crystals. The heating rate was controlled by a pro-grammable bath Huber Polystat K6 (Offenburg,Germany). The saturation temperature is determined bythe intersection of the curves of conductivity versus tem-perature for both wines, with and without addition of crys-tals.

VIII - SENSORY EVALUATION

The six expert panellists were members of « ComissãoVitivinícola Regional do Ribatejo (CVRR) », they weretrained and had previous experience. We asked to thepanellists the differences between the control wine andeach sample of the assembled wine, randomized beforepresentation. The attributes of the wine, corresponding tothe visual, nose and taste senses, as well as the globalappreciation of each wine were carried out. Only the winesA, treated with cation exchange resins, were submitted tosensorial evaluation, owing the availability of the paneltest.

IX - STATISTICAL ANALYSIS

The factorial treatment design contained two factors:ion-exchange resins (R1 and R2, or R1+R3 and R2+R3)and a proportion of the treated wine (0 %, 5 %, 10 %,15 %, 25 % and 100 %). The data were analyzed byAnalysis of Variance using SPSS 12.0 for Windows. Thetreatment means were separated by Scheffée test at the5 % significance level.

RESULTS AND DISCUSSION

I - EFFECT OF THE TYPE OF RESIN AND REGE-NERATING SOLUTION IN SOME WINE PARA-METERS

1) Cation exchange resins experiments

a) Influence of the mineral composition

The resins showed a general behavior that can beobserved in two differentiated phases. During the firstone, named the « load phase », important exchange reac-tions took place among the cations presented in the wineand the cation fixed into the resin. In the « unload phase »,there are not initial cations fixed into the resin availableto be transferred from the resin to the wine. At thismoment, new exchange reactions occur among the dis-solved wine cations with higher affinity and the fixedcations with less affinity. In this phase, part of the low-affinity fixed cations returns to the wine.

The results for R1 resin regenerated with differentsolutions are presented in tables I and II. The wines sub-jected to treatment with the R1 resin in sodium or hydro-gen form showed a large decrease in the potassium,calcium and magnesium content, demonstrating the goodaffinity of the resin to those cations. However, the winetreated with R1-Na (table I) revealed a wide release insodium from the structure of the resin, reaching a highconcentration in exceeding sodium (> 1g/L); this evi-dence is not suitable once the maxim limit of the excee-ding sodium content established by OIV (1990) is60 mg/L (express in NaCl), and for USA the limit is200 mg/L. The increase in sodium content was moreimportant in the red wine than in the white wine, due toa greater amount of cations in the red wine. Later, theconcentration of the potassium started to increase in thewine, indicating that it was reached the equilibrium bet-ween the sodium in the resin and the cations presentedin the wine; the cation exchange continued with the releaseof the potassium cation. The breakthrough point of thepotassium was verified around 50 bedvolumes for whitewine and 40 bedvolumes for red wine; during all the pro-cess we didn't find the breakthrough point to calcium,indicative of good affinity to this divalent cation. The R1-Na resin showed some affinity to iron.




The R1-Mg resin (table I) showed a smaller affinityto potassium than R1-Na resin, whose breakthrough pointto potassium was verified at 16 bedvolumes both to thewhite and the red wine. These results were in accord withWEINAND and DEDARDEL (1994) who reported thatthe affinity of exchange increases with the valence of theexchanger ion; the exchanger has more difficulty in repla-cing the magnesium for potassium; confirming this is thegood affinity verified to Ca2+. A great release of magne-sium into wine was observed. Nevertheless, this cationdoesn't cause any health problems, and doesn't have anyinfluence in sensory characteristics and in wine quality(RIBÉREAU-GAYON et al., 1977).

The R1-H resin (table II) showed a good affinity topotassium, sodium, calcium and magnesium. The varia-tion of the concentration of potassium and sodium duringthe process is similar; the breakthrough point of thesecations has occurred around 50 bedvolumes for whitewine and 40 bedvolumes for red wine. The resin had someaffinity to iron. The samples showed a considerabledecrease in pH to values less than 2.0 pH-values (figure 1)and remained constant during the load phase. Thisconfirms the cation exchange between H+ in the resinand the cations presented in the wine; later, when the ionicequilibrium was reached in the resin, the rate of the H+

decreased and the pH of the eluted wine picked up gra-dually to the pH of the control wine, what is consistent

with the previous results of MOURGUES (1993). Theincrease in titrable acidity is related to the increase of theH+ content; confirming the data obtained by WALKERet al. (2002). The variation of the pH in the eluted winestreated with resins in sodium or magnesium form wasnegligible.

The different forms of the R1 resin showed high affi-nity to calcium as it is a divalent cation.

Using the R2 resin (table II), the results showed agood affinity to potassium, calcium, sodium and magne-sium, similar behaviour observed to R1-H mentionedabove. The breakthrough point to potassium occurredaround 60 bedvolumes to white wine and 50 bedvolumesto red wine.

Both resins, R1 and R2, have shown small affinity tocopper, probably due to the small content of this metalpresented by our wines. Some authors (PALACIOS etal., 2001a; BENITEZ et al., 2002b) using other functio-nal resins have shown good affinity to copper, howevertheir wines had higher copper levels.

b) Influence on colour and phenolic composition

In general, for white wine (figure 2) it was obser-ved an initial quick decrease in the total phenol index andsome increase in the absorbance at 420 nm during the


Helena MIRA et al.

