A METHOD FOR INHIBITING THE PRODUCTION OF ENTEROTOXIN FROM CLOSTRIDIUM BOTULINUM IN CORNED BEEF, CHEESE AND CARBOHYDRATE FOOD PRODUCTS

Abstract: The growth of Clostridia and coliform bacteria and the production of Clostridium botulinum enterotoxin in corned beef, poultry products, cheese and carbohydrate food pro­ ducts are inhibited by adding to such products an effective amount of a compound selected from hypophosphorous acid and nontoxic water-soluble salts thereof. Such additives may be present in combination with minor amounts, for example, up to 52 ppm of sodium nitrite.

Description: COMPOSITIONS AND METHOD FOR INHIBITING THE GROWTH OF CLOSTRIDIA AND/OR COLIFORM BACTERIA IN CORNED BEEF, POULTRY PRODUCTS, CHEESE AND CARBOHYDRATE FOOD PRODUCTS This invention relates to a composition which inhibits the growth of various Clostridia and/or Coliform bacteria in corned beef, smoked poultry products, cheese and carbohydrate food products. It has long been standard practice to add sodium nitrite to preserve meat products such as ham, bacon, and other meats, for example, frankfurters, bologna, Thuringer sausages and salami. The sodium nitrite is added to inhibit the growth of Clostridium botulinum and the production of enterotoxin in the comminuted meat products during storage. The addition of sodium nitrite also maintains a pleasing pink color in the meat. The presence of sodium nitrite as a food additive, and particularly the presence of sodium nitrite in bacon and other smoked meats that are cooked at high temperatures, has become of increasing concern with the knowledge that sodium nitrite can combine with secondary and tertiary amines in cooked meats (particularly bacon) to form nitrosamines. Many nitrosamines have been shown to be carcinogens in animals, and the nitrosamine that is commonly found in fried bacon, nitrosopyrrolidine, is a known carcinogen. It is quite obvious that reducing the nitrites present in meat and smoked poultry products is a desirable goal, but it is also necessary to prevent the production of deadly botulinal toxin that may occur on storage. Because of the widespread concern with the use, toxicity and necessity of nitrite addition in food products, this problem has received increasing attention. French Patent Application No. 7709108 reduces the amount of sodium nitrite by substituting for a part of it large amounts of sorbic acid and its salts. This combination of additives has the disadvantage that some persons of the population have developed allergic reactions after eating nitrite/sorbate-smoked products. Another approach to solving the N-nitrosamine prob lem is the addition of materials to suppress N-nitros amine formation. A cooperative American Meat Institute study which involved eight firms using their commercial production techniques, indicated that in commercial production, a-tocopherol in combination with sodium erythorbate (isoascorbate) or sodium ascorbate did suppress N-nitrosamine formation. Dispersion of the a-tocopherol in the pickle was occasionally a problem, and a surface active agent was mixed with the a-tocopherol to improve dispersion. The lowest level of nitrosopyrrol idine (0.4 to 2 parts per million) was obtained with 120 parts per million nitrite, 550 parts per million ery thorbate or ascorbate and 550 parts per million a-tocopherol. Since June 15, 1978 the United States Department of Agriculture has required that all bacon produced using nitrite must employ 120 parts per million of sodium nitrite (or 148 parts per million of potassium nitrite) to prevent formation of botulinal toxin and 550 parts per million sodium ascorbate or sodium erythorbate to inhibit formation of nitrosamines More recently, the United States Department of Agriculture has approved a bacon process using a blend of------ microorganisms (LACTOBACILLI) that is incorporated in the curing pickle to promote production of lactic acid and reduce potential nitrosamine formation. During smoking, the culture reduces the pH of the meat which, in turn, reduces the residual nitrite content in the final product. Both factors, lower pH and reduced residual nitrite content, reduce subsequent nitrosamine formation at the time of frying. The current levels of 120 parts per million sodium nitrite and 550 parts per million sodium erythorbate (isoascorbate) are still employed in the process. Sodium nitrite, or in rare occasions nitrate which is converted to nitrite, is also used to preserve color and to prevent bacterial spoilage and outgrowth of the enterotoxin of Clostridium botulinum in corned beef and in smoked whole poultry, poultry breasts, poultry rolls, poultry "ham", and other cured and smoked poultry products. The increasing concern over the knowledge that sodium nitrite can combine with secondary and tertiary amines to form carcinogenic nitrosamines