USES AND APPLICATIONS OF FOOD GRADE PHOSPHATES
II. USES AND APPLICATIONS OF FOOD GRADE PHOSPHATES
Food grade phosphates are widely used in many foods for a variety of reasons. The phos- phates may be used to adjust pH (either acid or alkaline); buffer; sequester minerals; supplement minerals; either aid or inhibit coagulation; modify protein; disperse ingredi- ents, and inhibit caking. Table 5 shows the functions of a variety of the food grade phos- phates. The direct benefits would be to provide antioxidant activity; to thicken or gel dairy products; for emulsification (meats and cheeses); for color protection or cure color development; for water binding, and for chemical leavening. Foods in which phosphates are used include meats, poultry, seafood, dairy products, bakery products, fruits, vegeta- bles, sugars, oils (refining), confections, beverages, pet foods, and personal care products. Applications of the phosphates by food product are shown in Table 6 and by food phos- phate ( Table 7 ).
Food phosphates must be manufactured according to good manufacturing practices (GMP) (21 CFR §110) and either meet or exceed those standards identified in Food Chemi- cals Codex IV (FCC IV), when used in the United States, Canada, and most European countries. Globally, there are nine major manufacturers (in aggregate supplying ⬎75% of the products in commerce) of food grade phosphates, which include Albright & Wilson, Budenheim, FMC Corporation, Haifa Chemicals, Kemira, Prayon, Rhodia, BK Giulini Rotem, and Solutia. In 2000, Rhodia acquired Albright & Wilson, and FMC and Solutia formed the joint venture Astaris. It is important to use only those phosphates produced in accordance with FCC IV to assure safety (low arsenic and heavy metals). High purity products are also critical to avoid equipment failure in manufacturing operations and to prevent sensory defects. Other reasons for using food grade phosphates are shown in Table 8 . In 2000, Rhodia acquired Albright & Wilson, and FMC and Solutia formed the joint venture Astaris.
The most commonly used food phosphates are generally recognized as safe (GRAS) by the U.S. Food and Drug Administration (FDA) under Title 21 of the Code of Federal Regulations, Parts 182 and 184. Uses of the food grade phosphates are also covered in 9 CFR for meats; 21 CFR for foods, boiler water additives, adhesives, and indirect contact, and 27 CFR for alcoholic beverages.
Canadian regulations currently differ from U.S. regulations. In 1996, a proposal was introduced to streamline the format of Canadian regulations with the intention to harmo- nize with U.S. standards. The proposed changes divided food ingredients into categories which required either minimal or rigorous oversight. Table 9 summarizes the differences and similarities between the two NAFTA countries.
Phosphates are almost always certified as kosher and there is an increasing desire (a
Table 5 Functions of Phosphates as Food Ingredients Function
Ingredient
Acidulant
Monoammonium phosphate
Phosphoric acid
Monocalcium phosphate
Sodium acid pyrophosphate
Monopotassium phosphate
Sodium aluminum acid phosphate
Calcium acid pyrophosphate Adsorbent
Monosodium phosphate
Tricalcium phosphate
Alkalinity
Disodium phosphate
Sodium tripolyphosphate
Dipotassium phosphate
Tetrasodium pyrophosphate
Trisodium phosphate Anticoagulant
Potassium tripolyphosphate
Sodium hexametaphosphate
Buffering agent
Diammonium phosphate
Monopotassium phosphate
Disodium phosphate
Monosodium phosphate
Monoammonium phosphate
Trisodium phosphate
Monocalcium phosphate
Coagulant
Phosphoric acid
Tetrasodium pyrophosphate
Sodium acid pyrophosphate
Dispersing agent
Disodium phosphate
Sodium acid pyrophosphate
Sodium hexametaphosphate
Tetrasodium pyrophosphate
Sodium tripolyphosphate
Emulsifiers
Disodium phosphate
Tetrasodium phosphate
Sodium hexametaphosphate Flow conditioner
Trisodium phosphate
Tricalcium phosphate
Leavening agent
Calcium acid pyrophosphate
Monocalcium phosphate
Dicalcium phosphate
Sodium acid pyrophosphate
Sodium aluminum phosphate Mineral supplement
Dimagnesium phosphate
Dicalcium phosphate
Monopotassium phosphate
Dimagnesium phosphate
Monosodium phosphate
Dipotassium phosphate
Tricalcium phosphate
Disodium phosphate
Nutrient
Diammonium phosphate
Phosphoric acid
Monoammonium phosphate
Tripotassium phosphate
Monopotassium phosphate
Protein modifier
Disodium phosphate
Sodium tripolyphosphate
Monocalcium phosphate
Tetrasodium pyrophosphate
Potassium tripolyphosphate
Trisodium phosphate
Sodium acid pyrophosphate
Sequestrant
Sodium hexametaphosphate
Sodium tripolyphosphate
Sodium acid pyrophosphate
Tetrasodium pyrophosphate
A. Bakery Applications
In North America, the largest demand for the food grade phosphates is by the cereal and baking industries. These uses notably include the leavening of bakery products; pH adjustment and buffering; dough conditioning; enrichment; growth factors for yeasts; starch modification; and the manufacture of quick cooking cereals.
Chemical leavening to be discussed here is based upon the neutralization of common baking soda (typically sodium bicarbonate, but may be potassium or ammonium bicarbon-
Table 6 Food Product Ingredients Product
Ingredients Baked goods
Cakes, mixes MCP, SALP, SAPP, DCP, MAP, DAP, SALP, DMP Doughnuts
SAPP
Refrigerated dough
SAPP, SALP
Baking powder
MCP, SAPP, SALP
Beverages Noncarbonated
SHMP, STPP, MSP
Cola
H 3 PO 4
Root beer
H 3 PO 4
Milk-based H 3 PO 4 , DSP, TCP, MCP, TSPP, SHMP Dry mix
MSP, TCP, MCP
Candy and confections Chocolates
TSPP, TSP, SHMP
Icings and frostings
SAPP, TSPP, SHMP
Marshmallows
TSPP, SHMP
Cereals Dry cereal
DSP, TSP
Quick cooked
DSP
Cheese Cottage cheese
H 3 PO 4 , MCP
Imitation cheese
TSP, SHMP, STPP
Process cheese DSP, TSP, SHMP, TSPP, STPP, SALP Starter media
DSP, DKP
Chip dips
STPP, SHMP, DSP
Coffee Flavored, instant
DKP
Dairy Products Nondairy creamers
DKP, SHMP, TSPP
Frozen desserts DSP, MCP, TSPP, SHMP Sour cream
SHMP, STPP
Whipped toppings
TSPP, DSP, DKP
Eggs Whole
SHMP, MSP, MKP
Egg whites (dried)
SHMP, MSP, MKP
Fruit Canned fruits
MCP
Canned tomatoes
MCP
Juices
MCP, H 3 PO 4
Gelatin desserts
DSP, MSP
Gums Alginate, agar
DKP, TSPP
Carrageenan, other gums
DSP, SHMP, STPP
Ice cream Hard, soft, and imitation
DSP, TSPP, SHMP
Jams and jellies
H 3 PO 4
Lactose from whey
SHMP
Table 6 Continued Product
Ingredients Meat products
Ham, corned beef
STPP, phosphate blends
Bacon
STPP, phosphate blends
Sausage, franks, bologna
STPP, phosphate blends
Roast beef
STPP, phosphate blends
Blood processing
SHMP
Milk products Beverages
DSP, TSPP
Buttermilk
TSPP, H 3 PO 4
Cream
DSP, TSPP, SHMP
Evaporated and condensed
DSP
Nutrition products Commercial liquid diets
DCP, TCP, DKP, DSP
Enteral feedings
DCP, TCP, DKP, DSP
Infant foods MCP, DCP, TCP, DKP, DSP Isotonic beverages
DKP, MKP, DKP
‘‘Instant’’ breakfast preparations
DCP, TCP
Nutritional supplements DCP, TCP, MCP, DSP, DKP, DMP Vitamins
DCP, TCP, MCP, DSP, DKP Oils
STPP, SHMP
Pet foods STPP, MCP, H 3 PO 4 , DCP Processed potatoes
SAPP
Poultry
STPP, phosphate blends
Puddings
MCP, DSP, TSPP
Seafood Canned crab meat
SAPP
Fish and seafood
STPP, phosphate blends
Surimi Combination of TSPP, SAPP, STPP, and SHMP Canned tuna
Vegetables Potatoes
SAPP
Peas and beans
of carbon dioxide (CO 2 ), air, and steam. During the wet-mixing of doughs and batters, bubble formation is achieved by entrapment of air and/or CO 2 evolved from the neutraliza- tion by sodium bicarbonate of the leavening acid and/or other acidic components by fruit, flour, or fat. During bench time, additional CO 2 may evolve thus further expanding the dough or batter. Upon heating, final volume develops as a result of the CO 2 from any remaining active leavening agent; release of CO 2 dissolved in the aqueous portion; the generation of steam; and the thermal expansion of the gases.
Table 7 Applications of Phosphates as Food Ingredients by Product A&W product
Applications
Acids Phosphoric Acid
Beer
Fat and oils
Pet foods
Cola beverages
Fillings
Sugar
Yeast Orthophosphates Monoammonium phosphate
Cottage cheese
Jams and jellies
Yeast Diammonium phosphate
Breads and doughs
Cheese starter cultures
Breads and doughs
Cookies
Yeast
Cheese starter cultures
Crackers
Monosodium phosphate
Cola beverages
Egg yolks
Instant pudding
Dry powder beverages
Gelatin desserts
Isotonic beverages
Starch Disodium phosphate
Egg whites
Instant cheesecake
Breakfast cereal
Half-and-half
Nonfat dry milk
Cheese powders
Ice cream
Pasta
Chip dips
Imitation cheese
Pet food
Condensed milk
Infant food
Process cheese
Cream
Instant cheesecake
Starch
Evaporated milk
Instant pudding
Vitamin capsules
Flavored milk powders
Isotonic drinks
Whipped topping
Gelatin desserts
Trisodium phosphate
Cereals
Imitation cheese
Process cheese
Cheese powders
Isotonic beverages
Monopotassium phosphate
Breads and doughs
Isotonic beverages
Starter cultures
Dry powder beverages
Mineral supplement
Yeast
Eggs
Dipotassium phosphate
Dairy creamers
Isotonic beverages
Starter cultures
Dry powder beverages
Mineral supplement
Table 7 Continued A&W product
Applications
Monocalcium phosphate
Bakery mixes
Flour
Pet food
Baking powder
Fruit juices
Pudding
Canned fruits
Infant food
Yogurt
Dough conditioner
Microbial inhibitor
Dry powder beverages
Milk-based beverages
Dicalcium phosphate
Bakery mixes
Food bars
Multivitamin tablets
Cereals
Infant food
Pet food
Dry powder beverages
Milk-based beverages
Yogurt
Flour
Mineral supplementation
Tricalcium phosphate
Cereal
Milk-based beverages
Salt
Dry powders
Mineral supplementation
Spice blends
Grated and powder cheese
Multivitamins
Sugar
Infant food
Pet food
Sodium Aluminum Phosphate,
Self-rising flour Acidic
Bakery mixes
Baking powder
Pancake mixes
Waffle mixes
Sodium Aluminum Phosphate,
Process Cheese
Basic Dimagnesium Phosphate
Pancakes Pyrophosphates Sodium acid pyrophosphate
Cakes, biscuits
Muffins
Bakery mixes
Imitation cheese
Refrigerated doughs
Baking powder
Potatoes
Seafood
Canned seafood
Poultry
Vegetables
Cured meats
Process cheese
Icing and frostings
Processed meat
Tetrasodium pyrophosphate
Buttermilk
Instant pudding
Seafood
Cured meat
Marshmallows
Starch
Flavored mild powders
Pet food
Whipped topping
Ice cream
Poultry
Instant cheesecake
Processed meat
Tetrapotassium pyrophosphate
Cured meat
Pet food
Seafood
Flavored milk powders
Poultry
Starch
Instant cheesecake
Processed meat
Whipped topping
Instant pudding
Calcium acid pyrophosphate
Baking powder
Crackers
Whole grain breads
Dough conditioner
Frozen doughs
Polyphosphates Sodium tripolyphosphate
Egg whites
Process cheese
Whipped toppings
Meat
Sour cream
Yogurt
Noncarbonated beverages
Table syrup
Pet food
Vegetable protein
Sodium hexametaphosphate
Carrageenans and other gums
Half-and-half
Process cheese
Chip dip
Ice cream
Seafood
Cream
Jams and Jellies
Table syrup
Dairy beverage
Marshmallows
Vegetables (canned)
Noncarbonated soft drink
Whipped toppings
Poultry
Table 8 Guide to the Use of Food Grade Phosphates Factor
Lesser grades Export
Food grade
Food ingredients meeting FCC IV are mandated for prod-
Grades not meeting FCC IV standards are not permitted by
ucts exported to the United States, Canada, and Europe.
many importing countries.
Safety
Restrictions on heavy metals, toxins, and microbial patho-
May not be a safe substance for human consumption.
gens for responsible use and limits liability.
Purity
Inhibit equipment failures such as clogged injector needles
May cause clogged injector needles.
due to formation of mineral phosphate precipitates. Mineral impurities may cause the formation of crystalline
Sensory defects which have caused customs to impound im-
precipitates at product (e.g., scallop) surface.
ported product.
Mineral contaminants may catalyze oxidative reactions (ran-
Rancidity of fatty acids, greening of meat color, and devel-
cidity of lipids and loss of flavor and color).
opment of objectionable flavor.
Assayed for minimum and consistent levels of desired phos-
Assurance of product quality for consistent performance.
phate species. Nitrite/nitrate impurities may cause undesirable cured pig-
Pink color may be a defect and is illegal in most seafood
ment development.
species.
Appearance and color
Phosphate should be a white powder/granular substance
Gray, brown, or black specks or tones may carry over into
free of visible contaminants and discoloration.
the finished product.
Solubility
Should be rapid and complete for most sodium and all po-
Slow and incomplete dissolution is not time and process ef-
tassium phosphates.
ficient.
Good manufacturing practices
Standards tend to be more for worker protection rather and self-audits
Required for food grades.
than product safety.
