Food Chemistry 141 (2013) 795–801

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Food Chemistry

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Odour-active compounds in banana fruit cv. Giant Cavendish

0308-8146/$ - see front matter � 2013 Elsevier Ltd. All rights reserved.http://dx.doi.org/10.1016/j.foodchem.2013.03.064

⇑ Corresponding author. Tel.: +53 7 202 09 19.E-mail address: jpino@iiia.edu.cu (J.A. Pino).

Jorge A. Pino ⇑, Yanet FeblesFood Industry Research Institute, Carretera al Guatao km 3½, La Habana C.P. 19200, Cuba

a r t i c l e i n f o a b s t r a c t

Article history:Received 9 October 2012Received in revised form 5 February 2013Accepted 18 March 2013Available online 26 March 2013

Keywords:BananaVolatilesGas chromatography–mass spectrometryGas chromatography–olfactometryAroma extract dilution analysis

Application of solid-phase microextraction, simultaneous distillation–extraction and liquid–liquidextraction, combined with GC–FID, GC–MS, aroma extract dilution analysis, and odour activity valuewere used to analyse volatile compounds from banana fruit cv. Giant Cavendish and to estimate the mostodour-active compounds. The analyses led to the identification of 146 compounds, 124 of them were pos-itively identified. Thirty-one odourants were considered as odour-active compounds and contribute tothe typical banana aroma, eleven of them are reported for the first time as odour-active compounds.

� 2013 Elsevier Ltd. All rights reserved.

1. Introduction

Banana has one of the highest rates of production and consump-tion among all of the fresh fruits of the world. Many cultivars aregrown in various parts of the world, and are known to vary mark-edly in their flavour characteristics. Analytical research on thearoma compounds of this fruit carried out over 45 years was sum-marized and published by TNO (1996) and reviewed (Engel, Heid-las, & Tressl, 1990). The characteristic aroma of bananas arises froma complex mixture of compounds, these are esters of short-chainfatty acids, such as acetates, butanoates, and 3-methylbutyl esters(Macku & Jennings, 1987; Pérez, Sanz, Ríos, & Olías, 1993). Otherkey flavour compounds for bananas, present at extremely low lev-els, have been identified (Shiota, 1993). Nearly 250 volatile constit-uents have been identified for several fresh and processed bananaproducts; however, only some of them have been recognised asbanana flavour contributors. It is important to identify the tracecompounds contributing significantly to banana aroma. For thispurpose, it is necessary to achieve proper isolation (using adequatesolvent and solventless methods) and identification of odour-con-tributing constituents in combination with sensory evaluation ofthe fruit and its individual components. It has been shown for aconsiderable number of foods that all the volatiles present arenot able to interact with human olfactory receptors. Instead, onlya smaller number of the so-called key odourants are detected bythe human odourant receptors and, consequently, participate inthe creation of the respective aroma impression in the brain (Schi-eberle, 1995). An approach to separate odour-active volatiles from

the bulk of odourless food volatiles is GC–olfactometry on serialdilutions of aroma distillates, such aroma extract dilution analysis(AEDA) (Schieberle, 1995). Dilution to odour threshold techniques,such as AEDA, are useful methods for the screening of importantodourants in foods, but these methods do not permit a study onthe influence of the food matrix on odourant binding when match-ing the overall odour impression of the food. These limitations areresolved when the concentrations of the individual odourants arecorrelated with the respective odour thresholds using the odouractivity value (OAV) concept (Schieberle, 1995).

Because the knowledge on the key odourants in the final prod-uct is the prerequisite for studies on the influence of processingsteps, the aim of the present study was to determine the aromaprofile and odour-active compounds of banana cv. GiantCavendish, which is considered the most aromatic Cuban banana,by application of the aroma extract dilution analysis and odouractivity values.

2. Materials and methods

2.1. Fruits

Banana fruits (Musa spp. AAA group, cv. Giant Cavendish),selected on the basis of a similar ripening degree, were harvestedin the experimental station of the Tropical Fruit Institute in Alqui-zar (Cuba) from the 2011 crop season and immediately transportedto the laboratory. Three batches of five fruits in each were selectedand in each fruit four slices, along the fruit and parallel to the core,were cut and rapidly homogenised in a commercial homogenizer.The three batches were used for subsequent analyses.

796 J.A. Pino, Y. Febles / Food Chemistry 141 (2013) 795–801

2.2. Chemicals and reagents

Chemical standards were purchased from Sigma–Aldrich (St.Louis, MO), Fluka (Buchs, Switzerland), and Dallant (Barcelona,Spain). An n-alkane solution (C8–C32) was purchased fromSigma–Aldrich (St. Louis, MO). Anhydrous sodium sulphate, so-dium chloride and diethyl ether were purchased from Merck(Darmstadt, Germany); the solvent was redistilled and checkedfor purity.

