Mapeo del Proceso

Fortunella margarita (also called “Nagami kumquat” or “ovoid kumquat”) is the most familiar spe-cies in the Western world. It has an oval shape and a smooth, bright orange fl avedo. When eaten whole, the orange-like aroma of the peel and woody, fl oral, sweet notes complement very well the rather sour, acidic pulp. The volatile constituents of F. margarita were fi rst reported by Bernhard and Scrubis (1961). The oil was prepared by steam distillation of the epicarp of fruits harvested in California and studied by gas-liquid chromatography. This oil contained large amounts of limo-nene, some α-pinene, myrcene, aldehydes (decanal, citronellal) and terpenyl esters (geranyl acetate, terpinyl acetate, bornyl acetate, linalyl acetate). In 1983, Koyasako and Bernhard repeated the study using gas chromatographic and mass spectrometric techniques to identify and quantify the volatile components of F. margarita from California. The kumquat peel oil was obtained by simultaneous distillation extraction (SDE) of the peel. The major components were limonene (92.7%); sesquiter-pene hydrocarbons (0.4%); and oxygenated sesquiterpenoids (2.1%). Both studies showed that, com-pared to other citrus oils, kumquat oil contains a higher number of esters and less aldehydes. This observation was confi rmed by Kwag et al. (1992), who identifi ed limonene (96.5%); β-pinene (1.9%);

α-terpineol (0.4%); γ-terpinene (0.2%); β-terpineol (0.1%); geranyl acetate (0.07%); linalool (0.05%);

octyl acetate (0.04%); and terpinen-4-ol (0.04%) as major constituents in an extract prepared by SDE. Recently the cold-pressed peel oil of F. margarita from Sicily was analyzed by GC-MS and quantifi ed using FID percent with an internal standard and correction factors (Delort, 2007) (Table 2.1). Nonanal and decanal were almost totally absent. Interestingly, a series of less common terpenyl alcohols and acetates was identifi ed in trace amounts: 2,8-p-menthadien-1-ol, trans-isopiperitenyl acetate, 1,8(10)-p-menthadien-9-yl acetate, 1-p-menthen-9-yl acetate, and perillyl acetate. These compounds may contribute to the fruity-fl oral character of the peel.

TABLE 2.1 (continued)

Major Volatile Constituents Reported in Fortunella Peel and Leaf Oils

Phenols

Thymol 1.5

Carvacrol 3.5

N-Compounds

Methyl anthranilate 2.5

Notes: Compounds are listed by chemical class and in elution order from a nonpolar column. Only compounds >0.2% are reported. CPPO: cold-pressed peel oil; S.E.: solvent extract; S.D.: steam distillation; ^aα-pinene + ethyl butanoate.

b terpinyl acetate + geranial.

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TABLE 2.2 Major Volatile Constituents Reported in Japanese Citrus Peel and Leaf Oils C. aurantium (CPPO: Song et al., 2000a) C. aurantium (S.D.: Huang and Pu, 2000) C. depressa (S.D.: Fujita, 2004) C. depressa (H.D.: Fujita, 2004) C. fl aviculpus (S.E.: Katayama and Iwabuchi, 2002; CPPO: Choi, 2001) C. infl ata (CPPO: Minh Tu et al., 2003a) C. junos (CPPO: Song et al, 2000b) C. kinokuni (S.E.: Shiota and Ito, 1991) C. kinokuni (S.D.: Huang and Pu, 2000)

C. sphaerocarpa (CPPO: Minh Tu et al., 2002) C. sudachi (CPPO: Njoroge et al.,1995) C. taguma- sudachi (CPPO: Njoroge et al., 1996)