Uniformity of methods for
Described in FCC IV
Few, if any, exist.
product evaluation
Table 9 Deviation of Proposed Canadian Regulations from Existing Canadian and U.S. Regulation
Proposed
Existing Canadian
Canadian
Product
Exceptions (U.S.) H 3 PO 4
Food group
regulations
use level
United States use level
Chocolate, cocoa, cottage,
GMP X GMP
cheese, cream cottage cheese, gelatin, light milk chocolate, mono- and diglyc- erides, sweet chocolate
Cream and processed cheeses,
GMP X 0.5%-cream cheese;
cold-pack cheese food, whey
GMP, pasteurized
cheese
Neufchatel cheese
Fish protein
GMP X GMP
Unstandardized foods
GMP X GMP
Mono- and diglycerides
0.02% XII
GMP
Ale, beer, light beer, malt li-
quor, porter, stout a Mayonnaise, French dressing,
GMP XII
GMP
salad dressing a Ice cream mix
GMP X,XII
a Sherbet
0.75% XII
As in dry ingredients
a Ice milk mix
GMP X,XII
a Cream
GMP X
a Grape juice
GMP X Not permitted
a Jams
GMP X GMP
a Marmalade
GMP X GMP
a Jelly
GMP X GMP
a Liquid, dried, or frozen whole
GMP X Pasteurization aid
egg a Liquid, dried, or frozen yolk
GMP X do
a Liquid, dried, or frozen egg
GMP X do
white
Table 9 Continued
Proposed
Existing Canadian
Canadian
Product
Exceptions (U.S.) DAP Bread
Food group
regulations
use level
United States use level
2,500 ppm of
Ale, bacterial cultures, baking
GMP X,XIV
Deleted
GMP
powder, beer, malt liquor, porter, stout
Unstandardized bakery foods
GMP X GMP
Cottage cheese
GMP X
a Ice cream mix
GMP X
a Ice milk mix
GMP X
a Cream
GMP X
a Grape juice
GMP X
a Jams
GMP X
a Marmalade
GMP X
a Jelly
GMP X
a Liquid, dried, or frozen whole
GMP X
eggs a Liquid, dried, or frozen egg
GMP X
yolks a Liquid, dried, or frozen egg
GMP X
white
MAP Bread
2500 ppm of
Ale, bacterial cultures, baking,
GMP X Deleted
GMP
powder, beer, malt liquor, porter, stout
Unstandardized bakery foods
GMP X,XIV
GMP
Uncultured buttermilk
0.1% X GMP
Cider, honey wine, wine
GMP XIV
GMP
a Cottage cheese
GMP X
a Ice cream mix
GMP X
a Ice milk mix
GMP X
a Cream
GMP X
a Grape juice
GMP X
a Jams
GMP X
a Marmalade
GMP X
a Jelly
GMP X
a Liquid, dried, or frozen whole
GMP X
eggs a Liquid, dried, or frozen egg
GMP X
yolks a Liquid, dried, or frozen egg
GMP X
white DCP
Cream cheese and processed
3.5% IV 3.5%
cheese products Bread/baked goods
2,500 ppm
GMP
Desserts, toppings, and fillings
GMP
Gravy and sauces
GMP
Dry mixes
GMP
Chewing gum
GMP
Dried whey products
GMP
Fruit fillings and toppings
GMP
Canned berries, NTE 0.035% as Ca 2⫹
Table 9 Continued
Proposed
Existing Canadian
Canadian
Product
Exceptions (U.S.) Seasonings
Food group
regulations
use level
United States use level
GMP
Unstandardized foods
GMP IV,V,X
GMP
Flour
900 ppm VIII
Flour—U.S. use level:
flour bleaching, see 21 CFR 137.105; self-rising enriched flour, see 21 CFR 137.185
Bread
2,500 ppm of
600 mg Ca 2⫹ /lb fin-
flour
ished product
Unstandardized bakery foods
GMP
GMP
a Cottage cheese
GMP X
a Ice cream mix
GMP X
a Ice milk mix
GMP X,IV at 0.5%
a Cream
GMP IV,X
a Grape juice
GMP X
a Jams
GMP X
a Marmalade
GMP X
a Jelly
GMP X
a Liquid, dried, or frozen whole
GMP X
eggs a Liquid, dried, or frozen egg
GMP X
yolks a Liquid, dried, or frozen egg
GMP X
white a Cocoa products
GMP IV at 0.5%
a Sherbet
GMP IV
a Canned vegetables
GMP VI 21 CFR 155.170;
Firming agent
a Mincemeat
GMP IV
MCP Processed fruit and vegetables
GMP
Canned berries, 0.035% as Ca 2⫹
Fruit butter, GMP
Fruit jelly, GMP
Fruit preserves and jams, GMP
Canned peas, 350 ppm
Canned dry peas, Do. Canned tomatoes
Canned tomatoes 0.046 to 0.08% Ca 2⫹ of food Frozen dairy desserts
0.026% as Ca 2⫹
Ice cream Desserts, toppings, and fillings
GMP XII
GMP
not allowed
See 21 CFR §163 Beverages
GMP
Juices—not permitted Breakfast cereals
(Range 5 to 40%) Sauces
Baking powder
GMP X 1.0%
Dairy-based flavoring prepara-
GMP
tions Soups, snack foods
GMP
Unstandardized foods
GMP V,X
GMP
Canned apples
0.026% as Ca 2⫹
Canned vegetables, frozen
Firming agent apples
0.026% as Ca 2⫹
21 CFR 155.170;
Ale, beer, malt liquor, porter,
GMP X Deleted
stout Unstandardized dairy products
7500 ppm of
600 mg CA ⫹⫹ finished
flour XII
product enrichment
Flour
7500 ppm XII
960 mg Ca 2⫹ /lb; en-
richment, 0.25 to 0.75% by wt, phos- phated
Table 9 Continued
Proposed
Existing Canadian
Canadian
Product
Exceptions (U.S.) Unstandardized bakery foods
Food group
regulations
use level
United States use level
GMP
GMP
a Cottage cheese
GMP X
a Cream
GMP X
a Grape juice
GMP X
a Jams
GMP X
a Marmalade
GMP X
a Jelly
GMP X
a Liquid, dried or frozen whole
GMP X
eggs a Liquid, dried, or frozen egg
GMP X
yolks a Liquid, dried, or frozen egg
GMP X
white a Mayonnaise, French dressing,
GMP XII
salad dressing a Sherbet
GMP XII
a Canned vegetables
GMP VI
TCP Processed cheese products
not permitted
Ice cream Baked goods
Frozen dairy desserts
GMP XII
GMP
not permitted
GMP
Fruit fillings and toppings
Only canned berries Breakfast cereals
Condensed soups, dry soup
GMP
mixes Batter and breading
Juices not permitted Desserts, toppings, and fillings
Beverages
GMP
GMP
Dressings
GMP
Salt, seasoned salt to 2.0% I 2.0% GMP Prepared starch-based foods
0.2% GMP Dry cure
GMP I 0.5% in finished product Unstandardized dry mixes
GMP I 0.5% in finished product Oil soluble annatto
GMP I GMP Icing sugar
to 1.5% I GMP Unstandardized foods
GMP Flour
GMP IV,X
21 CFR 137.105 bleaching Liquid whey for drying (not in-
900 ppm VIII
GMP fant formula)
0.04% dried
whey prod- uct VIII
Unstandardized bakery foods
GMP Cocoa products
GMP
GMP IV
a Mince meat
GMP IV
a Sherbet
GMP IV,XII
a Mayonnaise, French dressing,
GMP XII
salad dressing a Cottage cheese
GMP X
a Ice cream mix
GMP X,XII
a Ice milk mix
GMP X,XII ; GMP IV
at 0.5%
a Cream
GMP IV,X
a Grape juice
GMP X
a Jams
GMP X
a Marmalade
GMP X
a Jelly
GMP X
a Liquid, dried, or frozen whole
GMP I,X
eggs a Liquid, dried, or frozen egg
GMP I,X
yolks a Liquid, dried, or frozen egg
GMP X
white aa
Table 9 Continued
Proposed
Existing Canadian
Canadian
Exceptions (U.S.) DKP
Product
Food group
regulations
use level
United States use level
DSP ⻫
⻫ Baked goods
GMP
⻫ Processed cheese and cream
3.5% IV 3.5%
cheese products ⻫
Processed cheese and cream
3.5% IV 3.5%
Not permitted
cheese products ⻫
⻫ Cottage cheese products
DSP, 0.5% IV 0.5%
Not permitted
⻫ ⻫ Evaporated milk products
DSP, GMP
GMP
⻫ ⻫ Sour cream
DSP, 0.05% IV 0.05%
GMP
⻫ ⻫ Cured meat and poultry prod-
DSP, 0.5% as
0.3% PO 4 0.5% by wt
ucts
DSP XII
⻫ ⻫ Solid cut meat and poultry and
DSP, 0.5% as
Fruit juices—not permitted ⻫
⻫ ⻫ Other beverages
GMP
⻫ Breakfast spreads
⻫ ⻫ Cocoa mixes
GMP
⻫ Desserts, toppings, and fillings
GMP
⻫ ⻫ Breakfast cereals, rice products
⻫ ⻫ Icings and table syrups
GMP
⻫ ⻫ Batter and breading
⻫ ⻫ Snack foods
GMP
⻫ ⻫ Vegetable oil creaming agents
GMP
and their emulsions
⻫ ⻫ Prepared starch based foods
GMP
⻫ ⻫ Frozen entrees
GMP
⻫ Milk and fluid milk products
Emulsifiers/stabilizers ⻫
GMP IV GMP
Mustard, pickles, relishes
GMP IV
⻫ Evaporated and concentrated
Emulsifiers/stabilizers milk ⻫
0.1% IV GMP
Frozen fish, glazed
GMP VIII
GMP
⻫ Frozen mushrooms
GMP VIII
GMP
⻫ Ale, bacterial cultures, beer,
GMP X deleted
GMP
cream, light beer, malt li- quor, porter, stout
⻫ Unstandardized foods
GMP X,XIII
GMP
Ice cream mix, ice milk mix,
Sherbet sherbet
GMP XII
0.2%, ice cream as,
contained in added ingredients
⻫ Ale, beer, cider, honey wine,
light beer, malt liquor, por- ter, stout, wine
⻫ ⻫ Cocoa products
⻫ ⻫ Mayonnaise, French dressing,
GMP XII
salad dressing ⻫
⻫ ⻫ Cottage cheese
GMP X
⻫ ⻫ Ice cream mix
GMP X,XII
⻫ ⻫ Ice milk mix
GMP X,XII ; GMP IV
at 0.5%
⻫ ⻫ Cream
GMP IV,X
⻫ ⻫ Grape juice
GMP X
⻫ ⻫ Jams
GMP X
⻫ ⻫ Marmalade
GMP X
Table 9 Continued
Proposed
Existing Canadian
Canadian
Exceptions (U.S.) ⻫
Product
Food group
regulations
use level
United States use level
⻫ Jelly
GMP X
⻫ ⻫ Liquid, dried or frozen whole
GMP X
eggs ⻫
⻫ Liquid, dried, or frozen egg
GMP X
yolks ⻫
⻫ Liquid, dried, or frozen egg
GMP X
white MKP
MSP ⻫
Ice cream ⻫
⻫ Frozen dairy desserts
GMP
Not permitted
⻫ Cured meat and poultry prod-
MSP, 0.5% as
0.3% PO 4 0.5% by wt
ucts
DSP XII
⻫ ⻫ Solid cut meat and poultry and
0.5% as DSP XII
Processed cheese and cream
3.5% IV 3.5%
cheese products ⻫
Processed cheese and cream
Not permitted
Not permitted
cheese products ⻫
Desserts, toppings, and fillings
GMP
Vanilla—not permitted ⻫
Unstandardized foods
GMP X,XII
⻫ ⻫ Ice cream mix, ice milk mix,
GMP XII
sherbet ⻫
⻫ Ale, beer, cider, honey wine,
GMP XIV
deleted
light beer, malt liquor, por- ter, stout, wine
⻫ ⻫ Seasonings
GMP
⻫ ⻫ Sauces
GMP
⻫ ⻫ Baked goods
Fruit juices—not permitted ⻫
GMP
⻫ Batter and breading
GMP
⻫ ⻫ Frozen entrees, starch-based
⻫ Snack foods
GMP
⻫ Unstandardized foods
GMP IV,X,XII
GMP
⻫ Ale, beer, light beer, malt li-
GMP X
quor, porter, stout ⻫
Solid cut, prepared and byprod-
0.5% as DSP XII
ucts of meat and poultry ⻫ a ⻫ a Mayonnaise, French dressing,
GMP XII
salad dressing ⻫ a a Ice cream mix
GMP XII
⻫ a a Sherbet
GMP XII at 0.5%
⻫ a a Ice milk mix
GMP XII
a ⻫ a Cocoa products
GMP IV
a ⻫ a Mincemeat
GMP IV
a ⻫ a Sherbet
GMP IV ; GMP XII
at 0.5%
a ⻫ a Cottage cheese
GMP X
a ⻫ a Ice cream mix
GMP X,XII
a ⻫ a Ice milk mix
GMP X,XII ; GMP IV
at 0.5%
a ⻫ a Cream
GMP IV,X
a ⻫ a Grape juice
GMP X
a ⻫ a Jams
GMP X
a ⻫ a Marmalade
GMP X
a ⻫ a Jelly
GMP X
a ⻫ a Liquid, dried, or frozen whole
Frozen only eggs a ⻫ a Liquid, dried, or frozen egg
GMP X MSP, MKP; 0.5%
Pasteurization aids yolks a ⻫ a Liquid, dried, or frozen egg
GMP X GMP
Whipping/pasteurization aids white
GMP X GMP
Table 9 Continued
Proposed
Existing Canadian
Canadian
Exceptions (U.S.) TKP
Product
Food group
regulations
use level
United States use level
TSP ⻫
Cream cheese and processed
TSP, 3.5% IV 3.5%
cheese products ⻫
Cream cheese and processed
Not permitted
cheese products ⻫
Fruit juices—not permitted ⻫
⻫ Fruit snacks
⻫ ⻫ Baked goods
Vanilla—not permitted ⻫
⻫ ⻫ Dry cure
GMP I
⻫ ⻫ Unstandardized dry mixes
GMP I GMP
⻫ ⻫ Oil soluble annatto
GMP I
⻫ ⻫ Icing sugar
To 1.5% I
⻫ ⻫ Unstandardized foods
GMP IV,X
⻫ ⻫ Liquid whey for drying (not in-
0.04% dried
fant formula)
whey prod- uct VIII
⻫ ⻫ Ice cream mix, ice milk mix
GMP XII
⻫ ⻫ Unstandardized bakery foods
GMP
⻫ Ale, beer, light beer, malt li-
GMP X deleted
quor, porter, stout ⻫
Unstandardized foods
GMP IV,X
GMP GMP
GMP IV
a ⻫ a Mincemeat
GMP IV
a ⻫ a Sherbet
GMP IV
a ⻫ a Cottage cheese
GMP X
a ⻫ a Ice cream mix
GMP X
a ⻫ a Ice milk mix
GMP X ; GMP IV at
a ⻫ a Cream
GMP IV,X
a ⻫ a Grape juice
GMP X
a ⻫ a Jams
GMP X
a ⻫ a Marmalade
GMP X
a ⻫ a Jelly
GMP X
a ⻫ a Liquid, dried, or frozen whole
GMP X
eggs a ⻫ a Liquid, dried, or frozen egg
GMP X
yolks a ⻫ a Liquid, dried, or frozen egg
GMP X
white KPMP SHMP
⻫ ⻫ Frozen dairy desserts (not sher-
0.2% SHMP Ice cream bet) ⻫
SHMP, 0.5% XII,IV
GMP
No direct addition ⻫
⻫ Sherbet
SHMP, 0.75% IV 0.75%
⻫ Infant formula
SHMP, 0.05% IV 0.05%
GMP
⻫ Cream cheese and processed
SHMP, 3.5% IV 3.5%
cheese products ⻫
Cream cheese and processed
KHMP, 3.5% IV 3.5%
cheese products ⻫
Mustard, pickles, relishes GMP IV GMP, SHMP ⻫
GMP, SHMP ⻫
Unstandardized foods
GMP IV,X,XII
Prepared fish and meat blends
0.1% SHMP IV 0.5%
⻫ Cream cheese and processed
Not permitted cheese products
Table 9 Continued
Proposed
Existing Canadian
Canadian
Exceptions (U.S.) ⻫
Product
Food group
regulations
use level
United States use level
Surimi-based products and
Not canned seafood canned seafood
canned sea- food IV,XII
⻫ Beef blood
SHMP 0.2% VIII
GMP, SHMP
⻫ Frozen fish, crustaceans and
SHMP, 0.5% as
0.5% by wt SHMP
molluscs
DSP VIII
⻫ Cured meat and poultry prod-
SHMP XII , 0.5% as
⻫ Solid cut meat and poultry and
their byproducts ⻫
Gelatin for marshmallows
SHMP, 2.0% VIII
GMP, SHMP
⻫ Fruit spreads
Varies, SHMP
⻫ Baked goods
GMP, SHMP
⻫ Beverages
Not vanilla ⻫
GMP, SHMP
Not vanilla ⻫
Flavors
GMP, SHMP
Breakfast cereals
GMP, SHMP
⻫ Fruit fillings and toppings
Canned—not permitted ⻫
GMP,SHMP
Snack foods
GMP, SHMP
⻫ Table syrups
500 ppm
GMP, SHMP
⻫ Sweetened glazes
GMP, SHMP
⻫ Sauces
GMP, SHMP
a ⻫ a Cocoa products
GMP IV
a ⻫ a Mincemeat
GMP IV
a ⻫ a Sherbet
GMP IV,XII
a ⻫ a Mayonnaise, French dressing,
GMP XII
GMP
salad dressing a ⻫ a Cottage cheese
GMP X
a ⻫ a Ice cream mix
GMP X,XII GMP X,XII
GMP X , GMP IV 0.5%
a ⻫ a Cream
GMP IV,X
GMP
a ⻫ a Grape juice
GMP X
a ⻫ a Jams
GMP X
a ⻫ a Marmalade
GMP X
a ⻫ a Jelly
GMP X
a ⻫ a Liquid, dried, or frozen whole
GMP X MSP, MKP; 0.5%
Frozen only
eggs a ⻫ a Liquid, dried, or frozen egg
Pasteurization aids yolks a ⻫ a Liquid, dried, or frozen egg
GMP X GMP
Whipping/pasteurization aids white TKPP
GMP VII,X
GMP
TSPP ⻫
⻫ Solid cut meat and poultry pre-
0.5% as DSP XII
0.3% PO 4 0.5% by wt
pared or byproducts ⻫
Processed cheese and cream
TSPP, 3.5% IV,X,XII
cheese prodcuts ⻫
Processed cheese and cream
