Chemical Profile Differentiation of Brazilian and Italian Grape Marc Spirits Using Chemometric Tools

Central Annals of Food Processing and Preservation Bringing Excellence in Open Access Research Article *Corresponding author Fernando M. Lanças, Institute of Chemistry of Sao Carlos, University of São Paulo, Brazil, Tel: 46-762-316-196; Chemical Profile Differentiation Email: [email protected] *This work is dedicated to the memory of Professor Douglas W. Franco (in memoriam) of Brazilian and Italian Grape Submitted: 12 April 2018 Accepted: 03 May 2018 Marc Spirits Using Chemometric Published: 05 May 2018 Copyright Tools © 2018 Lanças et al. ISSN: 2573-1033 Felipe A. Serafim1, Thiago Ohe1, Laura Agostinacchio2, Silmara F. OPEN ACCESS Buchviser1, Sauro Vittori2, and Fernando M. Lanças1* 1Institute of Chemistry of Sao Carlos, University of São Paulo, Brazil Keywords 2School of Pharmaceutical Sciences and Health Products, University of Camerino, Italiy • Grape marc spirits; Chemical profile; Traceability; Chemometrics; Geographical origin Abstract Twenty-one samples of grape marc spirits, fifteen from Italy (Grappa) and six from Brazil (Graspa) were analyzed to verify the content of 28 chemical compounds by GC-MS and GC-FID in order to evaluate their differences. The analytical data obtained were subjected to Analysis of Variance (ANOVA), Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA). ANOVA results showed that diethyl succinate, methanol, propanol and isoamyl alcohol presented different significance at 95%. The PCA and HCA treatment led to a discrimination of the two groups of grape marc spirits based upon the chemical differences found between their distillates. Although both distillates were obtained from the same raw material, the chemical description of each distillate allowed the traceability of their geographic identity PRACTICAL APPLICATION presence or not of the stem; but it is only the peeling with must incorporated in it that provide almost all compounds which, by Chromatography analysis followed by Chemometric tools distillation, characterize the distillate. The process of production were employed to establish the geographical origin of 21 of Grappa starts with the harvesting and grape crushing. The grape marc spirits being 15 Grappa from Italy and the others 6 most is then separated from the grape pomace mainly composed produced in Brazil. Hierarchical cluster analysis and principal by grape skins and seeds, with or without rasp. The pomace is component analysis were performed highlighting the chemical put in cooper stills (alembics) that are warmed in different ways, markers of each distillate that allowed the traceability of the starting the distillation process. The distilled can be submitted to grape marc spirits. an aging process using wooden containers, which contribute with INTRODUCTION Grape pomace distillates are beverage spirits produced different flavors enrichment. In average, 100kg of grape pomace from “vinaccia” (skins, seeds, stalks, stems and stalks from yields from 4 - 8 liters of pure grappa at 70% (v/v), which is grapes) being found in most European countries where there is normallyBrazil further produces diluted a similar to 45% alcoholic (v/v) distillate,[1-4]. also from grapes, traditional wine production. The European Union established employing a production system similar to the Italian one, which is known as graspa. According to the Brazilian legislation, graspa production of these alcoholic beverages establishing that in Spain, forthe instance,regulation the concerningdenomination the Orujo definition, as geographic denomination, indication and for being obtained from simple alcoholic distillates of grape marc, has an alcoholic content ranging from 35% - 54% v/v, at 20ºC, their distillates should be employed. In France the grape pomace with or without wine lees, and can be partially or selectively are named Marcs, in Greece Tsipouros, in Portugal Bagaceiras, in Yugoslavia Kommovica, in Turkey Raki and in Italy are known as same origin to regulate the congener’s contents [5]. rectified. It is allowed to cut with potable ethyl alcohol from the Grappas [1-4]. Geographical Indication (IG) isusually recognized The chemical composition of spirits like grappa, cachaça, knowledge, practices and other factors associated with a factors as for instance the varietal origin of the raw material, as a qualification strategy since it includes traditions, customs, territorial identity and its geographical origin. itscognac, storage whiskies, conditions, as well asthe several fermentative others, is step, influenced the distillation by several Grappa is an alcoholic distillate of commercial, cultural and technology, the aging time, and the different wood casks used historical importance, uniquely produced in Italy. The Italian “vinaccia” as the complex