combined with the knowledge, as described in EP 81 101 227.7, publication number 0037 887), that nitrites can be replaced by hypophosphorous acid or its salts to prevent formation of both the Clostridium botulinum enterotoxin and nitrosamines recommends the use of hypophosphorous acid and its nontoxic water-soluble salts in corned beef and in smoked poultry. When used throughout the following specification and claims, the term "smoked poultry" shall include but not be limited to smoked whole poultry, smoked poultry breasts, smoked poultry rolls, smoked poultry "ham", and other cured and smoked poultry products. Nitrates, which are converted to nitrites in the cheese to which they are added, have been used to make certain types of cheese in Europe since 1830. These types are typically Gouda, Edam, and many other Danish and West European types. The primary reason for the addition of nitrate to these cheeses is to prevent clostridial and coliform blowing. Regulations or accepted limits in certain European countries often limit the actual amount of nitrate added to cheese milk to 20 grams of potassium nitrate or sodium nitrate per 100 liters of cheese milk. In practice, the amounts vary from 5 to 20 grams per 100 liters of milk (50-200 ppm). Some countries have regulations that limit the amount of nitrate that may be present in cheese when it is consumed. These limits vary from 40 up to 60 milligrams of nitrate per kilogram of cheese (40 to 60 ppm). Cheese that is sold for consumption will generally contain no more than 50 parts per million of a nitrate salt and not more than 5 parts per million of a nitrite salt. Nitrate salts such as sodium and potassium nitrate are added during the preparation of Gouda and Edam cheese as mentioned above and in the manufacture of other types of cheese that have properties in common which make them very sensitive to blowing by Clostridia and coliform bacteria. Those cheese types that are quite sensitive to blowing have a relatively high pH, a relatively high water content, and require a long time to ripen at a relatively high temperature. One property that is characteristic of those cheeses which may be benefited by the additives of the present invention is that such cheeses are salted from the outside (brined) after pressing the cheese. That is, the curd is not salted. Under these conditions of high water content and low salt content, Clostridia spores, especially those of Clostridium tyrobutyricum and Clostridium perfringens which are present in the interior of the cheese, can germinate and "grow out". Once germinated and grown out, the bacteria can withstand a salt concentration higher than required to prevent the germination of the spores originally present. The germinating spores are particularly susceptible to the addition of nitrate, and are most probably killed by the nitrite that is produced from the nitrate, under the influence of the milk enzyme xanthine oxidase. It is believed that the process which prevents germination and the development of Clostridia is the combined action of nitrite that is produced from the added nitrate and by the slowly penetrating salt. It is not possible to use nitrite instead of nitrate because nitrite in cheese is not stable--so the initial concentration of nitrite that would be required to be effective would need to be so high as to inhibit the required lactic acid fermentation. No suitable substitute for the use of a nitrate in the manufacture of cheese has been found. Thus, at the time the present invention was made, the addition of nitrate to cheese milk was indispensible in the making of brined cheeses. This practice of adding nitrate to the cheese milk has been questioned on the ground that it may constitute a health hazard to the cheese consumer. The probability that the nitrate is added to cheese is reduced to form nitrite which may react with other constituents in the cheese to form nitrosamines is considered to be a risk factor. Moreover, experiments conducted by the United States Food and Drug Administration have shown that when Clostridium botulinum spores are added (injected into) a sealed package of process cheese, outgrowth of the enterotoxin was detected. Possibly because of the salt, and phosphate content of process cheese, outgrowth from spores that may be incorporated during mixing and pasteurizing has been considered to have a low probability. However, death from botulism has occurred in the United States following the ingestion of process cheese. Thus, the use of an additive for process cheese that would provide a margin of safety to cover insufficient mixing, inadequate pasteurizing, or too high a temperature during storage conditions may be required in the future. Throughout the specification and claims the term "carbohydrate food products" will define a food