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Capsicum, chillies, paprika, birds eye chilli
1 Introduction: classification and use
Many different varieties of the genus Capsicum are widely grown for their fruits, which may be eaten fresh, cooked, as a dried powder, in a sauce, or processed into oleoresin.1
There are three major products traded on the world market for use in food processing: paprika, oleoresin, and dried chilli (both whole and in powdered form). Some fresh fruits and some fermented mash is used for food processing, but these are relatively minor amounts and by necessity they are produced close to the processing facility.
The genus Capsicum belongs to the family Solanaceae. Within the genus Capsicum, five species are commonly recognized as domesticated: Capsicum annuum, C. baccatum, C. chinense, C. frutescens, and C. pubescens, while approximately 20 wild species have been documented. The genus Capsicum shares the distinction of being the first plants cultivated in the New World with beans (Phaseolus spp.), maize (Zea mays L.), and cucurbits (Cucurbitaceae).2 They are one of the first spices used by humans anywhere in the world. Widespread geographic distribution of C. annuum and C. frutescens from the New World to other continents occurred in the sixteenth century via Spanish and Portuguese traders, whereas the other species are little distributed outside South America.3 Most products used commercially for food processing are C. annuum.
The classification system for this genus is somewhat confusing in the literature. In
Spain, the Castilian word pimiento refers to any Capsicum species, but in the USA,
pimiento or pimento refers only to thick-walled, heart-shaped, non-pungent fruits from the species C. annuum. The Hungarians call all C. annuum fruits paprika, but paprika is defined in the world market as a ground, red powder derived from dried fruits with the desirable colour and flavour qualities. The word chile is the common name for any Capsicum species in Mexico, Central America and the Southwestern USA. In Asia, the spelling chilli is more common and is always associated with highly pungent varieties of C. annuum and C. frutescens, while the non-pungent sweet bell peppers are referred to as Capsicums. Pungent fruits of all cultivated Capsicum species as a collective class are called chillies in the Food and Agriculture Organization (FAO) Yearbook.4 Birds eye chillies are grown primarily in East Africa, but they are merely
small-fruited, highly pungent forms of C. annuum or C. frutescens. In this review, the following definitions will be used:
Oleoresin a viscous liquid derived by polar solvent extraction from ground powder of any Capsicum species; there are three types of oleoresin: paprika (used for colour), red pepper (used for colour and pungency), and Capsicum (used for pungency).
Paprika a ground, bright red, usually non-pungent powder used primarily for its colour and flavour in processed foods; all paprika varieties are C. annuum; paprika fruits are used to produce paprika oleoresin.
Chilli any pungent variety of any Capsicum species, but primarily C. annuum; chilli varieties may be used to produce red pepper oleoresin or Capsicum oleoresin.
Pepper(s) generic term describing the fruits of any Capsicum species, both pungent and non-pungent. Peppers are used as a colourant, flavourant, and/or as a source of pungency, depending
on the processed product. Peppers can be used fresh, dried, fermented, or as an oleoresin extract. They can be used whole, chopped, coarsely ground, or finely ground, with or without seeds. Various types of processed products containing primarily peppers include pickled fruits, chilli sauce, chilli powder (also known as cayenne powder), crushed red pepper flakes (with or without seeds), fermented mash, paprika, and three types of oleoresin. Other processed products that contain a significant proportion of peppers include fresh and processed salsas, curry powders, barbecue seasonings, chili powder (a mixture of chilli powder, oregano, cumin, and garlic powder), and many other foods.5
2 Chemical structure and stability The main source of pungency in peppers is the chemical group of alkaloid compounds called capsaicinoids (CAPS), which are produced in the fruit. The atomic structure of CAPS is similar to piperine (the active component of white and black pepper, Piper nigrum) and zingerone (the active component of ginger, Zingiber officinale). Capsaicin
(C18H27NO3, trans-8-methyl-N-vanillyl-6-nonenamide), shown in Fig. 1, is the most abundant CAPS, followed by dihydrocapsaicin, with minor amounts of nordihydrocapsaicin, homocapsaicin, homodihydrocapsaicin, and others. Capsaicin is a white crystalline, fat-soluble compound formed from homovanillic acid that is insoluble in water, odourless, and tasteless.3 Varieties of chilli differ widely in CAPS content. The amount of CAPS in a given variety can vary depending on the light intensity and temperature at which the plant is grown, the age of the fruit, and the position of the fruit on the plant. The first test developed to measure pungency was the Scoville test, first developed in 1912 by Wilbur Scoville.6 It measures heat as Scoville heat units (SHU) in a given dry weight of fruit tissue. Sweet peppers have 0
SHU, chillies with a slight bite may have 100 to 500 SHU, and the blistering habaneros have between 200,000 and 300,000. The red colour of mature pepper fruits is due to several related carotenoid pigments, including capsanthin (Fig. 2), capsorubin, cryptoxanthin, and zeaxanthin, which are present as fatty acid esters. The most important pigments are capsanthin and its isomer capsorubin, which make up 3060% and 618%, respectively, of the total carotenoids in the fruit.7 The intensity of the red colour is primarily a function of the amount of these two pigments; the Hungarian and Spanish varieties used for paprika have very high amounts of capsanthin and capsorubin compared to other varieties.7
Fig. 1 Chemical structure of capsaicin.