2.3. Standard chemical analysis

Soluble solids, total acidity (as anhydrous citric acid) and pHvalue were performed on the fruit pulp according to standardmethods (AOAC, 1997).

2.4. Headspace solid-phase microextraction (HS-SPME) analysis

Volatile compounds from the fresh fruit homogenate headspacewere extracted using four SPME fibre coatings: 100 lm PDMS,65 lm PDMS/DVB, 50/30 lm DVB/CAR/PDMS, and 85 lm CAR/PDMS (Supelco, Park, Bellefonte, Pa.). All the fibres were condi-tioned before use and cleaned between analyses by inserting theminto the GC injector, where they were kept at the recommendedtemperature, and, to prevent contamination, were used immedi-ately after conditioning. SPME extraction was performed at 40 �Con 3 g of stirred homogenate and 1 g NaCl contained in a 15 ml vialsealed with a PTFE-lined screw cap. A pre-extraction time of10 min, and an extraction time of 30 min, were applied. The sam-pling conditions were chosen after preliminary GC–FID analysesand were similar to those reported in other fruit studies (Aprea,Carlin, Giongo, Grisenti, & Gasperi, 2010; Markovic, Vahcic, Ganic,& Banovic, 2007; Quijano & Pino, 2007; Quijano & Pino, 2009; Thai-phanit & Anprung, 2010; Wang, Zhi, Chen, Bao, & Yang, 2007).

2.5. Isolation of volatile compounds by simultaneous distillation–extraction (SDE)

Volatile compounds were isolated according to a previouslyreported procedure (Pino, 2012; Pino, Mesa, Muñoz, Martí, & Mar-bot, 2005). Two hundred grams of fresh banana homogenate wasmixed with 600 ml of distilled water. 0.2 mg of methyl nonanoatewas then added as an internal standard, and the volatiles were iso-lated by means of SDE using 25 ml of diethyl ether (previouslyredistilled and checked as to purity) for 1 h. The aroma extractwas dried over anhydrous Na2SO4 and concentrated to 0.6 ml ina Kuderna-Danish evaporator with a Vigreux column (12 � 1 cm)and then to 0.2 ml with a gentle nitrogen stream. Extractions weremade from each of the three batches. The recovery and repeatabil-ity of the extraction procedure was tested for some compounds [3-methylbutan-1-ol, 2-methylpropyl acetate, hexanal, 3-methylbutylacetate, 3-methylbutyl butanoate, and eugenol]. Triplicate analy-ses were performed. The average recovery was 70%, and therelative standard deviations were <10%.

2.6. GC–FID and GC–MS analysis

A Konik 4000 A (Konik, Barcelona), equipped with a30 m � 0.25 mm � 0.25 lm HP-5 ms (Agilent, Palo Alto, CA)fused-silica capillary column and with a flame ionisation detector(FID) was used. Oven temperature was held at 50 �C for 2 minand then raised to 280 �C at 4 �C min�1 and held for 10 min. Carriergas (hydrogen) flow rate was 1 ml min�1. Injector and detectortemperatures were 250 �C. For the SDE extracts 1 ll was injectedin 1:10 split mode and for SPME extracts splitless mode (2 min)was applied. The retention times of a series of n-alkanes (C8–C32)

was used to calculate the retention indices for all identified com-pounds and for reference standards. Concentrations wereexpressed as mg methyl nonanoate equivalents kg�1 of freshweight, response factors being taken as 1.0 for all compounds withreference to the internal standard and a recovery factor of 70% wasconsidered. All analyses were replicated three times.

GC–MS analyses were performed on a Hewlett–Packard 6890Nseries II (Agilent, Palo Alto, CA) gas chromatograph with a similarfused capillary column as in GC–FID. The temperature programand carrier gas flow rate were the same, as in GC–FID. EIMS, elec-tron energy, 70 eV; ion source and connecting parts temperature,250 �C. The acquisition was performed in scanning mode (massrange m/z 35–400 u). Compounds were preliminarily identifiedby use of NIST 05, Wiley 6, NBS 75k, Adams (2001), and in-houseFlavorlib libraries, and then the identities of most were confirmedby comparison of their linear retention indices with those of refer-ence standards or with published data (Adams, 2001).

2.7. SPME direct gas chromatography (GC–O)

A Pye Unicam 204 (Cambridge, England), equipped with a sniff-ing port and a 0.75 mm injector liner, was supplied with a shortstainless steel capillary (25 cm � 0.4 mm i.d.). The flow rate ofthe carrier gas (H2) was 25 ml min�1, and the oven temperaturewas kept at 250 �C. The three SPME extracts were introduced insuccessive sequences into the GC port (splitless mode for 2 min,injector temperature at 250 �C). Because no chromatographic sep-aration was carried out by the short capillary, volatile compoundsarrived simultaneously at the sniffing port. Here, for each SPMEextract, a trained panel of three assessors perceived and evaluatedthe resulting global odour. Fibres were kept in the GC inlet untilthe end of the sensorial stimulus.