characterized by a high carbohydrate content and a low protein and fat content such that the ratio of carbohydrate to protein and fat (C/P & ) is greater than 1. Meat, fish and poultry products are characterized by a low ratio of carbohydrate to protein and fat, that is, C/P & is less than 1. At least 188 cases of infant botulism have been identified in the United States between 1975 and 1980. Products investigated for the presence of spores included dry cereals, commercially canned fruits, commercially canned fruit juice, fresh cooked carrots, honey, corn syrup, dry commercial baby formula, regular cows milk, nonfat milk and sugar. The original survey found 8 of 40 samples of corn syrups positive for Clostridium botulinum spores. A more recent survey found that 6 of 961 samples of corn syrups contained Clostridium botulinum spores. The preliminary data indicated that corn syrup could be a possible source of Clostridium botulinum spores. The amount of hypophosphite salt (or hypophosphorous acid) that is added may vary with the carbohydrate food, the particular hypophosphite salt and the presence or absence of sodium nitrite; and is effective in amounts of from about 500 to about 3000 parts per million. About 3000 parts per million of a hypophosphite salt is sufficient to inhibit or block the formation of enterotoxins from Clostridium botulinum if there is no nitrite in the carbohydrate product. One thousand parts per million of sodium hypophosphite is effective when as little as 40 parts per million of sodium nitrite is also present in the carbohydrate food product. As indicated above, the potassium and calcium or magnesium or manganese hypophosphite salts may be employed in similar amounts with good results. The choice of a particular hypophosphite salt will depend upon its cost and relative effectiveness, and the amount of hypophosphite salt may be reduced if sodium nitrite is also present in amounts between about 40 ppm and 120 ppm. Particularly preferred are carbohydrate food products containing from 2000 to about 3000 ppm of hypophosphorous acid or its nontoxic water-soluble salts. The combination of 40 ppm sodium nitrite with 1000 ppm of sodium hypophosphite is also highly effective. In the practice of the present invention, the hypophosphorous acid (or its nontoxic salt) may be added to the carbohydrate food product in solution or solid form. The present invention has particular application to the processing of baby foods and infant formulas wherein the hazards of botulism are believed to be particularly great due to the small body weight of the baby and the lack of flora in the lower gut. Examples of such carbohydrate food products having a C/P & fat ratio of more than 1 are listed in Table I. The addition of an effective amount, that is, about 1000 to about 3000 ppm of hypophosphorous acid or one of its nontoxic salts to such carbohydrate food products will inhibit the growth of Clostridium botulinum and the formation- of exterotoxins. In accordance with the present invention, the growth of various Clostridia and/or coliform bacteria and the production of botulinal toxin is inhibited during storage of corned beef, smoked poultry products, carbohydrates and natural or process cheese by addition thereto of an effective amount of a compound selected from the group consisting of hypophosphorous acid and its nontoxic water-soluble salts. Suitable salts of hypophosphorous acid that are useful as additives in the present invention are sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, manganese hypophosphite and magnesium hypophosphite. Sodium hypophosphite is conveniently used in the form of its monohydrate, NaH2PO2.R2O. When hypophosphorous acid or its nontoxic watersoluble salts are present in corned beef or smoked poultry in effective quantities, the amount (120 to 156 ppm) of sodium nitrite that is customarily added to such products may be reduced to one-third of that amount or eliminated entirely. The addition of hypophosphorous acid and/or a nontoxic water-soluble salt of hypophosphorous acid is believed to suppress or block the formation of N-nitrosamines upon cooking corned beef or smoked poultry products containing sodium nitrite. The amount of hypophosphite salt (or hypophosphorous acid) that is added may vary with the meat product, the particular salt and the presence or absence of sodium nitrite; and desirably is about 1000-3000 parts per million. It is preferred that about 3000 parts per million of hypophosphite salt be added if all sodium nitrite is eliminated from the comminuted meat product. About 1000 parts per million or less of sodium hypophosphite is effective when 40 parts per million of sodium nitrite is also present in the meat composition. As indicated above, the potassium and calcium or magnesium or manganese hypophosphite salts