Permitted Preservatives – Sulfur Dioxide

K Prabhakar, Sri Venkateswara Veterinary University, Tirupati, India

EN Mallika, NTR College of Veterinary Science, Gannavaram, India
Ó 2014 Elsevier Ltd. All rights reserved.
This article is a revision of the previous edition article by K Prabhakar, K S Reddy, volume 3, pp 1750–1754, Ó 1999, Elsevier Ltd.

Introduction very effective for purposes of disinfection. Grapes and cut fruits
are exposed to fumes of burning sulfur before dehydration or
Sulfur dioxide is an important chemical extensively used in the transportation.
processing and preservation of foods of both plant and animal
origin. It has been known since ancient times as a sanitizing
agent or antiseptic. It gained popularity as a preservative owing
to its apparent lack of toxicity in mammals. Its use was wide- Salts of Sulfurous Acid
spread in the United States and other countries in the Western
hemisphere until the early part of the twentieth century when Sulfite, bisulfate, and metabisulfite are extensively used in
incidents of abuses like masking the initial stage of spoilage in foods and beverages. They can be easily applied in dry form or
foods led to legislation to check indiscriminate and fraudulent as solutions. They are stable, economical, and comparatively
commercial applications. Sulfur dioxide is a colorless gas with free from heavy metal impurities. Sulfite solutions are easily
a characteristic odor. It is highly soluble in water and liquefies absorbed by fruits, which are dipped in the solution before
at
10  C. It is used in gaseous or liquefied form, or as its freezing or dehydration.
neutral and acid salts.

Liquid Sulfur Dioxide

Sulfur Compounds
Liquid SO2 is free from impurities and is commonly used in
The sulfur dioxide-generating compounds with application in wineries. Accurately measured quantities can be incorporated.
the food industry are as follows: Special steel containers are required for storage and trans-
portation, making it a costly source of SO2.
l Sulfur dioxide as a gas
l Sulfurous acid
l Salts of sulfurous acid, such as sodium sulfite, sodium
bisulfite, and potassium sulfite Range of Foods to Which Sulfites May Be Added
l Hydrosulfurous acid and its salt, sodium hydrosulfite
l Pyrosulfurous acid and its salt, sodium pyrosulfite or The range of foods into which sulfur dioxide is incorporated
metabisulfite. includes fruits, vegetables, fruit juices and concentrates, syrups,
The sulfur dioxide content of these compounds is listed in wines and jams, and to a lesser extent prawns, fish, minced
Table 1. meats, sausages, and mushrooms.
The maximum permissible levels of SO2 in some important
foods as specified by the Preservatives in Food Regulation 1979
Sulfur Dioxide Gas for the United Kingdom are listed in Table 2. Only slight
variations exist between the maximum levels permitted in
The gas is obtained directly by burning sulfur from natural
various products in different countries, because of universal
sources. It is the cheapest of all the sources of sulfur dioxide and
concern for consumer protection.

Table 1 Approximate theoretical available sulfur dioxide content of

various sources Antimicrobial Action of Sulfur Dioxide
Compounds Formula Availability (%)
Sulfur dioxide is highly soluble in water and forms sulfurous
Liquid sulfur dioxide SO2 100.00 acid, which dissociates into bisulfite or sulfite depending on
Sulfurous acid (6%) H2SO3 6.00 the pH. Undissociated sulfurous acid is claimed to be the main
Potassium sulfite K2SO3 33.00 antimicrobial agent inhibiting bacteria, yeasts, and molds.
Sodium sulfite Na2SO3 50.8 The possible mechanisms of inhibition by sulfurous acid
Potassium bisulfite KHSO3 53.3 are attributed to the following:
Sodium bisulfite NaHSO3 61.6
Potassium metabisulfite K2S2O5 67.4 l Reaction of bisulfite with acetaldehyde in the cell
Sodium metabisulfite Na2S2O5 57.7 l Reduction of essential disulfide linkages in enzymes
l Formation of bisulfite addition compounds that interfere
From Joslyn, M.A., Braverman, J.B.S., 1954. The chemistry and technology of the
pretreatment and preservation of fruit and vegetable products with sulphur dioxide with respiratory reactions involving nicotinamide adenine
and sulfites. Adv. Food Res. 5, 97–154. dinucleotide (NAD).