Not permitted
cheese products ⻫
Surimi-based products
0.1% PO 4 0.5%
⻫ Frozen fish, crustaceans, or mol-
In blends w/
STPP, and SAPP, NTE 0.5% as DSP VIII
Ice cream ⻫
⻫ Frozen dairy desserts
Frozen dairy desserts
GMP
Not permitted
⻫ Cured meat and poultry prod-
STPP, 0.5% as
0.3% PO 4 0.5% by wt
⻫ Desserts, toppings, fillings
GMP
⻫ Soups
GMP
Table 9 Continued
Proposed
Existing Canadian
Canadian
Exceptions (U.S.) ⻫
Product
Food group
regulations
use level
United States use level
⻫ ⻫ Meat tenderizers
GMP XII
0.5% by wt
⻫ Unstandardized foods
GMP IV,X,XII
GMP
⻫ Prepared fish and meat blends
0.1% IV 0.5% by wt
⻫ ⻫ Cured meat and poultry
0.5% as DSP XII
0.5% by wt
⻫ a a Ice cream mix
GMP XII
⻫ a a Sherbet
GMP XII at 0.5%
⻫ a a Ice milk mix
GMP XII
⻫ a a Mayonnaise, French dressing,
GMP XII
salad dressing a ⻫ a Cocoa products
GMP IV
a ⻫ a Mincemeat
GMP IV
a ⻫ a Sherbet
GMP IV,XII at 0.5%
a ⻫ a Mayonnaise, French dressing,
GMP XII
salad dressing a ⻫ a Cottage cheese
GMP X
a ⻫ a Ice cream mix
GMP X,XII
a ⻫ a Ice milk mix
GMP X,XII ; GMP IV
at 0.5%
a ⻫ a Cream
GMP IV,X
GMP
a ⻫ a Grape juice
GMP X
a ⻫ a Jams
GMP X
a ⻫ a Marmalade
GMP X
a ⻫ a Jelly
GMP X
a ⻫ a Liquid, dried, or frozen whole
GMP X
eggs a ⻫ a Liquid, dried, or frozen egg
GMP X
yolks a ⻫ a Liquid, dried, or frozen egg
GMP X
white
KTPP STPP ⻫
Surimi-based products 0.1% 0.5% ⻫
0.3% PO 4 0.5% by wt luscs ⻫
Frozen fish, crustaceans, or mol-
0.5% as DSP
Do. Do. ucts ⻫
Cured meat and poultry prod-
0.5% as DSP
Do. Do. ucts ⻫
Cured meat and poultry prod-
0.5% as DSP
0.1% 0.5% by wt poultry or their byproducts ⻫
Solid cut; prepared meat and
0.5% as DSP XII
Sauces 1.5% GMP ⻫
Vegetable oil creaming agnts or 25 ppm GMP their emulsions ⻫
Prepared fish and meat blends 0.1% IV 0.5% by wt ⻫
GMP ⻫
Unstandardized foods
GMP X,XII
0.5% by wt ⻫
Meat tenderizers
0.5% as DSP XII
Starch modification
0.4% phosphate
STPP, GMP
calculated as P
a ⻫ a Cocoa products
GMP IV
a ⻫ a Mincemeat
GMP IV
a ⻫ a Sherbet
GMP IV ; at 0.5% XII
a ⻫ a Mayonnaise, French dressing,
GMP XII
salad dressing a ⻫ a Cottage cheese
GMP X
a ⻫ a Ice cream mix
GMP X,XII
a ⻫ a Ice milk mix
GMP X,XII ; GMP IV
at 0.5%
a ⻫ a Cream
GMP IV,X
a ⻫ a Grape juice
GMP X
a ⻫ a Jams
GMP X
a ⻫ a Marmalade
GMP X
a ⻫ a Jelly
GMP X
Table 9 Continued
Proposed
Existing Canadian
Canadian
Product
Exceptions (U.S.) a ⻫ a Liquid, dried, or frozen whole
Food group
regulations
use level
United States use level
GMP X
eggs a ⻫ a Liquid, dried, or frozen egg
GMP X
yolks a ⻫ a Liquid, dried, or frozen egg
GMP X
white SAPP
Cream cheese or processed
3.5% IV 3.5%
cheese products Frozen fish, crustaceans, or mol-
In blends w/
0.3% PO 4 0.5% by wt
luscs
STPP and TSPP, total P NTE 0.5% as DSP
Canned seafoods
0.5% as DSP XII
0.3% PO 4 Specific species
Ice cream Cured meat and poultry prod-
Frozen dairy desserts
GMP XII
GMP
Not permitted
0.5% as DSP XII
0.3% as PO 4 0.5% by wt
ucts Solid cut; prepared meat and
0.5% as DSP XII
Do.
Do.
poultry or their byproducts Baked goods
GMP
Desserts, toppings, fillings
Dehydrated potato products,
2.0% as consumed
GMP
soup mixes Batter and breading
GMP
Snack foods
GMP
Prepared starch-based foods
GMP
Baking powder
GMP X GMP
Unstandardized foods
GMP X,XII
GMP
Cocoa products
GMP IV ; at 0.5% XII
Mayonnaise, French dressing,
GMP XII
salad dressing Cottage cheese
GMP X
Ice cream mix
GMP X,XII
Ice milk mix
GMP X,XII ; GMP IV
at 0.5%
Cream
GMP IV,X
Grape juice
Liquid, dried, or frozen whole
GMP X
eggs Liquid, dried, or frozen egg
GMP X
yolks Liquid, dried, or frozen egg
GMP X
white SALP
Cream cheese or process
3.5% IV 3.5%
cheese products Baked goods
Dry mixes
GMP
Not permitted in eggs alone Batter and breading
Egg-based foods
Unstandardized foods
GMP X GMP
Baking powder
GMP
GMP
a Cocoa products
GMP IV
a Mince meat
GMP IV
a Sherbet
GMP IV
Table 9 Continued
Proposed
Existing Canadian
Canadian
Product
Exceptions (U.S.) a Cottage cheese
Food group
regulations
use level
United States use level
GMP X
a Ice cream mix
GMP X
a Ice milk mix
GMP X ; at 0.5% IV
a Cream
GMP IV,X
a Grape juice
GMP X
a Jams
GMP X
a Marmalade
GMP X
a Jelly
GMP X
a Liquid, dried, or frozen whole
GMP X
eggs a Liquid, dried, or frozen egg
GMP X
yolks a Liquid, dried, or frozen egg
GMP X
white STMP
Starch modification
400 ppm calcu-
lated as P
Notes : Assume cold breakfast cereals. Seafood definitions proposed to be generic. Phosphates added to proposed regulations: TKP, KTPP, KPMP. a Citations listed in divisions other than Division 16.
I Anticaking agents: TCP. IV Emulsifying, gelling, stabilizing, and thickening agents: DCP, TCP, DKP, SAPP, SALP, SHMP, DSP, MSP, TSP, TSPP, STPP. VI Firming agents: DCP, MCP.
VII Miscellaneous food additives: DCP, TCP, SAPP, SHMP, DSP, TSPP, STPP. X pH adjusting agents, acid reacting materials, and water correcting agents: DAP, MAP, DCP, MCP, TCP, H 3 PO 4 , DKP, SAPP, SALP, SHMP, DSP, MSP, TSP, TSPP, STPP.
XII Sequestering agents: MCP, TCP, H 3 PO 4 , MKP, TKPP, DKP, SAPP, SHMP, DSP, MSP, TSPP, STPP.
XIII Starch modifying agents: STMP, STPP.
XIV Yeast foods: MAP, DAP (see p. 67–55), DCP, MCP, TCP, H 3 PO 4 , DKP, MKP.
Phosphates currently used in leavening applications include monocalcium phos- phate, [anhydrous and monohydrate (MCP-0 and MCP-1, respectively)], dicalcium phos- phate dihydrate (DCP-2), sodium aluminum phosphate (SALP), sodium ammonium sul- fate (SAS), sodium acid pyrophosphate (SAPP), diammonium phosphate (DAP), calcium acid pyrophosphate (CAPP), and dimagnesium phosphate (DMP). The SAPPs, MCPs, and SALPs are the most commonly used leavening acids (Table 10).
1. Rate of Reaction In order to better understand the selection of leavening phosphate for specific product
application, it is important to understand the dough rate of reaction (DROR). DROR mea- sures the reactivity (CO 2 generated) of leavening acid with soda during mixing (2 to 3 min) and, subsequent bench time (5 to 6 min at 27 °C) of a standard biscuit dough ( Table
11 ). In the United States, the CO 2 measured at 8 min is fairly standard while the 2-min
Table 10 Food Phosphates for Use in Bakery and Cereals Application
Phosphate functionality Baking powder
MCP-0, MCP-1, SAPP-28, or SALP phosphates function as leaven-
ing agents.
Batter and breading SAPP-40, SAPP-28, or SALP for stable bench time with rapid
(leavening) action upon heating.
Biscuit mixes SAPP-28 or SALP, slow acting at the bench, provide reactivity when heated and result in the desired coarse crumb texture. Cake mixes (layered)
SALP, MCP, SAPP, or DCP-2 used for leavening. Cake mixes (angel food)
MCP, SALP, or SAPP-40 used for leavening. Cookie mixes
SAPP-28, SALP, or MCP-1 used for leavening. Corn meal
Enrichment, MCP to 1.1 to 1.7 mg Ca/kg. Dough conditioners
MCP or DCP used for leavening.
Doughnut mixes SAPP-40 or SAPP-43 used for leavening. Fat free and reduced fat
MCP or SAPP used for leavening.
snacks Flour products
Enrichment, MCP to 960 mg/lb or 2.1 g/kg; Phosphated, MCP to 0.25 to 0.75% by weight; Self-rising, SAPP, MCP, or SALP ⫹
NaHCO 3 to a standard weight; Self-rising enriched flour, DCP may be added.
Frozen doughs
DCP or SALP used for leavening.
Hot cereals DSP to hasten cooking, 0.2 to 2.0% wt/wt. Hush puppy mixes
SAPP-28, SAPP-40, or MCP-0 used for leavening. Macaroni products
DSP to hasten cooking to 0.5 to 1.0% wt/wt. Modified starch
MSP, DSP, STPP, or PA for low temperature gel formation, to in- hibit freeze–thaw weep or high acid retorted foods. Pancake mixes
MCP-1, SALP, SAPP-28, or SAPP-40 used for leavening. Pizza mixes
MCP, SALP, SAPP, or DCP-2 used for added leavening (with
yeast).
Refrigerated biscuits Very slow ROR SAPP (22) or SALP for long-term chilled storage
without gas production (leavening).
Snack crackers SAPP-28 and MCP-1 for a double action leavening system at the bench (primary) and in the oven (secondary). Tortillas
Wheat only (corn nonleavened).
Table 11 Properties of Commercially Available Phosphate Leavening Acids
Percent leavening gas released
Phosphate Neutralizing
During leavening acid
2-min mix
8-min
baking SAPP 22
value
stage
bench action
measure is often cited in Europe. A soda blank, which is responsible for about 20% of the gas evolved, includes all ingredients except the leavening acid.
DROR is skewed upward by high temperatures, high moisture levels, aged shorten- ing, or flour (high acid value). It is skewed downward by sugar (which competes for water) and cations (such as calcium), which interact with acid salts thus hindering either their hydration or dissolution (Heidolph, 1996; Lajoie and Thomas, 1991).
Common baking powder is prepared with sodium bicarbonate, the leavening phos- phate and a diluent (i.e., starch) to inhibit reactivity during storage. In the preparation of
a dough or batter, wetting of the dry ingredients initiates the reaction between the bicarbon- ate and the acidulant to generate CO 2 . (The exceptions would include DCP-2, which is insoluble, and those acids that have been coated to inhibit reactivity, e.g., coated MCP- 0.) The rate of gas production and the degree to which the reaction progresses is dependent upon the speed with which the acidic compound dissolves.
2. Neutralizing Value Neutralizing value (NV) is defined as the weight of sodium bicarbonate neutralized by
100 parts of the acidulant. It is a measure of the acid required within a specific bakery formulation. Not all bakery products benefit by a neutral pH. Ellinger (1972a) reported that the end pH should range between 6.9 to 7.2 for white cakes, 7.2 to 7.5 for yellow cakes, and 7.1 to 8.0 for chocolate and devil’s food cakes. Color and flavor development is affected by end pH; a pH that is too low may result in a tartness and off-color, while excess bicarbonate (high pH) may result in a soapy flavor.
3. SAPP The SAPPs range in dough rate of reaction (ROR) from 22 to 43. SAPP-22 is the slowest
of its family and produces about 70% CO 2 at oven temperatures. This makes it most suitable for refrigerated biscuit doughs and cookies and frozen doughs and batters. SAPP-28 and -33 release about 60% CO 2 at oven temperatures and are more applica- ble to prepared cake mixes. SAPP-28 is most frequently used in baking powder. SAPP-
40 releases a theoretical 40% CO 2 in mixing and 50% at cook temperatures. SAPP-40 40 releases a theoretical 40% CO 2 in mixing and 50% at cook temperatures. SAPP-40
be used depending upon the end use. A limitation of the SAPPs is a ‘‘pyro’’ aftertaste in products with little sweetness (Reiman, 1977).
4. SALP SALP is also used in leavening systems that require a delayed ROR or 20 to 30% CO 2
evolved in mixing and bench times and the balance upon heating. Two types of SALP (the molar ratios indicating Na : Al : P) are available, SALP 1 : 3 : 8 [NaH 14 Al 3 (PO 4 ) 14 ⋅ 4H 2 O, or SALP4] and SALP 3 : 2 : 8 [Na 3 H 15 Al 2 (PO 4 ) 8 , or SALPA]. The SALPs may be used in combination with MCP and are included in mixes for waffles, pancakes, refrigerated bis- cuit doughs, frozen doughs, baking powder, and self-rising flours. SALP is resistant to cold temperatures and thus ideally suited to pancake preparations which may be prepared days in advance in institutional settings.
Concerns over the effect of aluminum on the development of Alzheimer’s disease have been debated and resulted, primarily in Europe, in the reformulation of many baked goods in favor of other leavening acids. Concerns about aluminum have now been deter- mined invalid.
5. DCP-2 DCP-2 is only sparingly soluble in liquids and reacts only at temperatures exceeding 135 °F
when it decomposes to MCP, free phosphoric acid, and hydroxyapatite (Toy, 1976). Its application is best suited for some cake mixes with a long bake time and high pH; cakes with high sugar content; frozen doughs; and, now, microwave cake mixes.
6. MCP-0 MCP-0 reacts to evolve CO 2 during mixing (15%), bench time (35%), and the balance
during heating. Most MCP-0 is coated with potassium or aluminum phosphates to delay its reactivity by 3–5 min at the bench (Chung, 1992). It is commonly blended with other leavening phosphates in dry mixes but may be used singly in self-rising flours and in baking powders.
7. MCP-1 MCP-1 is a very fast acting leavening phosphate. Its primary function is to rapidly create
a large number of gas cells during mixing which later serve as nuclei for expansion during heating (Chung, 1992). In mixing, up to 60% CO 2 is evolved. The balance of leavening is released after heating temperatures exceeding 140 °F since the initial reaction generates DCP. It has applications in phosphated flours, pancake and cookie mixes, double acting baking powder, reduced fat snack foods, and inhibiting ropiness in bread.