may be employed in similar amounts with good results. The choice of a particular hypophosphite salt will depend upon its cost and relative effectiveness. In the practice of the present invention, the hypophosphorous acid, or its nontoxic water-soluble salts, may be added to corned beef and smoked poultry in solution or solid form. The amount of hypophosphite salt (or hypophosphorous acid) that is added may vary with the cheese product and the particular processing steps and is desirably from about 300-3,000 parts per million. It is preferred, if no nitrite or nitrate salts have been added to the cheese, that the hypophosphorous acid or its salt be present within the range of about 500 to 2,000 parts per million. As indicated above, any water soluble salt of hypophosphorous acid may be employed in similar amounts with good results. The choice and amount of a particular hypophosphite salt, or the free acid will depend upon its cost and relative effectiveness. The hypophosphorous acid (or its salt) may be conveniently added to the cheese milk at the time that the cheese starter is added. The present invention is further illustrated by the following examples. Temperatures are in degrees centigrade and quantities are expressed in parts by weight and parts per million (ppm) unless otherwise indicated. EXAMPLE 1 Whole Smoked Turkey A 10 kilogram turkey is plucked, the pin feathers are removed and the turkey is washed prior to pumping. The turkey is pumped using a commercial automatic pump and needles with a pickle solution having the following composition: Water 63.4 kg Sodium Tripolyphosphate 3 kg Salt 30 kg Sodium Hypophosphite 3 kg Sodium Erythorbate 600 g After pumping, the turkey is placed in the pickle for 10 hours at 60C. After 10 hours in the pickle solution the concentration of sodium hypophosphite in the meat is about 3000 ppm. After curing, the turkey is removed from the pickle solution and allowed to drain for 15 minutes. The cured turkey is then smoked for 10 hours at 75-C, cooled in a 60C cooler overnight and packaged in a plastic overwrap. EXAMPLE 2 A whole smoked turkey may be prepared by the method described in Example 1 above except that the pickle solution employed will have the following composition: Water 65.36 kg Sodium Tripolyphosphate 3 kg Salt 30 kg Sodium Hypophosphite 1 kg Sodium Erythorbate 600 g Sodium Nitrite 40 g The cured and smoked turkey will contain about 1000 ppm sodium hypophosphite and about 40 ppm sodium nitrite. EXAMPLE 3 Turkey Ham Five kilograms of boneless, skinless turkey thigh meat is trimmed of excessive fat, blood vessels and tendons, and is placed for 30 hours in a pickle solution at 5"C containing the following ingredients: Water 48.75 kg Sodium Tripolyphosphate 3.1 kg Sugar 12.5 kg Salt 31.3 kg Sodium Hypophosphite 3.75 kg Sodium Erythorbate 600 g After curing, the thigh meat (containing about 3000 ppm sodium hypophosphite) is removed from the pickle solution and drained for 5 minutes. The product is then tumbled in a tumbler with 50 g of salt until the meat becomes tacky. One kilogram of deboned turkey meat, 60 g of monosodium glutamate and 60 g of pepper are added with continued tumbling for 3 minutes. The mixture is then stuffed into one kilogram (wet) fibrous casings using a mechanical stuffer. The product is next placed on a flat screen in a smokehouse and smoked for 1 hour at 65'C. After this, the smoked product may be chilled in cold water for 45 minutes, placed in a 6'C cooler overnight and packaged in a plastic overwrap for sale. The turkey ham will contain 3000 ppm sodium hypophosphite. EXAMPLE 4 A turkey ham may be prepared by the method described in Example 2 above except that the pickle solution employed will have the following composition: Water 63.7 kg Sodium Tripolyphosphate 3.1 kg Sugar 12.5 kg Salt 31.3 kg Sodium Hypophosphite 1.25 kg Sodium Erythorbate 600 g Sodium Nitrite 50 g This pickle results in a product containing about 1000 ppm of sodium hypophosphite and about 40 ppm of sodium nitrite. EXAMPLE 5 Smoked Chopped Chicken Loaf A chopped chicken loaf may be prepared by placing 10 kilograms of boneless chicken breast meat and 10 kilograms of boneless chicken thigh meat in a pickle solution having the composition: Water 54.5 kg Salt 40 kg Sodium Tripolyphosphate 2.5 kg Sodium Hypophosphite 3 kg After 24 hours in this pickle at 6iC, the pickled meat is removed, allowed to drain well and ground through a 2.5 cm plate. A smooth paste is prepared by grinding together 5.5 kg of chicken skin and 7.0 kg of defatted chicken broth. To this paste is added 10 kg of boneless chicken breast meat, 10 kg of boneless chicken thigh meat and 1.7 kg of sodium caseinate. The meat is chopped into large pieces measuring 2 x 5 cm in size, mixed with the coarse-ground pickled meat described in the preceding paragraph and