Fig. 2 Chemical structure of capsanthin.
CAPS in oleoresins are very stable compounds and generally do not break down, even during processing at high temperatures and during long storage periods. CAPS in dry products (fruits, powder, etc.) are not as stable as in oleoresins. The temperature at which the fruits are dried affects the CAPS content. For example, drying ripe fruits at 60sC to a final moisture content of 8% decreases CAPS content approximately 10%.8 If the fruits are held for extended periods of time at 60sC after reaching 8% moisture content as much as 50% of the CAPS may be lost.8 Once the fruits are dried, they typically lose 12% CAPS/month under cold ( 16sC) storage, and even more when stored under ambient conditions. Ground powder can lose as much as 5% CAPS/month depending on the fineness of the grind and the storage temperature.8 The red colour of paprika and chilli powder, on the other hand, is not as stable as oleoresin and CAPS, and much work has been done to optimize the processing and storage conditions for dried chillies and paprika to maximize the colour intensity for the longest period of time.9-11
3 Production
Reliable production figures for paprika and chillies are difficult to obtain because the FAO Yearbook combines production figures for green bell peppers and chillies into one figure for peppers. In 1997, the FAO reported that there were 1.33 million hectares of peppers grown, with an average yield of 12.3 t ha 1; total production was estimated at
16.4 million metric tons (MMT).4 The major pepper producing nations in terms of area are India, China, Indonesia, Ethiopia and Mexico.
3.1 Paprika production
Paprika is produced commercially in Spain, Portugal, Central Europe, Southern Africa, and the US, but Hungary is by far the most famous paprika-producing country, with approximately 8,000 ha devoted to the crop.4,12 Many food historians believe that Turks and Bulgarians of the Ottoman Empire brought peppers to Hungary in the sixteenth
century. Kalocsa and Szeged are the main centres of paprika production. Once the fruits are harvested, they are loosely stacked in long, narrow, cylindrical mesh bags made of red plastic and allowed to cure for 34 weeks. Then the peppers are washed, dried, crushed and finally ground into powder. The mill master selects the proportion of seeds to be ground with the pepper pods, to produce the desired level of pungency and colour in the paprika. During grinding, the crushed peppers are heated to release the oil in the seeds, which interacts with the pigment in the fruits to produce the intense red colour. Colour has no effect on the pungency of the paprika. Bright red paprikas may be sweet or pungent. Generally, the poorer-quality, pale red and brownish-coloured paprikas are pungent. Heat causes the natural sugar content of the fruits to caramelize slightly, which affects the taste and aroma of the paprika. During the process, if the fruits are heated too much, they will scorch. If they are not heated enough, the moisture content will be too high, and both the flavour and colour will be affected. Optimum moisture content is
8%.12 Only undamaged fruits less than a year old are used for the top grades of Hungarian paprika. Before non-pungent paprika varieties were available, the top grades of paprika were prepared by removing the dissepiment (ribs on the inside of the pericarp which are rich in CAPS) by special knives,13 but this method is no longer used.12
3.2 Oleoresin production
Oleoresin is a viscous liquid or semi-solid material derived by extraction from finely- ground powder, which contains the aroma and flavour of its source. Three types of oleoresin are produced. High-pungency Capsicum oleoresin is produced in India, Africa and China near the production areas of low cost, very pungent chilli varieties. Medium- pungency red pepper oleoresin is produced in many regions. Non-pungent paprika oleoresin is produced in Spain, Ethiopia, Morocco, Israel, India, USA, Mexico and South Africa.5 Oleoresin is extracted from finely ground chilli or paprika powder. A volatile non-aqueous solvent such as hexane, ether, or ethylene dichloride is added and allowed to thoroughly wet the material. The oleoresin enters into solution with the solvent, forming micella. After a period of time, the micella is removed, and the solvent replaced with fresh solvent to continue the extraction. The solvent is subsequently removed from the extract by evaporation at the lowest practical temperature to avoid loss of aromatic volatile compounds. This is done in two stages: the first stage removes approximately