Legend: nd - not detected; bv - bedvolumes; resin volume = 50 mL; flow = 6 ml.min-1

Table II - Evolution of cations and chloride anion content in the eluted white and red wine,using R1 and R2 resin in H+ form

Evolution de la concentration des cations et d'anion chlorure dans les vins blanc et rouge, après l'utilisation des résines R1et R2 sous forme H+

load phase, followed by a slow increase of the total phe-nols and a decrease of A420 until it reached similar valuesto the control wine. Phenolic parameters and chromaticcharacteristics of the red wine treated with R1-Na andR1-Mg (data not shown) revealed an initial decrease inthese parameters in the load phase, comparatively tocontrol wine; followed by a slow increase. Similar evo-lution was observed to the wine treated with resins in thehydrogen form, although the differences to the controlwine were higher. The results of the red wine treated withR1-H and R2-H indicated that it had an initial retentionof phenolic compounds in the matrix resin, expressed forthe reduction of total phenols index, total anthocyanins

content and total pigments colour, confirming later somerelease of the anthocyanins from the resin matrix (datanot shown), although these results didn't have relevantoenological implications.

c) Influence on the organic acid composition

As expected, the cation exchange did not affect theconcentration of the organic acids evaluated by HPLC(data not shown). The organic acid content in the whitewine A was the following: tartaric acid (3.8 g/L), malicacid (2.6 g/L), shikimic acid (40 mg/L), lactic acid(0.5 g/L) and citric acid (873 mg/L). The organic acid




Figure 1 - Evolution of pH and titrable acidity (TA) in treated wines B of the cation exchange R1-H

Évolution du pH et de l'acidité totale des vins B, après passage sur la résine échangeuse de cations R1-H

Figure 2 - Evolution of the total phenol indexand absorbance at 420 in treated white wine B

of the cation exchange R1-H

Évolution de l'indice de phénols totaux et de la A420 du vin blanc B après passage sur la résine échangeuse

de cations R1-H

Table III - Characteristics of eluted white wine B using double exchange with R1 and R3 resinsCaractéristiques du vin blanc B après passage sur les résines échangeuses R1 et R3

Legend: nd - not detected; na - not analysed, R1 - cation exchange resin in H+ form, R3 - anionexchange resin in OH- form; resin volume = 50 mL; flow = 6 ml.min-1

composition of the red wine A was the subsequent: tar-taric acid (2.3 g/L), malic acid (0.4 g/L), shikimic acid(35 mg/L), lactic acid (3.5 g/L) and citric acid (947 mg/L).The values obtained for organic acids analysis of thecontrol white and red wines B were presented in tablesVII and XIII, respectively.

2) Anion exchange resin experiments

The anion exchangers are commonly used in asso-ciation with the cation exchangers. Nevertheless, we havestudied the influence of the anion exchange in some winecharacteristics. The white and red wines showed signifi-cant variations in the colour characteristics from the begin-ning of the load phase. Concerning the white wine, thetotal phenol index and the absorbance at 420 nm pre-sented lower values when compared with the control wine(data not shown). The lightness increased for values nextto 100 % in the first samples; these results were in accor-dance with the visual observation in which the elutedwine showed totally transparent, due to a great retentionof the wine constituents in the matrix resin. In the initialphase of treatment, the red wine presented a decrease inthe content of the phenolic compounds as well as in atotal pigments colour and anthocyanin content compa-ratively to the control wine, probably due to adsorptionof phenolic compounds in the matrix resin, which contri-bute to a colour modification of the resin (visually iden-

tified). A large increase (from 50 % to 82 % in the first10 bv) of the polymerized pigment index can be relatedwith the possible retention of the monomeric pigmentsonce the total pigments decreased quickly.

It was verified a large increase (from 3.42 to 11.44 inthe first 10 bv) in the wine pH, great in the red wine, thisfact is consequence of ion exchange between OH- in theresin and the anions presented in the wine. It was alsoobserved a wide release of Cl- anion (from 32 mg/L to amaximum of 381 mg/L at the 35 bv), during the regene-ration of the resin, the dissolved OH- in the regenerationsolution were exchanged with the Cl- anions in the resin,but possibly some Cl- anions remained in the matrix resin,which later were exchanged with the wine anions.

The R3 resin has shown some affinity to organic acids,mainly to tartaric acid; despite that, the breakthroughpoint to tartaric acid was verified at around 20 bedvo-lumes and slightly earlier to the other organic acids. Asexpected, the anion resin doesn't be influence the cationscontent (data not shown).

3) Cation and anion exchange resins experiments

The two resins, in a sequential use, have presenteda similar behaviour; the wide differences between controland eluted wine were show in the first collected sample,


Helena MIRA et al.

Table IV - Characteristics of eluted red wine B using double exchange with R1 and R3 resinsCaractéristiques du vin rouge B après passage sur les résines échangeuses R1 et R3

Legend: nd - not detected; R1 - cation exchange resin in H+ form, R3 - anion exchange resin in OH- form; resinvolume = 50 mL; flow = 6 ml.min-1

nevertheless the values recovered progressively to thecontrol wine values.

a) Influence on the mineral composition

As it can be observed in table III, the white wine trea-ted with R1+R3 resins presented initially an importantdecrease in the concentration of all cations. The break-through point to potassium was around 60 bedvolumes,slightly upper than the verified in the previous experi-ment. The sodium had a similar behaviour as potassium.During the unload phase the concentrations of potassiumand sodium were higher than the ones shown by thecontrol. The concentrations of the calcium, magnesiumand iron were low and constant in the eluted wine duringthe whole experiment, due the good affinity of the resinto these cations. Initially, the chloride anion is partiallyretained in the anion resin matrix, but at 20 bedvolumesthe concentration of chlorides increases significantly, tovalues greater than the chlorides content of the controlwine. This suggests that, in addition to the release of fixedchloride anions, some chlorides which were not exchan-ged with the OH- during the operation of the resin rege-neration-phase were released in the load phase.

The results for white wine using R2+R3 resins (datanot shown) were similar to the observed with R1+R3resins, but the breakthrough point to potassium occurredat 50 bedvolumes; earlier than in the experiment withR1+R3 resins.

