Unit 6
Unit 6
6.0 Objectives
6.1 Introduction
6.2 Preservatives
Class I Preservatives
Class II Preservatives
6.3 Antioxidants
6.4 Acidulants
6.5 Colouring Agents
Natural Food Colourants
Synthetic Colourants
6.6 Flavouring Agents
6.7 Sweeteners
Nutritive Sweeteners
Non-nutritive Sweeteners
6.8 Miscellaneous Additives
6.9 Let Us Sum Up
6.10 Key Words
6.11 Answers to Check Your Progress Exercises
6.12 Some Useful Books
6.0 OBJECTIVES
After reading this unit, you should be able to answer:
• the definition of food additives;
• different types of food additives;
• their chemical properties and functions in foods; and
• their legal status for the purpose of adding to foods.
6.1 INTRODUCTION
Food additives have been used for centuries to enhance the quality of food
products. Smoke, alcohol, vinegar, and spices were used more than 10,000
years ago to preserve foods. Along with the developments in Food Chemistry
and Food preservation in the early 1900s, the use of food additives increased
significantly. The demand for new, tasty, convenient, and nutritious foods
continued to increase. As a result, by the early 1960s, over 2500 different
chemicals were being used in foods in many developed countries.
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Food Constituents Food additives are substances intentionally added for specific functions. The
number of additives being used in food today is very large. However, they can
be classified into a few types based on their functional properties. They may
include: 1) preservatives, 2) antioxidants, 3) acidulants, neutralizers and
buffers, 4) colouring agents, 5) flavouring agents, 6) sweeteners 7) nutritional
additives, and 8) miscellaneous additives.
6.2 PRESERVATIVES
From prehistoric times humans have attempted to preserve food products from
the deteriorative effects of microorganisms. Some chemical food preservatives
like salt, nitrites and sulphites have been in use for many years. Even though
newer packaging techniques, processing and storage methods are able to
preserve foods without chemical preservatives, even today these chemicals
play a significant role in protecting the food supply mainly because
preservation using chemical preservatives is cheaper and more convenient.
Under PFA, 1954, preservatives are classified into Class I and Class II
preservatives. Class I preservatives are also called natural preservatives. They
are, common salt, sugar, dextrose (glucose), spices, vinegar or acetic acid,
honey, and vegetable oils. There is no restriction to the addition of Class I
preservatives to any food.
Class II preservatives are, Benzoic acid and its salts, sulphurous acids and its
salts, nitrates or nitrites, sorbic acid and its sodium, potassium and calcium
salts, calcium or sodium propionates, lactic acid, sodium or calcium
propionate, methyl or propyl parahydroxy benzoic acid, sodium diacetate and
sodium potassium and calcium lactate.
Among the above preservatives, benzoates and sulphites are most widely used
for preservation of fruit and vegetable products. Sorbates have been permitted
for some products lately. Therefore, these and a few natural preservatives will
be dealt with in this unit.
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6.2.1 Class I Preservatives Food Additives
1) Salt (sodium chloride): Salt has been used as a preservative since the
beginning of recorded history. Pickling of fruits and vegetables and salting
of fish and meat are widely practiced. The anti- microbial activity of
sodium chloride is essentially related to its ability to reduce water activity
(aw) and create unfavourable conditions for microbial growth. As the water
activity of the external medium is reduced, microbial cells are subjected to
osmotic shock and rapidly lose water through plasmolysis. These results in
the cells ceasing to grow and either die or remain dormant. Aside from the
osmotic influence on microbial growth, other possible mechanisms include
limiting oxygen solubility in the medium and toxicity of chloride ions.
2) Acetic acid: Synthetic vinegar (dilute acetic acid) and brewed vinegar are
widely used as acidulants and antimicrobials. Vinegar pickles are common
in our country.
Acetic acid is more effective against yeasts and bacteria than moulds. Only
acetic, lactic and butyric bacteria are markedly tolerant to acetic acid. As is
the case with most other preservatives, acetic acid is also more effective at
lower pH. Generally, 1-2 % acetic acid is sufficient to inhibit most of the
organisms.
3) Sugar and spices: They also have preservative effects in many food
products. The main function of sugar is to reduce the water activity of the
medium thus inhibiting the growth of microorganisms. Many chemical
substances in spices (terpenes) have been shown to have antimicrobial
properties.
