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Flavonol Content and Biometrical Traits As a Tool for the Characterization Of Food Chemistry 140 (2013) 810–816 Contents lists available at SciVerse ScienceDirect Food Chemistry journal homepage: www.elsevier.com/locate/foodchem Flavonol content and biometrical traits as a tool for the characterization of ‘‘Cipolla di Giarratana’’: A traditional Sicilian onion landrace ⇑ Ezio Riggi a, Giovanni Avola a, Laura Siracusa b, , Giuseppe Ruberto b a Consiglio Nazionale delle Ricerche-Istituto per i Sistemi Agricoli e Forestali del Mediterraneo (CNR-ISAFOM), Str.le V. Lancia, Blocco Palma I, Zona Industriale, 95121 Catania, Italy b Consiglio Nazionale delle Ricerche-Istituto di Chimica Biomolecolare (CNR-ICB), Via Paolo Gaifami 18, 95126 Catania, Italy article info abstract Article history: ‘‘Cipolla di Giarratana’’, a locally cultivated white onion landrace, is listed as an item in the ‘List of Tra- Available online 10 November 2012 ditional Agro-food Products’ of the Italian Department for Agriculture and itemised as ‘slow food presid- ium’ by the Slow Food Foundation. Ten local accessions were investigated for their biomorphological and Keywords: biochemical characteristics in five experimental locations. High-performance liquid chromatography Allium cepa coupled with diode array detection and electron spray-mass spectrometry (HPLC/DAD/ESI-MS) was used Onion landrace to identify the phenolic profile and quantify phenolic content in bulbs: quercetin, quercetin 3,40 di-O- ‘‘Cipolla di Giarratana’’ glucoside and quercetin 40-O-glucoside were detected as major components. The ‘Cipolla di Giarratana’ Flavonols profile landrace is characterised by a high bulb weight (436 g) and high diameter (11 cm). The total flavonols Chemotaxonomic markers content ranged between 68 and 408 mg kgÀ1 bulb fresh weight in nine of the 10 collected accessions. The opportunity of considering flavonol patterns as chemotaxonomic descriptors in order to characterise onion germplasm is also discussed. Ó 2012 Elsevier Ltd. All rights reserved. 1. Introduction Vlase, & Parvu, 2010; Prinz, Ringl, Huefner, Pemp, & Kopp, 2007; Robles et al., 2003; Siracusa, Patanè, Avola, & Ruberto, 2012). Onion (Allium cepa L.) has been used as common food since an- Among the different flavonoid classes, exclusively compounds cient times (1550 BC) (Lanzotti, 2006). Onion bulbs are rich in sev- belonging to the subclass of flavonols, anthocyanins, and di-hydro- eral phytonutrients recognised as important elements of the flavonols have been detected in onion bulbs, with quercetin Mediterranean diet (carbohydrates, vitamins and minerals) and it (3,30,40,5,7 pentahydroxyflavone) and its derivatives as major com- has also been reported to have numerous medicinal and functional pounds detected (Rodríguez Galdón, Rodríguez Rodríguez, & Díaz properties such as antimicrobial, antispasmodic, anticholesterolae- Romero, 2008; Slimestad, Fossen, & Vågen, 2007). Onion flavonols mic, anticancer, and hypotensive (Prakash, Singh, & Upadhyay, have been demonstrated to be useful in varietal comparison 2007). The majority of these biological effects has been associated studies (Lee & Mitchell, 2011; Pérez-Gregorio, García-Falcón, with the presence of particular molecules belonging both to its pri- Simal-Gándara, Rogridues, & Almeida, 2010; Rodríguez Galdón, mary and secondary metabolism. Among them, flavonoids, espe- Peña-Méndez, Havel, Rodríguez Rodríguez, & Díaz Romero, 2010); cially flavonols, are undoubtedly the most abundant non volatile compositional studies on onion flavonols were also carried out to secondary metabolites present in onion bulbs. Flavonoids have monitor the changes in product quality with different post-harvest raised huge attention in the last decade due to their role in the pre- practises, storage conditions, light exposition and heating (Lee vention of several diseases associated with the progressive oxida- et al., 2008; Olsson, Gustavsson, & Vågen, 2010; Rodrigues, tion of living organisms. As a part of the so called ‘‘defensive Pérez-Gregorio, García-Falcón, Simal-Gándara, & Almeida, 2010), characters’’ of the plants, their profile and content depend on ge- cooking (Rodrigues, Pérez-Gregorio, García-Falcón, & Simal- netic factors but it is also influenced by environmental conditions Gándara, 2009) and to evaluate the best sanitising technology (temperature and soil water content during growing season) and and packaging system for onion storage (Pérez-Gregorio, García- agronomic management (fertilisation, stage of ripening at harvest, Falcón, & Simal-Gándara, 2011a; Pérez-Gregorio, González-Barreiro, biotic stress management), as extensively reported in recent liter- Rial-Otero, & Simal-Gándara, 2011b). ature (Figueiredo-González et al., 2012; Li et al., 2010; Parvu, Toiu, In this view, the use of onion flavonols as a differentiating tool could support the identification of the huge amount of local land- races that could counteract the globalisation of crop production ⇑ Corresponding author. Tel.: +39 0957338348; fax: +39 0957338310. leading to a narrow batch of grown varieties that dramatically E-mail address: [email protected] (L. Siracusa). threats biodiversity maintenance and trigger genetic erosion. 