C. tamur (CPPO, Choi, 2000) PeelLeafPeelLeafPeelPeelPeelPeelLeafPeelPeelPeelPeel Hydrocarbons α-Thujene0.71.3 α-Pinene0.62.0–4.43.5–5.72.0/0.80.42.02.34.20.71.61.01.3 Camphene0.2 Sabinene0.20.30.2–0.30.3–0.80.84.70.4 β-Pinene0.41.31.2–2.82.5–4.31.2/0.41.926.80.20.50.30.8 Myrcene2.22.51.6–1.90.9–1.83.3/1.524.60.41.50.820.21.31.82.3 α-Terpinene0.3–0.60.4–0.90.20.47 α-Phellandrene0.0–0.60.91.3 p-Cymene1.4–7.62.7–6.20.31.52.20.4 Limonene92.50.644.7–72.93.0–3.861.6/82.471.377.462.02.870.569.190.582.4 (Z)-β-Ocimene0.90.2 β-Phellandrene0.1–0.90.0–8.12.27.2 (E)-β-Ocimene0.32.30.92.80.8 δ-3-Carene0.6 γ-Terpinene15.2/30.429.4–55.013.1/8.89.420.413.52.67.54.27.7 α-Terpinolene0.40.9–1.51.5–2.20.8/0.40.31.30.30.20.4 β-Elemene0.0–3.22.0 β-Caryophyllene0.20.1–0.40.5–3.40.20.2 α-Humulene0.0–0.90.6 (E)-β-Farnesene2.9/1.80.30.50.40.70.80.6 germacrene D0.4–0.90.8–2.00.21.5 Valencene1.3/0.3 Bicyclogermacrene0–0.90.5–2.20.7 Germacrene A0.0–3.2 (E,E)-α-Farnesene0.32.2

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TABLE 2.2 (continued) Major Volatile Constituents Reported in Japanese Citrus Peel and Leaf Oils C. aurantium (CPPO: Song et al., 2000a) C. aurantium (S.D.: Huang and Pu, 2000) C. depressa (S.D.: Fujita, 2004) C. depressa (H.D.: Fujita, 2004) C. fl aviculpus (S.E.: Katayama and Iwabuchi, 2002; CPPO: Choi, 2001) C. infl ata (CPPO: Minh Tu et al., 2003a) C. junos (CPPO: Song et al., 2000b) C. kinokuni (S.E.: Shiota and Ito, 1991)

C. kinokuni (S.D.: Huang and Pu, 2000

C. sphaerocarpa (CPPO: Minh Tu et al., 2002) C. sudachi (CPPO: Njoroge et al.,1995) C. taguma- sudachi (CPPO: Njoroge et al., 1996) C. tamurana (CPPO, Choi, 2000)

C. yuko (CPPO: Njoroge et al., 1994) PeelLeafPeelLeafPeelPeelPeelPeelLeafPeelPeelPeelPeelPeel δ-Cadinene0.2–2.50.4–1.30.2 Germacrene B 0.2 Aldehydes (2E)-2-Hexenal0.0–0.7 Octanal0.60.7 Citronellal0.0–0.20.3 Decanal0.20–0.20.20.20.50.3 Ketones l-Carvone0.4 Piperitone0.4–1.30.0–17.4 Alcohols (3Z)-3-Hexen-1-ol0.4–1.5 Octanol0.7 Linalool0.239.81.0–2.810.0–17.41.1/0.40.21.60.523.00.31.40.2 Terpinen-4-ol0.2–0.30.2–0.40.20.4 α-Terpineol9.90.3/0.10.80.60.20.5 Citronellol0.0–0.2 Nerol1.7 Geraniol5.5 cis-Carveol0.6 (E)-Nerolidol0.0–0.20.2 Spathulenol0.0–0.4 Phytol0.0–0.4

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Esters Ethyl acetate0.3 Linalyl acetate1.424.8 Neryl acetate2.8 Geranyl acetate0.25.1 Phenols Thymol methyl ether0–0.90.0–7.3 Thymol0–2.60.0–12.00.49.8 Methoxythymol0.0–0.3 N-Compounds Methyl N-methyl anthranilate2.0 Notes: Compounds are listed by chemical class and in elution order from a nonpolar column. Only compounds >0.2% are reported. CPPO: cold-pressed peel oil; S.D.: steam distillate; S.E.: solv

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170 Citrus Oils

TABLE 2.3 Major Volatile Constituents Reported in Australian Native Citrus Peel and Leaf Oils C. australis (S.E.: Craske et al., 2005) C. australis (H.D.: Brophy and Goldsack, 2001) C. australasica (S.E.: Delort and Jaquier, 2009) C. australasica (H.D.: Brophy, 2001) C. garrowayi (H.D.: Brophy 2001, chem1/chem2) C. glauca (H.D.: Brophy, 2001) C. gracilis (H.D.: Brophy, 2001)

