Attokaran M. Natural Food Flavors and Colorants

326 Individual Flavors and Colorants

steady producer of oleoresin, mainly for its own use. In recent years, India, China,

and Peru have emerged as producers of raw material for paprika oleoresin. Indian

material has some capsaicin, but by successfully fractionating this out, India has

emerged as a major supplier of oleoresin. Not only did the oleoresin resemble that

of sweet paprika, but recovery of capsaicin also gave some economic advantage.

China, with its vast area for cultivation, ideal cold climate, and encouragement

given by the government to the extraction industry, may rise to the top of paprika

oleoresin world. The extraction industry in Peru showed promise but the growth is

uncertain.

India has two main varieties: Byadege and Tomato Chili. Both have perceptible

levels of capsaicin and allied compounds of dihydrocapsaicin and nor - dihydrocapsaicin

(for its chemical structure, see Chapter 25 on capsicum). A recent introduction to India

is the Wonder Hot variety, which has a low yield of oleoresin but contains more of

the red pigments.

The analysis of raw material from different countries is presented in Table 82.1 .

The units of color absorption ratio and others are explained later in the section on

“ units of color. ” In each category, there are top - , medium - , and low - grade varieties

especially based on color. The values should therefore be considered as trends rather

than as absolute values. It can be seen that low levels of capsaicin are present in

paprika from Zimbabwe, South Africa, China (II and III), Spain, and Azerbaijan. In

comparison, Indian varieties have a high level of capsaicin. In the matter of color

content, Byadege compares favorably to samples from outside India. But the absorp-

tion ratio of Byadege is low, indicating a lower level of red pigments. Wonder Hot in

particular and Tomato Chili both have a good absorption ratio. But lower yields of

oleoresin and color make both of these expensive as raw material. By introducing

fractionation to remove pungency, Byadege is now one of the most important raw

materials of oleoresin paprika in the world.

Table 82.1. Capsaicin and color content of paprikas from different regions

Variety Capsaicin

Content (%)

ASTA Color

of Chili

Yield of

100,000 cv O/R

Absorption

Ratio of O/R

Byadege 0.1 198.8 6.5 0.975

Tomato Chili (India) 0.08 133.4 4.0 0.982

Wonder Hot (India) 0.07 118.5 3.1 0.998

South Africa 0.03 221.0 6.3 0.968

Zimbabwe 0.007 288.0 7.6 0.960

China I 0.08 107.0 3.5 0.981

China II 0.04 212.4 7.1 0.980

China III 0.05 164.2 5.3 0.978

Spain (low grade) 0.02 100.7 4.4 0.974

Peru 0.06 188.0 5.7 0.974

Ethiopia 0.06 161.4 5.2 0.965

Mozambique 0.05 171.0 4.4 0.960

Afghanistan 0.09 177.7 5.5 0.974

Azerbaijan 0.04 156.0 4.7 0.962

O/R = oleoresin; 1 ASTA unit of color = 40.2 cv.

82 Paprika 327

Chemistry

Generally, dry paprika pods contain 15% protein, 8% fat, 55 – 58% carbohydrate, and

a ﬁ ber content of 20 – 22%. It is a rich source of ascorbic acid and also has small

amounts of B vitamins and vitamins A and E. Paprika has no essential oil.

The most important constituents of paprika and its oleoresin are the xanthophylls,

which are oxygenated carotenes. From earlier studies (Govindarajan 1987 ), the various

constituents present can be summarized and presented as in Table 82.2 . While carotenes

are yellow in color, the oxygenated derivatives have orange and red coloration. Among

these, the red pigments capsanthins and capsorubins are very important. Not only are

these red pigments responsible for the appealing red color of the products, but they also

get deposited in egg yolks of chickens that consume it as part of their feed. The

chemical structures of the color compounds are presented in Figure 82.1 (Fisher and

Kocis 1987 ). A Hungarian study about the development of pigments in maturing

paprika pods shows 34 carotenes accounting for 1.3 g/100 g on dry basis. Of this,

capsanthin accounts for 37%, zeaxanthin 8%, capsorubin 3.2%, and β - carotene 9%. For

more details of the pigments in paprika, the review by Deli and Molnar (2002) is useful.