For the red wines, the results observed using theR1+R3 resins or R2+R3 are quite similar. The break-through point to potassium was reached at 50 bedvolumesto the wine treated with R1+R3 resins (table IV) and at40 bedvolumes to the wine treated with R2+R3 (data notshown). Using R1+R3, the sodium had the same beha-viour as the potassium, although R2+R3 had showed lesscapacity to restraint the sodium. The two groups of resinsshowed a great reduction of calcium and magnesiumcontent. Relatively to Cl-, a significant retention in thefirst fractions was verified; being the breakthrough pointaround 20 bedvolumes, the same as is in the previousexperiments.

b) Influence on colour and phenolic composition

The results of the eluted white wine using doubleexchange with R1+R3 resins are presented in table III,and are similar to those observed using R2+R3 resins (datanot shown). As it can be observed, the double exchangepresented a great reduction in the phenolic compoundsand in the colour characteristics of the wine when com-pared to the treatment with only one resin. As mentioned,in general, it was observed bigger differences betweenthe first collected samples and the control wine followedby a slow increase until it reached the control wine values.

The reduction of the total phenols content and the absor-bance values at 420 nm indicating the retention of thephenolic constituents in the resins matrix which influen-ced the wine colour and increased the wine lightness.

The results of eluted red wines using R1+R3 resins(table IV) and R2+R3 resins (data not shown) were rathersimilar. The eluted wines showed important reduction inthe total phenols, total anthocyanins content and total pig-ment colour, probably due to a considerable retention ofthe phenolic constituents of the wine in the two resinsmatrix. The polymerized pigments index had a sharpincrease in the first collected samples and diminishedlater, however always presenting high values compara-tively to control wine, indicating that the ratio of poly-merized pigments in the eluted wine increased. Thevariations of the colour intensity, tonality and chromaticcharacteristics are related to the retention of the wineconstituents in the matrix resins and pH wine.

c) Effect in the organic acid composition

The experiments revealed that the resin had a betteraffinity to acid tartaric. For white wines, the results indi-cated that the breakthrough point to tartaric acid occur-red at around 20 bedvolumes and slightly earlier thanother organic acids. Similar results were observed withthe red wine.

d) Tartrate wine stabilization

The process of tartrate wine stabilization must be car-ried out during the load phase. In this phase, the potas-sium, calcium and other cations are retained with verygood effectiveness. However, if the treatment is pro-longed already to the load phase, some cations initiallyretained by the resin will be released to the wine, mainlymonovalent cations, according to the affinity laws. Thecycle volume of the process corresponding to the loadphase is in general 50 bedvolumes in the white wines and40 bedvolumes in the red wines.

Both resins demonstrated to be effective in redu-cing the content of calcium; the wines are that predispo-sed to Ca2+ precipitation can be stabilized with the ionexchange technology which is not entirely possible withcold treatment, as suggested by HERNÁNDEZ andMÍNGUEZ (1997), as this treatment is particularly tar-geted to potassium cation and tartaric anion of wines.

Given the effectiveness of the potassium and calciumremoval, the reduction in pH wine, and losses in phe-nolic compounds particularly the anthocyanins, is sui-table to treat the wine partially and blend it with the restof the wine.

II - TECHNOLOGICAL ASSAYS WITH WHITEAND RED WINES





Helena MIRA et al.

Tabl

e V

- M

ain

effe

cts

of c

atio

n-ex

chan

ge r

esin

s an

d di

ffer

ent p

ropo

rtio

ns o

f tre

ated

and

unt

reat

ed w

ine

by c

atio

n ex

chan

ge o

n so

me

whi

te w

ine

A c

hara

cter

istic

sIn

fluen

ce d

es r

ésin

es é

chan

geus

es d

e ca

tions

et d

es p

ropo

rtio

ns c

rois

sant

es d

e vi

n tr

aité

sur

les

cara

ctér

istiq

ues

du v

in b

lanc

A

Tre

atm

ent

mea

ns w

ere

sepa

rate

d by

Sch

effé

e te

st a

t th

e 5

% s

igni

fica

nce

leve

l. D

iffe

rent

let

ters

in

the

sam

e co

lum

n in

dica

te s

tatis

tical

ly s

igni

fica

nt d

iffe

renc

es:

* (p

≤0.0

5), *

* (p

≤0.0

1), n

s-no

t si

gnif

ican

t. R

1-

Na

catio

n ex

chan

ge r

esin

in s

odiu

m f

orm

; R1-

Mg

catio

n ex

chan

ge r

esin

in m

agne

sium

for

m; R

2 -

catio

n ex

chan

ge r

esin

in h

ydro

gen

form

¸ r

esin

vol

ume

= 5

0 m

L; f

low

= 2

.7 m

l.min

-1

Ipt -

Tot

al p

heno

ls in

dex;

A42

0-

Abs

orba

nce

at 4

20 n

m; L

*, a

* an

d b*

- C

IEL

AB

cor

dina

tes;

H2T

- T

arta

ric

Aci

d; T

A -

Titr

able

Aci

dity

; VA

- V

olat

ile A

cidi

ty




Tabl

e V

I - M

ain

effe

cts

of c

atio

n-ex

chan

ge r

esin

s an

d di

ffer

ent p

ropo

rtio

ns o

f tre

ated

and

unt

reat

ed w

ine

by p

roto

n ex

chan

ge o

n so

me

whi

te w

ine

B c

hara

cter

istic

sIn

fluen

ce d

es r

ésin

es é

chan

geus

es d

e ca

tions

en

cycl

e ac

ide

et d

es p

ropo

rtio

ns c

rois

sant

es d

e vi

n tr

aité

sur

les

cara

ctér

istiq

ues

du v

in b

lanc

B

Tre

atm

ent m

eans

wer

e se

para

ted

by S

chef

fée

test

at t

he 5

% s

igni

fica

nce

leve

l. D

iffe

rent

lette

rs in

the

sam

e co

lum

n in

dica

te s

tatis

tical

ly s

igni

fica

nt d

iffe

renc

es: *

(p≤

0.05

), *

* (p

≤0.0

1), n

s-no

t sig

nifi

cant

R1

and

R2

- ca

tion

exch

ange

res

ins

in h

ydro

gen

form

; res

in v

olum

e =

100

mL

; flo

w =

6 m

l.min

-1

Ipt -

Tot

al p

heno

ls in

dex;

A42

0-

Abs

orba

nce

at 4

20 n

m; L

*, a

* an

d b*

- C

IEL

AB

cor

dina

tes;

H2T

- T

arta

ric

Aci

d; T

A -

Titr

able

Aci

dity

; VA

- V

olat

ile A

cidi

ty


Helena MIRA et al.