Ropiness in bread is caused by the bacterium Bacillus subtilis (B. mesentericus). This microorganism is a spore former and it secretes a mucilagenous material which re- sembles stringiness in the center of a loaf of bread. Active or living bacilli will be destroyed by normal baking temperatures, however loaf internal temperatures may not reach a point sufficient to kill its spores. After the bread cools, surviving spores revert to a growth stage and begin to multiply rapidly in the favorable warm, moist and nutrient-rich environment provided by the fresh crumb. As the bacteria grow, enzymes are secreted which break down protein and starch in the bread. The bacteria also produce shiny (mucous) capsules
Table 12 Bread Defects: Ropiness in Bread Factors affecting development of ropy bread
Solution 1. Natural breads or those without preservative
Add monocalcium phosphate (MCP), 0.25%, ingredients
to inhibit B. subtilis growth. 2. Recycling small amounts of baked product
Eliminate use of recycled product. into the dough 3. Failure to frequently and thoroughly sanitize
Frequently wash and sanitize equipment. equipment used for fluid ingredients 4. Use of improperly wet processed ingredients
Control and reduce the temperature and hold- ing time for wet processed ingredients. 5. The presence of Bacillus spores in primarily
Control factors 2, 3, 4, 6, and 7. Use bacte- flour and sometimes in yeast or malt
rial inhibitors such as acetic acid and MCP.
6. Cracks and crevices in dough handling Repair/seal cracks and crevices. equipment 7. Holding dough too long at ambient or
Shorten holding times. warmer temperatures 8. Dough pH not sufficiently acidic
Add MCP to reduce dough pH.
similar to an overripe melon and a brown discoloration develop. Factors causing ropiness in bread are described in Table 12.
8. CAPP CAPP is manufactured by only a limited number of phosphate producers and is utilized
in a few specific applications. It has an NV of 67 and a DROR of 44 at 2 min and 51 at
8 min (Brose, 1993). It’s recommended uses include rye flour doughs, crackers, and frozen (yeast) doughs and for dough strengthening.
9. DAP and MAP The ammonium phosphates are used as leavening agents on a limited basis in the United
States. Their application is restricted to very low moisture cookies and crackers since higher moisture leads to ammoniacal off-flavors. They are more widely used as yeast nutrients and dough strengtheners.
10. DMP This is a recently patented leavening agent (Gard and Heidolph, 1995). It is heat activated
(40.5 to 43.5 °C) and intermediate between SALP (38 to 40.5°C) and DCP-2 (57 to 60°C). As a consequence, it may need to be used in combination with a faster leavening agent.
11. Sodium Aluminum Sulfate While not a phosphate, sodium aluminum sulfate (SAS) is worthy of mention. It is not
used alone as a leavening agent since it has too slow a DROR and may accelerate rancidity in flour-based mixes (Smith, 1991). Leavening occurs late in the baking cycle, which may make it desirable for products in which either a tunneling or blister effect is desirable, but not in cakes which require a uniform texture. SAS is used in commercial baking
12. Baking Powders Baking powders are formulated to be either single or double acting. They consist of the
leavening acid(s), sodium bicarbonate, and a diluent such as starch. Most commonly, MCP-1 and SAPP are the acidulants of double acting powders. Single acting powders generally contain MCP-1. In prepared cake mixes, the proportions of the leavening agents range from 10 to 20% of fast acting phosphates (MCP-0 or MCP-1) and 80 to 90% of delayed acting phosphates. Physical characteristics of either the bicarbonate, leavening acid, or added ingredients may cause defects in the finished product. A brief troubleshoot- ing guide is shown in Table 13 .
13. Dough Conditioning Dough conditioning is another important function of the phosphates. The polyelectrolyte
behavior of both gluten protein and of the phosphates assists in the strengthening of the dough and of the water holding capacity.
B. Cereal Applications
1. Quick Cooking Cereals DSP is a commonly added ingredient to cereals in order to expedite cooking. This is due
to both increasing the pH of the cooked cereal and partially gelatinizing the starch of those products soaked in phosphate solutions prior to cooking.
2. Pasta Products DSP may be added to macaroni formulations at levels ranging from 0.5 to 1.0% to hasten
cooking (21 CFR 139.110). Phosphates are used in the Asian noodle market in the form of kansui , which is a mixture of potassium and sodium carbonates and sodium and potassium phosphates. Kansui is permitted in Chinese but not Japanese noodles. The use level of kansui ranges from 1 to 2 g per kilogram of flour in dry noodles and from 0.5 to 1.7% in noodles for soup (Kubomura, 1998). Kansui interacts with the gluten to form the gum- like texture characteristic of the noodles and is associated with the characteristic yellow color and flavor development.
3. Starch Modification Modified starches play an important role in the development of processed prepared foods.
In all likelihood, their applications will be augmented with efforts to manufacture a greater array of low and reduced fat foods.
Starches are modified with any number of phosphates to form either starch phosphate monoesters or diesters. The resulting starch phosphate esters (SPE) are highly resistant to retrogradation, form gels at lower temperatures, and produce gels that are clearer and less viscous. The SPE monoesters are well suited to cold set puddings and pie fillings, while the SPE diesters are highly stable to acidic pH and to long and intense periods of heating. Kawana et al. (1990) reported on the use of a phosphoric crosslinked wheat flour, egg, and calcium phosphate coating to deep-fat fry shrimp that was subsequently vacuum packaged and retorted. There was no loss of the shrimp shape or texture.
Fortuna et al. (1990), increased the level of phosphorus substitution of starches. It
Table 13 Troubleshooting Guide for Bakery Products Problem
Solution
1. Dry mix reactivity Monitor moisture of finished mix (ⱕ3% moisture). Assure low moisture flour (⬍10% moisture). Increase soda granulation. Check storage temperature of mix; reduce if necessary. Check acid value of shortening. Check age of flour. Check packaging materials to assure transmission of excess mois-
ture. Monitor relative humidity of storage; geographic constants and/or seasonal fluctuations may require its control. 2. Bench over-reactivity
Cool added fluids (water temperatures may fluctuate up to 60 °F
seasonally). Cool mix areas. Change to leavening agent that has reduced bench time (oven re-
active and/or coated leaveners). Reduce holding time. Increase soda granulation. Check acid value of shortening. Check age of flour. Evaluate acidity of other added ingredients (e.g., fruits); coat if
necessary.
3. Poor after-bake volume
Increase amount of leavening agents. Change leavening acid to be high temperature reactive. Avoid overmixing. Alter bicarbonate levels to allow for either reduced sodium plus
increased ammonium bicarbonate to increase crown or use larger granulation sodium bicarbonate or add DCP-2 if a long bake time is possible.
4. Dry Texture Alter bicarbonate source to a potassium salt which encourages hu-
mectancy. Evaluate different SAPP grades. Avoid overmixing.
5. Color Black streaks
Reduce granulation of acid leavening.
Brown spots
Reduce particle size of bicarbonate
Dark color
Reduce pH of mix. Reduce bake time and/or temperature. Increase fluids to slow evaporation losses.
Pale color
Increase pH. Increase bake time/temperature. Reduce added fluids.
capacity compared to untreated starches. The greater the degree of phosphorylation, the lower the pasting temperature but with slightly greater viscosity.
In an extension of their studies, Fortuna (1991) evaluated distarch phosphates of potato, maize, wheat, rye, and triticale origin for a variety of physicochemical factors. Distarch phosphates of potato origin showed lower reducing capacity, higher water binding capacity, and higher gel viscosity than those of cereal origin. This may be related to the naturally greater level of phosphorus indigenous to the potato.
In efforts to identify useful characteristics of other starches, Teo et al. (1993) evalu- ated the functionality of sago and tapioca roasted in the presence of urea and phosphate (3M) at pH 3.5 and 120 °C. Chang and Lii (1992) reduced the amount of phosphate required to modify corn and cassava starches by employing extrusion. This process, however, may have led to damage of the starch molecule, which resulted in lower gelatinization tempera- tures, lower enthalpies, and reduced paste viscosities.
C. Meat, Poultry, and Seafood
Processed meat, poultry, and seafood benefit from the use of phosphates in many ways. These include buffering; pH control; solubility; water binding; emulsion development and stability; color development and stability; and inhibition of oxidation (Table 14) (Strack and Oetker, 1992).
Early studies focused on the use of phosphates in muscle foods to decrease cook– cool losses. Froning (1965) held whole poultry carcasses in 6% solutions of ‘‘mixed’’ polyphosphates for 15 h. It was determined that there were no significant differences in total water uptake by the carcasses prior to cooking. After heating, the polyphosphate soaked-meat had significantly (p ⬍ 0.5) less cook–cool loss, pH was elevated (from 6.1 to 6.6), and moisture of the meat was 6.2% greater than the control.
By and large, the most commonly used phosphate is STPP, followed by blends. Blends commonly consist of STPP and SHMP as a base with varying levels of SAPP and TSPP. There is increasing interest in the potassium phosphates (TKPP, KTPP) for end products with reduced sodium content. The alkaline phosphates (STPP, TSPP, KTPP, TKPP) increase pH and serve to increase water binding and emulsion development. Cure color development may be delayed by elevated pH, and therefore time may be required before heat processing. SAPP is an acid phosphate (pH 4.0 to 4.2) and is not normally used alone due to the adverse effect of low pH on water holding capacity. SHMP has
Table 14 Function of Phosphates in Meat Systems Reduce requirement for NaCl—phosphate and NaCl act synergistically
Reduce development of ‘‘warmed-over’’ flavor (WOF) Protect color Assist color development in cured products Reduce cook–cool loss Reduce thaw-drip loss Protect proteins in freezing and frozen storage Inhibit lipid oxidation Develop and stabilize emulsions Allow myosin to form a ‘‘sol’’ and a ‘‘gel’’ upon heating Enhance succulence of the cooked product Reduce development of ‘‘warmed-over’’ flavor (WOF) Protect color Assist color development in cured products Reduce cook–cool loss Reduce thaw-drip loss Protect proteins in freezing and frozen storage Inhibit lipid oxidation Develop and stabilize emulsions Allow myosin to form a ‘‘sol’’ and a ‘‘gel’’ upon heating Enhance succulence of the cooked product
1. Phosphates, Sodium Chloride, and Their Interactions Before the advent of phosphate use meat processing frequently required the use of high
levels of sodium chloride in order to promote emulsion development. Maesso et al. (1970) studied the effects of mechanical action (beating for 3 min) and pH adjustment (with either NaOH or HCl to pH 5.0, 6.5, or 8.0) on poultry muscle in order to elucidate the mechanism of phosphate action. The investigators determined that tensile strength (Instron force to pull apart the meat) increased with pH, and therefore polyphosphate and NaCl in combina- tion acted by simply altering surface pH.
Schults et al. (1972) evaluated the effects of (0.5%) TSPP, STPP, SHMP, and two blends of STPP and SHMP with and without NaCl on the physicochemical aspects of beef muscles (longissimus, biceps femoris, and semimembranosus). TSPP in combination with NaCl had the greatest effect on pH rise in all three muscle types. Naturally, the pH of biceps femoris was about 0.2 greater than the other two muscle types. Swelling of muscle fibers was markedly greater with pyrophosphates plus NaCl compared to the other phosphate treatments. Shrink was consistently reduced by the synergism with NaCl but less so with the SHMP treatment. It was theorized that under low (1 to 2%) NaCl concen- tration, there was an ion exchange of calcium for sodium on the meat proteins. At 3 to 4% NaCl swelling is reduced due to the exchange of potassium and magnesium by sodium. At levels of 5 to 10%, NaCl exhibits solely an ionic effect.
Schwartz and Mandigo (1976) evaluated the effect of 20 combinations of salt and STPP on restructured pork after 4 weeks storage at ⫺23°C. There was a synergistic effect
of STPP and NaCl upon TBA values, thaw-drip loss, improved cooked color, aroma, flavor, eating texture, cook–cool loss, raw color, and improved juiciness of the restructured chops. Optimal levels were determined to be 0.75% salt and 0.125% STPP.
Clarke et al. (1987) evaluated the concentration of NaCl (1.3, 2.0, 2.6, or 3.3%) needed to reduce cook–cool loss in beef comminutes. Use of 2.6% NaCl resulted in the least amount of cook–cool loss (20 to 35%); however; this was reduced to 1.0 to 1.4% upon the addition of 0.4% STPP to the batter. Strack and Oetker (1992) have described the polyelectrolyte behavior of the polyphosphates in a muscle food system. This behavior contributes to protein hydration and dispersion.
Offer and Trinick (1983) determined that pyrophosphate (10 mM) of beef myofibrils, in combination with reduced levels of sodium chloride, extracted the A-band completely beginning at both ends. This effect was confirmed by Voyle et al. (1984) with pork. In the absence of pyrophosphate, however, only the center of the A-band was extracted. Lewis et al. (1986) determined from 5-g pork, beef, chicken, and cod samples that an A/I overlap composed of denatured actomyosin and connection was formed, while unasso- ciated myosin and actin were probably dispersed (sol) through the meat structure in the form of a water-holding gel (post–heat treatment). Trout and Schmidt (1987) concluded that at high ionic strengths (⬎0.25) pyrophosphate affected hydrophobic interactions which stabilize the protein structure and thus the thermal stability of the protein. Elevating pH (1 M NaOH), in combination with pyrophosphate, increased the temperature (from
70 to 87 °C) for and the extent of protein aggregation. Yagi et al. (1985) confirmed that 70 to 87 °C) for and the extent of protein aggregation. Yagi et al. (1985) confirmed that
Water retention is correlated with increased pH and is normally associated with the use of alkaline polyphosphates such as sodium tripolyphosphate. Orthophosphates have virtually no effect on water binding. Pyrophosphates are associated with improved protein solubility (myosin) and water binding. Consequently, water binding is dependent upon the type of phosphate used, and specific physicochemical reactions may require the use of blends.
SAPP, SHMP, or STPP (0.4%) were used in reduced salt (20 to 40%) turkey frank- furters (Barbut et al., 1988a). In formulations containing 40% less salt, phosphates im- proved emulsion stability and yields. While STPP improved firmness, flavor was not con- sidered to be fresh. SAPP improved plumpness and enhanced salt flavor intensity. This was attributed to pH of the frankfurter (pH 6.1, SAPP and pH 6.5, STPP) and the sequestra- tion of metal ions by the SAPP. If flavor had been altered by sequestration of metal ions alone, SAPP and SHMP should have shown a similar effect.
Studies by Kim and Han (1991) evaluated the gel strength of mixed pork myofibrillar and plasma protein. The gel strength of the mixture and myofibrillar protein solubility showed a significant increase when NaCl content was increased from 2 to 3%. By adding 0.3% polyphosphate in the presence of 2% NaCl, the gel strength increased fourfold.
Steinmann and Fischer (1993) investigated the level of NaCl and temperature on emulsion development and stability of a frankfurterlike sausage. It was determined that cooling lean meat with liquid nitrogen while mixing and the addition of SAPP resulted in greater extraction of salt soluble proteins and an increased stability of the emulsion.
Schantz and Bowers (1993) evaluated the effects of varying and mixed levels of NaCl (1.5 to 2.0%), STPP (0 to 0.5%), and SAPP (0 to 0.25%) on turkey sausages. A trained sensory panel showed increased saltiness with the presence of either polyphos- phate. In the presence of 1.5% of NaCl, high SAPP, and low STPP, firmness decreased. It should, however, be noted that SAPP has a pH 4.2 and STPP a pH of 9.5 to 10.2. Therefore the pH effect was of some importance. Sensory evaluation also indicated that as the level of STPP increased and NaCl decreased, a slight soapy off-flavor was detected. The effects of pH and sensory evaluation clearly indicate another practical aspect of the use of polyphosphate blends.
Robe and Xiong (1993) evaluated the effect of phosphates on longissimus dorsi (LD, white), serratus ventralis (SV, red), and vastus intermedius (VI, red) salt soluble proteins (SSP). The SSP suspensions showed pseudoplastic flow. STPP (0.25%) decreased the shear stress of both LD and SV samples. Addition of STPP resulted in reduced dynamic shear storage modulus of all three muscle types. This effect was not duplicated in the presence of similar ionic strengths of NaCl.