Units of Color

The strength of oleoresin paprika is expressed as “ color value ” (cv). This value is

empirical, originally intended to represent the highest dilution at which color is just

Table 82.2. Carotenoid pigments in paprika

Component Present at

Different Maturity

Color on

TLC Plate

Relative Amounts as % in Saponiﬁ ed

Extracts of Ripe Paprika

Chlorophyll a Green

Chlorophyll b Green

β - Carotene Yellow 11.6 – 18.6

β - Carotene 5 – 6 epoxide Yellow

β - Carotene 5,6, 5 ′ 6 ′ diepoxide Yellow

β - Cryptoxanthin Orange 4.2 – 12.3

β - Cryptoxanthin, mono - and diepoxide Yellow

Mutotoxanthin Yellow

Lutein Orange

Zeaxanthin Orange 2.3 – 6.5

Antheraxanthin Yellow 1.6 – 9.2

Violaxanthin Yellow 7.1 – 9.9

Luteoxanthin a Yellow

Luteoxanthin b Yellow

Auroxanthin –

Neoxanthin Yellow

Cryptocapsin Orange 1.8 – 5.1

Capsanthin Red 31.7 – 38.1

Capsanthin epoxide Red 0.9 – 4.2

Capsanthin isomers Red

Capsorubin Red 6.4 – 10.3

Capsorubin isomer Red

TLC, thin layer chromatography.

328 Individual Flavors and Colorants

noticeable under standard conditions. But this subjective determination is now replaced

by spectrophotometric reading at 460 nm. The color of paprika fruit is generally

expressed as ASTA units; 1 ASTA unit is equal to 40.2 cv.

Nearly 40% of the paprika oleoresin produced is used for blending in chicken feed

where red pigments are valuable. The red pigment and trans - capsanthin expressed as

percentage of the total carotenoids estimated by spectrophotometer and HPLC, respec-

tively, are signiﬁ cant. But a simple way of ﬁ nding the level of red pigments is by

spectrophotometric determination of the absorption ratio, which is the ratio of absorp-

tion at 470 nm over absorption at 455 nm. The higher the value, the higher the content

of red pigment. A value of 0.96 shows a low level of red pigments.

Oleoresin

Since the seeds do not contain color, they are removed. Fine powdering gives a better

yield. But to avoid channeling, it is best to make the powder into pellets when extrac-

tion is carried out in a vertical percolator in batch countercurrent method. Continuous

extraction, with a chain moving the powder, yields good results without pelletizing.

In Spain, China, and countries other than India, the extraction solvent used is hexane.

The miscella is then freed of the solvent to obtain oleoresin with a yield of 7 – 8% of

oleoresin with 100,000 cv.

Figure 82.1. Carotenoid pigments of paprika.

R Q

Capsanthin b d Cryptocapsin a d

-Carotene a a Zeaxanthin b b

Violaxanthin c c Antheraxanthin b c

Cryptoxanthin a b Capsanthin epoxide c d

Capsorubin d d

b

R

Q

a

HO

O

C

c

d

b

82 Paprika 329

Indian paprikas, like Byadege, have some pungency and a capsaicin content of

around 0.1%. Extraction is carried out using a mixture of acetone and hexane (25:75).

The oleoresin so obtained will contain capsaicin along with color. This is then washed

free of capsaicin using aqueous methanol or ethanol containing 20 – 30% water. It is

possible to remove most of the capsaicin to obtain an oleoresin containing less than

200 ppm of capsaicin. Such an oleoresin is comparable to one produced using sweet

paprika of Spain. The usual yield of oleoresin with Byadege is 5 – 6% of oleoresin of

100,000 cv. The capsaicin recovered is a valuable by - product. As already mentioned

in Chapter 25 on capsicum, this capsaicin - rich fraction, often referred to as the color -

pungent fraction, may show poor dispersibility in ﬁ xed oil. Therefore, it can be used

in regular capsicum oleoresin in low proportions.

It is this innovation of the partitioning of capsaicin during the extraction of paprika,

which is somewhat hot, that made India the dominant supplier of oleoresin paprika,

although China is beginning to surpass India.