Sulphur dioxide and sulphites: Sulphur dioxide and its various salts have a
long history of use dating back to the times of the ancient Greeks. They have
been used extensively as antimicrobials and to prevent enzymatic and
nonenzymatic browning in a variety of food products.
Sulphurous acid inhibits yeasts, moulds and bacteria. However, yeasts and
moulds are less sensitive than bacteria. That is the reason why sulphur dioxide
is used at low concentrations (about 100 ppm) during grape juice fermentation
to control the growth of other microorganisms and facilitate growth of yeast.
Sulphur dioxide and sulphites are permitted under PFA for a number of
products like fruit pulps, squashes, syrups, crushes, cordials, wines, RTS
beverages, and dehydrated fruits and vegetables. Sulphur dioxide is also used
as an antibrowning agent. Fruits are exposed to fumes of burning sulphur
before drying to prevent browning and also insect and microbial attack.
Sulphite solutions are also used as dip solution for vegetables before drying or
dehydration.
Sulphur dioxide and several sulphites have GRAS status. However, sulphites
cannot be used in meats and in foods that are sources of the vitamin thiamine.
As sulphites have strong bleaching action on plant pigments like anthocyanins,
they should not be used for preserving such products. It has been found that
sulphites show allergic responses in certain individuals, such as steroid-
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dependent asthmatics. This has led to ban of use of sulphites on raw fruits and Food Additives
vegetables in many countries.
Sorbic acid and sorbates: Sorbic acid and its sodium, potassium and calcium
salts are collectively known as sorbates. Sorbic acid is present in some berries
like berries of the mountain ash berry (rowanberry). It is a trans-trans,
unsaturated monocarboxylic fatty acid.
The acid is a white crystalline powder and is slightly soluble in water (0.16%
at 20oC). The potassium salt, which is highly soluble in water (58.2% at 20oC),
is mostly used as the preservative. However for preservation of oils like corn
oil, the acid is used because the salt is practically insoluble.
In the case of sorbic acid also, the undissociated acid has the highest
antimicrobial activity. Therefore, sorbic acid is also more effective at low pH.
However the dissociated acid also shows microbial action, though of a lower
order. At pH above 6, the dissociated acid is responsible for more than 50% of
the inhibition observed. This is the reason why sorbates are preferred for
products like chapatti and cheese.
Sorbates inhibit most of the species of yeasts and moulds. Several species of
bacteria are also inhibited by sorbates. At present under PFA, sorbates are
permitted for only a few fruit and vegetable products. They include jams,
jellies, marmalades, glazed or candied fruits, fruit bars, fruit juice concentrates
and prunes. Some of the other products include cheese, flour confectionary,
smoked fish, preserved chapatties and fat spreads. Sorbic acid and potassium
sorbate have GRAS status.
Nitrites: Nitrites have been used in meat curing for many centuries. For meat
curing, nitrite is used along with a mixture of salt, sugar, spices, and ascorbate.
Nitrite contributes to the development of the characteristic colour, flavour, and
texture improvement and preservative effects.
Nitrites are white or pale yellow hygroscopic crystals. Sodium nitrite is quite
soluble in water. Nitrite has a strong inhibitory action against Clostridium
botulinum and several other microorganisms. It is more effective below neutral
pH (below 7.0). Along with salt, nitrite exhibits stronger antimicrobial action.
2. How are preservatives classified under PFA? List the Class I preservatives.
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3. List the permitted (PFA) Class II preservatives. What are the functions of
sulphites in foods?
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6.3 ANTIOXIDANTS
Antioxidants play important role in preserving fats, oils and fatty foods. You
have already learnt the chemistry of oils and fats. They are essentially fatty
acid esters of glycerine. The fatty acids can be either saturated or unsaturated.
The unsaturated fatty acids in fats and oils can undergo oxidation during
storage leading to rancidity development. Along with rancidity development,
vitamin destruction, discolouration and even toxic effects are possible.
You have already learnt that tocopherols present in many vegetable oils have
antioxidant property. Similarly, ascorbic acid and lecithin have antioxidant
properties. However, the major antioxidants commercially used in foods, fats
and oils are phenolic compounds and are generally referred to as phenolic
antioxidants. Certain metals like iron and copper present in foods are strong
catalysts of fat oxidation and may react with antioxidants to cause
discolouration. Food acids like citric acid have the ability to bind these metals.