containing the distillates is responsible by its characteristic bouquet [6-12]. in the aging process. Consequently the chemical profile of the solid parts of the grape, like peelings and grape seed, in the In spite of a rigorous quality control about food and beverages Legislation defines Cite this article: Serafim FA, Ohe T, Agostinacchio L, Buchviser SF, Vittori S, et al. (2018) Chemical Profile Differentiation of Brazilian and Italian Grape Marc Spirits Using Chemometric Tools. Ann Food Process Preserv 3(1): 1021. Lanças et al. (2018) Email: [email protected] Central Bringing Excellence in Open Access production by the international community, the concentration of compounds that might present carcinogenic properties, a maintenance period of 15min. including pesticide residues and carbamates, as example, must isothermal period of 4 min, an increase to 200°C at 5°C/min, and Ethyl carbamates analysis: be constantly evaluated [13-17]. carbamate concentration was performed as previously described For years the USA market was invaded by products by [22], through direct sample Determinationinjection without of theprevious ethyl generically named grappa, frequently presenting very low quality treatment into a gas chromatograph model GC17A (Shimadzu, that ruined grappa’s image and creating a strong rejection to this Tokyo, Japan) hyphened to a mass-selective detector model its reputation, which happened in sync with the boom of Italian eV) as the ionization source. The mass spectrometer detector winesbeverage. in the Just USA from culture, ‘80s and which ‘90s thatdemanded grappa a began product recuperating with high operatedQP 5050A in (Shimadzu, the SIM mode Tokyo, (m Japan)z 62) andusing propyl electron carbamate impact was(70 quality. -1). The inlet and detector / In order to avoid any misunderstandings regarding to used as an internal standard (150µg L provenance of its products, the chemical traceability has allowed interface temperatures were 250°C and 230°C, respectively. The the pattern recognition of every step of the production of foods, oven temperature was programmed to 90°C (2 min); 10 °C/min beverages and other products, ensuring the consumer protection, to 150°C (0 min); 40 °C/min to 230°C (10 min). The injected its geographical traceability and, consequently its quality [18- addition.volume was 1.0 µL in the splitless mode. The ethyl carbamate quantification was carried out through authentic standard Esters, terpene, lactone and ionones analysis: (Italy)20]. The and aiming Graspa of (Brazil)this manuscript in order isto to establish describe differences the chemical on theprofile chemical of 28 targetcomposition compounds between present these in types21 samples of distillates. of Grappa In ethyl valerate, ethyl caproate, ethyl lactate, ethyl caprylate, addition, this work includes the development of statistical tools ethylDetermination 3-hydroxybutyrate, of ethyl acetate, ethyl caprate,butyl acetate, ethyl isopentyl2-furoate, acetate,diethyl able to identify theirs geographical origin based on multivariate succinate isoamyl laurate, linalool, -terpineol, -citronellol, analysis. geraniol, -ionone, y-octalactone, eugenol and farnesol, were α β MATERIALS AND METHODS Tokyo, Japan),α hyphenated to a mass selective detector model QP carried out in a gas chromatograph model GC20I0 (Shimadzu, Samples eV) as the ionization source. O-cymene was used as an internal All samples of grape marcs were collected from the producer standard.20I0 PLUS The (Shimadzu, target analytes Tokyo, were Japan) separated using electron through impact a capillary (70 at the moment of the distillation and stored under refrigeration (6-8°C), hence eliminating variables such as aging time, addition of water, or storage effects. The samples were stored in glass column coated with an esterifies polyethyleneglycol phase (HP- bottles, protected from light and kept at 4°C. All analyses were FFAP; 50,0m x 0,20mm x 0,33um film). The oven temperature performed in duplicate. was programmed to 60°C (2 minutes); 10°C/min to 210°C. The mode.inlet and detector interface temperatures were 220°C and 230°C, Reagents respectively. The injected volume was 1.0 µL in the splitless The reagents ethyl acetate, butyl acetate, isopentyl acetate, Statistical and multivariate analyses ethyl valerate, ethyl caproate, ethyl lactate, ethyl caprylate, : Analysis of ethyl 3-hydroxybutyrate, ethyl caprate, ethyl 2-furoate, diethyl variance (ANOVA) with significance level of 95% (α = 0.05) succinate, isoamyllaurate, methanol, 2-butanol, propanol, concentrationwas preliminarily values used in thefor alembicthe identification fractions. Theof the ANOVA statistically results weresignificant checked differences using Tukey’s among test. the secondary compound mean ethylisobutanol,

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