Tabl

e V

II -

Mai

n ef

fect

s of

ion-

exch

ange

res

ins

and

diff

eren

t pro

port

ions

of t

reat

ed a

nd u

ntre

ated

whi

te w

ine

B b

y ca

tion

and

anio

n ex

chan

ge o

n so

me

win

e ch

arac

teri

stic

sIn

fluen

ce d

u do

uble

exc

hang

e ca

tioni

que-

anio

niqu

e et

des

pro

port

ions

cro

issa

ntes

de

vin

trai

té

sur

les

cara

ctér

istiq

ues

du v

in B

Tre

atm

ent m

eans

wer

e se

para

ted

by S

chef

fée

test

at t

he 5

% s

igni

fica

nce

leve

l. D

iffe

rent

lette

rs in

the

sam

e co

lum

n in

dica

te s

tatis

tical

ly s

igni

fica

nt d

iffe

renc

es: *

(p≤

0.05

), *

* (p

≤0.0

1), n

s-no

t sig

nifi

cant

R1,

R2

- ca

tion

exch

ange

res

ins

in H

+ f

orm

; R3

- an

ion

exch

ange

res

in in

OH

- fo

rm¸

resi

n vo

lum

e =

100

mL

; flo

w =

6 m

l.min

-1

Ipt -

Tot

al p

heno

ls in

dex;

A42

0-

Abs

orba

nce

at 4

20 n

m; L

*, a

* an

d b*

- C

IEL

AB

cor

dina

tes;

TA

- T

itrab

le A

cidi

ty; V

A -

Vol

atile

Aci

dity

, H

2T -

Tar

tari

c A

cid;

Mal

. Ac-

* M

alic

aci

d; L

act.

Ac.

- L

actic

aci

d.

In order to examine the effect of the ion exchangetreatments in the tartrate stability, phenolic, mineral andorganic acid composition, the eluted wines were partiallyblended with untreated wine, to produce lots with diffe-rent proportions of treated wine. We have studied if thedifferent lots were stable, without significant modifica-tions in the sensory attributes and also it they satisfied therequirements of the OIV (1995).

1) White wines

The results using R1 resin in magnesium or sodiumform, comparatively to R2 resin (in H+ form) are repor-ted in table V (wine A). According to the results obtainedin the first year of assays, we have used in the 2nd yearR1 and R2 resins only in H+ form. The characterizationsof wines resulting from the mixture of treated wine withR1 or R2 resins are presented in table VI (wine B). Theresults obtained by double ion-exchange resins are repor-ted in table VII.

a) Effects in the phenolic content and wine chroma-tic characteristics

The comparison of the R1 resin in magnesium andsodium form and R2 resin (table V) indicated that thewine resulting from the mixture of the control wine withthe treated wine with R1-Mg resin was higher in total phe-nolic content as well as the absorbance at 420 nm thanlots resultant of the mixtures of treated wine with othersresins. Concerning the wine B (table VI), the R2 resinshowed higher adsorption of the phenolic compoundsthan R1. About the wine chromatic characteristics wehave obtained no differences in the lightness, but signifi-cant variations in A420 as well as a* and b* coordinates.

As it can be observed, when the percentage of treatedwine in the mixture increased, the phenolic compoundsdecreased significantly, as compared to control wine. Theabsorbance at 420 nm slightly decreased in wine A andslightly increased in wine B; probably these variationsare related to the adsorption of wine compounds in theresins matrix and also with the pH wine variation. In bothwines (A and B), the a* coordinate increased along withthe percentage of treated wine and the b* decreased. Theresults showed that the treated wines were significantlydifferent than the control wine; however, wines with dif-ferent proportions of treated wine presented intermediatecharacteristics between the control wine and 100 % oftreated wine. These results are consistent with those obtai-ned by MOURGUES (1993), WEINDARD andDEDARDEL (1994) and BENITEZ et al. (2002a, b).

The two groups of resins (R1+R3) and (R2+R3) sho-wed similar behaviour relatively to phenolic constituentsand wine chromatic characteristics. As the percentage oftreated wine in the mixtures increased, the concentration

in total phenols decreased; however this decrease washigher in the double ion exchange than in the cationexchange. The results revealed a slight increase in thelightness, and decrease in the a* and b* coordinates, pos-sibly due to some retention of the wine constituents inthe resin matrix (table VII).

b) Effect in the mineral composition

Confirming the previous assays, R1-Na and R2-Hresins have shown more ability than R1-Mg in removingthe potassium.

As expected, the wine treated with R1-Na resin sho-wed higher sodium content, as already shown. Theconcentration of sodium in the 25 % of treated wine was204 mg/l, while for 100 % was 480 mg/l confirmingthe large release of this cation to the wine, although thetreated wine with R1-Mg presented high magnesiumcontent.

When both resins were in the H+ form (table VI), theresins revealed good affinity to potassium and calciumand some to iron, when the percentage of treated wine inthe lots increased, the cation contents decreased, and thewine pH lowered. For the 100 % treated wine, the sumof cations was < 2 mg/l and the pH < 2.0. As suggestedby PALACIOS et al. (2001b) and BENITEZ et al. (2002a)the reduction in phenolic compounds content and the par-tial elimination of metal cations in the wines, as iron andcopper, are interesting to increase the oxidative stability,which is especially important mainly in white wines.

As expected, there weren't any significant differencesin the chloride anion content in the wines treated withcation resins.

The results obtained for double exchange, with thetwo groups of resins, confirm those presented with thecation exchange. As the percentage of treated wine in themixtures increased, the concentration in cations decrea-sed; nevertheless, the variation in chlorides content wasnot significant.

c) Effect in pH, titratable and volatile acidity

The lots with wines treated with resins in Mg2+ orNa+ forms showed no significant variations in pH values.The wines treated with resins in acid cycle presented asignificant decrease in pH to values low 2.0, although themixtures with a certain percentage of treated wine revea-led some decrease in pH, but never more than 0.3 pHunits, as established by OIV (1995, 1998). The winesshowed a slight increase in total acidity due to the increasein concentration of the H+. This is an important aspect towines produced in countries with hot climate, which isthe case of Portugal, as suggested by MIRANDA PATO





Helena MIRA et al.