Therefore, the antioxidants are usually added along with citric acid.
The most widely used phenolic antioxidants for fats and oils are i) butylated
hydroxy anisole (BHA), ii) butylated hydroxy toluene (BHT), iii) propyl
gallate and iv) tert-butyl hydroquinone (TBHQ).
Butylated hydroxy anisole (BHA): BHA is a white, waxy solid that is usually
tableted to minimize caking during storage. It is readily soluble in glycerides
and organic solvents and insoluble in water and has a distinct phenolic odour.
BHA is quite stable during normal processing and storage of fatty foods.
Therefore, it is considered to have good carry-through effect. However, being
volatile at high temperatures, BHA may be lost partially during deep fat frying.
Propyl gallate: Propyl gallate is the n-propyl ester of 3,4,5- trihydroxy benzoic
acid or gallic acid. It is a white to light grey powder. It has low oil solubility
and significant water solubility. Though it has very good antioxidative
properties, due to its heat-labile nature; it has very little carry-through
properties especially under alkaline conditions encountered in baked foods.
Therefore, propyl gallate is used in combination with other antioxidants like
BHA thus providing the combined effects of improved storage stability and
carry-through protection.
As mentioned earlier, among the food additives, perhaps the antioxidants are
the most widely used. They are used in vegetable oils, meat products,
confections and chewing gums, cereal products like breakfast cereals, bakery
products etc. Use of the antioxidants in fruit and vegetable products though
limited, is of considerable commercial importance. Some of them include fruit
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Food Constituents nuts like walnut, almonds, cashew nuts; citrus oils, dehydrated potato products
like powder, flakes and granules.
Under PFA, all the above phenolic antioxidants except BHT have been
permitted with restrictions. Additionally, lecithin and ascorbil palmitate are
also permitted for specific food products.
6.4 ACIDULANTS
Citric acid is perhaps the most widely used organic acid. It is a tricarboxylic
acid abundantly present in citrus and many other fruits. Even though it used to
be produced from citrus fruits, at present most of the commercial citric acid is
manufactured by fermentation. Citric acid is a white crystalline powder, easily
soluble in water. Commercial citric acid is available as the monohydrate. It is
hygroscopic in nature. Therefore, citric acid is not very suitable for use in dry
food formulations.
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• Sequestering: Bind metal ions and enhance the function of antioxidants. Food Additives
Most of the food acidulants are permitted under PFA with certain restrictions.
Under PFA, the following natural and synthetic colours are permitted at
present with restrictions on their maximum levels and the specific food
products.
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Food Constituents Natural colouring matters
1. Beta carotene
2. Beta – apo -8’-carotenal
3. Methyl ester of beta – apo - 8’- carotenoic acid
4. Ethyl ester of beta – apo - 8’- carotenoic acid
5. Canthaxanthin
6. Chlorophyll
7. Riboflavin (lactoflavin)
8. Caramel
9. Annato
10. Saffron
11. Curcumin (or turmeric)
Carotenoids: Carotenoids are responsible for the yellow, orange and red
pigments in a number of plants and animal foods. Carotenoids are classified
into three groups. i) Carotenes – These are hydrocarbons containing β-ionone
rings and possess vitamin-A activity. Ex. β-Carotene present in carrots,
chillies, soybean. ii) Lycopenes – These are carotenoids not having β-ionone
rings and do not possess vitamin-A activity. Lycopene is present in tomato,
apricot, watermelon, and red guavas. iii) Xantohphylls − These are oxygenated
derivatives of carotene. These have β-ionone rings, but do not possess vitamin-
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A activity. They are present in papaya, orange peel, and yellow maize. iv) α- Food Additives
Carotene − This is similar to β-carotene in its biological activity.
Chemically carotenoids are poly –enes composed of isoprene units. They are
fat soluble and fairly heat stable. During processing of fruits and vegetables,
partial loss of carotene takes place. They are stable at pH 2–7. As a result of
their chemical structure, which contains conjugated double bonds, carotenoids
are very sensitive to oxidation. Ascorbic acid can protect β -carotene by
serving as an antioxidant. “Nature-identical” synthetic β -carotene is marketed
in forms that confer protection from oxidation.