Sensory analysis sessions were performed only after suitabletraining. Panellists were first familiarised with fresh banana andasked to agree on a common list of descriptors. After that theywere familiarised with the direct GC–O device. A similarity testwas performed in triplicate on the three SPME odours issued fromthe same homogenate. Sniffers were asked to smell the referencejuice (3 ml) contained in a plastic cup sealed with a pierced capat 22 �C. They had to memorise the odour and then describe itusing the descriptors list. Then they evaluated, with the directGC–O device, the different extracts, rating their similarity to thereference using a 10 cm scale ranging from 0 (close to the refer-ence) to 10 (far from the reference). They were also asked to givedescriptors. SPME extracts were injected every 5 min. Panellistshad to smell the reference before each sample evaluation.

2.8. Gas chromatography–olfactometry analysis of SPME extract

The odour active compounds of DVB/CAR/PDMS SPME extractswere analysed by high-resolution GC–O on a Hewlett–Packard6890N series II equipped with a FID and a sniffing port. After sam-pling, the SPME fibres were placed into the injection port of the GCequipped with a 0.75 mm i.d. liner for 5 min at 250 �C; for the first2 min the purge was off and then for the remaining 3 min thepurge was onto further clean the fibre. Operating conditions werethose described before in GC–FID. The GC effluent was split 1:1between the FID and the sniffing port (both at 250 �C). The sniffingport, mounted on a detector base of the GC, consisted of a cylindri-cally shaped aluminium device (40 mm � 25 mm i.d.) with a bev-elled top and a central drill hole, housing the capillary. Anonhumidifed airflow (30 ml min�1) was used as the make-upgas. Injection volume was 1 ll. A panel of three assessors (sameas for direct GC–O experiments) evaluated the effluents. For eachodour stimulus, panellists recorded the detection time and gavean odour description. GC–O frequency analysis was performed fol-

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lowing the methodology described by Chaintreau (2001a). Thepanellists responded to and recorded the retention time anddescriptor of the aroma compounds. Each sample was sniffed intriplicate by each panellist. When a volatile compound was de-tected at least twice, this analyte was determined to be a declaredaroma compound. Volatile compounds which were detected withthe same descriptors, at least three times, were considered asodour-active compounds.

2.9. Gas chromatography–olfactometry analysis of SDE extract

GC–O analyses were performed with a gas chromatographHewlett–Packard 6890N series II instrument. The fused capillarycolumn, temperature program and carrier gas flow rate were thesame as in GC–FID. During a GC–O run, the nose of the panellistwas placed closely above the top of the sniffing port and the odourof the effluent was evaluated. If an odour was recognised, theretention time was marked in the chromatogram, and the odourquality was assigned. The GC–O analyses were performed, at least,by two panellists.

2.10. Aroma extract dilution analysis (AEDA)

The flavour dilution (FD) factors of the odour-active compoundswere determined by GC–O of serial dilutions using the AEDA ap-proach (Schieberle, 1995). The dilution series were evaluated bysniffing: the original aroma extract was stepwise diluted withdiethyl ether (1 + 1) until no odourant was detectable by sniffingof the high dilution. GC–O was performed with 1 ll aliquots andthe FD factors obtained by two panellists were averaged.

3. Results and discussion

The general characteristics of the fruit pulp were: soluble solids21.5% ± 0.2%, total acidity 0.56% ± 0.01% (as citric acid), and pH4.48 ± 0.01, which are typical of a mature fruit.

Four fibre coatings were compared for the extraction of bananavolatiles: PDMS, PDMS/DVB, DVB/CAR/PDMS, and CAR/PDMS. Mic-roextractions were made with the same time and temperatureconditions. The results showed that, although PDMS (nonpolarcoating) was more sensitive to esters than PDMS/DVB (polar coat-ing) and PDMS/DVB was more sensitive to alcohols than PDMS, thebest overall extraction efficiency was obtained when DVB/CAR/PDMS coating was used. However, taking into account that theaim of this study was to extract the odourant compounds, we alsochecked which coating extracted most of these compounds. Thus,the extracts obtained using different kinds of coating fibre werealso analysed by GC–O, and the results agreed with the first ones.The similarity scaling obtained for the three SPME global odourswith respect to the reference sample were DVB/CAR/PDMS(2.0 ± 0.1), PDMS/DVB (3.7 ± 0.3), PDMS (6.2 ± 0.4), and CAR/PDMS(8.3 ± 0.5). Therefore, the DVB/CAR/PDMS was chosen as the fibrewhich generated the most representative odour.