C. inodora (H.D.: Brophy, 2001) PeelLeafPeelLeafLeafLeafLeafLeaf Hydrocarbons α-Thujene0.20.8 α-Pinene1.378.40.45.018.2/0.040.92.2 Camphene0.40.2/0.00.4 Sabinene2.20.80.62.00.3 β-Pinene13.12.30.40.40.2/0.014.42.3 Myrcene1.03.71.74.41.2/0.01.40.80.2 α-Terpinene0.3 α-Phellandrene0.30.9 p-Cymene0.514.8 Limonene35.12.173.512.80.4/0.21.33.7 (Z)-β-Ocimene0.41.52.10.2/0.2 β-Phellandrene1.520.20.5/0.00.6 (E)-β-Ocimene0.20.20.34.80.0/0.5 δ-3-Carene0.31.0 γ-Terpinene11.22.633.8 α-Terpinolene0.40.51.9 Bicycloelemene0.40.20.6 δ-Elemene0.20.51.9/0.24.9 α-Cubebene4.4/0.2 α-Copaene0.8/0.7 β-Bourbonene0.0/0.23.3 β-Elemene0.70.20.3/2.00.6 β-Caryophyllene1.00.20.512.0/17.67.44.7 α-Bergamotene1.6

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γ-Elemene1.3 α-Humulene0.22.7/2.91.40.20.6 Germacrene D0.50.27.70.0/2.123.7 β-Selinene5.6/8.2 Cadina-1,4-diene1.9/1.11.0 Viridifl orene0.50.4 α-Selinene4.1/5.0 Bicyclogermacrene1.70.619.87.0/2.96.210.217.3 (E,E)-α-Farnesene3.30.22.82.0/1.71.0 β-Bisabolene2.8 δ-Cadinene0.20.63.0/1.62.6 Calamenene0.0/0.5 Germacrene B0.98.1 Ethers Caryophyllene oxide0.4/1.8 Aldehydes Nonanal0.8 Citronellal2.64.3 Decanal0.80.4 Neral4.5 Geranial7.3 Ketones Isomenthone7.5 Piperitone0.5 Alcohols Linalool oxide (furanoid) isomer 19.6 Linalool oxide (furanoid) isomer 2

5.0 Linalool0.31.01.80.30.33.0 Terpinen-4-ol α-Terpineol0.70.30.20.4 continued

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172 Citrus Oils

TABLE 2.3 (continued) Major Volatile Constituents Reported in Australian Native Citrus Peel and Leaf Oils C. australis (S.E.: Craske et al., 2005) C. australis (H.D.: Brophy and Goldsack, 2001) C. australasica (S.E.: Delort and Jaquier, 2009) C. australasica (H.D.: Brophy, 2001) C. garrowayi (H.D.: Brophy 2001, chem1/chem2) C. glauca (H.D.: Brophy, 2001) C. gracilis (H.D.: Brophy, 2001)

C. inodora (H.D.: Brophy, 2001) PeelLeafPeelLeafLeafLeafLeafLeaf Citronellol0.40.9 (E)-Nerolidol20.4 Spathulenol 0.50.0/0.31.81.82.7 Ledol0.41.9/2.1 Globulol1.40.69.3/9.60.50.41.0 Viridifl orol3.20.89.2/9.20.30.30.8 epi-Cubenol0.0/0.6 Cubenol0.0/0.3 T-cadinol0.0/1.3 α-Bisabolol0.0/2.7 Phytol5.00.0/1.93.9 Esters Neryl acetate0.4 Geranyl acetate0.4 Coumarins 7-Methoxycoumarin1.1 5,7- Dimethoxycoumarin3.4 Iso-bergaptene0.2 Bergaptene0.4 Isopimpinellin3.5 Notes: Compounds are listed by chemical class and in elution order from a nonpolar column. Only compounds >0.2% are reported. S.E.: solvent extract; H.D.: hydrodistillate; chem: chemotype.