108 Encyclopedia of Food Microbiology, Volume 3 http://dx.doi.org/10.1016/B978-0-12-384730-0.00264-0

 PRESERVATIVES j Permitted Preservatives – Sulfur Dioxide 109

Table 2 Maximum UK permitted levels of SO2 Composition of the Food and Food Products
Maximum SO2 level Foods containing higher levels of components that form inert
Food product (mg kg
1) complexes on reaction with SO2 cannot be effectively preserved
with SO2 alone, especially at room temperature.
Fruits, fruit pulp, tomato pulp 350
Fruit spread 100
Grape juice products 70 Influence of pH
Jams 100
Mushrooms, frozen 50 The antimicrobial action of SO2 is more effective in foods with
Pickles 100 acidic pH. Two to four times as much SO2 is required to inhibit
Raw peeled potatoes 50 growth at pH 3.5 compared with pH 2.5. At higher pH values
Salad dressing 100 like 7, sulfites do not appear to have significant inhibitory
Sauces 100 action on yeasts and molds and very high levels are required to
Soft drinks for consumption without dilution 70 control growth of bacteria. Acid is commonly added to lower
Dehydrated potatoes 550
the pH of foods, enabling preservation with lower levels of
Dehydrated cabbage 2500
SO2. Sulfites are being used in antimicrobial edible coatings.
Yogurt 60
Beer 70
Wine 450 Effect of Heat
Flour for biscuits 200
Desserts, fruit-based milk and cream 100 Heating to high temperatures drives off SO2 from foods and
Sausages or sausage meat 450 considerably reduces the antimicrobial effects. On heating, the
Hamburgers or similar products 450 sulfur compound decomposes and the free component escapes
by volatilization. At pasteurization temperatures, it is reported
to increase the thermal death rate of microorganisms present
and enables more rapid destruction of microbes.
Factors Influencing Antimicrobial Action
Initial Microbial Population and the Stage of Growth Temperature of Storage

The initial level of bacterial contamination affects the preser- A synergistic action of lower temperatures and SO2 addition is
vative efficacy of SO2. Minced meat samples containing claimed by some investigators, as more pronounced bacterio-
300 ppm of sulfur dioxide during refrigerated storage revealed static effects were observed in minced meat samples stored at
spoilage on the 6th day for samples with an initial contami- lower temperatures than at higher temperatures (Table 3).
nation level of 7.6  107 cfu g
1, compared with spoilage on It is generally assumed that sulfite preservation of foods at
the 13th day for samples with an initial microbial load of room temperature competes with refrigerated storage of foods
6.9  105 cfu g
1. without any additives.

Type of Microorganisms Present

Table 3 Approximate shelf life of minced meats at different storage
Strains like acetic acid bacteria, yeasts, and molds are effec- temperatures, with or without SO2
tively eliminated through incorporation of SO2. The inhib-
Preservation
itory effect also depends on the levels of SO2 incorporated storage temperatures (  C) Without SO2 With SO2
and maintained. Coliaerogenous bacteria were not affected by
150 ppm, but at 450 ppm, their multiplication was totally 7 3–5 days 13 days
inhibited. Cyclopiazonic acid produced by Aspergillus species 15 1–2 days 6–7 days
and Penicillium was inhibited by potassium metabisulfite. 22 <20 h 1–2 days