Classical GC–O was applied to DVB/CAR/PDMS extract to finddiscriminant odourant zones in their olfactograms, and then toidentify the aroma compounds responsible for these odours. Table1 shows the odour detected by panellists and the correspondingidentified compounds from the 116 detected compounds. Nineteencompounds were detected as contributing to the overall bananaaroma. Among them, 3-methylbutyl acetate (ripe banana),3-methylbutyl butanoate (fruity, banana-like), 3-methylbutyl 3-methylbutanoate (fruity, banana peel), (E)-2-hexenal (intensegreen-fruity), and eugenol (spicy) were the most-odour activecompounds in the SPME extract. These three esters were the mostabundant in the chromatographic profile, and also had high detec-

tion frequencies. It is interesting to note that other compoundswith very low proportions like eugenol (0.7% of the total chromato-graphic area), hexanal (0.2%), and elemicin (0.4%) also had highdetection frequencies.

Esters seemed to be the most important aroma compounds inbanana and possess fruity-banana notes. These three major estershave been reported as key compounds in fruity banana flavour(Berger, Drawert, & Kollmannsberger, 1986; Cosio & René, 1996;Jordán, Tandon, Shaw, & Goodner, 2001; McCarthy, Wyman, & Pal-mer, 1964; Pino & Roncal, 2009; Quast, 1976; Schwab, Davidovich-Rikanati, & Lewinsohn, 2008; Shiota, 1993; Thaiphanit & Anprung,2010). Thaiphanit and Anprung (2010) and Jordán et al. (2001)found that 2-methylpropyl acetate is an odour active compound,whereas Pino (2009) concluded that ethyl acetate and butyl acetateare important aroma contributors. Shiota (1993) reported that2-pentyl, 2-hexyl and 2-heptyl esters could be sensory importantin banana and that other several esters, like (Z)-4-octen-1-yl ace-tate, (Z)-4-octen-1-yl 3-methylbutanoate, (Z)-5-octen-1-yl3-methylbutanoate, and (Z)-4-decen-1-yl 3-methylbutanoate hadodour notes which contribute to the fruity aroma. Nursten(1970) reported that eugenol and elemicin contributed to the spicyaroma of the ripe banana, whereas Jordán et al. (2001) concludedthat hexanal and (E)-2-hexenal are important odour-active com-pounds in banana.

The application of SPME combined with GC–O does not provideimmediate information about the contribution of all odourants tothe overall aroma. The reason is that only the high and medium-volatile compounds are isolated by this headspace isolation meth-od. Therefore, to investigate the contribution of individual com-pounds to banana aroma, the volatile compounds had to bequantified in the fresh banana homogenate by means of SDE. Thepossibilities and limitations of SDE as a pre-concentration tech-nique for trace analysis of organics have been investigated, its use-fulness for the enrichment of very different types of samples haspreviously been reported (Chaintreau, 2001b) and it is used toinvestigate the volatile compounds in many fruits (Nogueira, Fer-nandes, & Nascimento, 2003; Pino, 2012, 2013; Tamura, Boonbu-rung, Yoshizawa, & Varayanond, 2001). The application of SDEmight cause losses of highly volatile compounds and, conse-quently, an underestimation of their aroma contribution. By com-bining the SPME–GC–O with SDE–GC–O, this difference in theevaluation of the contributions of volatiles can be overcome.

The entire volatile compounds from banana, isolated by SDEwith diethyl ether, were evaluated by three experts (same as fordirect GC–O experiments) by smelling a drop of the extract on acardboard smelling strip, as done by perfumers. After evaporationof the solvent, all experts agreed that the extract evoked the char-acteristic fruity and sweet aroma of the fruit, thereby indicatingthat the method used for aroma isolation was appropriate.

A total of 146 volatiles were detected in banana SDE extract,124 of them were positively identified (Table 2). Positive identifi-cations were achieved by comparison of linear retention indicesand mass spectra with those of standard reference compoundsanalysed under identical experimental conditions. Tentative iden-tifications were based on matching linear retention indices andmass spectra of unknowns against those reported in commerciallibraries. The identified volatiles constituted 120 mg kg�1 of thefruit composition. This amount is similar to 106 mg kg�1 reportedfor this cultivar in Cuba (Pino, Fernández, & Rosado, 1995), and116 mg kg�1 found in the same cultivar grown in Madeira(Nogueira et al., 2003), both isolated with the same technique. Jor-dán et al. (2001) reported 131 mg kg�1 for the cv. Cavendish fromHonduras, while Aurore, Ginies, Ganou-Parfait, Renard, and Fah-rasmane (2011) found 23.2 mg kg�1 for the cv. Cavendish fromFrench West Indies, both isolated with solvent extraction.

