Elsevier

Food Research International

Volume 71, May 2015, Pages 108-117
Food Research International

Evaluation of the effect of fenhexamid and mepanipyrim in the volatile composition of Tempranillo and Graciano wines

https://doi.org/10.1016/j.foodres.2015.02.025Get rights and content

Highlights

  • Norisoprenoids, in Graciano wines, increased in the presence of fungicide residues.

  • Ripe fruit nuances were increased mainly as a result of enhancing dry plum notes.

  • This is mainly due to the enhancement of β-damascenone.

  • Residues of mepanipyrim slightly increased banana nuances.

  • Isopentyl acetate increased in wine treated with mepanipyrim.

Abstract

Grapes from Vitis vinifera var. Tempranillo and Graciano of La Rioja (North Central Spain) were vinified after addition of two fungicides (mepanipyrim and fenhexamid) at concentrations corresponding to their MRLs. These fungicides are commonly used in the vine growing to control botrytis disease. The fungicide effect throughout winemaking on the volatile composition and aroma profile of the final wines was evaluated, together with the level of fungicide residues in the final wines that were found to be safe for consumers. Concentrations of C13-norisoprenoids in Graciano wines obtained after the addition of both active substances showed the greatest variations with respect to control wine; whereas the concentration of volatile compounds in Tempranillo wines were seemingly unaffected by the presence of fungicide residues. On the other hand, the aroma profile of monovarietal red wines was evaluated by using odorant series which included volatile compounds with similar odour descriptors. In this sense, supplementation with the antifungals seemed to increase the OAV for the ripe fruit series with respect to the control wines in Graciano wines.

Introduction

The application of fungicides is a mandatory practice during vine growing to avoid losses caused by the incidence of fungal diseases (especially, botrytis, powdery mildew and downy mildew). However, even if Good Agricultural Practices (GAPs) are followed, fungicide residues may remain on grapes and be transferred to must and wine during winemaking (Cabras and Conte, 2001, Cabras et al., 1998, Fernández et al., 2005, González-Rodríguez, Cancho-Grande and Simal-Gándara, 2009, González-Rodríguez, Cancho-Grande, Torrado-Agrasar, Simal-Gándara and Mazaira-Pérez, 2009, Navarro et al., 1999). The presence of such residues below their maximum residue levels (MRLs) can alter yeast growth and metabolism during alcoholic and malolactic fermentations (Cabras et al., 2003, Cus and Raspor, 2008, González-Rodríguez, Cancho-Grande, Torrado-Agrasar, Simal-Gándara and Mazaira-Pérez, 2009, González-Rodríguez, González-Barreiro, et al., 2011, Noguerol-Pato, Torrado-Agrasar, González-Barreiro, Cancho-Grande and Simal-Gándara, 2014a, Sarris et al., 2009), and hence the biosynthesis of volatile compounds and their concentrations in the final wine.