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TABLE 2.4 Major Volatile Constituents Reported in Other Citrus Peel, Leaf, and Juice Oils C. ichangensis (CPPO: Lota et al., 2002/ Sawamura, 2000) C. ichangensis (H.D.: Lota et al., 2002) C. limetta (S.E.: Naef and Velluz, 2003/ S.D.: Sattar, 1992) C. nobilis (CPPO: Dharmawan et al., 2009) C. nobilis (S.E.: Dharmawan et al., 2009) Poncirus trifoliata (S.D.: Scora et al., 1966) Poncirus trifoliata (S.D.: Scora et al., 1969)

Poncirus trifoliata (S.D.: Scora et al., 1966) PeelLeafPeelPeelJuicePeelLeafJuice Hydrocarbons α-Thujene0.5/01.30.2 α-Pinene1.4/3.33.50.8/0.90.40.61.20.4 Camphene0.3 Sabinene0.9/0.91.80.2/0.0 β-Pinene4.5/1.814.02.9/2.10.40.50.8 Myrcene1.6/0.71.22.20.420.429.80.4 α-Terpinene0.4/2.40.8 α-Phellandrene0.6/00.70.0/0.23.8 p-Cymene0.3/02.10.0/1.41.91.5 Limonene63.8/68.83.585.1/60.295.789.640.71.8 (Z)-β-Ocimene0.3/0 β-Phellandrene4.2/3.75.1 (E)-β-Ocimene4.013.2 γ-Terpinene18.0/16.036.10.0/11.80.313.54.31.6 α-Terpinolene0.8/0.71.80.0/3.00.6 β-Caryophyllene0.20.0/0.4 α-Bergamotene0.8/0.0 α-Humulene0.2/0 Germacrene D0.4/0.20.8/0.0 β-Bisabolene0.2/01.0/0.0 δ-Cadinene0.3 continued

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TABLE 2.4 (continued) Major Volatile Constituents Reported in Other Citrus Peel, Leaf, and Juice Oils C. ichangensis (CPPO: Lota et al., 2002/ Sawamura, 2000) C. ichangensis (H.D.: Lota et al., 2002) C. limetta (S.E.: Naef and Velluz, 2003/ S.D.: Sattar, 1992) C. nobilis (CPPO: Dharmawan et al., 2009) C. nobilis (S.E.: Dharmawan et al., 2009) Poncirus trifoliata (S.D.: Scora et al., 1966) Poncirus trifoliata (S.D.: Scora et al., 1969)

Poncirus trifoliata (S.D.: Scora et al., 1966) PeelLeafPeelPeelJuicePeelLeafJuice Ethers trans-8,9-Epoxy-1-p- menthene

0.3/0.0 Aldehydes Furfural1.11.1 Octanal0.0/0.60.80.3 Nonanal0.20.20.41.6 Citronellal1.72.6/0.00.52.40.2 Decanal0.20.50.3 Neral2.30.0/0.60.40.7 Geranial3.40.0/1.30.20.20.4 Undecanal0.3 Ketones l-Carvone0.5 6-Methyl-hept-5-en-2- one

0.6 Piperitone Alcohols Octanol0.5 cis-Linalool oxide (furanoid)

0.3 Linalool0.2/0.24.60.6/1.90.50.60.713.0 Isopulegol0.7

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Nonanol1.79.8 Terpinen-4-ol0.40.2 α-Terpineol0.0/0.30.30.0/1.31.00.92.41.7 Citronellol1.10.2/0.00.8 Nerol2.50.60.4 Geraniol0.70.0/0.2 (E)-Nerolidol0.2 Esters 3-Octyl acetate0.5 Octyl acetate0.40.4 Linalyl acetate0.0/0.20.3 Neryl formate1.90.5 Nonyl acetate0.4 Terpinyl acetate0.5/0.00.3 Citronellyl acetate0.2/0.00.30.3/0.00.30.5 Neryl acetate0.3/0.04.40.0/0.525.20.4 Geranyl acetate0.40.0/0.30.40.42.60.5 Neryl butyrate3.7 Geranyl butyrate1.4 Phenols Thymol1.2 Carvacrol0.8 p-Vinylguaiacol0.4 N-Compounds Methyl anthranilate1.0 Notes: Compounds are listed by chemical class and in elution order from a nonpolar column. Only compounds >0.2% are reported. CPPO: cold-pressed peel oil; S.E: solvent extract; S.D.: steam distillate; H.D.: hydrodistillate.