Table 1Banana odour-active compounds identified by SPME GC–O.

Compound LRIa Odour description Detection frequency

Ethyl acetate 615 Ethereal-fruity, sweet 72-Methylpropyl acetate 770 Ethereal, rum-like 6Hexanal 803 Green greasy 6Butyl acetate 811 Ethereal-fruity 62-Pentyl acetate 854 Banana 7(E)-2-Hexenal 858 Intense green-fruity 83-Methylbutyl acetate 881 Ripe banana 92-Methylpropyl butanoate 958 Fruity 33-Methylbutyl butanoate 974 Fruity, banana-like 92-Pentyl 3-methylbutanoate 1084 Banana 53-Methylbutyl 3-methylbutanote 1106 Fruity, banana peel 92-Hexyl butanoate 1122 Banana 4(Z)-4-Octen-1-yl acetateb 1200 Fruity, pear-like 3Eugenol 1366 Spicy 8(Z)-4-Octen-1-yl 3-metylbutanoateb 1424 Banana, fruity 4(Z)-4-Octen-1-yl pentanoateb 1440 Banana 4(Z)-5-Octen-1-yl 3-methylbutanoateb 1448 Banana-like 4Elemicin 1560 Spicy 6(Z)-4-Decen-1-yl 3-methylbutanoateb 1645 Banana 3

a LRI = Lineal retention index in HP-5 ms column.b tentative identification (only by matching LRI and/or mass spectra from libraries).

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The semi-quantitative distribution of the fruit volatiles chemi-cal families included esters (55.4%), alcohols (17.5%), phenols andderivatives (12.0%), ketones (6.9%), aldehydes (6.5%), acids (1.4%),and miscellaneous compounds (0.2%). Major components(>8 mg kg�1) were 3-methylbutyl acetate, 3-methylbutan-1-ol,eugenol, 3-methylbutyl 3-methylbutanoate, 2-methylpropylacetate and 2-pentyl acetate. These volatiles have been reportedas major compounds in previous studies (Aurore et al., 2011; Brat,Thi Hoang, Soler, Reynes, & Brillouet, 2004; Jordán et al., 2001;Nogueira et al., 2003; Pino et al., 1995).

The volatiles extracted by SDE from banana were analysed byAEDA and OAV to find the most potent odourants. As it is summa-rized in Table 2, the results revealed 38 odourants with importantFD factors (ranging from 8 to 1024), which have been arranged fol-lowing their retention indices. The compounds with highest FDfactors were hexanal, 3-methylbutyl acetate, 3-methylbutyl but-anoate, and eugenol. All of them have been reported as importantodourants in banana fruit (Berger et al., 1986; Cosio & René, 1996;Jordán et al., 2001; Nitz, Berger, Leupold, & Drawert, 1984; Pino,2009; Quast, 1976; Shiota, 1993; Thaiphanit & Anprung, 2010).Other compounds with significant FD factors (512) were ethyl2-methylpropanoate, 2-pentyl acetate, (E)-2-hexenal, hexyl ace-tate, and 3-methylbutyl 3-methylbutanoate. All of them werereported in previous studies as important aroma contributors ofother cultivars (Berger et al., 1986; Cosio & René, 1996; Jordánet al., 2001; Nitz et al., 1984; Quast, 1976; Schwab et al., 2008; Shi-ota, 1993; Thaiphanit & Anprung, 2010), except ethyl 2-methylpropanoate.

Another odourants with FD factor = 256 were 2,3-butanedioneand 3-methylbutanal. Of them, only 3-methylbutanal has beenreported as an important odourant in banana fruit (Jordán et al.,2001). With FD factor = 128 were 2-pentanone, butyl3-methylbutanoate, 4-methyl-2-methoxyphenol, (Z)-4-octen-1-yl3-methylbutanoate, (Z)-4-octen-1-yl pentanoate, and elemicin. Ofthem, only the last four compounds have been found as importantodourants in banana fruit (Nursten, 1970; Shiota, 1993; Pino &Roncal, 2009).

Other odourants with FD factor = 64 were propyl acetate,3-methylbutanol, 2-methylpropyl acetate, butyl acetate,2-methylpropyl 2-methylpropanoate, 2-methylpropyl butanoate,2-methoxy-4-vinylphenol, 2-pentyl 3-methylbutanoate, hexyl 2-methylbutanoate, and (Z)-5-octen-1-yl 3-methylbutanoate. All ofthese have been reported as important odourants in this fruit

(Berger et al., 1986; Cosio & René, 1996; Jordán et al., 2001; Miran-da, Nogueira, Pontes, & Rezende, 2001; Nitz et al., 1984; Pino,2009; Quast, 1976; Schwab et al., 2008; Shiota, 1993; Thaiphanit& Anprung, 2010), with the exceptions of propyl acetate, hexyl 2-methylbutanoate and 2-methoxy-4-vinylphenol.