Anjaneyulu et al. (1990a) studied the difference between phosphate action versus pH adjustment on end pH, water holding capacity (WHC), salt soluble protein content, emulsifying capacity (EC), cook–cool loss (CCL), emulsion stability (ES), patty yield, and shrinkage of finely minced buffalo meat (biceps femoris). The treatments consisted of 2% NaCl plus 0.5% polyphosphate (65% tetrasodium pyrophosphate, 17.5% sodium tripolyphosphate, and 17.5% sodium acid pyrophosphate), 2% NaCl with pH adjustment (with NaOH) to equal that of the phosphate treatment, and a control without either NaCl or added polyphosphate. The results indicated improved EC, ES, patty yield, and WHC and decreased CCL and shrinkage in the treatments in the following sequence: polyphos- Anjaneyulu et al. (1990a) studied the difference between phosphate action versus pH adjustment on end pH, water holding capacity (WHC), salt soluble protein content, emulsifying capacity (EC), cook–cool loss (CCL), emulsion stability (ES), patty yield, and shrinkage of finely minced buffalo meat (biceps femoris). The treatments consisted of 2% NaCl plus 0.5% polyphosphate (65% tetrasodium pyrophosphate, 17.5% sodium tripolyphosphate, and 17.5% sodium acid pyrophosphate), 2% NaCl with pH adjustment (with NaOH) to equal that of the phosphate treatment, and a control without either NaCl or added polyphosphate. The results indicated improved EC, ES, patty yield, and WHC and decreased CCL and shrinkage in the treatments in the following sequence: polyphos-
In an extension of their studies, Anjaneyulu et al. (1990b) evaluated buffalo chunked and ground meat treated with 2% NaCl, 2% NaCl plus 0.5% phosphate, or no added ingredients (control) during holding at 2 to 3 °C for up to 9 days. The results indicated that phosphate addition overcame the negative effects of NaCl by showing improved color and sensory quality. There was a synergistic effect on WHC and reduced CCL after hold- ing for 5 days. Curiously, pH, EC, SSP, TBA, ES, and yield were thought to be superior for the control versus the NaCl plus phosphate treatment at 9 days. Incorporation of oxygen via equivalent mix times may have proven different for parameters associated with oxida- tion. In addition, short preblend holding prior to heating is frequently employed with commercial manufacture of restructured meats. Here, a long holding after preblending and overmixing may have adversely affected EC and ES. In native protein (not thermally denatured), STPP is broken down rapidly by muscle phosphatases. However, the pyro- phosphatases are more slowly hydrolyzed (Hamm, 1986). This would explain the lost (positive) effect normally attributed to the polyphosphates.
Later studies by Anjaneyulu and Sharma (1991) indicated that EC and ES of pre- cooked buffalo meat patties during refrigerated storage were favorably affected by the presence of a polyphosphate blend. Additionally, oxidative rancidity, as indicated by TBA values, was inhibited by the presence of polyphosphates.
2. Protein Functionality—Process Effects Barbut (1988) evaluated the effect of serial levels of NaCl with and without added poly-
phosphate (STPP, SHMP, and SAPP), chop time, and speed on the ES of mechanically deboned chicken meat (MDCM). The results indicated that slow chop speed (40 versus 100 rpm), reduced time (66 versus 165 s) and low NaCl (1.5 versus 2.0 or 2.5%) plus polyphosphate enhanced ES. Ostensibly, pH was 6.71 versus 6.55 versus 6.23 with the use of STPP, SHMP, and SAPP, respectively. It is interesting to note that SHMP imparted greater stability than either STPP or SAPP in terms of cook–cool loss. SHMP is normally better associated with sequestration rather than meat protein functionality. Since calcium is associated with reduced STPP functionality (Regenstein and Rank Stamm, 1979a,b,c), it may be presumed that excess calcium naturally occurring in the MDCM may interfere with emulsion stability. Here, SHMP sequestered the calcium. STPP tends to form colloi- dal masses with calcium and thus is less available to react at the protein surface. SAPP would be highly active under these conditions and would act synergistically with NaCl to yield enhanced coating of the fat by myofibrillar proteins.
Gariepy et al. (1994) compared the effects of hot and cold boning (HB and CB, respectively) of beef chucks from electrically stimulated cattle carcasses at varying levels of NaCl (0 to 2%) with and without STPP. The results indicated that bologna prepared from HB mince containing 2% NaCl and CB mince containing STPP showed similar cooking yields and were greater than those of CB minces without STPP (p ⬎ 0.05). STPP provided an equalizing effect to compensate for process differences.
3. Protein Functionality—Chilled and Frozen Storage Chen et al. (1991) evaluated the effectiveness of TSPP and STPP with and without sucrose
and sorbitol (1 : 1) on chicken surimi during a 14-week period of frozen storage (⫺18°C) or at 4 °C. The results indicated that a combination of sucrose (4%) and sorbitol (4%) and and sorbitol (1 : 1) on chicken surimi during a 14-week period of frozen storage (⫺18°C) or at 4 °C. The results indicated that a combination of sucrose (4%) and sorbitol (4%) and
These results are interesting but different from those observed with finfish-based surimi. Most phosphate-based cryoprotectants consist of a blend of STPP and TSPP and are used at a level of 0.4 to 0.5% and in combination with 8% sucrose and sorbitol (1 : 1). Similarly, functionality of sulfhydryl groups is associated with positive gel attributes of finfish-based surimi (Chang-Lee et al., 1989,1990; Pacheco-Aguilar et al., 1989).
Park et al. (1993) evaluated the effect of polydextrose (8%) with and without sodium tripolyphosphate and tetrasodium pyrophosphate (1 : 1) at the 0.55 level on the functional properties of pre- and postrigor beef. Although the authors did not determine a synergistic, cryoprotective effect on the treated prerigor beef, addition of the ingredients to an untreated control thawed after 5 months frozen storage did result in superior protein functionality. This effect was attributed to the presence of phosphate.
4. Lipid Oxidation Akamittath et al. (1990) evaluated the impact of NaCl with and without polyphosphate
on the stability of lipid and color in restructured beef, pork, and turkey steaks stored at ⫺10°C for 16, 8, and 8 weeks, respectively. The polyphosphates were effective in delaying
lipid oxidation in beef (4 weeks), turkey (6 weeks), and pork (8 weeks). Discoloration and lipid oxidation occurred simultaneously in pork and turkey, but discoloration preceded oxidation in beef. This work reaffirmed that lipid oxidation may be accelerated by pigment oxidation.
Mikkelsen et al. (1991) evaluated polyphosphates for lipid oxidation and color qual- ity during retail display. As with the previous researchers, color stability, which was an initial ‘‘blooming’’ on the fresh ground beef patties, was reduced in frozen storage. The surface discoloration was linearly correlated with the metmyoglobin level of the total myoglobin extracts and, therefore, was used to track oxymyoglobin oxidation in frozen storage.
Oxidation of oxymyoglobin varied by phosphate type and in aqueous extracts or minced beef. Levels of sodium di-, or triphosphate or trimetaphosphates were added at levels ranging from 0.2 to 5.0%. Lipid oxidation was inhibited by no phosphate ⬍ trimeta- phosphate ⬍ di- or triphosphate. The latter phosphates also counteracted the oxidative effect of added NaCl.
Craig et al. (1991) added STPP or sodium ascorbate monophosphate (SAMP) at levels ranging from 0.3 to 0.5% to ground turkey that was cooked, vacuum packaged, and frozen. Although a soapy flavor was present, the phosphate salts inhibited the develop- ment of rancid flavor, hexanal, and bathphenathroline-chelatable (nonheme) iron; and the salts decreased cook–cool losses, which is reflected by increased moisture content of the meat.
5. Thermal Effects Trout and Schmidt (1987) evaluated the effects of ionic strength (0.12 to 0.52), pH (5.5
to 6.0), concentration of TSPP (0 to 0.31%), and cook temperature (52 to 87 °C) on cook yield and tensile strength of beef homogenates. Generally, ionic strength between 0.32 to to 6.0), concentration of TSPP (0 to 0.31%), and cook temperature (52 to 87 °C) on cook yield and tensile strength of beef homogenates. Generally, ionic strength between 0.32 to
Since TSPP and NaCl are insoluble in nonpolar lipids, their concentration in the aqueous phase in fat free products is considerably lower than in fat-containing products, i.e., 0.5% in low fat systems and 0.3% in high fat systems. This work would be analogous to 20% fat products.
Trout and Schmidt (1987) also noted that at higher ionic strength, TSPP tended to negate the adverse impact of hydrophobic interactions with heat. NaCl increased the temperature of aggregation and the tendency to undergo syneresis; this impact was en- hanced by the presence of TSPP. At pH 5.5 in the absence of TSPP, syneresis began at
70 °C and at pH 6.0; in the presence of TSPP, syneresis was initiated at 87°C. Robe and Xiong (1992) investigated the effect of phosphates on thermal transitions of pork salt soluble protein aggregation. The SSP transitions of the control (pH 6.0) were one or two for red muscle and three for white muscle. Addition of ortho-, pyro-, tripoly-, and hexametaphosphates up to 1% increased SSP transition temperature and altered transi- tion patterns. This effect did not occur in the presence of NaCl at comparable ionic strengths. SSP transitions were most affected by STPP (0.15 to 0.25%) at pH 6.0 or lower. Red and white SSP responded differently to phosphate and showed different thermal prop- erties. The authors concluded that red and white muscle types should undergo different processing treatments for optimal quality meat products.
Robe and Xiong (1994) extended their studies on the three aforementioned muscle types to the thermal aggregation of SSP in the presence of STPP. The SSP solutions were heated between 40 to 70 °C with 0 to 0.2% STPP with protein aggregation measured by turbidity. SSP aggregation followed first order kinetics with rate and extent mediated by red fiber content. STPP increased the temperature for aggregation, but the rate varied by muscle type. STPP caused a 10 to 11.5% reduction in the activation energy for SSP aggregation. Muscles vary in thermal properties and response to treatment with STPP.
6. Nontraditional Phosphates Zorba et al. (1993a) prepared emulsions with beef (fat level adjusted with sheep tail fat)
using a model system of a Turkish style meat emulsion to evaluate the effects of oil, temperature, NaCl, and DKP. Emulsion stability (ES) and emulsion viscosity (EV) were enhanced in the presence of DKP (to 0.75%). ES was increased by an average of 3.8% in the presence of 0.5 to 0.75% DKP over a control (no phosphate). The EV increased by 22.3 to 27.0 by 0.5 and 0.75% DKP, respectively. It is interesting to note that NaCl (2.5%) had no statistical effect on EV.
In a continuation, Zorba et al. (1993b) determined that emulsion capacity (EC) in- creased an average of 9.5% in the presence of DKP over a control. Using electron micros- copy, it was observed that DKP resulted in diminished protein aggregates and a homoge- nous emulsion.
7. Novel Applications of Phosphates in Muscle Foods Farouk et al. (1992) investigated the effects of postexsanguination infusion on the compo-
sition, tenderness, and functional properties of beef. Between infused and control animals, there were no significant differences in WHC, and very low correlations were determined between tenderness, moisture, and ether-extractable fat.
8. Seafood Applications Among the legitimate functional goals for the use of phosphates in seafoods are retention
of natural moisture and flavor, inhibition of fluid losses during shipment and prior to sale, emulsification, inhibition of oxidation of flavors and lipids by chelation of heavy metals, and cryoprotection to extend shelf-life. Properly used, phosphates impart no flavor. Key applications are shown in Table 15.
a. Application of Phosphates. Phosphates are generally applied by dipping in, spraying with, or tumbling in a phosphate solution. Injector needle systems may also be used with and without added tumbling. Dry addition is used in comminuted meat systems, e.g., surimi and fish sausage formulations.
The most predictable way to apply phosphates is through vacuum tumbling, if done properly and the structure of the flesh can withstand mechanical action. Contrary to some practices, tumbling in an excess of solution results in protein extraction rather than absorp- tion of solution. This uniform and rapid means of treating the muscle offsets the ineffi- ciency of protracted holding in phosphate-based solutions (soaking).
It has been demonstrated that treating finfish prior to smoking requires different phosphate concentrations depending on the dimensions of the fillets and/or pieces. For example, with the same size pieces of flesh (within selected species), a 5% phosphate dip requires 24 h treatment time, while a 25% phosphate dip requires only 2 s (Wekell and Teeney, 1988) to reach equal processing effects, i.e., inhibition of surface curd formation and reduced cook–cool losses. This is especially valuable when delicate muscle structure eliminates tumbling as an option. Caution should be exercised when applying phosphates to fish of different muscle thickness, muscle types (e.g., interspecies variation), and initial moisture content (spawning).
Table 15 Food Phosphates for Use in Seafood Application
Phosphate functionality Canned salmon
STPP or STPP/SHMP combinations to inhibit curd for-
mation
Canned tuna SAPP to inhibit struvite formation. Pasteurized crab
SAPP to inhibit blue discoloration of the meat Canned abalone
SAPP and citric acid to inhibit blackening Mechanical peeling of shrimp
STPP to assist cleavage of immature collagen and to firm
the flesh
Kamaboko/surimi-based analogs Mixtures of SAPP, TSPP, STPP, and SHMP Frozen fish blocks
STPP or STPP/SHMP combinations for solubilizing surface
proteins to prevent voids
Fresh scallops STPP or phosphate blends to inhibit excessive exudate after
harvest
Smoked fish STPP or STPP/SHMP blends to retain flavor Peeled shrimp
STPP treatment before freezing to decrease thaw-drip loss, or STPP treatment prior to cooking to decrease cook– cool loss
Fresh or frozen fillets STPP or phosphate blends to retain natural moisture, inhibit color and lipid oxidation, reduce drip, and protect native protein Fresh or frozen fillets STPP or phosphate blends to retain natural moisture, inhibit color and lipid oxidation, reduce drip, and protect native protein
The HP ratio then would not be realistic for many species or at certain times of year. This value is based upon Kjeldahl protein to moisture (overnight drying at 100 to 105 °C).
In theory, determination of total phosphorus in seafoods might be a useful marker of phosphate treatment; however, it is not necessarily accurate. For example, Crawford (1980) determined that the natural level of phosphorus in fresh shrimp (Pandulus jordani) ranged from 537 to 727 mg/100 g. Shrimp of the same history showed increases of 81 ⫾
39 and (base not given) ⫾110 mg of phosphorus, respectively, after treatment with either
1.5 or 6% phosphate solutions for 5 min. In shrimp (Pandulus jordani), the natural varia- tion in phosphorus exceeded that added by responsible treatment. Total natural phosphorus has also been reported to vary in lobster, blue mussels, squid, anchovies, carp, capelin, catfish, Atlantic cod, eel, hake, herring, yellow leather- jacket, European pilchard, and albacore tuna (Sidwell, 1981). Penetration of phosphate, and therefore phosphorus content, will also vary according to concentration of solution used, variations in muscle thickness, subsequent processing, etc.
Other methods to screen for added phosphates include high pressure liquid chroma- tography (HPLC), ion chromatography, and thin layer chromatography. Wood and Clark (1988) have reviewed the difficulties associated with these phosphate determinations.
Biochemical decomposition of condensed phosphates necessitates assaying immedi- ately after treatment of the seafood species. Hydrolysis of condensed phosphates occurs due to muscle alkaline phosphatase activity during the posttreatment (lag) time prior to cooking. Sutton (1973) determined that sodium tripolyphosphate is rapidly hydrolyzed to pyrophosphate (phosphate dimer) and orthophosphate (phosphate monomer) in cod muscle at either 0 or 25 °C.
It has also been determined that after 2 weeks of frozen storage (⫺26°C), only 12% of the total phosphorus in raw shrimp muscle corresponded to the originally added sodium
tripolyphosphate. By 10 weeks, phosphorus levels corresponded to 45% orthophosphate (Tenhet et al., 1981). Clearly, in treated seafood muscle the condensed phosphates were unstable over time.
C. Mechanism of Action phosphates as processing aids. Crawford (1980) was instrumental in developing
a protocol for the treatment of Pacific shrimp (Pandulus jordani) to be mechanically cooked and peeled. Use of the phosphates resulted in a firming of the flesh and more effective cleavage of immature collagen, which connects the body to the shell. These a protocol for the treatment of Pacific shrimp (Pandulus jordani) to be mechanically cooked and peeled. Use of the phosphates resulted in a firming of the flesh and more effective cleavage of immature collagen, which connects the body to the shell. These
A process for using low concentrations (1 to 2%) of sodium tripolyphosphate in either flaked or crushed ice was patented by Stone (1981). Use of this ice increased the yield of shrimp and effectively reduced moisture and nutrient loss. Shrimp stored in phosphated ice could be overexposed to polyphosphates if treated again during further in-plant processing, which could cause either off-flavor, ⬎0.5% resid- ual phosphate, or both.
preservation of freshness.
d. Specialty Blends. Among products for extending the shelf-life of fish fillets, Craw- ford (1984,1985) developed a patented blend consisting of sodium tripolyphosphate, so- dium hexametaphosphate, citric acid, and potassium sorbate. Fish fillets were dipped into either distilled water or (ca.) 12% treatment solutions. The shelf-life (aerobic plate count ⱕ
1 ⫻ 10 6 CFU/g) for treated samples was 12.4 days, and that of the control (water-dipped) was 6.8 days. Both control and treated fillets increased in weight by 4% after 60 s of
immersion. Those dipped in the patented blend remained at their stated package weight throughout the 14 days of storage at 5 °C, while the controls, dipped in water, dropped below the initial weight within 4 days of chill storage. Shelf-life extension would most likely be increased due to (1) the antimicrobial activity contributed by the sorbic acid and (2) the sequestration by phosphates of enzyme (metal) cofactors.