Sulfur Dioxide-Producing Sources

Behavior of Sulfur Dioxide in Foods
Equilibrium between various forms of SO2-undissociated
sulfurous acid, free sulfite, or bisulfite ions and hydroxysulfo- Several reaction products are formed through reversible and
nates is determined by pH, temperature, composition, and irreversible reactions in SO2-treated foods. The amounts of
storage condition of foods. interaction products vary in different foods depending on the
processing and storage conditions. Because of these reactions,
SO2 has multifarious functions in addition to its antimicrobial
Free and Bound Components of Added Sulfur Dioxide
effects. It can act as an antioxidant, as a bleaching agent, as
The free or unbound component of added SO2 has the signif- a color fixative, and as an inhibitor of enzymic discolorations
icant antimicrobial action. It is claimed that the inhibition and nonenzymic browning. The interaction products of
power of the free component of added SO2 is 30–60 times reversible reactions of sulfites do not pose serious problems as
more effective than that of the bound component. most of them are unstable. Addition of SO2 to menadione,
110 PRESERVATIVES j Permitted Preservatives – Sulfur Dioxide

a water-soluble synthetic form of vitamin K, is reported to Reducing and Bleaching Actions

result in the formation of a reversible sulfonate adduct, which
readily dissociates in animals to become a source of vitamin Sulfurous acid and the acid sulfites reduce many colored
K. Irreversible reactions, however, like cleavage of thiamin compounds to colorless derivatives. Dried cut fruits with slight
have nutritional significance. darkening can be almost completely restored to their original
color by treating with SO2 probably owing to the formation of
colorless compounds. In sugar processing, SO2 bleaches the
Inhibition of Enzymic Discoloration naturally occurring pigments such as anthocyanins and other
colored nonsugars and also reduces darkening during evapo-
Enzymic browning is a result of processes involved in the ration and crystallization owing to its combination with
production of pigments from enzymically oxidized phenolic reducing sugars. As a reducing agent, it keeps reductones in the
compounds of natural origin. Sulfites form inactive inactive reduced form rather than in the active dehydro form.
complexes with enzymes or combine with breakdown The attractive bright pink color of sulfited minced meat
products to form stable complexes, thus inhibiting enzyme- samples is maintained until spoilage during storage at 7–15  C.
induced formation of abnormal colors in fruits and vegeta- This color fixation property of SO2 is attributed to its ability to
bles during processing and storage. Sulfite dips are used to maintain heme iron in the reduced state. Studies revealed
control discoloration due to enzymic browning in frozen increased consumer preference for cooked sulfited minced
stored fruits and vegetables, as food enzymes are not meat samples. Sulfites also prevent gray discoloration in
destroyed by freezing. The development of white specks minced meats and raw sausages when they are exposed to air.
during storage in prawns can be controlled with the use of Sodium metabisulfite has been used extensively in the mush-
10% salt and 0.04% sodium metabisulfite solution without room industry as a whitening agent.
loss of nutrients. The formulations based on 4-hexyl-resor-
cinol and sulfides can delay the appearance of melanosis in
prawns by inhibiting polyphenoloxidase activity. Commer- Losses from Binding to Food Constituents
cial sulfides can inhibit luminescent bacterial growth.