blended by mixing with 300 g of salt, 200 g of pepper, 100 g of sugar, 60 g of sodium tripolyphosphate, 60 g of sodium hypophosphite and 500 g of monosodium glutamate. The mixture is stuffed into fibrous casings using a pneumatic stuffer; the stuffed casings are placed in wire cages measuring 9.5 x 8.2 cm and compressed. The product is then smoked for 4 hours until the internal temperature reaches 75*C. The resulting chopped chicken loaf is then chilled, stored for 16 hours at 6iC and packaged. The product will contain about 3000 ppm of sodium hypophosphite. EXAMPLE 6 A smoked, chopped chicken loaf may be prepared by the method described above in Example 5 substituting for the pickle employed in that example a pickle having the following composition: Water 56.46 kg Salt 40 kg Sodium Tripolyphosphate 2.5 kg Sodium Hypophosphite 1 kg Sodium Nitrite 40 g Twenty grams of sodium hypophosphite and 0.8 g of sodium nitrite are added in the second step and blended with the 300 g of salt, 200 g of pepper, 100 g of sugar, 60 g of sodium tripolyphosphate and 500 g of monosodium glutamate. The resulting product contains about 1000 ppm of sodium hypophosphite and about 40 ppm of sodium nitrite in the meat. EXAMPLE 7 Corned Beef Corned beef is cut into sections 7.5 cm thick and placed in a pickle of the following composition maintained at 6C: Sodium Chloride 37 kg Sucrose 5 kg Sodium Tripolyphosphate 3 kg Sodium Erythorbate 400 g Sodium Nitrate 40 g Sodium Hypophosphite 1 kg Spices (Allspice & Laurel) 300 g Water 53.26 kg After two weeks the meat sections are removed from the pickle solution and packaged with a small amount of pickle in sealed, water-tight plastic bags. The packaged corned beef contains about 1000 ppm of sodium hypophosphite and about 40 ppm of sodium nitrite. EXAMPLE 8 Corned beef may be prepared as described above in Example 7 by substituting for the pickle solution a pickle having the following composition: Sodium Chloride 37 kg Sucrose 5 kg Sodium Tripolyphosphate 3 kg Sodium Erythorbate 400 g Sodium Hypophosphite 3 kg Spices (Allspice & Laurel) 300 g Water 51.3 kg The packaged corned beef contains about 3000 ppm of sodium hypophosphite and no sodium nitrite. EXAMPLE 9 Edam Cheese Five hundred kilograms of whole milk containing 3% butterfat is pasteurized by heating at 720C for 16 seconds and then cooling to 30*C. The warm milk is pumped into a standard rectangular-shaped, jacketed vessel and 75 ml of annatto cheese color and 2.5 kg of an active lactic cheese starter are added with stirring. To the milk is then added with additional agitation 140 ml of single strength rennet (1:15,000) diluted with 5.5 liters of water. Finally, 500 g of sodium hypophosphite (1,000 ppm, based on whole milk) is added and the milk is stirred for 3 minutes longer. The vessel is then covered and allowed to stand for 15 minutes to allow the curd to form. The curd is cut into 1.5 cm cubes and permitted to remain undisturbed for 5 minutes. The curd cubes are then cooked in whey, using steam in the jacket of the vessel to heat the whey to a temperature of 35'C. This cooking takes place over a 15 minute period with steady agitation, during which time the temperature of the whey increases from room temperature at a rate of 0.80C per minute to the final temperature of 35C. When the temperature of the whey reaches the 35it, the curds are stirred for 30 minutes during which time the curds become more firm (but not rubbery). The exit gate from the vessel is then opened and the whey is drained off until the level of the whey is just above the level of the bed of curds. The warm curds are rapidly ladled into metal molds that are sized to contain 2.5 kg and lined with cheese cloth. The molds are preheated with warm water so that the temperature remains above 30-C to speed separation of the whey from the curds in the mold. Heavy lids are placed in position on the mold and allowed to press down on the curd and force out the whey, followed by placing the molds under light pressure for 30 minutes to compact the curd. Finally, balls of curd are removed from the mold and washed in sweet whey at 21eC. The balls of curd are wrapped in 15 cm wide cheese cloths, replaced in the molds, and pressed for 10 hours at 0.5 kilogram per square centimeter. Concave wheels of cheese formed in this manner are removed from the mold and cloths and immersed in a saturated aqueous brine solution (23% sodium chloride) at 10'C for 10 days. During this time, the wheels of cheese are turned daily and sprinkled with coarse salt on their surfaces. After 10 days the cheese wheels are removed from the brine, washed and dried. The cheese wheels are then placed on wooden shelves in a room at 15iC and 90% relative humidity. Each wheel is turned and lightly rubbed with salt daily for 2 weeks and twice daily for 3 additional