0308-8146/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.foodchem.2012.10.134 E. Riggi et al. / Food Chemistry 140 (2013) 810–816 811 Moreover, all these efforts for landraces characterization, in the ber sample vial and a 3 mL of a acidic-alcoholic solution (5% formic context of European agriculture can be addressed to obtain protec- acid in methanol) was added. The samples were then maintained tion of geographical indications (PGI) or protection of designation at room temperature (20 °C) overnight, in the dark and under vig- of origin (PDO) that strongly support the economic sustainability orous shaking (350 rpm). The resulting heterogeneous mixtures, for farmers adopting typical landraces, but that can only be still containing solid residues, were centrifuged (20 min at awarded if a product’s differential value can be clearly demon- 4000 rpm) and then filtered with PTFE filters (13 mm diameter, strated (EC Regulation, 2006). To delimit geographical origin objec- 0.45 lm pore size, Pall Life Science), thus obtaining ca. 2,5 mL of tively, it is fundamental to know the importance of genetic and clear pale yellow solutions, ready for analyses. When required, environmental factors in the phenotypes of the products that reach the above mentioned analytical samples were stored for shorts consumers (Florez et al., 2009). In this scenario, a Sicilian tradi- periods (one week at the most) at À20 °C under nitrogen atmo- tional onion landrace, ‘‘Cipolla di Giarratana’’, characterised by sphere. The whole analytical batch thus consisted of 165 samples. white large bulbs and sweet taste, and registered as Slow Food Pre- sidium, need to receive scientific attention to avoid the extinction 2.2.3. HPLC/DAD/ESI-MS analyses risk threatening this population such as many other niche products For a representative number of samples (one replicate for each cultivated in restricted areas. The present study was carried out to thesis = 55 samples), a variable aliquots (0.8–1 mL) of the above asses the flavonol profile and biomorphological traits of ‘‘Cipolla di mentioned solutions were transferred into standard laboratory Giarratana’’ and to evaluate its homogeneity within the local land- vials and brought to dryness in vacuum with a rotary evaporator race and between different experimental sites. (Heidolph Laborota 400). The resulting yellowish residues were then re-dissolved in 250 lL of the original extraction solution 2. Material and methods and submitted to qualitative analyses. Onion extracts were ana- lysed by HPLC/DAD/ESI-MS using a Waters instrument (Waters 2.1. Plant material and experimental design Italia S.p.A., Milano, Italy) consisting of a 1525 Binary HPLC Pump, a PDA 996 Photodiode Array Detector (DAD) and a Micromass ZQ The ‘‘Cipolla di Giarratana’’ landrace is actually cultivated in a Mass Analyser equipped with a ESI Z-spray source. DAD analyses restricted area involving no more then 30 farmers, growing genetic were acquired in the range between 700 and 190 nm. Total ion cur- material self reproduced by ten of them in confined conditions to rent (TIC) chromatograms were acquired in negative mode, using a prevent cross pollination. During March 2010, seeds of all the ten cone voltage of À20 V in the mass range between 80 and 1000 m/z accessions of this local landrace have been collected. A genotypes units. The other parameters used for the acquisition of the TICs batch including the ten accessions, and a white onion standard were the following: capillary voltage: 2.75 kV; source tempera- variety (Tonda Musona), adopted as control, was grown in five ture: 150 °C; desolvation temperature: 260 °C; gas flow (L/h): Locations (L): two located in the area where this population is tra- 400 (desolvation) and 210 (cone). Chromatographic runs were per- ditionally cultivated (Giarratana, SE Sicily, 450–600 m above sea formed using a reverse-phase column (Ascentis C18, 250 Â 4.6 mm, level – L1, L3), two in different areas with similar average altitude 5 lm particle size, Supelco, Sigma Aldrich, Italy); onion polyphe- (Palazzolo Acreide – L6 and Chiaramonte Gulfi – L5, SE Sicily, 650 nols were eluted with the following gradient of B (acetonitrile) in and 450 m a.s.l, respectively), and one in the South East coast of A (2.5% solution of formic acid in water): t = 0 min, B = 15%; Sicily (Scicli – L6, 5 m a.s.l.). The same randomised blocks
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