Sulfur dioxide is highly reactive with other components in
foods; hence it does not persist for long periods. A large part of
Inhibition of Nonenzymic Browning the SO2 added to foods remains fixed or bound. Glucose,
aldehydes, ketonelike substances, pectin, and so on present in
Nonenzymic browning involves reactions between amino foods determine the extent of binding of added SO2 in foods.
groups and carbonyl groups leading to the formation of However, 0.2% potassium metabisulfite with 2% citric acid can
insoluble, dark-colored compounds with a bitter taste. Sulfur extend the shelf life of tofu without disturbing its sensory
dioxide is the most commonly used chemical to inhibit properties and without losses.
nonenzymic browning in foods. Inhibition of browning reac- Glucose binds SO2 in a reversible manner. The extent of
tions by SO2 is attributed to the stabilization of the interme- binding is reported to be related to the total concentration of
diate compounds formed. It combines reversibly with reducing soluble solids in the food. Combination of bisulfites with
sugars and aldehyde intermediates and irreversibly with certain sugars is much slower than with aldehydes and ketones and the
unsaturated aldehyde intermediates. products formed are relatively less stable. Sulfur dioxide after
The appearance of heat-processed and canned vegetables, combination with sugars or aldehydes exercises very little
fruits, fish, and comminuted meat products like sausages can antimicrobial action.
be improved through the inhibition of nonenzymic browning. When increased levels of SO2 are added to foods, the
White wines are treated with SO2 gas or metabisulfite to inhibit proportion of the free component increases. At low pH, the
nonenzymic brown discoloration during storage. Sulfur combination of SO2 with glucose is delayed, ensuring that
dioxide also inhibits nonenzymic browning in dehydrated more time is available for the SO2 to act on the microorganisms
fruits and vegetables during storage at ambient temperatures. present.
Levels of SO2 decrease considerably during storage. Loss of
SO2 in sealed bottles of wine initially containing up to
Antioxidant Properties 400 ppm ranges between 20 and 50%. In minced meat
samples incorporating 450 ppm of SO2, levels started to
Sulfur dioxide in the form of a gas or a sulfite dip during decrease within a few hours. During storage at 7  C, levels of
processing and storage of dehydrated vegetables, fruits, and SO2 decreased to around 295 ppm after the first day, to
grape juice prevents loss of ascorbic acid. It is used in canned 270 ppm on the third day, to 240 ppm on the fifth day, and
tomato sauce to prevent carotenoid oxidation and to preserve stabilized at 200 ppm on days 7–13, after which spoilage was
the bright color. It is added to beer as a solution in water to observed. In samples stored at 15  C, residual SO2 levels
inhibit adverse changes in flavor due to oxidation by dissolved decreased to 350 ppm on the first day, 280 ppm on the third
oxygen. Lipids in sausages and comminuted meat products are day, and 220 ppm on the fifth day. Spoilage was noticed on
protected from oxidation changes if sulfite or metabisulfite is the sixth day of storage when the residual level was 120 ppm.
included. It also prevents the oxidation of the essential oils and Reduction in the concentration of SO2 is faster at higher
carotenoids and inhibits development of abnormal color and temperatures and it also coincides with increased microbial
flavor in citrus juices. loads.
 PRESERVATIVES j Permitted Preservatives – Sulfur Dioxide 111