weeks. After this 5 week curing period, the cheeses are waxed and allowed to ripen for 4 months at 15'C. Similar results are obtained when 2,000 parts per million of hypophosphorous acid is substituted for 1,000 parts per million of sodium hypophosphite. EXAMPLE 10 Gouda Cheese Five hundred kilograms of whole milk containing 3% butterfat is pasteurized and placed in a jacketed vessel with 75 ml of annatto cheese color and 2.5 kg of an active lactic cheese starter as described above in Example 1. To the milk is then added, with agitation, 140 ml of single strength rennet (1:15,000) that has been diluted with 5.5 liters of water. Then, 1000 g of sodium hypophosphite (2,000 ppm, based on whole milk) is added with stirring for 3 minutes longer, and the vessel is covered and allowed to stand for 15 minutes to permit the curd to form. The curd is cut into 0.3 cm diameter grains and permitted to remain undisturbed for 5 minutes. The curd cubes are cooked in whey using steam in the vessel jacket to heat the whey to a temperature of 35'C. This cooking takes place over a 15 minute period at which time the temperature of whey increases at a rate of 0.80C from room temperature to the final temperature of 35*C. The whey is drained from the vessel through an exit gate until the level of the whey is just above the level of the bed of curds. The warm curds are then ladled into metal molds sized to contain 5.5 kg, lined with cheese cloth and previously warmed in hot water. The molds are filled as rapidly as possible to prevent cooling and keep the temperature above 30"C. Heavy lids are placed on the molds and allowed to press down on the curds forcing out the whey. The molds of whey are then placed under a light pressure for 30 minutes, removed from the mold and washed in sweet whey at 210C. The curd balls are then rewrapped in 15 cm wide cheese cloths, replaced in the molds and pressed for 10 hours at 0.7 kilogram per square centimeter. Flat wheels of cheese are removed from the molds and cloths and immersed in aqueous saturated brine solution (23% NaCl) at 10-C for 2 days. After 2 days, the wheels are removed from the brine solution placed on a shelf and washed with a wet cloth, while turning daily over a period of 5 weeks. The cheese is then coated with an orange wax and ripened for 3 months at 15-C. Similar results are obtained when 2,000 parts per million of potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite or manganese hypophosphite are substituted for the 1,000 parts per million of sodium hypophosphite. EXAMPLE 11 Cheddar Type Process Cheese Foods To a steam jacketed mixing kettle provided with a motor driven agitator and previously heated to 30'C is added 275 kg of cheddar cheese, 50 kg of cheese whey solids, 32.5 kg of skim milk solids, and 75 kg water. This mixture is agitated for 10 minutes and 17.5 kg of cream (80% butterfat), 7.5 kg of salt, 10 kg of disodium orthophosphate-duohydrate, 0.5 kg of sodium hypophosphite (1,000 ppm) and 0.5 kg of paprika coloring are added. Mixing and heating are continued until the contents of the kettle reaches 60-C. Steam, at 1.0 kg per square centimeter is then injected directly into the kettle at a rate to bring the temperature of the cheese up to 75-C and maintained that temperature at 75'C for 3 minutes. The steam condensate from this heating step amounts to 32 kg of water. At this point, the emulsified mass is a smooth, velvet-appearing, homogeneous product. The contents of the kettle are emptied immediately into molds and permitted to cool to room temperature. The process cheese food is removed from the molds and wrapped for distribution. If desired, 2,000 parts per million of hypophosphorous acid or a different non-toxic water soluble salt of hypophosphoric acid may be substituted for the 1,000 parts per million of sodium hypophosphite. EXAMPLE 12 To 99.8 kg of light corn syrup is added with stirring 200 g (2000 ppm) of sodium hypophosphite. The mixture is heated to the boiling point and bottled hot in glass jars. EXAMPLE 13 To 99.95 kg of an aqueous sucrose solution (70* Brix) is added with stirring 50 g (500 ppm) of sodium hypophosphite. The mixture is heated to the boiling point and bottled hot. EXAMPLE 14 To 99.7 kg of strained clover honey is added with stirring 300 g (3000 ppm) of sodium hypophosphite. The mixture is heated to 240"F (115.5'C) for 3 minutes and bottled hot. EXAMPLE 15 A dry rice cereal may be prepared by mixing thoroughly the following ingredients: Banana Puree 33 kg Rice Flour 25 kg Sucrose 20 kg Soya Protein Concentrate 10 kg Dextrose 8 kg Soya Oil 1.7 kg Calcium Carbonate 1.0 kg Soya Lecithin 400 g Sodium Hypophosphite 300 g Electrolytic Iron 30 g Niacinamide 30 g Riboflavin 20 g Thiamin 20 g The product is packaged in cardboard boxes and protected from atmospheric moisture with a sealed paraffin