Betalains: Betalains are found in plants such as red beets, amaranthus flowers,
bougainvillea, cactus fruits etc. Betalain colours range from red to yellow. The
red beet is the most common commercial source of these pigments. Betalains
are sensitive to pH, light and heat. These compounds are most stable at pH 4 –
5. Because of the carbohydrates present in betalains, the colourants tend to
impart beet flavour to the food.
Chlorophylls are soluble in alcohol, diethyl ether, benzene, acetone etc. but
insoluble in water. Some metal ions like iron, zinc and copper react with
chlorophyll and the green colour becomes brighter. In alkaline pH, the colour
of chlorophyll is better retained. Chlorophylls are heat sensitive and during
processing of fruits and vegetables containing chlorophyll, the green colour is
lost and turns brown. When vegetables containing chlorophyll is cooked, the
central Mg atom is replaced by hydrogen atom and loses it’s colour forming
pheophytin. Chlorophylls may be stabilized by replacement of the magnesium
ion in the compound with copper.
Paprika oleoresin, which is orange red to deep red, is the extract of mild
capsicum (Capcicum annum). Like curcumin, paprica oleoresin is also water
insoluble. Paprika and turmeric oleoresins are available in various standardized
forms.
Saffron is generally stable toward light, oxidation and pH and has a high
tinctorial strength.
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Food Constituents 6.5.2 Synthetic Colourants
Synthetic colourants, also known as coal tar dyes or aniline dyes were earlier
manufactured from coal tar derivatives. Although the colourants were highly
purified before they were added to foods, the negative connotation of their
association with coal tar resulted in much unfavourable publicity. As a result,
synthetic colourants are no longer manufactured from coal tar derivatives but
instead are developed from highly purified petrochemicals.
As can be seen from the table above, the permitted synthetic colorants belong
to five chemical classes viz. azo, xanthene, pyrazole, indigoid and
triarylmethane. You may notice that all together there are three red, two
yellow, two blue and one green colour permitted under PFA. All these colours
are water-soluble. As mentioned earlier, these colours are more resistant to
chemical reaction, pH and heat compared to natural colourants.
Flavour like colour of foods has a great bearing on acceptance of foods and
therefore, has enormous commercial importance. It apparently has no
nutritional value although some studies have indicated that taste can alter
intestinal absorption of glucose and fat metabolism. Flavour is defined in
several ways. One definition is: “sensation produced by a material taken in
the mouth, perceived principally by the senses of taste and smell, and also
by general pain, tactile and temperature receptors in the mouth”.
Food flavours is a very vast subject. You will be learning sensory perception
and analysis of flavour in a subsequent unit. In this section you will learn some
essential aspects of the chemistry and application of food flavourings.
During the early days, people used spices to enhance or modify the flavour of
foods. Along with the developments in synthetic chemistry and analytical
techniques like gas chromatography and mass spectrometry, there was a spurt
in synthetic flavour compounds and identification of the flavour compounds in
various foods and processed products. The role of sensory analytical
techniques in flavour research is very significant. One major finding was that
most of the food flavours were due to a combination of a number of chemical
compounds and only in a few cases, one single compound was responsible for
the characteristic flavour of a food. Few examples are menthol in peppermint,
benzaldehyde in bitter almond, citral in lime peel, amyl acetate in ripe banana,
cinnamaldehyde in cinnamon etc. Therefore, it became apparent that creation
of a food flavour is not an easy task. However, with a combination of art and
scientific know-how, today a large number of flavour formulations are
available. It is an extremely large industry. Food flavourings are classified into
three groups.
3. Artificial flavouring substances: They are those substances, which have not
been identified, in natural products intended for human consumption either
processed or not.
The natural flavours include spice oleoresins and oils, essential oils like citrus
oils; fruit aroma concentrates like apple aroma concentrate etc. As indicated
earlier, the number of synthetic flavour substances is extremely large.
Therefore, instead of listing the permitted flavouring substances, only those,
which are not permitted, are specified under PFA. In this connection it is
important to note that the concentrations of the flavour chemicals in natural or
synthetic flavours to impart the desired flavour perception are extremely low,
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Food Constituents of the order of parts per million or parts per billion. As they have self-limiting
property, maximum permissible limits are not stipulated.
6.7 SWEETENERS
Like any other carbohydrate, sucrose is also a nutrient providing energy to the
human system. Over the years, sucrose has been implicated in obesity
development and associated diseases and also dental caries. Besides, diabetes
has become a common disease among large sections of the population. As a
result there is a general trend towards reducing energy intake. This has resulted
in development of sucrose alternatives.