Since aroma is one of the most appreciated attributes in wines, the potential effect of residues of fungicides in the concentration of volatile compounds of wines and, consequently, in wine sensory quality has become a matter of substantial oenological concern. Many papers deals with the influence of pesticides on the natural microflora and on added yeasts, but only few relate this effect on yeast activity with volatile compounds. Aubert et al. (1997) concluded that flusilazole treatments influenced the formation of alcohols during fermentation by a direct action on the metabolism pathways of yeast. Oliva, Navarro, Barba, Navarro, and Salinas (1999) related the decrease in the concentration of isobutanol in wines obtained from grapes treated with pesticides to a lower assimilation of valine by the yeast. Also, it was observed by Oliva, Zalacaín, Payá, Salinas, and Barba (2008) that the application of famoxadone, fenhexamid, fluquinconazole, kresoxim-methyl and trifloxystrobin, under GAPs, and quinoxyfen, kresoxim-methyl, fluquinconazole and trifloxystrobin, under Critical Agricultural Practices (CAPs) significantly affected the aroma composition of Monastrell red wines. This fact was attributed to an effect either on the yeast fermentative activity or in their glycosidase activity. García et al. (2004) evaluated the effect of cyprodinil, fludioxonil and pyrimethanil on the aroma composition of white wines obtained by inoculation of sterile must with Saccharomyces cerevisiae (S. cerevisiae) strains and they found that most of volatile compounds being altered their levels in the studied wines. Sarris et al. (2009) observed that the biosynthesis of volatile compounds participating positively in the aroma was deactivated with the addition of quinoxyfen to the medium. González-Rodríguez, Noguerol-Pato, González-Barreiro, Cancho-Grande, and Simal-Gándara (2011b) observed that the application of several fungicides under GAPs seemed to increase the concentration of some fermentative compounds such as ethyl esters and acetates in Godello white wines. After that, González-Álvarez, González-Barreiro, Cancho-Grande, and Simal-Gándara (2012) studied the effect of other fungicides (cyazofamid, famoxadone, mandipropamid and valifenalate) applied under CAPs on the aromatic content of Godello white wines; they found that several fermentative volatile compounds were affected by the presence of such fungicide residues. Additionally, tebuconazole residues seemed to alter the aroma composition of Mencía red wines, especially regarding to 1-hexanol and several ethyl esters (Noguerol-Pato, González-Rodríguez, González-Barreiro, Cancho-Grande, & Simal-Gándara, 2011). Noguerol-Pato, Torrado-Agrasar, González-Barreiro, Cancho-Grande, and Simal-Gándara (2014a) observed that residues of ametoctradin, dimethomorph and mepanipyrim seemed to alter the sugars-to-ethanol yield of S. cerevisiae yeasts during alcoholic fermentation as well as the synthesis of volatile compounds of fermentative origin. Recently, some authors have assessed the effects of the application of resistance inducers or elicitors (products able to elicit the plant defence mechanisms against pathogens such as chitosan, benzothiadiazole and methyl jasmonate) in vineyard on wine aroma compounds. These compounds led to changes in the volatiles content of grapes and wines, as well as in the sensory attributes of wines made from grapes treated with these products (Gómez-Plaza et al., 2012, Ruiz-García et al., 2014, Vitalini et al., 2014).

In the current work, the effect of two anti-botrytis fungicides (mepanipyrim and fenhexamid) widely used in the grape-growing on the biosynthesis of volatile compounds during winemaking process, and, hence, on the aroma profile of the resulting wines was assessed. Mepanipyrim and fenhexamid present different biochemical mode of action in the biosynthetic pathways of plant pathogens; the former, which belong to the anilino-pyrimidines group, acts at amino acids and protein synthesis level and the latter, from the hydroxyanilide group, affects the sterol biosynthesis in membranes. They were added directly to crushed grapes so the contact between fungicides and grapes during their growth was avoided. In this way, the possible effect of fungicide residues on the aroma of the final wines can be attributed exclusively to alterations in the fermentative step. Besides, in order to assure the worst-case scenario that could be found in a vineyard according to the current legislation, commercial products containing the active substances were added to Tempranillo and Graciano crushed grapes at their corresponding MRLs. Vitis vinifera Tempranillo var. is the most characteristic variety of the Qualified Designation of Origin “Rioja” and the foundation of the identity of its red wines; Graciano, for its part, is also an autochthonous variety which has shown to be an excellent complement to Tempranillo in the ageing process. Even though we have already studied the effect of kresoxim-methyl + boscalid and metrafenone in these wines (Noguerol-Pato, Sieiro-Sampedro, González-Barreiro, Cancho-Grande, & Simal-Gándara, 2014b), so far, the effect of mepanipyrim and fenhexamid on Tempranillo and Graciano must fermentation and aroma biosynthesis was never studied.