95% in a standard film evaporator, and then the concentrated micella passes through a partial vacuum that removes the rest of the solvent and reduces the micella to oleoresin. The remaining solvent held in the mass of the extracted powder is recovered by very high vacuum. Typical yield of oleoresin depends on the solvent used and ranges from 11.5
16.5%.5 The oleoresin pungency depends on the pungency of the original powder. Paprika oleoresin has little to no pungency, and is used for its colour and flavour properties, while Capsicum oleoresin can have CAPS levels up to 10%, and is used primarily as a source of high pungency.
3.3 Dry chilli production Chilli peppers are typically produced on small farms, less than 1 ha in size, in areas where cheap labour is available for harvesting. The largest producer is India, with an estimated
894,000 ha devoted to the crop annually. India is the largest exporter of dried chilli in the world. The second-largest producer is China, which grows an estimated 216,000 ha annually and also exports sizeable quantities of dried chilli.14 Fruits are typically allowed
to partially dry on the plant, then harvested and placed in well-ventilated areas receiving direct sunlight for drying. Sun drying can result in bleached fruits, especially if rainfall is received during the drying period, and the fruits may have extraneous matter adhering to them. In more advanced regions, the use of controlled drying improves the quality of the dried fruits. The best drying temperature is 6070sC; this gives maximum colour values and longest colour retention time. Higher temperatures tend to caramelize the sugars present in the fruits and give them a dark colour. The optimum moisture content is approximately 10%.15-17
4 Main uses in food processing
There are many uses of peppers in food processing, including as a food colourant, as a source of pungency in food, as a source of flavour, as a source of pain relief for pharmaceutical use, and as a repellent. In many cases two or more of these properties are included in the same product; for example, paprika may be a source of colour, pungency, and flavour.
4.1 Colour
People whose diets are largely colourless starches, such as rice or maize, use peppers to add colour to their bland, achromatic diets. Paprika, paprika oleoresin, red pepper oleoresin, and dried chilli may all serve as a source of red colour in various processed products, but the primary sources of red colour are paprika and paprika oleoresin. Paprika is used in many products where no pungency is desired, but the colour, flavour, and texture of a finely ground powder is desired. These include processed lunchmeats, sausages, cheeses and other dairy products, soups, sauces, and snacks such as potato chips. Paprika oleoresin is used as a colour and flavour additive in many products where the texture is important and small particles of paprika powder would be undesirable.5
4.2 Pungency
Red pepper oleoresin is used as a source of both colour and pungency in canned meats, sausages, smoked pork, sandwich spreads, soups, and in dispersed form in some drinks such as ginger ale. Capsicum oleoresin is used as a source of pungency in many products, especially chilli sauces with extremely high SHU ratings. Oleoresin has considerable advantages over dried chilli including more stable colour retention, easier to handle compared to the rather bulky dried chilli, and the ability to mix and dilute oleoresin with other substances to produce a range of colour and/or pungency values. Dried chilli is also used as a source of both colour and pungency, particularly in the production of crushed red peppers, chilli powder and chilli sauces.
4.3 Flavour
Paprika is valued for its flavour in many products in addition to its colour. Dried chilli is also valued for its contribution to flavour in chilli sauces and chilli powders. The flavouring principle is associated with volatile aromatic compounds and colour. As a general rule, when the colour of paprika or chilli powder fades, the flavour also disappears.