Oleoresin paprika is a clear, dark red, oily liquid, nearly free of hotness and without

any off - ﬂ avor of rancidity or mustiness. The most traded grade is 100,000 cv followed

by 40,000 cv. It is traded in smaller quantities in other color values from 20,000 to

160,000 cv.

As already mentioned for chicken feed grade, the red pigments should be high as

they are the ones deposited in egg yolk. Generally, the acceptable limit of trans -

capsanthin is above 38% of the total carotenes. That would mean that oleoresin paprika

of 100,000 cv should have over 24 g of t - capsanthin/kg of oleoresin. The levels of the

β - carotene and capsanthins are given in Table 82.3 .

Generally, antioxidants are used to extend the shelf life of the color. In earlier days,

processors used to add ethoxyquin as a cheap antioxidant. However, due to toxicity,

this is now discouraged. Rosemary with its natural antioxidants is widely accepted

(see Chapter 86 on rosemary). A very efﬁ cient antioxidant is tocopherol. Phenolic

compounds in the following order have been found to be effective antioxidants: BHT,

α - tocopherol, epi - gallocatechin gallate, quercetin, rosmarinic acid, and 3 - caffeic acid

(Cuvellier and Berset 2005 ).

Paprika color is relatively stable to light compared with other natural colors such

as curcumin, but the oleoresin requires storage in an environment free of light and

heat. Heat treatment above 100 ° C will destroy some pigments.

Table 82.3. Analysis of paprika raw materials for carotenes and capsanthins

Variety β - Carotene %

(Area %)

t - Capsanthin %

(Area %)

C - capsanthin %

(Area %)

Byadege (India) 10 – 13 35 – 38 14 – 17

Tomato (India) 8 – 10 37 – 40 16 – 18

Wonder Hot (India) 5 – 8 38 – 43 18 – 22

Chinese 7 – 11 38 – 42 11 – 14

South African 11 – 13 39 – 41 12 – 14

Zimbabwe 10 – 12 35 – 38 15 – 17

330 Individual Flavors and Colorants

Analytical Method

The color as ASTA units is estimated using the ASTA method of measuring the absorp-

tion at 460 nm of oleoresin at speciﬁ ed dilution. Oleoresin manufacturers follow the

method standardized by the Mayonnaise Salad Dressing (MSD 10 method) manufac-

turers. In this method, 1 g of oleoresin is diluted to 10,000 with acetone read at 462 nm.

The absorption so obtained is multiplied by a factor of 66,000.

The red percentage of paprika oleoresin is determined by ﬁ nding the absorption at

495 nm and at 422 nm and using the following formula:

%... Red

Absorption at 495

Absorption at 422

=×−72 5 24 5

The percentage of trans - capsanthin is calculated by the ratio of the area of t -

capsanthin to the total area, when oleoresin is passed through an HPLC silica column

using an eluting mixture of hexane and acetone 80:20. The absorption ratio is given

under “ units of color. ”

Uses

Paprika oleoresin is used as a natural color in a wide range of foods such as meats,

seafoods, vegetables, soups, dressings, and sauces. Being a natural color, it can also

be used in dairy products where use of synthetic color is discouraged. In a wide range

of specialized meat products, such as sausages, frankfurters, and bolognas, the paprika

color is found very attractive. Being essentially a spice oleoresin, it can be used

to standardize tomato ketchup color, especially when poorly colored tomatoes

are used.

One of paprika ’ s major uses is to mix it with chicken feed to yield a reddish yolk.

Such eggs are used in parts of Japan, Korea, and Mexico. Saponiﬁ cation of the xan-

thophylls improves the ability to impart color to yolk (Galobart et al. 2004 ).

Capsanthin and capsorubin with 3 - hydroxy - k - end group show strong quenching

activity of singlet oxygen and inhibition of lipid peroxide. The pigment exhibits anti -

lung cancer effect and can be a good chromopreventive agent in carcinogenesis

(Maoka et al. 2004 ).

Identiﬁ cation Numbers

FEMA No. CAS US/CFR E - No.