Another group of odourants, with the low FD factor = 32 were2-heptanone, 2-heptanol, butyl butanoate, ethyl 3-hydroxyhex-anoate, and 2-undecanone. With the exceptions of 2-undecanone,the others odourants have been reported of special importancefor the aroma of banana fruit (Jordán et al., 2001; Miranda et al.,2001; Pino, 2009).

A last group with rather low FD factors (8–16) included anotherfour volatiles, from which 1-butanol, (Z)-3-hexen-1-ol, and (E)-3-hepten-2-one. Of them, only (Z)-3-hexen-1-ol has been foundas important odourant in banana fruit (Miranda et al., 2001; Pino,2009).

Dilution to odour threshold techniques, such as AEDA, do notpermit a study on the influence of the food matrix on odourantbinding nor on the interactions of odourants when matching theoverall odour impression of the food. Therefore, the OAV concept(Schieberle, 1995) was applied in this study to the odourants of ba-nana (Table 3). Although it is known that the odour thresholdsmight be influenced by nonvolatile fruit compounds, water is themain constituent of banana. Therefore, the odour thresholds forall the volatiles under investigation were taken from thosereported in aqueous solutions. Results suggested that 31 odourantsshould contribute to the characteristic aroma of banana cv. GiantCavendish, because their contents exceeded or were identical totheir odour thresholds (Table 3). Six compounds could not be eval-uated because their odour thresholds are unknown. Following thisprocedure, the compounds with the highest OAV were identified as3-methylbutyl butanoate, 3-methylbutyl acetate, eugenol, andhexanal with their characteristic banana, spicy and green grassyodours. However, another 27 odourants have OAVs P 1 and prob-ably contribute to the aroma of banana cv. Giant Cavendish (Table3). The potentially important odourants obtained with the odouractivity approach is a refinement of that provided by the AEDAand corrects some of the defects of the AEDA technique. Ethylacetate has an OAV < 1, so its contribution could be not importantto the aroma.

Sensory studies need to be done to determine the actual contri-bution of these volatile compounds to this banana cultivar, includ-ing model and omission experiments.

Table 2Volatile compounds from banana isolated by SDE.

Compound LRIa mg kg�1 Standarddeviation

Acetaldehyde 527 tb –Ethanol 537 1.41 0.142,3-Butanedione 595 0.41 0.04Ethyl acetate 612 2.74 0.242-Methylpropanol 625 4.09 0.323-Methylbutanal 654 0.12 0.011-Butanol 668 0.80 0.042-Pentanone 688 5.39 0.252-Pentanol 708 3.91 0.263-Hydroxy-2-butanone 712 t –Propyl acetate 716 0.45 0.033-Methylbutan-1-ol 741 9.02 0.36Ethyl 2-methylpropanoate 751 0.07 0.012-Methylpropyl acetate 767 7.19 0.272,3-Hexanedione 786 0.05 0.012-Hexanone 792 0.14 0.01Hexanal 802 2.78 0.24Ethyl butanoate 805 0.01 0.01Butyl acetate 811 1.26 0.153-Methylbutanoic acid 836 0.09 0.012-Pentyl acetate 853 7.12 0.27(E)-2-Hexenal 856 4.56 0.31(Z)-3-Hexen-1-ol 860 0.10 0.01m-Xylene 863 0.09 0.01(Z)-2-Hexen-1-ol 866 t –1-Hexanol 871 t –4-Heptanone 876 t –3-Methylbutyl acetate 880 19.43 1.552-Methylbutyl acetate 883 t –3-Methyl-3-buten-1-yl acetatec 885 0.19 0.01(Z)-4-Hepten-2-ol 887 1.36 0.142-Heptanone 890 0.37 0.023-Acetoxy-2-butanonec 893 0.34 0.02(E)-4-Hepten-2-onec 896 0.60 0.03Propyl butanoate 899 t –2-Heptanol 902 0.42 0.03(E,E)-2,4-Hexadienal 910 t –c-Butyrolactone 915 t –2-Methylpropyl 2-methylpropanoate 918 0.36 0.02(E)-2-Hepten-4-onec 922 0.86 0.04Tricyclene 930 t –(E)-3-Hepten-2-onec 933 0.11 0.012-Hexyl acetatec 937 0.29 0.02Propyl 3-methylbutanoate 940 t –Butyl 2-methylpropanoate 950 0.03 0.012-Methylpropyl butanoate 955 1.66 0.14Benzaldehyde 960 t –Ethyl 2-hydroxy-3-methylbutanoate 968 0.08 0.023-Methylbutyl propanoate 972 0.02 0.012-Pentyl 2-methylpropanoate 980 0.02 0.01Butyl butanoate 995 0.27 0.02Ethyl hexanoate 998 t –n-Decane 1000 0.02 0.012-Methylpropyl 2-methylbutanoate 1006 0.13 0.022-Methylpropyl 3-methylbutanoate 1009 0.76 0.03Hexyl acetate 1012 1.36 0.043-Methylbutyl 2-methylpropanoate 1017 t –(E)-4-Hexen-1-yl acetate 1019 0.04 0.01(Z)-4-Hexen-1-yl acetate 1021 0.21 0.022-Pentyl butanoatec 1024 1.08 0.03p-Cymene 1026 t –Limonene 1029 t –(E)-4-Hepten-2-yl acetatec 1032 0.24 0.02(Z)-4-Hepten-2-yl acetatec 1038 3.48 0.25Butyl 3-methylbutanoate 1048 0.20 0.023-Methylbutyl butanoate 1056 5.12 0.361-Phenylethanol 1063 t –2,3-Butanediol diacetate 1064 0.09 0.01Acetophenone 1068 0.01 0.013-Oxo-2-butyl butanoatec 1070 0.23 0.024-Nonanonec 1073 0.05 0.012-Pentyl 3-methylbutanoate 1085 0.25 0.022-Nonanone 1090 t –