Section snippets

Chemicals

Dichloromethane, methanol and water (HPLC quality) were purchased from Sigma-Aldrich (Steinheim, German), whilst ethanol absolute (HPLC grade) was acquired from Scharlau (Barcelona, Spain); anhydrous sodium sulphate for residue analysis was obtained from Panreac (Barcelona, Spain). The sorbent material used for solid-phase extraction (SPE) was Strata-X from Phenomenex (Torrance, CA, USA). Small apparatus such as an Ultrasons-H ultrasound bath (JP Selecta, Barcelona, Spain), a Reax Top vortex

Results and discussion

Table 1 shows the residual concentrations of fungicides in the monovarietal red wines. As can be seen, a decrease in the fungicide content was observed at the end of the fermentation with respect to the initial concentration (which corresponds to their LMRs). Mean transfer factors from Tempranillo and Graciano grapes to wines (calculated for each fungicide on having divided the concentration in the final wines between the concentration in crushed grapes) were as follows: 0.082 for mepanipyrim

Conclusions

Probably as a consequence of the adsorption of fungicide residues onto the solid particles during winemaking, the transfer factors from grape to wine were 0.082 for mepanipyrim and 0.48 for fenhexamid. Fenhexamid transfer factor was the highest, but in any case the winemaking contributed to the decrease of its residues in wines to half the MRL in grapes, making the final wines a safe product for consumers. Moreover, the total concentration of volatile compounds in Tempranillo and Graciano wines

Acknowledgements

This work was granted by EU FEDER funds (SXU-SUG 2013) and by the Spanish Ministry of Education and Science grant (AGL2011-30378-C03-01). R. Noguerol-Pato acknowledges the grant from the Spanish Researchers Resources Program. The authors are also very grateful to Dr. Mª Teresa Martínez and Dr. Jesús Sanz for their work to obtain the analyzed samples.

References (44)

  • R. Noguerol-Pato et al.

    Influence of tebuconazole residues on the aroma composition of Mencía red wines

    Food Chemistry

    (2011)
  • R. Noguerol-Pato et al.

    Influence of new generation fungicides on Saccharomyces cerevisiae growth, grape must fermentation and aroma biosynthesis

    Food Chemistry

    (2014)
  • J. Oliva et al.

    Effect of the use of recent commercial fungicides, under good and critical agricultural practices, on the aroma composition of Monastrell red wines

    Analytica Chimica Acta

    (2008)
  • R. Perestrelo et al.

    Optimisation of solid-phase microextraction combined with gas chromatography–mass spectrometry based methodology to establish the global volatile signature in pulp and skin of Vitis vinifera L. grape varieties

    Talanta

    (2011)
  • S. Vitalini et al.

    The application of chitosan and benzothiadiazole in the vineyard (Vitis vinífera L. cv Groppello Gentile) changes the aromatic profile and sensory attributes of wine

    Food Chemistry

    (2014)
  • C. Aubert et al.

    Effects of flusilazole, a sterol biosynthesis inhibitor fungicide, on the free and bound aroma fraction of Muscat of Alexandria wines

    Journal International des Sciences de la Vigne et du Vin

    (1997)
  • R. Baumes

    Los constituyentes volátiles de la etapa prefermentativa

  • T. Cabaroglu et al.

    Free and bound volatile composition of red wines of Vitis vinifera L. cv. Okuzgozu and Bogazkere grown in Turkey

    American Journal of Enology and Viticulture

    (2002)
  • P. Cabras et al.

    Fate of azoxystrobin, fluazinam, kresoxim-methyl, mepanipyrim, and tetraconazole from vine to wine

    Journal of Agricultural and Food Chemistry

    (1998)
  • P. Cabras et al.

    Pesticide residues in grapes and wine in Italy

    Food Additives and Contaminants

    (2001)
  • P. Cabras et al.

    Interaction between fenhexamid and yeasts during the alcoholic fermentation of Saccharomyces cerevisiae

    Journal of Agricultural and Food Chemistry

    (2003)
  • J. Crouzet

    Los constituyentes volátiles de la etapa prefermentativa

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