4.4 Pharmaceutical
Capsicum oleoresin is the primary form of peppers used for pharmaceutical purposes. Here the primary requirement is the CAPS level. Further refinement of the oleoresin may be performed to produce pure capsaicin. At least two types of pain relief products are currently being marketed, including creams containing 0.75% capsaicin (for example, ZostrixTM), and plasters containing 3% oleoresin (for example, VorwerkTM). Several types of capsules containing chilli powder (cayenne powder) with a range of capsaicin levels are currently being marketed.
5 Functional properties and toxicity
Peppers are well-known for their health benefits. Herbalists have long promoted peppers for their health-enhancing effects. These include clearing the lungs and sinuses, protecting the stomach by increasing the flow of digestive juices, triggering the brain to release endorphins (natural painkillers), making your mouth water, which helps to neutralize cavity-causing acids, and helping protect the body against cancer through anti- oxidant activity.3
5.1 Toxicity
The acute toxicity of capsaicin has been measured in several animal species. In mice, the
LD50 values for CAPS depended on the mode of administration, ranging from 0.56
(intravenous) to 512 (dermal) mg kg-1 body weight. Death was due to respiratory paralysis.18 To reach the LD50 value for human oral administration, the average person would have to drink 1.5 quarts of Tabasco sauce. The painfulness of the CAPS is a self- limiting factor in their role as a human food ingredient; you can only eat so much at one time. No death has ever been recorded due to CAPS-induced respiratory failure, and the investigators concluded that the acute toxicity of CAPS as a food additive in man was negligible.18 The effect of sub-chronic toxic doses has been examined in rats. Adult rats exhibited no noticeable behavioural or physiological changes when given sub-chronic doses of crude chilli extract by stomach tube for 60 days. Food consumption was significantly higher but body weight was lower than the control group after 60 days.19
5.2 Functional benefits
CAPS stimulates sensory neurons in the skin and mouth cavity, creating a sensation of warmth that increases to severe pain (type C nociceptive fibre pain) with higher doses. The neurons produce the neuropeptide Substance P (SP), which delivers the message of pain. Repeated exposure of a neuron to capsaicin depletes SP, reducing or eliminating the pain sensation in many people.20 Thus the use of CAPS in pain relief has two modes of action: the sensation of heat, which may help sore muscles and arthritic joints feel better, and the depletion of SP, which reduces the pain sensation in the exposed area. Peppers have been reported to contain an anticoagulant that helps prevent the blood clots that can cause heart attacks.3 Foods containing CAPS increase the thermic effects of food (TEF). The TEF is the slight increase in the bodys metabolic rate after consumption of a meal. A meal containing foods with CAPS can increase the bodys TEF up to 25% for three hours.3 The role of CAPS in triggering the brain to release endorphins (natural painkillers) is well-known. As more CAPS is consumed, the body releases more
endorphins, causing one to feel a mild euphoria a natural high! Regular consumption has only a slight desensitizing effect.
The Hungarian scientist Albert Szent-Gyorgyi won the 1937 Nobel Prize for isolating ascorbic acid, better known as vitamin C, from peppers. Peppers are also high in vitamin A, vitamin E, and potassium, and low in sodium. One hundred grams of fresh red chilli pepper has 240 mg of vitamin C (five times higher than an orange), 11,000 IU of vitamin A, and 0.7 mg of vitamin E. Vitamin C is sensitive to heat and drying but vitamin A is very stable, and paprika and dried chilli both contain relatively high amounts of this important nutrient.5
6 Quality issues The quality parameters of paprika, oleoresin, and dried chilli focus primarily on colour, pungency, and microbial and insect contamination, but vary depending on the product and the intended end use.