Table 2 (continued)

Compound LRIa mg kg�1 Standarddeviation

3-Methylbutyl 2-methylbutanoate 1100 0.52 0.043-Methylbutyl 3-methylbutanoate 1103 8.22 0.332-Phenylethanol 1107 t –2-Hexyl butanoate 1124 0.08 0.01Ethyl 3-hydroxyhexanoate 1130 0.16 0.02Ethyl 3-oxohexanoate 1135 0.05 0.01Hexyl 2-methylpropanoate 1148 t –2-Methylpropyl hexanoate 1152 0.01 0.013-Methylbutyl pentanoate 1154 0.07 0.01Methyl 2-methyloctanoate 1158 0.08 0.02Benzyl acetate 1162 t –2-Heptyl butanoate 1170 t –(E)-4-Hepten-2-yl butanoatec 1176 0.05 0.011,4-Dimethoxybenzene 1184 t –(Z)-3-Hexen-1-yl butanoate 1188 t –4-Methyl-2-methoxyphenol 1190 0.82 0.03Hexyl butanoate 1194 t –1-Phenylethyl acetate 1197 t –(Z)-4-Octen-1-yl acetatec 1199 0.06 0.01(Z)-4-Hexen-1-yl butanoatec 1202 0.02 0.01Octyl acetate 1214 t –(Z)-4-Hepten-2-yl butanoatec 1222 0.98 0.06(Z)-3-Hexen-1-yl 2-methylbutanoate 1230 0.02 0.013,4-Dimethoxytoluene 1234 1.18 0.04Hexyl 2-methylbutanoate 1238 0.34 0.02(Z)-3-Hexen-1-yl 3-methylbutanoate 1240 t –3-Methylbutyl hexanoate 1249 0.09 0.01(E)-3-Hexen-1-yl 3-methylbutanoate 1255 0.13 0.022-Phenylethyl acetate 1260 0.04 0.01(E)-4-Hepten-2-yl 3-

methylbutanoatec1262 0.06 0.01

(Z)-4-Hepten-2-yl 3-methylbutanoatec

1264 0.36 0.01

Ethyl 3-acetoxyhexanoatec 1268 t –2-Undecanone 1294 0.09 0.012-Methoxy-4-vinylphenol 1323 0.05 0.01Eugenol 1363 8.94 0.353-Phenylpropyl acetate 1382 t –n-Tetradecane 1400 0.02 0.01Methyl eugenol 1407 0.56 0.02(Z)-Isoeugenol 1408 t –Methyl decadienoatec 1414 0.08 0.01(Z)-4-Octen-1-yl 3-methylbutanoatec 1425 0.16 0.02(E)-a-Ionone 1430 t –(Z)-4-Octen-1-yl pentanoatec 1438 t –(Z)-5-Octen-1-yl 3-methylbutanoatec 1444 0.14 0.01(E)-Isoeugenol 1451 0.02 0.01(E)-b-Ionone 1487 0.04 0.012-Phenylethyl 3-methylbutanoate 1490 0.10 0.012-Tridecanone 1492 0.09 0.01(E)-Methyl isoeugenol 1496 t –5-Methoxyeugenol 1555 0.14 0.02Elemicin 1559 2.02 0.14Dodecanoic acid 1568 0.07 0.01n-Hexadecane 1600 0.02 0.01(Z)-Isoelemicin 1636 t –Hydrocinnamyl 2-methylpropanoate 1641 0.10 0.02(Z)-4-Decen-1-yl 3-

methylbutanoatec1646 0.09 0.01

2-Methylpropyl (E)-cinnamate 1654 0.06 0.01(E)-Isoelemicin 1657 t –Acetosyringone 1730 0.71 0.042-Pentadecanone 1695 0.13 0.02n-Heptadecane 1700 t –2-Pentadecanol 1704 0.03 0.013-Methylbutyl (E)-cinnamate 1783 0.16 0.02Tetradecanoic acid 1786 0.31 0.03Ethyl tetradecanoate 1796 t –n-Octadecane 1800 0.04 0.013-Methylbutyl dodecanoate 1846 0.08 0.02Pentadecanoic acid 1868 0.30 0.03n-Nonadecane 1900 t –Hexadecanoic acid 1960 0.09 0.01