Tabl

e V

III

- Tar

trat

e st

abili

ty e

valu

atio

n of

the

mix

ture

s in

diff

eren

t pro

port

ions

of t

reat

ed a

nd u

ntre

ated

whi

te w

ine

by c

atio

n ex

chan

ge r

esin

s, b

y ca

tion

and

anio

n ex

chan

ge r

esin

s an

d co

ld tr

eatm

ent (

tem

pera

ture

of s

atur

atio

n an

d m

ini-c

onta

ct te

st)

Éva

luat

ion

de la

sta

bilit

é ta

rtri

que

des

vins

ave

c pr

opor

tions

cro

issa

ntes

de

vin

trai

té p

ar r

ésin

es c

atio

niqu

es

et d

u vi

n st

abili

sé p

ar le

froi

d (m

étho

de d

e la

tem

péra

ture

de

satu

ratio

n ou

test

de

min

i-con

tact

)

R1-

Na

catio

n ex

chan

ge r

esin

in s

odiu

m f

orm

; R1-

Mg

catio

n ex

chan

ge r

esin

in m

agne

sium

for

m; R

2 -

catio

n ex

chan

ge r

esin

in h

ydro

gen

form

(1961) and MOURGUES (1993). In addition, we haveverified a slight decrease in volatile acidity.

For double cation-anion exchange, the wine pH suf-fered a slight reduction with increment in the percen-tage of treated wine. However, the pH did not decreasemore than 0.3 pH units in the studied percentages, whatis in accordance with the imposed restrictions from OIV(1995). As the percentage of treated wine in the mixturesincreased, the titrable and volatile acidity decreased com-paratively to the control wine.

d) Effect in the organic acid composition

No important differences in organic acid concentra-tion were observed for both resins in different forms andany percentages of treated wine (data no shown).

It can be observed that the two groups of resins had asimilar behaviour in what concerns to the organic acidcomposition (table VII). The results showed that, exceptto shikimic acid, as the percentage of treated wine in themixtures increased, the organic acids content decreased.

e) Wine tartrate stability evaluation

The results of wine tartrate stabilization are presentedin table VIII; we can see the values of the temperaturesof saturation for the different wines (A and B wines) aswell as the results of the Boulton test for wine B. As it canbe observed to wine A, no percentage of treated wine withR1-Mg and R1-Na has revealed stable. Only the 25 %wine treated with R2 resin was stable. For wine B, the tar-trate stability was evaluated by two methods, neverthe-less different results were obtained. The results ofmini-contact method revealed that the totality of the winelots which were treated with R1 resin were stable, whilefor mixtures with wine treated with R2 resin, only themixtures with more than 5 % of treated wine showed sta-bility. Concerning the results to the temperature of satu-ration showed that the mixtures were stable with 10 %treated wine with R1-H but required 25 % of treated winewith R2 resin. This is in accordance with our previousworks, where the highest affinities to potassium and cal-cium with R1 resin was evidenced. The cold treatment(one month at 0 ºC) was not enough to stabilize the wine,which can be explained by the fact that a treatment at 0 ºChave not been sufficient to induce the tartrate salts pre-cipitation or probably this was also due to an abnormalcontent of protector colloids in the wine.

The results for the double cation-anion revealed formini-contact method, the treated wines with (R1+R3)resins were stable for all proportions, while using (R2+R3)resins only the wines with more than 5 % treated wineshowed stables. However, according to the results of satu-ration temperature, the wines with mixture of treated wineusing (R1+R3) resins were stable for proportions higher

than 5 %, while for wine treated with (R2+R3) resinsonly the wine with 25 % of treated wine was stable. Thisis in accordance with our previous work with cationexchanger resins; therefore the double cation-anionexchange did not present better results than the cationexchange.

f) Sensory evaluation

In table IX, we present the average of the scores oftreated wines with different cationic resins, and also theaverage of the different percentages of treated wine. Nosignificant differences in sensory attributes of the mix-tures were observed.

2) Red wines

The results using R1 resin in magnesium form com-paratively to R2 resin (in H+ form) are reported in table X(wine A), and the results using both resins in H+ form arepresented in table XI (wine B).

a) Effects in the phenolic composition and wine chro-matics characteristics

The ion exchange influences to certain extent, thephenolic compounds and chromatic characteristics. Theslight decrease in the phenol compounds, verified withthe increase of the percentage of treated wine in lots, wasevidenced by the diminution in total phenol concentra-tion, anthocyanins content and by the decrease in pig-ment colour, probably due to some pigments retention inthe resins' surface, which is in conformity with the resultsobtained by other authors (WALKER et al., 2002, BENI-TEZ et al., 2002a). In addition, we observed an increasein polymerized pigments, possibly explained by the reten-tion of small pigments, like the monomeric anthocyaninsin the resins. In order to examine the effect of ion exchangetreatments in the anthocyanins composition, an HPLCanalysis was carried out for wine B. The results are repor-ted in table XII. We can observe that the wines treatedwith R1 resin showed higher reduction in anthocyaninscontents than the wines treated with R2, confirming theresults obtained for total anthocyanins. Generally, thecontent of theses all compounds decreased along withthe increase in treated wine, and the eluted wine (100 %)presented significantly lower contents of these com-pounds. The group of the 3-monoglucosides has presen-ted the highest reduction, probably due to the highestconcentration in wine.

On the other hand, the verified diminution in the winepH is able to influence the chromatic characteristics; whatthis is consistent with the work of HERNÁNDEZ andMÍNGUEZ (1997). The ion exchange increased thecolour intensity and decreased the tonality, what was alsoobserved by WALKER et al. (2002).





Helena MIRA et al.