6.1 Paprika quality Paprika always refers to a ground product prepared of highly coloured, mild or sweet red fruits. The main quality factors are colour and pungency. There are eight grades of Hungarian paprika (Table 1). The condition of the fruits at harvest, and to some extent the manner in which they are processed, determines which grade of paprika will be made from them. Fruits are graded at harvest for colour, pungency and aroma. The Grade 1 fruits are used to make the best grades of paprika (special, capsaicin-free, and delicatesse), while Grade 2 fruits are used to make lower grades of paprika (fine sweet, semi-sweet). Fruits from later harvests and those rejected from higher grades are used for rose, while spotted fruits not belonging to any other grade are used for pungent, which is the lowest grade. Spanish paprika is divided into three types (sweet, semi-sweet, and pungent) by pungency, and each type is divided into three grades (extra, select, and ordinary) by colour, ash content and moisture content. The best Spanish paprika is sweet, extra grade, with no pungency, bright fiery red colour and only 0% moisture.5
Microbial contamination by bacteria such as Bacillus cereus, B. subtilis, and Clostridium perfringens,21-23 yeasts, and aflatoxin-producing moulds such as Aspergillus flavus, A. glaucus, and A. niger24 have been reported. A total bacterial plate count below 10,000/ gram is desirable, with yeast, mould and coliforms below 1000/gram.25 Major health hazard organisms such as E. coli, Salmonella, and Shigella must be negative. Control by fumigation with ethylene oxide is generally recognized as safe by many countries, as long as fumigant residues do not exceed international standards.26 Ethylene oxide is toxic and requires special vacuum equipment and technical skill to administer, but it vaporizes rapidly from the material, leaving little residue, and it has no effect on colour, pungency, or flavour, so it is generally considered the most effective method.25 Paprika that is processed and stored properly generally does not have problems with insect contamination.27
6.2 Oleoresin quality The quality specifications for the different types of oleoresin are given in Table 2. Three types of oleoresin are specified, based on the pungency and colour values.
Quality characteristics
Acid-
(%) (%) (%) (%) (sieve #)
1) Special Bright, fiery none or very pure, very 10.0 5.0 0.3 12.0 0.45
red colour little aromatic
2) Capsaicin-free Bright red none pure, sweet 10.0 5.5 0.4 13.0 0.50
(mild table) some bitterness
3) Delicatesse Bright red, barely typical pure 10.0 6.0 0.45 14.0 0.50
(table) darker or light detectable aroma
4) (hot table)b Bright red, less pungent typical pure 10.0 6.0 0.45 14.0 0.50
darker or light aroma
5) Fine sweet Dark or yellowish red less pungent aromatic 10.0 6.5 0.5 16.0 0.50
6) Semi-sweet Darker to yellowish pungent less typical 10.0 7.0 0.7 17.0 0.63
red aroma
7) Rose (pink) Dull red to markedly typical 10.0 0 0.8 NSc 0.63
pale yellow pungent aroma
to greenish
a 100% of the powder can pass through sieve no.
b Similar to Delicatesse, but with a CAPS minimum of 25 mg 100 g 1.
c Not specified.
Type of oleoresin
Number EOA no. 244 EOA no. 245 EOA no. 246
Preparation Solvent extraction Solvent extraction Solvent extraction of dried ripe fruita of dried ripe fruit of dried ripe fruit
Appearance Clear, red or light Deep red Deep red amber, viscous
Odour/taste very pungent, aromatic pungent, aromatic aromatic
SHU >480,000 >240,000 0
Colourb <4,000 <20,000 40,000100,000
Soluble in:
Benzyl benzoate yes yes yes
Alcohol partly, with oily layer partly, with oily layer partly, with oily layer
Fixed oils yes yes yes
a Residual solvent limits: <25 ppm hexane, <30 ppm ethylene chloride or acetone, or <50 ppm isopropyl or methyl alcohol for all oleoresins.
b Colour is determined by measuring the absorbance of a 0.01% solution of oleoresin in acetone at 258 nm. The absorbance value is multiplied by 61,000 to convert to total colour units.
Capsicum oleoresin has very high pungency and low colour, and is used as a source of pungency where colour is not important. Red pepper oleoresin has both moderate pungency and colour, and is used where both traits are important. Paprika oleoresin has very high colour and little or no pungency. Importers of Capsicum oleoresin prefer a pungency value in the range of 610% CAPS (1,000,0001,600,000 SHU).5 Oleoresin that is processed and stored properly has few problems with microbial or insect contamination.
