Evaluation of the effect of fenhexamid and mepanipyrim in the volatile composition of Tempranillo and 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.
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