Indian researchers reported on the preservation of salted pink perch (Nemipterus japonicus ) without preservatives or with a combination of sodium benzoate, potassium sorbate, SAPP, and butylated hydroxyanisole (Khuntia et al., 1993). The preserved fish showed decreased total volatile base nitrogen, amino acid nitrogen, TBA, free fatty acids, and aerobic plate counts over their controls when held in either chilled or ambient tempera- ture. The preservative effect was somewhat enhanced at ambient temperature.
e. Frozen Seafood. Researchers at Texas A&M University reported that sodium tri- polyphosphate dissolved slowly in seawater (Duxbury, 1986). In addition, fresh, shell-on, and peeled shrimp (Gulf of Mexico) became translucent and slippery to the touch after dipping in solutions of phosphate–sea water. This led to subsequent treatments which included 5 minute dips in water and 2, 4, or 5% condensed phosphates. Using a blend of sodium tripolyphosphate and hexametaphosphate resulted in rapid solubilization of the condensed phosphate, and more desirable sensory (touch) properties. The dipped shrimp were frozen and stored at ⫺26°C for 2 weeks. Upon thawing and cooking (4 min), those shrimp dipped in the 4% blend for 5 min lost 0.8% weight after frozen storage (control, 2.0% loss) and 19.8% after cooking (control, 25.3% loss). It was concluded that addition of these phosphate blends imparted a cryoprotective effect.
Woyewoda and Bligh (1986) dipped Atlantic cod fillets into 12% solutions of so- dium tripolyphosphate, sodium metaphosphate blends, or no solution and a control, respec- tively, for 45 s and stored each treatment at either ⫺12°C or ⫺30°C for up to 26 weeks. Phosphate-treated cod showed decreased thaw and cooked drip loss and resulted in higher Woyewoda and Bligh (1986) dipped Atlantic cod fillets into 12% solutions of so- dium tripolyphosphate, sodium metaphosphate blends, or no solution and a control, respec- tively, for 45 s and stored each treatment at either ⫺12°C or ⫺30°C for up to 26 weeks. Phosphate-treated cod showed decreased thaw and cooked drip loss and resulted in higher
Ohta and Yamada (1990) evaluated the effect of K, P, Na, and Cl on the denaturation of fish (chub mackerel, black porgy, yellowfin tuna, and rock bream) species held at ⫺6°C.
It is agreed that the ion concentration of the unfrozen portion of muscle juices would be higher in K and P than in Na and Cl. Ohta and Yamada (1990) indicated that phosphates and chlorides may be related to denaturation of protein in frozen stored fish. It is more likely that high phosphorus, and especially potassium phosphates, lead to freezing point depression at a far lower molarity than their chloride counterparts. Furthermore, the lower the frozen storage temperature, the greater the ATPase activity and soluble myofibrillar protein over time.
f. Surimi. Surimi is the minced, washed, and refined flesh of finfish, which is now used in the manufacture of imitation shrimp, crab, and lobster. Originally, surimi was prepared and steam cooked as a means of preservation for later consumption. Typically, lean, white flesh species with a low flavor profile are preferred in the manufacture of surimi. The fish are mechanically skinned and deboned; the flesh is washed in cold, potable water to re- move pigment and some lipid and sarcoplasmic proteins (low levels of NaCl may be added to the wash water), refined to remove residual pieces of skin and bone, and dewatered (since the flesh tends to absorb moisture during the washing). Depending upon the species, refinement may follow dewatering in order to minimize losses due to fines and to maximize yield. The mince is mixed with 8% sucrose and sorbitol and up to 0.5% sodium phosphates for cryoprotection of the concentrated myofibrillar protein; the product is packaged in 40- lb blocks and blast frozen. Alaska pollock has been processed in great quantity and Pacific whiting is now caught for this purpose.
Surimi quality is based upon gel (or jelly) strength of the kamaboko. Surimi is blended with water, salt, and phosphate to prepare a sol. After heating the sol becomes
a protein crosslinked gel (kamaboko). Methods to determine gel strength may be based upon the fold test (no breaks after a circle is folded twice into a quarter) or mechanical methods (Instron testing for hardness, gumminess, cohesiveness, and chewiness; torsion testing and like procedures). The highest quality (SA grade) is positively correlated with myofibrillar protein solubility (r ⫽ 0.9849) and Ca 2⫹ -ATPase activity (r ⫽ 0.9584) as reported by Kim and Cho (1992). It has been well documented that the myofibrillar pro- teins of seafood protein are sensitive to the effects of chilled and frozen storage and that their solubility and the activity of the ATPase decrease with the length and temperature of frozen storage; hence the need for added cryoprotectants.
Sucrose and sorbitol are commonly used cryoprotectants, but sweetness and expense limit their addition to 4% each. Matsumoto and Noguchi (1992) reported that some Japa- nese processors now use a mixture of sorbitol, polyphosphates, and a glycerine ester of fatty acids for cryoprotection. Sucrose may also lead to discoloration of the surimi over time (Yu et al., 1994). These researchers reported that sucrose acts by increasing the surface tension of water and by preventing withdrawal of water from proteins. Yu et al. (1994) studied the cryoprotective effect of SAPP and STP and concluded that STP was superior. This could be explained by the greater anionic nature of STP than SAPP. The polyphosphates are sorbed onto the surface of the protein and cause the dispersion shown in the electron micrographs of Sato et al. (1990). Dziezak (1990) explained that the poly- Sucrose and sorbitol are commonly used cryoprotectants, but sweetness and expense limit their addition to 4% each. Matsumoto and Noguchi (1992) reported that some Japa- nese processors now use a mixture of sorbitol, polyphosphates, and a glycerine ester of fatty acids for cryoprotection. Sucrose may also lead to discoloration of the surimi over time (Yu et al., 1994). These researchers reported that sucrose acts by increasing the surface tension of water and by preventing withdrawal of water from proteins. Yu et al. (1994) studied the cryoprotective effect of SAPP and STP and concluded that STP was superior. This could be explained by the greater anionic nature of STP than SAPP. The polyphosphates are sorbed onto the surface of the protein and cause the dispersion shown in the electron micrographs of Sato et al. (1990). Dziezak (1990) explained that the poly-
g. Thermally Processed Seafoods. Struvite, or magnesium ammonium phosphate, may
be formed in thermally processed seafoods (e.g., canned tuna and crab). Sodium acid pyrophosphate can be used to sequester magnesium ions and thus inhibit struvite crystals, which resemble broken glass.
Salmon may develop a surface curd (denatured protein) if either held on ice for a protracted length of time or frozen prior to canning. The curd may constitute up to 4% of the pack by weight and may be considered questionable by many consumers.
Curd was significantly (p ⱕ 0.05) reduced by dipping sockeye salmon steaks for 2 to 120 s in 15 to 20% solutions of a condensed phosphate blend (sodium tripolyphosphate
and sodium hexametaphosphate) and by dipping for 30 to 120 s in 5 to 10% solutions (Wekell and Teeney, 1988). To avoid dipping, Wekell and Teeny (1988) verified that there was a 68% reduction in curd formation by dry addition of the phosphate blend prior to sealing the can. Although it was estimated that 1.0% polyphosphate would be needed to completely inhibit curd formation, this would exceed the legal limits for phosphate in canned salmon.
Domestically, phosphate is not uniformly allowed in canned salmon except for a temporary allowance granted to several processors. Its use in canned salmon has, however, been given provisional approval by the Canadian government.
Phosphates provide significant benefit to the seafood industry when there is a large harvest within close proximity, and, conversely, there are limited quotes (i.e., freezing fillets to extend wholesale/retail availability). Spawning salmonids may represent one of the most important applications since the muscle has been physicochemically altered. Such finfish contain reduced levels of myofibrillar proteins which lead to impaired muscle water holding capacity. This is parallel with elevated levels of sarcoplasmic proteins and total moisture, a combination conducive to curd development.
Crapo and Crawford (1991) evaluated the effect of holding backed (removal of the back and viscera) Dungeness crab (Cancer magister) in 10% solutions of a blend of STP and SHMP at 2 to 4 °C for 0 to 240 min. Treated crabs were either boiled or steam cooked for 4 to 20 min. The results indicated that moisture was not significantly increased in treated crabs versus the controls; phosphorus content was increased by 78 mg/100 g wet weight basis; yield was improved by approximately 8.5%, and sensory acceptance was improved. Furthermore, the authors determined that cooking time over 8 min (in steam) resulted in reduced yields. It is important to note that this protocol would not be applicable to all crab species since most mid-Atlantic and Gulf states mandate that live crabs be retort cooked prior to picking.
h. Troubleshooting. Often when phosphates are added in excess, a glassine look devel- ops. This is particularly noticeable on shrimp. There are regulatory constraints to the use of polyphosphates along with organoleptic problems (a soapy taste) if the phosphates are used in excess. The glassine appearance probably occurs more in error than through intentional overuse of phosphates since there are no standard or defined procedures for their application. Most industrial protocols have been developed by trial and error and/ or have been based upon far more resilient terrestrial muscle.
mation of a ‘‘floc’’ on the surface of certain species. Mineral content and pH of the muscle will exacerbate the formation of this crystalline precipitate.
Polyphosphate insolubility is related to water quality and to the individual type of condensed phosphate. Minerals in hard water will compete with some types of polyphos- phate for solubility. In addition, not all forms of polyphosphate are readily soluble in water.
Erratic functionality of phosphates also may be caused by either heating phosphates to promote solubility or using old solutions. Many of the polyphosphates are prone to hydrolysis, and the monomeric forms will not perform the same as the polymers.
i. Economic Fraud and Legal Limits. Recently, the use of phosphates in some segments of the seafood industry has been subject to government scrutiny. When improperly used, excessive absorption of moisture may lead to charges of economic fraud by the U.S. Food and Drug Administration. It is important to note, however, that seafood myofibrillar proteins readily denature at refrigeration temperatures (5 °C) and may lose up to 80% of their water-binding capacity within 5 days (Morey et al., 1982), while similar changes to beef muscle take in excess of 45 days at ⬎20°C (Lampila, 1991). Responsible use of food grade phosphates prevents economic fraud by seafood processors by aiding the processed muscle to retain natural juices and thus avoid excessive drip loss. Excessive drip loss can lead to fluid weeping to the extent that net stated weight is not met and the product becomes violative.
Research conducted by Crawford (1984,1985) verified that phosphate treated and controlled (water dipped) rockfish fillets increased 4% in weight after a 60-s immersion. Those dipped in the phosphate remained at their stated package weight throughout the 14 days of storage at 5 °C, while the controls, dipped in water, dropped below the initial weight within 4 days of chill storage.
Fresh, shell-on and peeled shrimp (Gulf of Mexico) were treated for 5 min in water and 2, 4, or 5% polyphosphate solutions. The shrimp were frozen and stored at ⫺26°C
for 2 weeks. Upon thawing and cooking (4 min), those shrimp dipped in the 4% blend for 5 min lost 0.8% weight after frozen storage (control, 2.0% loss) and 19.8% after cooking (control, 25.3% loss). It was concluded that addition of these phosphate blends imparted a cryoprotective effect (Duxbury, 1986).
Food grade phosphates and their products should not be cited only as ingredients to promote economic fraud. They impart numerous positive attributes within the seafood and food industry. These negative connotations related to economic adulteration reflect adversely on an ingredient which provides many advantages to the industry.
Phosphates are used as processing aids in the mechanical peeling of Pacific North- west shrimp (Crawford, 1980,1988); to prevent struvite formation in canned tuna (CFR, 1997); to inhibit curd formation in canned salmon (Wekell and Teeny, 1988); as cryopro- tectants to seafood quality during freezing and frozen storage (Woyewoda and Bligh, 1988); and in specialty blends to better control bacterial outgrowth and inhibit drip loss in finish (Crawford, 1984,1985). Recent researches by Applewhite et al. (1992,1993) have demonstrated that trained sensory panels prefer phosphate treated scallops and shrimp. Juiciness and tenderness were cited as some of the preferred characteristics over the un- treated controls.
Proposals have been submitted to limiting moisture content (to 80% or less) of selected seafood species as a means of predicting economic fraud promulgated by the use Proposals have been submitted to limiting moisture content (to 80% or less) of selected seafood species as a means of predicting economic fraud promulgated by the use
it is well documented that moisture content of a given species will vary widely. The moisture content of commercially harvested seafood muscle is 80% or greater in species, including, but not limited to, soft-shell blue crab, some molluscs, and postspawned finfish (Lampila, 1992,1994; Sidwell, 1981).
Webb et al. (1969) determined that the moisture content of bay scallop meats was significantly different at the 5% level between harvest years, sounds, locations within the sounds and among months, and within locations. These researchers (Webb et al., 1969) also determined that the moisture content (monthly sampling) of land-shucked bay and Calico scallops ranged between 74.15 to 83.66% and 76.12 to 81.86%, respectively.
In New Zealand (Hughes et al., 1980), scallops were determined to contain between
82.3 to 82.4% moisture. It should be noted that these meats were shucked into plastic bags (presumably to prevent hydration via melting ice), iced, and transported directly to the laboratory for analysis. This does not relate to current industry practice but was done to preclude moisture addition due to melting ice.
In April 1994, the FDA Office of Seafood conceded that the use of sodium tripoly- phosphate in the treatment of mechanically cooked and peeled Pacific shrimp did not result in a humectant effect and was indeed a processing aid (Billy, 1994). Treatment of shrimp with phosphate solutions prior to cooking and mechanical peeling served to better cleave immature collagen and therefore increased meat recovery and reduce added water.
The maximum permitted legal level in processed meat and poultry is 0.5% by weight of the final product and serves as the current guideline where their use is permitted. Poly- phosphates are now allowed in certain seafood species (CFR, 1997). They are, however, self-limiting. If much more than 0.5% of the high pH phosphates, such as sodium tripoly- phosphate, is used, flavor and appearance will be adversely affected. A guide to trouble- shooting the most common problems associated with meat, poultry, and seafood is shown in Table 16 .
D. Dairy Applications
1. Cheese The primary use of phosphates in dairy products is in the production of pasteurized process
cheeses and sauces. Wines, due to tartrates, were the original emulsifier for fondue. So- dium potassium tartrate (Rochelle salt) was used early in the 20th century for emulsifica- tion. It was abandoned due to a tendency to cause sandiness and resulted in cheese that was brittle, mealy, and had poor slice characteristics.
In 1912, J. L. Kraft developed a process to heat, melt, and stir pieces of cheddar cheese to produce a homogenous, preserved product. Nine years later, Elmer Eldredge at the Phenix Cheese Company was the first to use DSP-2 in process cheese to make a product with a uniform melt, smooth texture, and good slice characteristics (Zehren and Nusbaum, 1992).
The principles for manufacturing process cheese are essentially unchanged. Cheese emulsification is a process that undergoes the physical transition of gel–sol–gel. It takes place due to chemical (emulsifying salts), thermal (heating), and mechanical (stirring) action.
Process cheese is manufactured by blending young and mature ground cheeses with
Table 16 Troubleshooting Guide for Meat, Poultry, and Seafood Problem
Solution
Phosphate dissolves Dissolve phosphate before NaCl and other added ingredients. If slowly
H 2 O hardness is a factor, either softening or use of a phosphate blend may be required.
Clumping of phosphate Phosphate should be introduced into water agitated with sufficient vortex to prevent settling. A slow rate of addition best assures wetting and dissolution.
‘‘Whiskering’’ Crystalline precipitates are orthophosphate, which appear due to surface desiccation, excess solids competing for available H 2 O, or uneven distribution of phosphate. Prevent drying by monitor- ing cooking end point temperature and introducing well-circu- lated humidity, if possible. Reduce added solids, usually NaCl. Introduce physical measures to assure even distribution of brines.