Tabl

e IX

- Se

nsor

y an

alys

is r

esul

ts o

f the

win

e st

abili

zed

by c

atio

n ex

chan

ge re

sins

. Val

ues

of th

e sc

ores

from

1 (m

inim

um) t

o 5

(max

imum

) for

eac

h at

trib

ute,

exce

pt g

loba

l app

reci

atio

n th

at is

from

1 to

20

Rés

ulta

ts d

e l'a

naly

se s

enso

riel

le d

es v

ins

stab

ilisé

s pa

r ré

sine

s éc

hang

euse

s de

cat

ions

. Cla

ssifi

catio

n de

1 (m

inim

um) à

5 (m

axim

um) p

our

chaq

ue a

ttri

but,

exce

pté

appr

écia

tion

glob

ale

(de

1 à

20)

R1-

Na

catio

n ex

chan

ge r

esin

in s

odiu

m f

orm

; R1-

Mg

catio

n ex

chan

ge r

esin

in m

agne

sium

for

m; R

2 -

catio

n ex

chan

ge r

esin

in h

ydro

gen

form

; a -

not

eva

luat

ed.




Tabl

e X

- M

ain

effe

cts

of c

atio

n-ex

chan

ge r

esin

s an

d pr

opor

tions

of t

reat

ed w

ine

on s

ome

red

win

e A

cha

ract

eris

tics

Influ

ence

des

rés

ines

éch

ange

uses

de

catio

ns e

t des

pro

port

ions

cro

issa

ntes

de

vin

trai

té s

ur le

s ca

ract

éris

tique

s du

vin

A

Tre

atm

ent m

eans

wer

e se

para

ted

by S

chef

fée

test

at t

he 5

% s

igni

fica

nce

leve

l. D

iffe

rent

lette

rs in

the

sam

e co

lum

n in

dica

te s

tatis

tical

ly s

igni

fica

nt d

iffe

renc

es: *

(p≤

0.05

), *

* (p

≤0.0

1), n

s-no

t sig

nifi

cant

, nd-

not

dete

cted

; na-

not

ana

lyse

d

R1-

Mg:

cat

ion

exch

ange

res

in in

Mg2

+fo

rm; R

2 -

catio

n ex

chan

ge r

esin

in H

+fo

rm; r

esin

vol

ume

= 5

0 m

L; f

low

= 2

.7 m

l.min

-1

Ipt-

tot

al p

heno

ls i

ndex

; In

t -

colo

ur i

nten

sity

; T

on -

Ton

alit

y; L

*;a*

, b*

- C

IEL

AB

coo

rdin

ates

; A

nt -

Tot

al A

ntho

cyan

ins

(exp

ress

mg/

L M

alvi

din-

3-gl

ucos

ide)

; P

GT

- T

otal

pig

men

ts c

olou

r; I

PP

-Po

lym

eriz

ed P

igm

ents

Ind

ex; K

- p

otas

sium

; Ca

- C

alci

um; N

a -

Sodi

um; M

g -

Mag

nesi

um; C

u -

Cop

per;

Fe

- Ir

on; C

l - C

hlor

ide;

H2T

- T

arta

ric

Aci

d; T

A -

Titr

able

Aci

dity

(g/

L ta

rtra

te a

cid)

; VA

- V

olat

ileA

cidi

ty (

g/L

ace

tic a

cid)

.


Helena MIRA et al.

Tabl

e X

I - M

ain

effe

cts

of c

atio

n-ex

chan

ge r

esin

s an

d pr

opor

tions

of t

reat

ed w

ine

on s

ome

red

win

e B

cha

ract

eris

tics

Influ

ence

des

rés

ines

éch

ange

uses

de

catio

ns e

t des

pro

port

ions

cro

issa

ntes

de

vin

trai

té s

ur le

s ca

ract

éris

tique

s du

vin

B

Tre

atm

ent m

eans

wer

e se

para

ted

by S

chef

fée

test

at t

he 5

% s

igni

fica

nce

leve

l. D

iffe

rent

lette

rs in

the

sam

e co

lum

n in

dica

te s

tatis

tical

ly s

igni

fica

nt d

iffe

renc

es: *

(p≤

0.05

), *

* (p

≤0.0

1), n

s-no

t sig

nifi

cant

, nd-

not

dete

cted

R1-

H: c

atio

n ex

chan

ge r

esin

in H

+fo

rm; R

2 -

catio

n ex

chan

ge r

esin

in H

+fo

rm; r

esin

vol

ume

= 1

00 m

L; f

low

= 6

ml.m

in-1

Ipt-

tot

al p

heno

ls i

ndex

; In

t -

colo

ur i

nten

sity

; T

on -

Ton

alit

y; L

*, a

*, b

* -

CIE

LA

B c

oord

inat

es;

Ant

- T

otal

Ant

hocy

anin

s (e

xpre

ss m

g/L

Mal

vidi

n-3-

gluc

osid

e);

PG

T -

Tot

al p

igm

ents

col

our;

IP

P -

Poly

mer

ized

Pig

men

ts I

ndex

; K -

pot

assi

um; C

a -

Cal

cium

; Na

- So

dium

; Mg

- M

agne

sium

; Cu

- C

oppe

r; F

e -

Iron

; Cl -

Chl

orid

e; H

2T -

Tar

tari

c A

cid;

TA

- T

itrab

le A

cidi

ty (

g/L

tart

rate

aci

d); V

A -

Vol

atile

Aci

dity

(g/

L a

cetic

aci

d).




Tabl

e X

II -

Mai

n ef

fect

s of

ion-

exch

ange

res

ins

and

prop

ortio

ns o

f tre

ated

win

e on

mon

omer

ic a

ntho

cyan

ins

(mg/

L) o

f red

win

e B

Influ

ence

des

rés

ines

éch

ange

uses

d'io

ns e

t des

pro

port

ions

cro

issa

ntes

de

vin

trai

té s

ur le

s an

thoc

yani

nes

mon

omér

ique

s (m

g/L

) du

vin

B

Tre

atm

ent m

eans

wer

e se

para

ted

by S

chef

fée

test

at t

he 5

% s

igni

fica

nce

leve

l. D

iffe

rent

lette

rs in

the

sam

e co

lum

n in

dica

te s

tatis

tical

ly s

igni

fica

nt d

iffe

renc

es: *

(p

≤0.