Importance of Species and Strain Tolerance have revealed, however, that humans consuming up to
200 mg of SO2 per day showed no signs of thiamin defi-
Sulfur dioxide is reported to have selective antiseptic action. ciency. This reaction need not be taken as a serious disad-
Acetic acid bacteria, lactic acid bacteria, and coliaerogenous vantage since some nutrient losses are expected in almost all
bacteria are more sensitive than others. This compound is popular commercial methods of food preservation. Adverse
most effective against Gram-negative bacteria. Several studies effects were not observed even with chronic sulfite admin-
indicate a general decline in the growth of spoilage organ- istration. Chronically ingested sulfite does not accumulate in
isms and also of added cultures of Clostridium botulinum, the tissues or reach levels hazardous to human health
Clostridium sporogenes, Clostridium perfringens, and Salmonella because of its rapid metabolic removal. However, problems
typhimurium in minced meats with SO2 levels of 450 ppm. may occur in humans affected with sulfite oxidase deficiency
Bactericidal effect was found to be significant within 3 h of disease.
the addition of Salmonella enteritidis and Yersinia enter- The possibilities of undesirable interactions between SO2
ocolitica. Germination of bacterial spores also was found to and other dietary components or cellular constituents
be affected. In minced meats without preservative, all groups leading to interference in metabolic processes or damage to
of bacteria multiply throughout the storage period, whereas the structural integrity of proteins have not been evidenced
in sulfited samples only a portion of the microflora causes in human systems; hence, SO2 is considered to be a safe
spoilage. preservative if used in permitted levels. A few cases of allergic
During storage of minced meat samples with 450 ppm of reactions observed in asthma patients after consumption of
SO2 at 7  C, coliforms, salt-tolerant bacteria and streptococci sulfited foods such as pickled onions were found to be due
did not reveal significant changes in their numbers. Lactoba- to the presence of very high levels of SO2. If foods are pro-
cilli, however, were significantly inhibited by day 9 when cessed at permitted levels of SO2, such problems may not
spoilage was noticed. These organisms play a major role in the arise.
spoilage of vacuum-packaged meats during refrigerated storage.
It is to be explored whether extension of refrigerated storage life
of vacuum-packaged meats is possible with the addition of SO2 Conclusion
or sulfites in a safe way. In a minced meat sample with
450 ppm of SO2 stored at 15  C, lactobacilli, salt-tolerant The rapid strides made by the processed and convenience
bacteria, and enterococci showed significant increases after food industry would not have been possible without the
a lag phase of 4–5 days. A combination of 0.6% chitosan with use of traditional and chemical preservatives. In view of
170 ppm of sulfite retarded growth of spoilage organisms for concerns about potential toxicity to the consumers in the
24 days. long run, the worldwide trend is to restrict the use of
Among yeasts, fermentative types are more resistant than these preservatives to well below their legally permitted
true aerobic species. Certain desirable strains of yeasts required levels. No single permitted preservative fulfills the needed
for fermentation are made sulfite resistant through gradual requirements of effectiveness and absolute safety. Sulfur
sensitization. Such resistant yeasts are utilized for fermentation dioxide is no exception to this, in spite of its proven effec-
in winemaking at levels of SO2 at which other undesirable tiveness and safety as indicated by its continued usage in
strains of yeasts and molds do not develop. a wide range of foods. Future development will lead to the
optimum utilization of combinations of permitted preser-
vatives so that their individual levels of incorporation can be
Toxic Effects in Humans greatly reduced without compromising the safety and
stability of food products. A combination of 50 ppm of
The extensive use of SO2 in the form of sulfites, bisulfites and sorbate and 50 ppm of SO2 is reported to have inactivated
metabisulfites in foods and beverages the world over indicates yeasts such as Saccharomyces cerevisiae during heating, even in
that allergic reactions and residual toxicity problems in the presence of glucose. The food industry requires the
consumers are almost nil in the normal pattern of human continued use of preservatives like SO2 in traditional ways
exposure. In spite of its high reactivity with biologically until synergistic combinations have undergone detailed
important molecules, SO2 is oxidized to sulfate by sulfite investigations on enhanced safety.
oxidase enzyme and excreted in urine safely. The enzyme
sulfite oxidase is reported to be present at higher than
adequate levels in liver and other tissues of the human body.
See also: Preservatives: Classification and Properties;
The capacity of the mammalian sulfite oxidase for sulfite
Preservatives: Traditional Preservatives – Organic Acids;
oxidation is reported to be extremely high in relation to the
Preservatives: Traditional Preservatives – Wood Smoke;
normal sulfite load expected from both endogenous and
Preservatives: Permitted Preservatives – Benzoic Acid;
exogenous sources.
Permitted Preservatives – Hydroxybenzoic Acid; Permitted
Sulfites are known to destroy thiamin (vitamin B1) in
Preservatives: Nitrites and Nitrates; Preservatives: Permitted
foods by cleavage of thiamin into 4-methyl-5-hydroxyethyl
Preservatives – Sorbic Acid; Spoilage of Animal Products:
thiazole and the sulfonic acid of 2, 5-dimethyl-4-amino- Seafood; Wines: Microbiology of Winemaking; Production
pyrimidine. This cleavage is completed within 24–48 h at
of Special Wines; Wine Spoilage Yeasts and Bacteria; Advances
a pH of 5.0 and at room temperatures. Hence, sulfites are
in Processing Technologies to Preserve and Enhance the Safety
not used in foods that are major sources of thiamin. Studies
of Fresh and Fresh-Cut Fruits and Vegetables.
112 PRESERVATIVES j Permitted Preservatives – Sulfur Dioxide