6.3 Dried chilli quality
Like the other forms of peppers used in food processing, colour and pungency are the major quality factors, as well as aroma. Factors that affect the colour of dried chillies include the cultivar, the stage of maturity at harvest and subsequent curing, fruit drying conditions, and the final moisture content. At less than 10% moisture, the colour appears bleached, while at levels greater than 10% there is darkening, possibly caused by non-enzymatic browning. The colour of crushed or ground chilli powder deteriorates faster than whole chillies, due to the auto-catalyzed degradation of carotenoids. The major factor influencing colour retention during storage is the temperature, followed by the moisture content. The effect of air, light, and type of container is minimal. The optimum storage conditions for chilli powder colour retention are 16sC and 1011% moisture.2829 The American Spice Trade Association (ASTA) has set standards for measuring colour in pepper products that are widely followed. Samples are extracted acetone and the absorbance is read by a spectrophotometer at 460 nm.30 Values are expressed as ASTA units; a value greater than 200 is considered a very deep red colour. Commercial samples of chilli powder normally range from 100200 ASTA units, and a premium may be paid by processors for lots with extractable colour greater than 140 units.
The standard for measuring pungency in all forms of peppers is Scoville Heat Units
(SHU). The concept was introduced in 1912, when Wilbur L. Scoville, a pharmacologist with Parke Davis, developed the Scoville Organoleptic Test.6 A panel of five people is used as heat samplers. The panel analyzes a solution made of exact weights of dried chillies dissolved in alcohol and diluted with sugar water. The pungency of the peppers is rated in multiples of one hundred SHU. A majority of three samplers has to agree on one value before any sample is given a value. This method is subjective, especially as it depends on the tasters palate and sensitivity to pungency. Also, the human palate quickly becomes desensitized to CAPS after tasting more than a few samples within a short period of time. It has largely been replaced by high-pressure liquid chromatography
(HPLC), which is relatively rapid and reliable compared to the Scoville Organoleptic Test.31 Results are reported as ppm CAPS, which can be converted to SHU or other units by the following scale: 1 ppm = 16 SHU = 0.0001% = 0.001 mg g. 1 Pure capsaicin =
16,000,000 SHU.
Microbial contamination is also a problem in dried chilli, and the same standards used for paprika also apply to dried chilli. In addition, insect contamination can be a problem, particularly the universal drugstore beetle, Stegobium paniceum (Linn.) and the cigarette beetle, Lasioderma serricorn (Fab.).32 Insect damage is three-fold, first by the physical loss as frass, second by the loss of quality due to broken pods and loose seed, and third by mould growth and entry of mites due to insect holes in the fruit walls. Control can be achieved by fumigation with insecticidal chemicals, although their use must be monitored carefully and fumigant residues must be within the limits set by international standards.33
The control method used depends on the quantity, the technological capability and the cost.
6.4 Adulteration
Several types of adulteration are possible and have been reported at various times. Whole dried chillies may be adulterated by adding sub-standard dried fruits, which are darkened or bleached, by adding moisture to increase the weight of a load, or by coating with mineral oil or synthetic dyes such as coal tar red to improve the colour and appearance.5
A more difficult problem is the addition of varieties or harvests that vary in CAPS and colour but have similar shape, size, and visual colour. Only testing of representative samples and sub-samples can determine if a lot is homogeneous. Chilli powder may be adulterated in many ways, some of which are very difficult to detect without sophisticated tests such as HPLC analysis, and pure standards must always be used for comparison. Chilli powder may be adulterated by adding extra amounts of bleached pericarp, seeds, calyx, and peduncle to increase bulk without visibly affecting appearance. Other reported adulterants include artificial dyes, almond shell dust, and dried red beet pulp.
Filth, such as insect fragments, rodent droppings and hairs, and fungal spores are an indication of poor handling and storage. Heavy metals and chemical residues from pesticides represent another adulteration problem. Pesticide residues reported in chilli powder include chlorinated hydrocarbons, DDT, Dieldrin, Endrin, and lindane, but generally in very low levels. Oleoresin may be adulterated by adding synthetic saturated acid vanillylamides such as pelargonic vanillylamide. Detection of these adulterants can be done by sophisticated gas chromatography of the saponified extract5 or by thin-layer chromatography coupled with HPLC.8
7 References
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