Discoloration Biochemical reactions involving muscle pigments, lipids, miner- als, oxygen, or combinations may result in discoloration. Using a polyphosphate blend (containing SHMP) can be useful to se- quester copper, iron, and magnesium to inhibit discoloration. Pockets of alkalinity may cause browning. Brines must be evenly distributed through the muscle.
Flavor defects Uneven distribution of solutions can result in soapy flavors. An al- kaline ‘‘bite’’ can result from either inadvertent overuse or treatment of products with extremely delicate flavor profiles.
Glassy surface appearance The absorption of phosphates during dip applications will vary significantly among species, and particularly with seafood. For most seafoods, only seconds (at high brine concentrations) to a few minutes (at lower brine concentrations) may be required to assure adequate treatment.
Freezer burn Polyphosphates are used as cryoprotectants for isolated and native protein. Temperature fluctuations and package headspace can re- sult in significant migration of the moisture phase from the muscle surface. Shrink and vacuum packaging will minimize this occurrence.
Reduced yields Insufficient treatment of the product; loose packaging, slow freez- ing, and fluctuating temperatures in frozen storage; acidic pH; naturally hard or highly alkaline water; overcooking; and /or in- adequate smokehouse humidity or air circulation may lead to re- ductions in yield.
agitation. Cheese sauces contain more added water and, frequently, modified starch. The salts, added in order to peptize the protein, undergo ion exchange with calcium to form the soluble sodium paracaseinate and bind water through electrostatic bonds of the peptide chains (Zehren and Nusbaum, 1992; Berger et al., 1989). The net effect is to form a stable emulsion with even slice, melt, or spread/flow characteristics. Most notably, process cheeses are desirable to prevent protein agglomeration and fat separation in subsequent heating.
Preferably, melting salts will have polyvalent anions, form alkaline solutions, com- Preferably, melting salts will have polyvalent anions, form alkaline solutions, com-
The phosphates permitted in cheeses according to 21 CFR 133 include MSP, DSP, DKP, TSP, SHMP, SAPP, TSPP, and SALP. Use levels are permitted to 3.0% in the United States. Canada is more liberal with the permitted phosphates and allows use to 3.5%. Care should be taken when using the maximum allowable level of either DSP or TSP, since it may cause crystal formation (Table 17).
Recently, a patent was granted for a ‘‘superphosphate’’ which is described to contain
73 to 77% P (as P 2 O 5 ) with less than 2% metaphosphate (Merkenich et al., 1993). It is an acidic, long chain (8 to 20) polyphosphate which is possibly crosslinked. It has been reported to have some preservative effects in process cheese presumably due to sequestra- tion of metal ions and its resistance to hydrolysis by heat and enzymes.
Zboralski (1986) patented a formulation for calcium supplemented process cheese containing TCP (0.4 to 1.6%). Normally, this would be considered an anomaly since too high a level of calcium phosphate causes a sandy mouth-feel. The formulation was de- scribed to impart increased creaminess and gloss to the finished product. It is important to note that TCP sold as a calcium supplement for orange juice or as an anticaking agent would not be suitable. TCP for the described formulation would need to be 50 to 100% beta-TCP, be micronized (particle size 1 to 20 µm), have a large surface area, and consist
of a CaO : P 2 O 5 ratio between 2.5 : 1 to 3.1 : 1. By current manufacturing methods, this would be an expensive form of TCP.
Table 17 Troubleshooting Guide to Crystal Formation in Process Cheese Event
Cause
High pH
Too much TSP-12. Too much DSP-2. Raw ingredient pH is too high (very mature cheese tends to have a
high pH). In combination with low (⬍50°F) storage temperature precipitates
crystallization.
Presence of DKP DKP (75%) in combination with DSP (25%) at a level of 2.3%
emulsifying salts.
Citrates May result in the formation of tricalcium citrate tetrahydrate under conditions of high pH and low (37 to 45 °F) temperature. Other added ingredients
Cheeses containing high levels of tyrosine which act as ‘‘seed’’ for
precipitation. Excess addition of either whey or skim milk powder, which results in the formation of lactose crystals (i.e., the concentration of lac- tose in the water phase is 16.9% at 60 °F)
Tartrates Although not commonly used, the presence of tartrates can lead to the formation of calcium tartrate crystals. Physical factors
Uneven distribution of DSP within the cheese mixture. Inadequate time/temperature for melting of the crystals.
Mechanical Conditions conducive to the formation of crystals as deposits on the cooling belt, uneven surfaces on the deflector rollers, etc.
As previously indicated, process cheese is typically manufactured with a blend of young and mature cheeses. Kalab et al. (1991) described a study in which white or unrip- ened cheeses were incorporated at 8, 16, or 33% in the manufacture of processed cheese. Characteristically, white cheeses which do not melt when heated alone would lend intact casein and whey proteins as well as the advantage of blending without the need for aging the cheese. At all three levels of addition, the meltability of the cheese increased in the presence of TSP. Firmness of the processed cheese was unaffected at the 8 and 16% levels of white cheese, but did increase at the 33% level. This lends a broader application of cheeses for the production of cheese dips, spreads, and sauces.
Cheese powders were prepared from cheddar cheeses ranging from 2 to 8 months. Slurries of the cheeses were prepared with total solids (TS) ranging from 21 to 35%. Either trisodium citrate (TSC) in equal combination with DSP or DSP alone (2.5, 3.0, or 3.5%) were added to the slurries. The results indicated that sensory and physical properties of the reconstituted cheese spread were maximally achieved by using 3.0% DSP (Vipan and Tewari, 1992).
Trecker and Monckton (1990) have evaluated the use of DSP to parmesan cheese either before or after drying (to 19–24% moisture) to prevent subsequent oiling off. DSP added to the cheese dissolved into the matrix to inhibit agglomeration and oil-off at ambi- ent and greater storage temperatures.
Agusti (1993) used MCP in the production of mancheo cheese (a natural cheese). Its presence resulted in a reduction of coagulation time by 5 to 10 min, a firmer curd, lower moisture loss during ripening, and more intense flavor and aroma in the finished product.
Less than 9% of calcium in skim milk is retained in the curd of cottage cheese. This led Demott (1990) to evaluate the impact of CaCl 2 , MSP, DSP, SAPP, or STPP to skim milk to determine if the calcium content of cottage cheese curd could be increased. Levels of phosphate used were approximately 0.5 g/L. SAPP and STPP resulted in curd con- taining about nine times the calcium of the control. Curd containing STPP was firmer than either the control or SAPP treatments but was mealy.
2. Milk Products Phosphates are also used in the manufacture of milk products such as chocolate milk
(TSPP aids in the suspension of cocoa), in drying milks to aid in rehydration, and in concentrated milks ( Table 18 ). Either SHMP or TSPP may be added to ice cream to prevent churning (a sandiness or grittiness) of the fat. Allowable uses of phosphates to standardized dairy products are cited in 21 CFR parts 131, 133, and 135.
Pouliot and Boulet (1991) surveyed the variation in heat stability of concentrated milk over a 12-month period. The buffer capacity of the milk showed a seasonal variation being greatest in the summer and lowest in the winter. This effect was overcome by adding DSP to increase the pH by one unit to between pH 6 to 7 to enhance thermostabilization.
The seasonal variation is related to diet. Feeding silage tends to cause milk which is naturally low in phosphates and citrates (Hegenbart, 1990). After homogenization, the emulsion may break down with separation of the milk components. Added phosphates and citrates will overcome this problem.
Mil and van de Koning (1992) confirmed the seasonal variation in heat stability of milk described by Pouliot and Boulet (1991). By adding DSP to milk to be spray-dried, the pH was favorably adjusted to cause a shift in heat stability and enhanced rehydration
Table 18 Food Phosphates for Use in Dairy Foods and Desserts Application
Function Buttermilk
H 3 PO 4 used as an acidulant or TSPP used as a stabilizer. Chocolate/malted milk
TSPP is added for dispersion of the chocolate and to maintain
suspension of the solids.
Cottage cheese Phosphoric acid or MCP may be added to reduce the pH to
4.5 to 4.7.
Evaporated milk DSP is often used (0.1%) to protect protein (casein) from co- Low and whole fat dry milk
agulating during canning/drying.
Fermented dairy products Sour cream may contain those phosphates (STPP, SHMP) that improve texture, prevent syneresis, or extend shelf-life. Yo- gurt may contain phosphates that act as stabilizers.
Fluid dairy products (includes Phosphates may be added as stabilizers and/or emulsifiers. low fat milk, cream, half- and-half, and eggnog)
Ice cream DSP, TSPP, or SHMP (0.1 to 0.2%) may be added to prevent
churning of the fat.
Imitation coffee creamers DKP is most often used to adjust pH and prevent ‘‘feath- ering.’’ For neutral flavor characteristics, DKP is preferred over DSP (1.0 to 2.0%, dry weight). SHMP or STPP may also be used.
Instant puddings TSPP alone (to set the gel) or in combination with either Cheesecake filling
DSP-O or MCP-1 (to hasten setting) are used. Processed cheese
‘‘Emulsifying salt’’ (primarily orthophosphates and sometimes pyrophosphates) and SHMP are added (to 3%) in order to alter the melt, flow, and slicing properties of cheese. So- dium phosphates are used for ion exchange with calcium in the cheese base.
Starter cultures Nutrients: DSP, MSP, MAP, DAP, MKP, DKP. Whipped toppings
DSP (0.1 to 1.0%) is added as a foam stabilizer; TSPP or
SHMP.
Khan et al. (1992) confirmed the stabilizing effect of phosphates in sterilized buffalo milk. The effect was greatest at pH ⬎ 6.5 using MSP, DSP, and SHMP at levels ranging
between 25 to 100 mg/m. Although MSP has a detrimental effect due to pH reduction in cow’s milk, Loter (1983) reported that MSP could be used to make acidified milk heat stable to protein coagulation.
Montilla and Calvo (1997) used a commercial phosphate blend consisting of MSP, DSP, and TSP (Turrixin ST, now BK Giulini Rotem) to enhance the heat stability of goat milk. Goat milk is less resistant to thermal denaturation than cow milk. Goat milk has low (5% total) alpha sl -casein relative to cow milk (38% of total) (Mora-Gutierrez et al., 1993). Levels (0.09%) of Turrixin ST were determined to be effective against UHT dena- turation without altering pH. The effect was attributed to changes in ionic calcium and equilibrium of micellar calcium phosphate.
DSP has been repeatedly reported to stabilize the proteins of evaporated, condensed, and dried milk products. Harwalkar and Vreeman (1978a) demonstrated that DSP did cause accelerated age gelation in UHT-treated milk and that SHMP (1.5 g/kg) in fact DSP has been repeatedly reported to stabilize the proteins of evaporated, condensed, and dried milk products. Harwalkar and Vreeman (1978a) demonstrated that DSP did cause accelerated age gelation in UHT-treated milk and that SHMP (1.5 g/kg) in fact
Kocak and Zadow (1986) extended this work and added either sodium citrate (3 g/ kg) or SHMP (1 g/kg) to UHT milk. It was determined that apparent viscosity of the SHMP-treated sample was unchanged at 500 days storage and that this resulted in a sixfold extension in shelf-life. This effect was dependent upon a low initial psychrotrophic count in the raw milk (2.7 ⫻ 10 3 CFU/mL).
Earlier work (Kocak and Zadow, 1985) indicated that the effect of SHMP to inhibit age gelation in UHT milk could vary tremendously depending upon the phosphate manu- facturer. The previous study described the use of thin layer chromatography to evaluate the SHMP from different suppliers. Indeed, SHMP from one supplier contained large amounts of unpolymerized material (orthophosphates, pyrophosphates, STPP, and TSPP). Caution should be exercised when ordering samples of SHMP since it is manufactured in short, medium, and long chain forms. Each will have some different physicochemical properties.
3. Protein Gelation Xiong (1992) evaluated the effect of ions and ionic strength on the thermal aggregation
of whey proteins. Whey protein isolate was dialyzed against distilled, deionized water to remove calcium and small molecules. Sodium phosphate (5 mM) inhibited protein aggre- gation (1.2 mg/mL) when heated to 100 °C, while 20 to 50 mM concentrations caused aggregation at 77 °C. The addition of 0.6M NaCl plus 50 mM sodium phosphate (pH 7.0 to 7.5) resulted in a dramatic increase in protein aggregation.
Matsudomi et al. (1992) evaluated the effect of gelation and gel properties by vary- ing the ratios of alpha-lactalbumin (La) and beta-lactoglobulin (Lg) in a 100 mM potas- sium phosphate buffer (pH 6.8). Four percent solutions of Lg gelled, while 8% solutions of La did not gel upon heating at 80 °C for 30 min. The addition of 6% La to 2% Lg formed gels at lower heating temperatures due to sulfhydryl–disulfide interchange. A similar effect was noted using bovine serum albumin (BSA) and La in a 100 mM sodium phosphate buffer (Matsudomi et al., 1993).
Calcium caseinate (25 to 45% solids), SHMP (long chain, 0.5% concentration), and carrageenan (1 to 4%) or starches (wheat or potato, 2.5 to 5%) were used to prepare gels with properties similar to kamaboko (Konstance, 1993). At 35 to 45% levels of calcium caseinate, 0.5% SHMP, and carrageenan (1 to 2%) gels, properties of hardness, cohesive- ness, and water holding capacity (not elasticity) were similar to kamaboko. It was deter- mined that cohesiveness was dependent upon the added phosphate. The long chain SHMP was responsible for calcium binding and linkages that improved the gel matrix.
4. Reduced Fat Formulations Reduced fat formulations have gained popularity in the United States. This is related to
recommendations to reduce dietary fat to 30% or less of total daily caloric intake. Keogh (1993) described a method for the production of a water-in-oil emulsion (75 :
25 w/w) for low fat spreads. Sodium caseinate, starch, and sodium and hydrogen ions contributed to water binding, increased aqueous phase viscosity, and emulsion stability.
Melachouris et al. (1992), described a technique for reforming casein micelles to
be suitable in coffee whiteners or in reduced fat formulations (frozen and refrigerated desserts, puddings, whipped toppings, sauces and dips). High shear was used to process
a casein material (0.1 to 0.4 µm) without a micellar structure; soluble calcium salts, sodium hydroxide (to adjust pH to 6.0), and phosphates (DSP, DKP, TSP, TKP, or TSPP) were added to stabilized the reformed ‘‘micelle.’’ The resultant product can be spray-dried and will have a fat content of about 0.5%.
E. Vegetable and Fruit Processing
The two most important functions of phosphates in vegetable and fruit processing are chelating metal ions and acidification. Ellinger (1972b) covered this topic extensively, and Molins (1991) updated this topic noting that little work had been published in the intervening two decades (Table 19). Greatest attention will therefore be provided to the primary uses of phosphates in vegetable and fruit processing.
Potato processing is the main use of phosphates in the processing of vegetables. It is used to inhibit the after-cook blackening of the cut potato surface. Talley et al. (1969) published an extensive bibliography related to the after-cook discoloration of potatoes. The discoloration is due to oxidation of o-diphenolic compounds in the presence of metal ions. Typically, a dilute (ca. 1%) SAPP solution heated to 140–160 °F is sprayed onto the cut potato surface in order to complex ferrous ions in a colorless form. Iron content of the potato will vary by region and from year to year, and the concentration of the diphenols will increase according to the size of the potato (Siciliano et al., 1969; Heisler et al., 1969) and with its length of post-harvest storage. Sweet potatoes have grown in popularity, and they are also treated with SAPP to inhibit discoloration.
F. Beverages
Carbonated (cola and root beer) beverages contain phosphoric acid, which functions as an acidulant and contributes specific, tart flavor properties. Typically about 0.05 and 0.1%
Table 19 Use of Food Phosphates in Fruits and Vegetables Application
Function Canned berries
MCP (0.035% calculated as Ca) in combination with pectic acid (polygalacturonic acid) results in a firming of texture. Canned peas, tomatoes, bean
Calcium salts may be added as firming agents (peas, 0.035%; sprouts, lima beans, car-
tomatoes, 0.045 to 0.08%, calculated as calcium). rots, green sweet peppers, red sweet peppers, and potatoes
French fries A dilute (1 to 2%) SAPP spray is applied to the cut French fries to sequester iron. This inhibits blackening of the po- tato after the par-fry.