Paprika oleoresin 2834 84625 - 29 - 6 – 160 c

Carotenes and β - carotene – – – 160 a

References

Cuvellier , Marie - Elisabeth ; and Berset , Claudette . 2005 . Phenolic compounds and plant extracts protect

paprika against UV - induced discoloration . Int. J. Food Sci. Technol. 40 ( 1 ), 67 – 73 .

Deli , Jozsef ; and Molnar , Peter . 2002 . Paprika carotenoids: analysis, isolation, structure elucidation . Curr.

Org. Chem. 6 ( 13 ), 1197 – 1219 .

82 Paprika 331

Fisher , Carolyn ; and Kocis , John A. 1987 . Separation of paprika pigments by HPLC . J. Agric. Food Chem.

35 , 55 – 57 .

Galobart , J. ; Sala , R. , Rincon - Carruyo , X. , Manzanilla , E.G. , Vila , B. ; and Gasa , J. 2004 . Egg yolk color

as affected by saponiﬁ cation of different natural pigmenting sources . J. Appl. Poult. Res. 13 ( 2 ),

328 – 334 .

Govindarajan , V.S. 1987 . Capsicum - production, technology, chemistry and quality: part III . CRC Crit. Rev.

Food Sci. Nutr. 24 ( 3 ), 245 – 355 .

Maoka , Takashi ; Enjo , Fumio ; Takuda , Harukuni ; and Nishino , Hoyoku . 2004 . Biological function and

cancer prevention by paprika ( Capsicum annuum L.) carotenoids . Food Food Ingredients J. Jpn. 209

( 3 ), 203 – 210 (Japanese) ( Chem. Abstr. 141 :33170).

Introduction

Parsley is used in European, American, and Middle Eastern cookery. Like coriander

leaf, parsley is also used in various preparations. However, the intensity of ﬂ avor is

milder for parsley than for coriander. Parsley is believed to have originated in Sardinia.

Early medical men, such as Dioscorides and Theophrastus, mentioned parsley ’ s

medical uses. The herb used as seasoning has curly leaves, different from the ﬂ at -

leafed variety Petroselinum neapolitanum . There is also a variety that is cultivated for

its thick roots known as Hamburg root parsley, used mainly in Central and Eastern

Europe. However, these varieties of parsley are not generally made into extractives.

Plant Material

Parsley is a cool weather plant, and so it is cultivated in temperate countries. In sub-

tropical regions, the plant grows well at high altitude where the temperature remains

low. The main growing areas are Mediterranean Europe, Algeria in North Africa, and

the states of Louisiana and California in the United States. It is also cultivated in

Western Europe, Canada, Japan, and Middle Eastern countries.

The plant is biennial with a green stem and many branches. The height of the plant

is 60 – 65 cm. The leaves are sometimes divided and sometimes very curly. The herb,

on drying, assumes a pale green color with a pleasant, spicy aroma. The ﬂ avor is tangy,

sweet, and typically spicy.

The parsley has an essential oil, which is responsible for its ﬁ ne ﬂ avor. It also has

fatty oil, which has petroselenic acid up to 75% and has industrial use. Dried parsley

has 22% protein, 52% carbohydrates, 5% fat, 10% ﬁ ber, and minerals, especially

calcium and potassium.

Essential Oil

Parsley herb oil is obtained from the aerial parts containing immature fruits. The yield

is only 0.25%. The volatile oil obtained from the ﬂ owering top has excellent aroma

characteristics but the yield is very low, only about 0.06%.

On the other hand, if the plant is allowed to grow, the fruit becomes mature. On

drying, this is referred to as parsley seed. On distillation at commercial scale for 40 – 45

hours, parsley seed oil is obtained with a yield of 2.5%.

Parsley

Petroselinum crispum Miller ( Umbelliferae )

83

333

Natural Food Flavors and Colorants Mathew Attokaran

334 Individual Flavors and Colorants

The essential oil from the parsley herb contains apiole, which is a phenolic ether

and contributes signiﬁ cantly to the ﬂ avor. It also has terpene hydrocarbon, α - pinene,

and a small amount of myristicine. Some oxygenated compounds are also present in

the oil from the herb.