05),

**

(p≤

0.01

), n

s-no

t sig

nifi

cant

, nd

- no

t det

ecte

d. R

1 an

d R

2 -

catio

n ex

chan

ge r

esin

s in

H+

form

; R3

- an

ion

exch

ange

res

in in

OH

-fo

rm

Df3

glc:

Del

phin

idin

-3-m

onog

luco

side

; C

y3gl

c: C

yani

din-

3-m

onog

luco

side

; P

t3gc

lc:

Pet

unid

in-3

-mon

oglu

cosi

de;

Pn3

glc:

Peo

nidi

n-3-

mon

oglu

cosi

de;

Mv3

glc:

Mal

vidi

n-3-

mon

oglu

cosi

de;

sum

of

the

3-m

onog

luco

side

s of

the

Df,

Cy,

Pt,

Pn, M

v; D

f3ac

glc:

Del

phin

idin

-3-m

onog

luco

side

-ace

tate

; Pt3

acgl

c: P

etun

idin

-3-m

onog

luco

side

-ace

tate

; Pn3

acgl

c: P

eoni

din-

3-m

onog

luco

side

-ace

tate

; Mv3

acgl

c: M

alvi

din-

3-m

onog

luco

side

-ace

tate

; ∑A

cetic

aci

d es

ters

- S

um o

f th

e ac

etic

aci

d es

ters

; Df3

cmgl

c: D

elph

inid

in-3

-mon

oglu

cosi

de-p

-cou

mar

ate;

Pt3

cmgl

c: P

etun

idin

-3-m

onog

luco

side

-p-c

oum

arat

e; P

n3cm

glc:

Peo

nidi

n-3-

mon

oglu

cosi

de-p

-cou

mar

ate;

Mv3

cmgl

c: M

alvi

din-

3-m

onog

luco

side

-cou

mar

ate;

∑C

oum

aric

aci

d es

ters

- s

um o

f th

e C

oum

aric

aci

d es

ters

; Mv3

glcp

y: M

alvi

din-

3-m

onog

luco

side

-pir

uvat

e (V

itisi

n A

).


Helena MIRA et al.

Tabl

e X

III

- Mai

n E

ffec

ts o

f Dou

ble

catio

n-an

ion

exch

ange

res

ins

and

prop

ortio

ns o

f tre

ated

win

e on

red

win

e B

cha

ract

eris

tics

Influ

ence

du

doub

le é

chan

ge c

atio

niqu

e-an

ioni

que

et d

es p

ropo

rtio

ns c

rois

sant

es d

e vi

n tr

aité

sur

la c

ompo

sitio

n du

vin

B

Tre

atm

ent m

eans

wer

e se

para

ted

by S

chef

fée

test

at t

he 5

% s

igni

fica

nce

leve

l. D

iffe

rent

lette

rs in

the

sam

e co

lum

n in

dica

te s

tatis

tical

ly s

igni

fica

nt d

iffe

renc

es: *

(p≤

0.05

), *

* (p

≤0.0

1), n

s-no

t sig

nifi

cant

, nd-

not d

etec

ted.

R1,

R2

- ca

tion

exch

ange

res

ins

in H

+ f

orm

; R3

- an

ion

exch

ange

res

in in

OH

-fo

rm. R

esin

vol

ume

= 1

00 m

L; f

low

= 6

ml.m

in-1

.

Ipt-

tot

al p

heno

ls i

ndex

; In

t -

colo

ur i

nten

sity

; T

on -

Ton

alit

y; L

*, a

*, b

* -

CIE

LA

B c

oord

inat

es;

Ant

- T

otal

Ant

hocy

anin

s (e

xpre

ss m

g/L

Mal

vidi

n-3-

gluc

osid

e);

PG

T -

Tot

al p

igm

ents

col

our;

IP

P -

Poly

mer

ized

Pig

men

ts I

ndex

; K -

pot

assi

um; C

a -

Cal

cium

; Na

- So

dium

; Mg

- M

agne

sium

; Cu

- C

oppe

r; F

e -

Iron

; Cl -

Chl

orid

e; H

2T -

Tar

tari

c A

cid;

TA

- T

itrab

le A

cidi

ty (

g/L

tart

rate

aci

d), V

A -

Vol

atile

Aci

dity

(g/

L a

cetic

aci

d).




R1-

Mg

catio

n ex

chan

ge r

esin

in m

agne

sium

for

m; R

1 an

d R

2 -

catio

n ex

chan

ge r

esin

s in

H+

form

; R3

- an

ion

exch

ange

res

in in

OH

-fo

rm

R1

and

R2

- ca

tion

exch

ange

res

ins

in H

+ f

orm

.

Tabl

e X

IV -

Tart

rate

sta

bilit

y re

sults

of r

ed w

ine

trea

ted

with

cat

ion

exch

ange

r's

resi

ns, c

atio

n an

d an

ion

exch

ange

res

ins

and

cold

trea

tmen

t (m

ini-c

onta

ct a

ndte

mpe

ratu

re o

f sat

urat

ion)

Éva

luat

ion

de la

sta

bilit

é ta

rtri

que

des

vins

ave

c pr

opor

tions

cro

issa

ntes

de

vin

trai

té p

ar r

ésin

es c

atio

niqu

es e

t du

vin

stab

ilisé

par

le fr

oid

(mét

hode

de

la te

mpé

ratu

re d

e sa

tura

tion

et d

u te

st d

e m

ini-c

onta

ct)

To double cation-anionic exchange (table XIII), thetwo groups of resins (R1+R3) and (R2+R3) had quitesimilar behaviour. Comparatively to a cation exchange,the double exchange showed higher pigments adsorp-tion, presumably because the exposed surface is higher.The decrease in total phenol content, total anthocyaninsconcentration and total pigments increased with the per-centage of treated wine. In what respects the individualanthocyanins (table XII), the two groups of resins havea similar behaviour for several anthocyanins confirmingthe result obtained to the total anthocyanins concentra-tion. However, as was verified above, the individual antho-cyanins concentration decreased along with an increasein percentage of treated wine, indicating the retentionof these compounds in the resins matrix. The results ofanthocyanins families showed that the double cation-anion exchange removed more anthocyanins than thecation exchange, except for esters with acetic acid.

b) Effect in the mineral composition

The R1 resin in Mg2+ form showed to be less effi-cient than in H+ form or R2-H resin to potassium remo-val, once the affinity to resin increases with the cationvalence (WEINAND and DEDARDEL, 1994); this mayhave implications in the tartrate stabilization.