There are two types of sucrose alternatives viz. nutritive and non-nutritive
sweeteners. Nutritive sweeteners also called calorie sweeteners are usually
carbohydrates or carbohydrate derivatives. Non-nutritive sweeteners include a
range of natural products and some synthetic chemicals.
You have already learnt about glucose, glucose syrup, fructose and high
fructose syrup and their relative sweetness in an earlier unit. In this section you
will be learning about a few other nutritive sweeteners.
Sorbitol: Sorbitol is a six carbon sugar alcohol that was originally found in the
berries of mountain ash. It is chemically produced from glucose for
commercial use. It is highly soluble in water (72% at 25oC). Sorbitol has half
the sweetness of sucrose.
Xylitol: Xylitol (xylit) is a pentiol found in most fruits and berries as well as
xylan (a polysaccharide) containing plant materials. It is also produced by
microbiological methods. Xylitol is a crystalline substance, having good water
solubility (64 % at 25oC). It has sweetness and caloric content equal to sucrose.
However, because xylitol is absorbed slowly, it does not cause increase in
blood glucose level as glucose or sucrose. Therefore, it is used in diabetic
foods also.
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6.7.2 Non-Nutritive Sweeteners Food Additives
Saccharin: Saccharin was synthesised way back in 1879. During the two world
wars, the use of saccharin as a sweetener increased due to the scarcity of sugar
and became an accepted sweetener for special dietary and dietetic foods even
though its safety has repeatedly been questioned.
Saccharin is a general name used for saccharin, sodium saccharin and calcium
saccharin. Chemically saccharin is 1,2-benzisothiazol-3 (2H)-one-1, 1-dioxide.
Saccharin and sodium saccharin are white crystalline powders soluble in water.
They are about 500 times sweeter than sucrose. It has good stability during
cooking and baking of food products but leaves a slight bitter metallic
aftertaste. It is permitted as a sweetener in several countries including India
with restrictions.
Cyclamates are not without safety questions. Therefore its usage is only
allowed with restrictions like most other non-nutritive sweeteners. The use of
cyclamates is not permitted under PFA. Its ADI value is 11 mg/Kg body
weight.
The number of substances in this category though very large, is not used
extensively in fruit and vegetable products. Therefore, only a few of them will
be dealt with in this section. They include emulsifiers and stabilizers, firming
agents, anticaking agents, clarifying agents etc.
Emulsifying and stabilizing agents are essentially used for emulsifying and
stabilizing dispersions of oils and fats in aqueous media. They include different
types of gums (you have learnt under ‘carbohydrates’), esters of fatty acids,
lecithin, ester gums (glycerol esters of wood rosin) etc.
Firming agents like calcium chloride are used to firm the texture of canned
fruits and aluminium sulphate added to pickles.
Anticaking agents are used to impart free flowing properties to dry products.
Examples are silicates in potato flakes, dehydrated vegetable powders, cocoa
powders, salt; tricalcium phosphate in spices, and fruit powders; and starches
in icing sugar etc.
Clarifying agents are used to clarify fruit juices and wines and chill proofing
of beer. Gelatin is a typical example of a clarifying agent.
A large number of additives are used in foods for different functions. Some are
used as preservatives, which prevent microbial spoilage while antioxidants
preserve food against oxidative deterioration. Acidulants have dual roles of
preservation as well as imparting the desired taste. Colourants and flavouring
agents are added essentially to enhance the acceptability of foods. There are
also other additives having functions like texture modification, clarification,
imparting free flowing characteristics to food powders etc.
All the food additives are not free from suspected health hazards. Therefore,
their use in foods is restricted by food legislations.
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Food Constituents 3. Your answer should include the following points:
• PH reduction
• Buffering
• Flavouring
• Ponceau
• Carmoisine
• Erythrosine
• Sunset yellow etc
• Calorie sweeteners
• Sucrose, glucose, fructose etc
• Non calorie sweeteners
• Synthetic
• Saccharin, cyclamate, aspartame, acesulfame K
• Calcium chloride
• Tri calcium phosphate
• Gelatine
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Food Additives
6.12 SOME USEFUL BOOKS
1. Larry Branen, A., Michael Davidson, P., and Seppo Salminen (1990) (Eds.)
Food Additives, Marcel Dekker, Inc., New York and Basel.
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