Further Reading Krishna Reddy, V., Reddy, S.M., 1990. Efficacy of food preservation in the control of
cyclopiazine acid production by penicillium griseofulvum. Journal of Food and
Science Technology 27 (3), 180–181.
Alvarez, O.M., Caballero, M.E.L., Montero, P., Guillen, M.G., 2005. A 4-hexyl resor- Premi, B.R., Sethi, V., Maini, S.B., 1999. Effects of steeping preservatives on the Aonia
cinol- based formulation to prevent melanosis and microbial growth in chilled (Emblica officinalis Gaerln) fruits during storage. Journal of Food Science and
Tiger prawn (Marsupenaeus japonicus) from aqua culture. Journal of Food Science
Technology 36, 244–247.
70 (9), M 415–M 422. Roberts, A.C., McVeeny, D.J., 1972. The uses of sulphur dioxide in the food industry.
Austin, R.K., Clay, W., Phimphivong, S., Smilanick, J.L., Henson, D.J., 1997. Patterns A review. Journal of Food Technology 7, 221–238.
of sulfite residue persistence in seedless grapes during three months of repeated Roller, S., Sagoo, S., Board, R., Mahony, T.O., Caplice, E., Fitzgerald, G., Fogden, M.,
sulfur dioxide fumigations. American Journal of Enology and Viticulture 48 (1), Owen, M., Fletcher, M., 2002. Novel combination of chitosan, carnocin and
121–124. sulphite for preservation of chilled pork sausage. Meat Science. 62 (2),
Burke, C.S., 1980. International legislation. In: Tilbury, R.H. (Ed.), Developments in 165–177.
Food Preservatives, vol. 1. Applied Science Publishers, London, p. 25. Sinskey, A.J., 1980. Mode of action and effective application, pp. 111–136.
Cerrutti, P., Alzamora, S.M., Chirife, J., 1988. Effect of potassium sorbate and sodium In: Tilbury, R.H. (Ed.), Developments in Food Preservatives, vol. 1. Applied
bisulfite on thermal inactivation of Saccharomyces cerevisiae in media of lowered Science Publishers, London, p. 111.
water activity. Journal of Food Science 53 (6), 1911–1912. Stammati, A., Zanetti, C., Pizzoferrato, L., Quattrucci, E., Tranquilli, G.B., 1992. In vitro
Chauhan, S.K., Tyagi, S.M., Chauhan, G.S., 1998. Effect of various preservatives model for the evaluation of toxicity and anti nutritional effects of sulphites. Food
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Studdert, V.P., Labuc, R.H., 1991. Thiamin deficiency in cats and associated with feeding
Duvenhage, J.A., 1994. Control of post-harvest decay and browning of litchi fruit by meat preserved with sulphur dioxide. Australian Veterinary Journal 68 (2), 54–57.
sodium metabisulphite and low pH dips – an update. In: Litchi Year Book, vol. 6. Taylor, S.L., Bush, R.K., 1986. Sulfides as food ingredients. Food Technology 40
South African Litchi Growers Association. 36–38. (6), 47.
Gray, T.J.B., 1980. Toxicology. In: Tilbury, R.H. (Ed.), Developments in Food Preser- Taylor, S.L., Higley, N.A., Bush, R.K., 1986. Sulfite in foods, uses, analytical methods,
vatives, vol. 1. Applied Science Publishers, London, p. 53. residues, fate, exposure assessment, metabolism, toxicity and hypersensitivity.
Gunnison, A.F., 1981. Sulphite toxicity: a critical review of in vitro and in vivo data. Advances in Food Research 30, 1.
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pretreatment and preservation of fruit and vegetable products with sulphur dioxide Usseglio-Tomasset, L., 1992. Properties and use of sulphur dioxide. Food Additives
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