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TABLE 2.5 Selection of Key Odor-Impact Compounds Found by Means of AEDA and GC-Olfactometry in Peel Oils of Less Common Citrus Species F. japonica (Choi, 2005) C. aurantium L. var. cyathifera (Song, 2000a) C. fl aviculpus (Choi 2002; Katayama and Iwabuchi, 2002; Choi, 2001) C. infl ata (Minh Tu et al., 2003b; Njoroge, 1994) C. junos (Miyazawa et al., 2009; Yukawa et al., 1994; Escher et al., 2006; Song, 2000b) C. kinokuni (Shiota, 1991) C. sphaerocarpa (Minh Tu et al., 2003b; Minh Tu et al. 2002; Yang, 1992) C. sudachi (Yang, 2000; Mookdasanit et al., 2003) C. tamurana (Choi, 2001)

C. limetta (Naef and Velluz, 2003)

C. nobilis (Fisher et al., 2008; Dharmawan et al., 2009)

Poncirus trifoliata (Starkenmann et al., 2007) Hydrocarbons α-Pinene Camphene× Myrcene××× Limonene×× (E)-β-Ocimene×× Tetradecane× β-Elemene× β-Copaene× (E)-β-Farnesene× (E,E)-α-Farnesene× Aldehydes (3Z)-3-Hexenal× Octanal ××× Nonanal× Citronellal××a× Decanal× (2E,4E)-2,4-Nonadienal× Cumin aldehyde× Neral×× (2E)-2-Decenal××× Geranial× Perillaldehyde×× (2E,4E)-2,4-Decadienal× (2E)-2-Undecenal× × (5Z)-5-Dodecenal×

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Dodecanal× (2E,6Z)-2,6-Dodecadienal× (2E)-2-Dodecenal× × Tridecanal× β-Sinensal× α-Sinensal× Ketones Carvone× Raspberry ketone× Methyl epijasmonate×× Nootkatone×× (6Z,8E)-6,8,10-Undecatrien-3- one (yuzunone)

×b Alcohols Octanol×× cis-Linalool oxide (furanoid)××× trans-Linalool oxide (furanoid)×× Linalool×××× Borneol× Terpinen-4-ol× α-Terpineol×× trans-Carveol× Citronellol××× Nerol× Geraniol×× Perillyl alcohol×× β-Elemol× (E)-Nerolidol× Cedrol× (E,E)-Farnesol× (6Z,8E)-6,8,10-Undecatrien-4-ol (yuzuol)

×b Esters Ethyl 2-methylbutanoate× Octyl acetate×× Citronellyl formate×× Geranyl acetate Neryl acetate× continued

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178 Citrus Oils

TABLE 2.5 (continued) Selection of Key Odor-Impact Compounds Found by Means of AEDA and GC-Olfactometry in Peel Oils of Less Common Citrus Species F. japonica (Choi, 2005) C. aurantium L. var. cyathifera (Song, 2000) C. fl aviculpus (Choi 2002; Katayama and Iwabuchi, 2002; Choi, 2001) C. infl ata (Minh Tu et al., 2003; Njoroge, 1994) C. junos (Miyazawa et al., 2009; Yukawa et al., 1994; Escher et al., 2006; Song 2000) C. kinokuni (Shiota, 1991) C. sphaerocarpa (Minh Tu et al., 2003b; Minh Tu et al., 2002; Yang, 1992) C. sudachi (Yang, 2000; Mookdasanit et al., 2003) C. tamurana (Choi, 2001)

C. limetta (Naef and Velluz, 2003)

C. nobilis (Fisher et al., 2008; Dharmawan et al., 2009)

Poncirus trifoliata (Starkenmann et al., 2007) Linalyl acetate×× Citronellyl acetate×× × (E,E)-Farnesyl acetate× Phenols Eugenol× Carvacrol× Lactones Wine lactone× Yuzu lactone×× Ethers Dill ether× 1,8-Cineole× cis-Limonene oxide×× trans-Limonene oxide N-Compounds Methyl N-methyl anthranilate×

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Sulfur compounds Methyltrisulfi de× Diisopropyl disulfi de× 1-Phenylethanethiol×b p-Menth-1-ene-8-thiol× 3-Mercapto-3-methyl-1-butanol×b 4-Mercapto-4-methyl-2- pentanone

× 3-Mercapto-1-hexanol×b 3-Methyl-3-mercaptobutyl acetate

×b 3-Methyl-3-mercaptobutyl butanoate

×b 3-Mercaptohexyl acetate×b 3-Mercaptohexyl butanoate×b Notes: a Isomer (R)-(+)-citronellal; b Newly identifi ed.

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180 Citrus Oils