(continued on next page)

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Table 2 (continued)

Compound LRIa mg kg�1 Standarddeviation

n-Heneicosane 2100 t –Oleic acid 2141 t –Octadecanoic acid 2200 0.80 0.08

a LRI = Lineal retention index in HP-5 ms column.b tr = < 0.01 mg kg�1.c Tentative identification (only by matching LRI and/or mass spectra from libraries).

Table 3Odour-active (FD P 32) volatile compounds identified in banana.

Compound Odour threshold (lg kg�1) Odour quality FDa OAVb

2,3-Butanedione 1c Butter 256 408Ethyl acetate 5000d Ethereal-fruity, sweety 32 <13-Methylbutanal 0.5c Malt 256 2401-Butanol 500d Winey 8 22-Pentanone 50e Banana, sweety 128 108Propyl acetate 54f Ethereal-fruity 64 83-Methylbutan-1-ol 220c Fruity-winey 64 41Ethyl 2-methylpropanoate 0.1g Sweet-fruity 512 6902-Methylpropyl acetate 66g Ethereal 64 1092-Pentyl acetate ndh Banana 512 ndHexanal 2.4c Green grassy 1024 1157Butyl acetate 66g Ethereal-fruity 64 19(E)-2-Hexenal 17g Green-intense fruity 512 268(Z)-3-Hexen-1-ol 70g Fresh grass 8 13-Methylbutyl acetate 2d Ripe banana 1024 97152-Heptanone 140d Fruity-spicy 32 32-Heptanol 400i Fruity, pungent 32 12-Methylpropyl 2-methylpropanoate 30g Sweet-fruity 64 12(E)-3-Hepten-2-one 56g Grass 8 22-Methylpropyl butanoate 30g Frutal 64 55Butyl butanoate 100g Sweet-fruity 32 3Hexyl acetate 2g Sweet-fruity 512 681Butyl 3-methylbutanoate 17g Ethereal-fruity 128 123-Methylbutyl butanoate 0.1d Banana 1024 51,2102-Pentyl 3-methylbutanoate nd Banana 64 nd3-Methylbutyl 3-methylbutanoate 65i Banana peel 512 1272-Hexyl butanoate nd Banana 128 ndEthyl 3-hydroxyhexanoate 100i Green fruit 32 22-Methoxy-4-methylphenol 21c Spicy, sweet 128 39Hexyl 2-methylbutanoate 22g Fruity, pungent 64 152-Undecanone 7g Fruity, grass 32 132-Methoxy-4-vinylphenol 5c Intense spicy 64 11Eugenol 6d Spicy 1024 1490(Z)-4-Octen-1-yl 3-methylbutanoate nd Banana 128 nd(Z)-4-Octen-1-yl pentanoate nd Banana 128 nd(Z)-5-Octen-1-yl 3-methylbutanoate nd Banana-like 64 nd(E)-b-Ionone 3.5c Fruity 32 10Elemicin 100i Spicy 128 20

a Flavour dilution factor.b Odour activity values were calculated by dividing the concentrations by the respective odour threshold.c Czerny et al. (2008).d Pino and Mesa (2006).e Ulrich, Hoberg, Rapp, and Keeke (1997).f Pino and Quijano (2012).g Leffigwell and Assoc. (2011).h nd = no data.i Pino and Roncal (2009).

800 J.A. Pino, Y. Febles / Food Chemistry 141 (2013) 795–801

4. Conclusions

A total of 146 volatiles were detected, 124 of them were posi-tively identified in banana cv. Giant Cavendish. The compositionof banana fruit volatiles included 75 esters, 18 ketones, 14 phenolsand derivatives, 7 aldehydes, 13 alcohols, 7 acids, and 12 miscella-

neous compounds. This study revealed potent odourants that areresponsible for the overall aroma of this banana cultivar by appli-cation of the aroma extract dilution analysis and by odour activityvalues. Thirty-one odourants were considered as odour-activecompounds, from which eleven of them are reported for the firsttime as important odourant of banana fruit.

J.A. Pino, Y. Febles / Food Chemistry 141 (2013) 795–801 801

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