coated paper barrier. EXAMPLE 16 A peach cobbler may be prepared by stirring together the following ingredients: Peaches 45 kg Water 25 kg Sugar 20 kg Corn Starch 5 kg Wheat Flour 2.7 kg Ascorbic Acid 1.0 kg Cinnamon Extract 700 g Citric Acid 550 g Sodium Hypophosphite 50 g The mixture is heated to the boiling point and maintained at this temperature for 5 minutes. This product is packaged in glass jars while hot and the closed jars are heated to 240'F (115.50C) in an autoclave and maintained at that temperature for 3 minutes. EXAMPLE 17 A vanilla custard pudding may be prepared by stirring together the following ingredients: Water 40 kg Milk 30 kg Sugar 20 kg Corn Starch 6.5 kg Egg Yolks 2.0 kg Vanilla 1.1 kg Sodium Hypophosphite 300 g The mixture is heated at 143 -145F (61.2-62.5-C) for 30 minutes and packaged in glass jars. EXAMPLE 18 A milk-free concentrate formula may be prepared by emulsifying the following ingredients: Water 75 kg Sugar 11 kg Soya Oil 6.5 kg Soya Protein 5 kg Tapioca Dextrin 1.5 kg Disodium Phosphate 300 g Potassium Chloride 300 g Sodium HYPophosPhite 200 q EMI18.1 <tb> 1-methionine <tb> Dimagnesium <SEP> Phosphate <tb> Choline <SEP> Chloride <tb> Ferrous <SEP> Sulfate <tb> Inositol <tb> Zinc <SEP> Sulfate <SEP> 200 <SEP> g <tb> Vitamin <SEP> A <SEP> Palmitate <tb> Cupric <SEP> Sulfate <tb> Manganese <SEP> Sulfate <tb> Thiamin <SEP> Hydrochlorite <tb> EMI19.1 <tb> Riboflavin <tb> Folic <SEP> Acid <tb> This product is packaged in cans, heated to 240'F (115.5 C) in an autoclave and maintained at that temperature for 3 minutes. EXAMPLE 19 Green beans may be prepared by cooking in a pressure cooker: Beans 90 kg Water 8.8 kg Salt 760 g Sodium Bypophosphite 300 g Sodium Nitrite 40 g The product is canned, heated to 240iC (115.5'C) in an autoclave and maintained at that temperature for 5 minutes. EXAMPLE 20 Whole kernel corn may be prepared by cooking in a pressure cooker: Whole Kernel Corn 88 kg Water 9.4 kg Sugar 1.7 kg Salt 600 g Sodium Hypophosphite 300 g The product is canned, heated to 240F ( 115.5-C) in an autoclave and maintained at that temperature for 5 minutes. EXAMPLE 21 Mashed carrots may be prepared by cooking in a pressure cooker: Carrots 90 kg Water 8 kg Sugar 1.4 kg Salt 500 g Sodium Hypophosphite 100 g The product is canned, heated to 2400F (115.50C) in an autoclave and maintained at that temperature for 5 minutes. TABLE I BABY FOODS Carixr 3 4 Protein1 Fat2 hydrate C/P & 4 Cereals, precooked, dry other cereal products: Barley, added nutrients 13.4 1.2 73.6 5.0 High protein, added nutrients 35.2 3.7 48.1 1.2 Mixed, added nutrients 15.2 2.9 70.6 3.9 Oatmeal, added nutrients 16.5 5.5 66.0 3.0 Rice, added nutrients 6.6 1.6 80.0 9.8 Teething biscuit 11.1 2.3 78.0 5.8 Desserts, canned: Custard pudding, all flavors 2.3 1.8 18.6 4.5 Fruit pudding with starch base, milk and/or egg (banana, orange, or pine apple) 1.2 .9 21.6 10.3 Dinners, canned - cereal, vegetable, meat mixture (approx. 28-48 protein): : Beef noodle dinner 2.8 1.1 6.8 1.7 Chicken Noodle Dinner 2.1 1.3 7.2 2.1 Macaroni, tanatoes, meat and cereal 2.6 2.0 9.6 2.1 Split peas, vegetables, and ham or bacon 4.0 2.1 11.2 1.8 Vegetables and bacon, with cereal 1.7 2.9 8.7 1.9 Vegetables and beef, with cereal 2.7 1.6 7.6 1.8 Vegetables and chicken, with cereal 2.1 1.4 7.7 2.2 STABLE I (Con't) Carbcr Fat2 Carbo- 3 4 proteins Fat hydrate C/P & 4 Vegetables and ham, with cereal 2.8 2.2 8.3 1.7 Vegetables and lamb, with cereal 2.2 2.0 7.7 1.8 Vegetables and liver, with cereal 3.1 .4 7.8 2.2 Vegetables and liver, with bacon and cereal 2.4 1.9 7.5 1.7 Vegetables and turkey, with cereal 2.1 .8 7.2 2.5 Fruits and Fruit products with or without thickening, canned: : Applesauce .2 .2 18.6 46.5 Applesauce and apricots .3 .1 22.6 56.5 Bananas (with tapioca or cornstarch, added ascorbic acid), strained .3 .2 21.6 36.0 Bananas and pineapple (with tapioca or cornstarch) .4 .1 20.7 41.4 Fruit dessert with tapioca (apricot, pineapple, ant/or orange) .3 .3 21.5 35.8 Peaches .6 .2 20.7 25.9 Pears .3 .1 17.1 42.7 Pears and pineapple .4 .2 17.6 29.3 Plums with tapioca, strained .4 .2 24.3 40.5 Prunes with tapioca .3 .2 22.4 44.8 Vegetables, canned: Beans, green 1.4 .1 5.1 3.1 Beets, strained 1.4 .1 8.3 5.5 Carrots .7 .1 6.8 8.5 Mixed vegetables including TABLE I (Con't) Carbo- Protein Fat2 hydrate3 C/ P & 4 C/P & 4 vegetable soup 1.6 .3 8.5 4.5 Peas, strained 4.2 .2 9.3 2.1 Vegetables, canned: : Spinach, creamed 2.3 .7 7.5 2.5 Squash .7 .1 6.2 7.7 Sweet potatoes 1.0 .2 15.5 51.7 Tomato soup, strained 1.9 .1 13.5 6.7 1 The weight of protein (grams) in a 100 gran sample. 2 The weight of fat (grams) in a 100 gran sample. 3 The weight of carbohydrate (grams) in a 100 gram sample. 4 The weight of carbohydrate in a 100 gram sample divided by the weight of protein plus the weight of fat in that sample.