When the two resins were used in H+ form (table XI),the resins presented similar behaviour concerning thepotassium cation, nevertheless the R1 resin removed morecalcium than R2, and the R2 resin showed to removemore magnesium and iron than R1. The resins didn't showany affinity to copper. As the percentage of treated winein the lots increased, the cation contents decreased signi-ficantly. As expected, there weren't significant differencesin the concentration of chloride anion of the wines trea-ted with cationic resins, as already observed in whitewines.

The double exchange (table XIII) showed results simi-lar to be obtained in experiments with cationic resins. Itwas verified that R3 removed a certain quantity of chlo-ride anion, so the treated wine presented less quantityof this anion comparatively to the control wine.

c) Effect in the organic acid composition

As expected, the cation resins did not influence theorganic acids content (data not shown). In doubleexchange (table XIII), only tartaric and citric acids wereremoved with anion resin, as it was also observed for thewhite wine.

d) Effect in pH, titrable and volatile acidity

According to the previous observations, the wine pHdecreased with an increase of the percentage of treatedwine; however we have verified that the pH didn't decrease


Helena MIRA et al.

to values below 3.0 and didn't decreased to more than0.3 pH units in any of the studied proportions, accordingto the imposed limitations of the OIV (1995). The titrableacidity increased along with the increase H+ content inwine submitted to cation exchange. This can be a posi-tive aspect to wines produced in countries with hot cli-mate, as suggested by MIRANDA PATO (1961) andMOURGUES (1993). As observed to white wines, wehave verified some decrease in the volatile acidity, whichis difficult to explain using the cation exchange.

The effect of the double ionic exchange in pH, titrableand volatile acidity is reported in table XIII. As in cationexchange, the wine pH decreased with a proportion oftreated wine, but more slowly, although never decreasedto values less than 2.37. However, the titrable acidity pre-sented no significant differences as observed in whitewines. The volatile acidity of the wines decreased slightlywith a proportion of treated wine, and the eluted winepresented significant differences comparatively to thecontrol wine as was verified with the white wine andcation exchange.

e) Sensory evaluation

Only the wine A was submitted to sensory evalua-tion by panel taste. The average of the scores, of the attri-butes of the wines with different percentages of treatedwine with R1-Mg and R2-H resins, are presented intable IX. The data indicated there were no significant dif-ferences between treated wines and control wine. Thepanel taste indicated that the wines with highest pro-portion in treated wine (25 %) are not significantly dif-ferent from the control wine. However, further researchis needed to investigate if and why the ion exchangeaffects the sensory attributes of the wine, particularly thedouble cation-anion exchange.

f) Wine tartrate stability evaluation

The results of tartrate wine stabilization are presen-ted in table XIV. For wine A, the two used methods forevaluation of the tartrate stability gave different results.Through the mini-contact test, only the wines with morethan 5 % of treated wine with R1 resin presented stable,while for treated wine with R2, the 5 % was enough tostabilize the wine. However, according to the saturationtemperature method, the wines with mixture of treatedwine with R1 resin were not stable, whereas only the winewith 25 % of treated wine with R2 resin was stable.

The wine B became stable for all proportions and forthe two resins, as well as by cold stabilization.

Using double cation-anion exchange, the wine becamestable for all the proportions and for the two groups of

resins, as well as when using the classic process, in accor-dance with the observed with the cation exchange resins.

CONCLUSION

The R2 resin showed to be more efficient to enhancethe tartrate stabilization than R1 in Mg2+ form; howe-ver in H+ form, the behaviour of both resins was simi-lar. Both resins presented a good retention for K+ and forCa2+, the main cations implicated in wine tartrate insta-bility. In respect of the double cation-anion exchange, theresults about tartrate stabilization were similar to thoseobtained with only cation exchange resins.

The assembled wines presented a slight decrease inthe concentration of total phenols, higher in doubleexchange, due to the retention of some phenol compoundsin the resin surface. Some differences were also observedin chromatic characteristics, which can be due to the varia-tion in pH and to the retention of some wine constituents.A trained panel has not found differences between trea-ted and untreated wines. In fact, the cation exchange didnot affect negatively the wine quality attributes, which isan interesting result on a practical point of view.

The technology of cation exchange resins in H+ formis an effective procedure for tartrate stabilization of wines,respecting the limitations imposed by OIV. In addition,the wines were stabilized concerning tartrate precipita-tions, using cation exchange resins in H+ form, withoutprevious cold treatment, which could be really an alter-native oenological practice, especially when consideringalso economical and energy aspects.

Acknowledgements : The authors thank to the AGRO Program(project nº23, measure 8.1 of the Ministry of the Agriculture of Portugal)for the financial support of this work; to PRODEP - Action 5.3 -Advanced training of university teachers (Ministry of Education ofPortugal); to Comissão Vitivinícola Regional do Ribatejo (CVRR)for providing the wines, to CVRR panel tasters and to Multifiltra(Lisboa, Portugal) for giving us the resins. Special thanks to Mr. InácioDias (Ecohídrica, Lisboa, Portugal) for the collaboration to this study.

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Manuscrit reçu le 16 octobre 2006 ; accepté pour publication, après modifications le 27 novembre 2006

USE OF ION EXCHANGE RESINS FOR TARTRATE WINE ...

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