Prakash (1990) reviewed the various investigations and reported the presence of

myristicine, α - pinene, small amounts of aldehydes, ketones and phenols, and β -

phellandrene. A large number of less volatile components have also been reported

(Kasting et al. 1972 ), which may not be signiﬁ cant in volatile oil, but could be impor-

tant in oleoresin.

A study of herb oil in Egypt using GC and GC - MS shows myrcene (23.75%),

β - phellandrene (19.47%), and myristicine 8.79% (El - Nikeety et al. 2000 ). Other

compounds have been detected, including 5 - undecen - 3 - yne, cyclohexene, 1 - methyl -

4 - (5 - methyl - 1 - methyene - 4 - hexenyl), and 2 - pyridinamine - 4 - methyl. Storage studies

prove that the best conditions for storage of the oil are in a dark glass or aluminum

bottle kept at freezing temperature.

The seed oil has 0.5 – 1.5% α - pinene, 3 – 5% β - pinene, 1 – 2% myrcene, 35 – 40%

limonene, and 15 – 20% apiole. The seed has apiin, which is a glyceride of apigenin

with sugar moities glucose and apiose.

Parsley seed volatile oil has a slight greenish tint when made in a commercial plant.

It has a spicy aroma with a slightly bitter taste.

Parsley herb oil, as per the FCC, is a yellow to light - brown mobile liquid. It is

soluble in fatty oils, in mineral oils, and in alcohol with haziness. It is only slightly

soluble in propylene glycol and is insoluble in glycerol.

Physical characteristics of parsley herb oil as deﬁ ned by the FCC are as follows.

Optical rotation + 1 to − 9 °

Refractive index 1.503 – 1.530 at 20 ° C

Speciﬁ c gravity 0.908 – 0.940

Parsley seed oil, according to the FCC, is a yellow to light - brown oily liquid with

solubility characteristics similar to those of the herb oil. Physical characteristics as

deﬁ ned by the FCC are as follows.

Optical rotation − 4 to − 10 °

Refractive index 1.513 – 1.522 at 20 ° C

Speciﬁ c gravity 1.040 – 1.080

Oleoresin

After grinding and extracting the dry herb with acetone, the oleoresin is obtained. The

yield is about 4% and oleoresin contains 2 – 6% volatile oil. The oleoresin is an oily,

viscous material with a spicy aroma and bitter taste. It is generally used after dilution

for convenience of handling.

On extraction of the seed with solvents such as ethylene dichloride or a mixture of

acetone and hexane, an oleoresin is obtained with a yield of 12 – 14% and volatile oil

content of about 18%.

83 Parsley 335

Extraction of the deoiled seed powder with hexane gives a resin with a yield of

about 12%. The required quantity of previously produced volatile oil can be blended

with this.

Parsley seed oleoresin is an oily liquid with dark brown color and a background

green shade. It has pleasant, spicy aroma and slightly bitter taste.

Uses

Parsley is used in various meat preparations, salad dressings, snacks, and baked foods.

It is also well liked in some beverages and condiments. Both the oil and the oleoresin

are convenient for processed foods of the above description. Parsley is reported to

cause skin reactions, though this can be avoided through use of extractives, which do

not contain allergens. The herb is recognized as having many medical qualities, some

of which are present in the oleoresins.

Identiﬁ cation Numbers

FEMA No. CAS US/CFR E - No.

Parsley leaf oil 2836 8000 - 68 - 8 182.20 –

Parsley seed oil – 8000 - 68 - 8 182.20 –

Parsley seed extract/oleoresin 2837 8000 - 68 - 8 182.20 –

84012 - 33 - 09

References

El - Nikeety , M.M.A. ; El - Akel , A.T.M. ; El - Hady , M.M.I. Abd ; and Badei , A.Z.M. 2000 . Changes in physical

properties and chemical constituents of parsley herb volatile during storage . Egypt J. Food Sci . 1998 –

2000 , 26 – 28 , 35 – 49 ( Chem. Abstr. 133 :42449).

Kasting , R. , Anderson , J. ; and Von Sydow , F. 1972 . Volatile constituents in leaves of parsley . Phytochemistry

11 , 277 – 280 .

Prakash , V. 1990 . Leafy Spices . Boston : CRC Press , pp. 65 – 68 .

Attokaran M. Natural Food Flavors and Colorants

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