Claims: Claims: 1. A food product that is resistant to the outgrowth of Clostridia and/or coliform bacteria, and the formation of enterotoxins, selected from corned beef, smoked poultry, cheese and carbohydrate food product characterized by said food product containing an effective amount of a compound selected from hypophosphorous acid and its nontoxic water-soluble salts and optionally containing up to 52 ppm of sodium nitrite. 2. A food product of claim 1 resistant to the outgrowth of Clostridium botulinum and the formation of enterotoxins characterized in that it contains 300 ppm to 3000 ppm of a compound selected from hypophosphorous acid and its nontoxic water-soluble salts. 3. The food product of claim 1 or 2 characterized in that the product is corned beef or smoked poultry and contains 1000 ppm to 3000 ppm of a compound selected from hypophosphorous acid and its nontoxic water-soluble salts and from zero to 52 ppm of sodium nitrite. 4. The corned beef of claim 3 wherein said compound is selected from hypophosphorous acid and sodium hypophosphite. 5. The carbohydrate food product of claim 1 or 2 characterized by containing from 500 ppm to 3000 ppm of a compound selected from hypophosphorous acid and its nontoxic water-soluble salts. 6. The food product of claim 5 characterized by containing hypophosphorous acid or sodium hypophosphite. 7. The food product of claim 5 or 6 characterized by containing at least 1000 ppm of sodium hypophosphite and at least 40 ppm of sodium nitrite. 8. A cheese food product of claims 1 or 2 characterized by containing 300 ppm to 3000 ppm of a compound selected from hypophosphorous acid and its non-toxic water-soluble salts. 9. The cheese product of claim 8 characterized in that the cheese product is a natural cheese. 10. The natural or process cheese of claim 9 wherein the amount of said compound is from about 500 parts per million to about 2,000 parts per million. 11. The natural or process cheese of claim 9 or 10 characterized in that the compound is selected from hypophosphorous acid, sodium hypophosphite monohydrate, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite and manganese hypophosphite. 12. A method of inhibiting the production of enterotoxin from Clostridium botulinum in corned beef, cheese, smoked poultry and carbohydrate food product characterized by adding thereto an effective amount of a compound selected from hypophosphorous acid and its nontoxic water-soluble salts and optionally containing up to 52 ppm of sodium nitrite. 13. The method of claim 12 characterized by adding thereto from 300 ppm to 3000 ppm of the selected compound. 14. The method of claim 12 or 13 characterized in that 1000 to 3000 ppm of hypophosphorus acid or its nontoxic water-soluble salts and 40 to 52 ppm of sodium nitrite is also added to the corned beef or smoked poultry. 15. The carbohydrate food product of claims 1, 2 or 3 characterized in that the food product is honey or corn syrup containing 500 ppm to 3000 ppm of a compound selected from the group consisting of hypophosphorous acid and its nontoxic water-soluble salts. 16. The product of claim 5 characterized by containing from 500 ppm to 3000 ppm of sodium hypophosphite and optionally containing up to 52 ppm of sodium nitrite. 17. A method of inhibiting the production of enterotoxin from Clostridium botulinum in natural or processed cheese characterized by the step of adding thereto an effective amount of a compound selected from the group consisting of hypophosphorous acid and its non-toxic water-soluble salts. 18. The method of claim 17 wherein the amount of said compound is from about 300 parts per million to about 3,000 parts per million. 19. The method of claim 18 characterized in that the compound is selected from hypophosphorous acid. 20. The product of any of claims 1, 2, 3, 5, or 8 characterized in that the compound is selected from hypophosphorus acid, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite and manganese hypophosphite.

Inventors: JADLOCKI, JOSEPH FRANCIS, JR., THOMPSON, JOHN SEYMOUR
Applicants: FMC CORPORATION
Application year: 1982
Main classification: A23B4
IPC codes: A23C19, A23B4, A23L3