Fruit butter Phosphoric acid may be added to acidify or to preserve
(amount varies).
Fruit jelly, jam, and preserves Phosphates may be added as acidifiers or buffers. Peas and beans
SHMP is applied to the peas and beans to inhibit toughening of the skin (by sequestering calcium).
phosphoric acid is used in colas and root beers, respectively. Other phosphates and bever- age applications are described in Table 20.
Orange juice has been supplemented with calcium (TCP) in the United States for the past 12 years, and approval is now pending by the Canadian government (Solomon, 1997). The levels added range from 0.1 to 0.2% by weight, which is in the range for that occurring in milk (0.12%) (Burkes et al., 1995). Calcium supplementation of fruit juice has gained in popularity due to the association of inadequate dietary calcium and the development of osteoporosis. In the United States, milk consumption generally decreases with age due to an increased consumption of soft drinks, coffee and tea, and alcoholic beverages.
Canton (1994) has patented a dry formulation for use with coffee to form a foamed head typical of that of steam generator prepared coffee (espresso or Cuban coffee). This novel preparation consists, in approximate amounts, of sugar (90%), gelatinized starch (5%), sodium bicarbonate (3%), MCP (1%), and SALP (1%). The leavening phosphates are employed to react to generate gas bubbles in the range of 1–2 mm in diameter (foam) and the gelatinized starch stabilizes the foam and aids to form the skin.
In the United States, there is a large market for isotonic beverages intended for consumption after vigorous exercise and during physical work in hot and humid climates. An example of an isotonic beverage to replace electrolytes, nutrients, and energy lost during exercise has been patented (Hastings, 1992). This formulation consisted (in percent- ages) of fructose (72.2), maltodextrin (16.7), citric acid (5.2), lemon flavor (1.6), TCP (1.4), potassium citrate (0.9), salt (0.7), hydrogenated soy oil (0.6), vitamin C (0.3), MgO (0.2), zinc monomethionate (0.1), chromemate (0.1), and a trace of beta carotene. This beverage would supply approximately 50% of the adult daily requirement of calcium. Phosphorus loading is of importance as well, since Cade et al. (1984) demonstrated that
Table 20 Phosphoric Acid and Phosphates in Beverages Application
Function Colas and root beer
Phosphoric acid or phosphate
H 3 PO 4 Acidulant and flavor Dry beverage mixes
MCP
Nonhygroscopic partial (50%) re- placement for citric acid
Anticaking agent; clouding agent; nutritional supplement Fruit juices/cider
TCP
MCP; H 3 PO 4 Acidulants
SHMP
Stabilizer; shelf-life extension
Calcium supplement Isotonic formulations
TCP
Sodium or potassium supplement Noncarbonated beverages
MSP; MKP
SHMP; STPP
Sequestrant; shelf-life extension
Calcium supplement Nutritional formulations
TCP
MCP; DCP; TCP; MKP;
Mineral supplement
DKP; TKPP; MSP
Inhibit age gelation Evaporated, condensed,
UHT milk
SHMP
Inhibit protein coagulation or dried milk Nondairy creamer
DSP
Inhibit feathering Beer and wine
DKP; MKP
DAP
Yeast nutrient
SHMP
Prevent clouding Prevent clouding
The effect of DSP and DKP on emulsion stability of liquids prepared with soy protein isolate (SPI) has been reported by Hwang et al. (1992). Emulsion stability was greatest when either DSP or DKP was added prior to emulsification and under unfavorable conditions: pH 4.5, the isoelectric point of the SPI.
Barnes et al. (1992) investigated the effect of various stabilizers in a model milk beverage system which was sweetened, acidified, and carbonated in order to prevent a two layer separation from occurring while simulating the viscosity of 2% milk. DSP, DAP, or sodium bicarbonate at levels of 0.3% prevented separation of the beverage for up to
21 days.
G. Oils and Dressings
The refinement of oils has been well documented (Ellinger, 1972b). The phosphates are used in both alkalai and acid refining protocol as well as during bleaching. Recently, Taylor et al. (1992) described the manufacture of zirconium silicate (an intercalate), bonded using phosphate, phosphonate, or phosphites, to remove carotenoids (yellow to red pigments) of palm, cottonseed, and grapeseed oils and chlorophyll (green pigment) soya oil.
Attempts to reduce dietary fat have led to the development of nonstick spray coatings for cookware. Clapp and Campbell (1992) described a formulation that consisted of phos- phate salt derivatives of mono- and diglycerides, vegetable oils, a blocking agent (one of which may be baking powder), a suspending agent, and a propellant for spraying from an aerosol container. This formulation is claimed to be stable to 400 to 500 °F (204 to 260 °C), which is superior to lecithin-based sprays, which tend to char at temperatures of 350 °F (176.6°C).
Reduced fat, low fat, and fat free products have shown explosive growth in recent years. The two major limitations include texture and flavor defects due to the use of hydro- colloids, which have distinctly different texture and flavor carrier profiles. Coutant and Wong (1994) patented a formulation to include 1.5 to 3.0% TCP in reduced fat liquid products, focusing on salad dressings. The presence of TCP enhanced opacity and smooth- ness, while concomitantly reducing ‘‘gloppiness’’ or the tendency to pour unevenly or have a ‘‘ gloppy flow.’’ Although it is not stated, it is presumed that a TCP with a small particle size would be preferred for greatest smoothness. Other uses of phosphates in oils and dressings are shown in Table 21 .
H. Eggs
Phosphates are used in many egg products for a variety of technical and functional effects. Shell-on eggs may be washed in weak phosphate solutions to sequester iron, an accelerator of egg spoilage. Preservation of natural color, improved whipping, foam height, and sensi- tization of Salmonella are shown in Table 22 .
Reduction of cholesterol in egg yolks using acid alone or a combination of salt and acid has also been patented (Lombardo and Kijowski, 1994). This process involves the
Table 21 Food Phosphates for Use in Salad Dressings, Fats, and Oils Application
Function
Diet salad dressings H 3 PO 4 acts as an acidulant to impart flavor; acidity may act to control pH and inhibit microbial growth.
French dressing
SHMP sequesters calcium to aid added thickeners.
Margarine STPP acts as a stabilizer. Mayonnaise
SHMP acts as a sequestrant. Oil refining
H 3 PO 4 is used in acid and alkalai refining.
Salad dressing Phosphates act as sequestrants, stabilizers, and thickening aids.
and water and a second stream of oil and cholesterol. Although the preferred acid is acetic, phosphoric, ascorbic, and the like are also suitable.
I. Oral Care Products
Common oral care products include gels, toothpastes, mouthwashes, lozenges, and chew- ing gum. Sodium monofluorophosphate (SMFP) has been used in toothpaste for decades to supply additional fluoride. DCP-2 is included for its abrasive properties, which include polishing and whitening the teeth (Nathoo et al., 1991, 1992; Chan et al., 1990). More recently, reports have been issued relating to restoration of the tooth surface or a repair of scratches and early enamel caries and remineralization of exposed roots (Schumann et al., 1992; Tung, 1992; Cheng et al., 1991) by DCP which is strengthened by fluoride. Another patent (Winston and Usen, 1996) has included any one or a combination of DKP, DCP-2, DSP, SHMP, SMFP, and MKP to remineralize teeth.
TSPP is often added to inhibit demineralization of the enamel (Featherstone and Mazzanobile, 1993). Saito (1991) determined that a combination of TSPP (20 ppm) and casein phosphopeptide (40 ppm) synergistically inhibited hydroxyapatite formation (dental
Table 22 Food Phosphates for Use in Eggs Application
Function
Egg yolks—dried, frozen, STPP and SHMP protect protein from coagulation and MSP or or refrigerated
MKP aid to preserve natural color.
Egg whites—dried H 3 PO 4 to adjust pH for reduction of glucose. STPP (1.3 to 2.0%) and SHMP (2.3 to 3.0%) improve subsequent whipping ability and stability to frozen storage. SHMP (2.5% dry wt) aids to de- crease whip time, increase foam height, and stability and toler- ance to overbeating.
Egg whites—frozen MSP or MKP preserve color. SHMP and STPP improve whipping
ability.
Egg whites—refrigerated MSP lowers the pH (from 9.3 to ca. 8.0) for better tolerance to overbeating of pasteurized egg whites. SHMP (2%) overcomes effects of yolk contamination on foam development.
Liquid eggs MSP or MKP (0.5%) preserves color. SHMP (0.5%) plus CaCl 2 during pasteurization (130 to 135 °F; 54 to 57°C) enhance pro- tein stability and reduction of Salmonella.
calculus) and patented their inclusion in a toothpaste formulation. Winston et al. (1991) patented a dentifrice (anticalculus) formulation which contained sodium bicarbonate to displace TKPP (which may impart a bitter flavor at high levels) and reduced TSPP. Drake et al. (1994) investigated the effect of pyrophosphate on oral bacteria (Streptococcus san- guis, S. mutans (serotype C), Actinomyces viscosus, A. naeslundii) commonly associated with supragingival plaque. All species were susceptible to TSPP at minimal inhibitory concentrations (0.67% wt/vol; 25mM). Pronounced growth inhibition (over 24 h) of S. mutans was observed after two 5-min exposures to TSPP in combinations with sodium dodecyl sulfate (Drake et al., 1994).
Toothpaste and mouthwash formulations to prevent dental calculus containing other phosphates have also been patented. White et al. (1990) included the use of STPP and either MSP or TSP; Gaffar et al. (1990) included combinations of TSPP, SMFP, and polyvinyl phosphonate (to inhibit enzymic hydrolysis of TSPP) and Gershon et al. (1991) described an oral rinse for removing dental plaque containing DSP-0 and MSP.
J. Pet Foods
Phosphates are included in many pet food applications, which include wet and dry food and snacks and treats. STPP and TSPP are frequently included in canned foods to maintain the integrity of the pack or to bind the ingredients into a cohesive mass or chunk. MCP, DCP, and TCP are used as calcium sources. Phosphoric acid is used as an acidulant to treat meat byproducts during the production of either a high or low viscosity hydrolysate ingredient used in, for example, extruded pellets and flavor sprays, respectively.
Awareness of human dental health and the implications that bacterial gum infections can lead to an infected pericardium has lead to research into the prevention of calculus in dogs and cats. Scaglione et al. (1989) determined that application of a solution con- taining TSPP (5.42%) and trisodium pyrophosphate (1.85%) showed a significant reduc- tion in tartar accumulation in dogs. These researchers patented a dry biscuit formulation containing flour, soy meal, meat and bone meal, TSPP, wheat meal, tallow, natural flavors, salt, trisodium pyrophosphate, DCP, bone meal, dough conditioners, CaCO, and a vitamin premix. The dry biscuit, when chewed, cleans tooth surfaces, removes tartar, and exercises and massages the gums. Scaglione and Staples (1989a) later patented a dry biscuit formula- tion without DCP but containing the two aforementioned sodium phosphates in lesser amounts. This was followed by a patent for a biscuit coating containing only trisodium pyrophosphate (Scaglione and Staples, 1989b).
Spanier et al. (1989) applied reduced levels of TSPP and trisodium phosphate (1.5% and 0.5%, respectively) to dogs’ teeth and noted reduction of tartar over a 30-day period. These observations resulted in a patent for processing rawhide treats containing sodium phosphates to reduce tartar when chewed/eaten. Spanier and Ekpo (1989) subsequently patented a process to coat the rawhide treat with a flavored, tartar control solution.
K. Miscellaneous Uses of Food Grade Phosphates
1. Candy and Confections DCP agglomerated with lecithin and sugar is used to produce a nonchalky chewing gum
base (Carroll et al., 1985). It also acts to control hydration of the gum and control the amorphous, cohesive mass.
2. Pigment Integrity Washino and Moriwaki (1989) patented a process to protect rutin from UV irradiation.
This process involved the conversion of rutin to quercetin 3-O-monoglucoside and subse- quently a water-soluble flavonol glycoside. Sugar syrup was mixed with purple corn pig- ment (5 ppm), flavonol glycoside (0.5 ppm), sodium erythorbate (1 ppm), and SHMP (0.1 ppm) and after 16 h of UV treatment resulted in 83% remaining pigment.
3. Flavor Ugawa et al. (1992) investigated the effects of either NaCl or sodium phosphate on the
sweetness of the amino acids glycine, alanine, and serine. It was determined that 30 mM NaCl added to 100 mM of amino acid was equivalent to 500 to 600 mM amino acid while sodium phosphate affected sweetness only slightly. Aoki and Hata described the addition of apatite heated to 10 °C (beta-TCP) to improve the flavor of rice.
4. Insect Control TCP (2%) was added to whole and dehulled sorghum flour (Rao and Vimala, 1993). It
was determined to control insect infestation during storage. This has previously been re- ported to be effective in wheat flour and works by abrasive action under the insect wing.
L. Microbial Inhibition
A number of reports have been published related to the antimicrobial effects of the food phosphates. While the food phosphates are not considered direct preservatives, they can impart some desirable properties when used as acidulants or in combination with other food ingredients.
Rajkowski et al. (1994) evaluated the antimicrobial effect of SHMP [13 (medium chain) at 0.5 and 1.0%] in either the presence or absence of NaCl in UHT sterilized milk. Either Listeria monocytogenes or Staphylococcus aureus were inoculated into the substrate
at a level of 10 3 CFU/mL. Cultures were incubated at 12, 19, 28, or 37 °C for up to 48 h. No significant inhibition of growth was determined due to the presence of SHMP alone or in combination with NaCl. This was attributed to the presence of calcium and magne- sium in the milk. SHMP is known to form soluble calcium complexes with milk casein. This phosphate (1% solution) typically has a pH of 6.9; it is also a very weak buffer and therefore would not have exerted a strong pH effect.
Lee et al. (1994) confirmed that S. aureus would not be inhibited by sodium ultra- phosphate (UP, sodium acid hexametaphosphate) and SHMP (chain length, ca. 20) in the presence of either 10 mM calcium or magnesium or by TSPP in the presence of 10 mM iron. These effects were noted if the minerals were added prior to inoculation or 1 h after inoculation. Chang and Lee (1990) confirmed that bacterial inhibition mediated by SHMP
was decreased by CaCl 2 , KCl, and MgSO 4 . Jen and Shelef (1986) noted that inhibitory effects of STPP were overcome by calcium and iron but not zinc or magnesium.
A number of studies have described the autoclave sterilization of the phosphates within the culture media. This will result in hydrolysis of pyro-, tripoly-, and hexa- meta- phosphates to orthophosphate. Therefore, the results will not reflect anything related to any phosphate longer than an orthophosphate. Phosphate solutions should be filter steril- ized and added to cooled, sterile media.
The antimicrobial effect (initial load 10 CFU/mL) use of SHMP (chain length 3 to The antimicrobial effect (initial load 10 CFU/mL) use of SHMP (chain length 3 to
These patents are significantly narrower relative to antibacterial and antifungal claims cited by Kohl and Ellinger (1972). These authors evaluated the impact of polyphos- phates (chain length 16 to 37, 0.5 to 1.0% wt/wt) on products ranging from apple juice and egg whites to fish fillets. In some products the synergistic effect of sorbates, benzoates, and proprionates to inhibit fungi was noted.
Nisin in combination with SHMP was investigated for inhibitory effects on the growth of Escherichia coli 0157:H7 and Salmonella typhimurium. Although SHMP en- hanced the effect of nisin, EDTA was more effective in reducing bacterial populations in vitro (Cutter and Siragusa, 1995a). These effects were not reproducible in situ using lean beef tissue as the substrate (Cutter and Siragusa, 1995b).
Yen et al. (1991) evaluated, individually and in combination, the effect of cure ingredients [NaCl, dextrose, nitrite, erythorbate, and phosphates (0.4% STPP plus SHMP)] on the inhibition of L. monocytogenes in ground pork. Fresh pork was mixed with the
cure ingredients, inoculated with 10 7 to 10 8 CFU/g L. monocytogenes, and cooked in a water bath to 63 °C. It was not determined if the phosphates enhanced heat lethality or inhibited recovery of injured cells (0.8 log reduction). Most disturbing was the fact that the greatest protective effect to the organism was noted in the presence of all cure ingredients.
Li et al. (1993) determined no STPP mediated microbial inhibition in either cooked or uncooked ground turkey meat. In ground, raw turkey meat, the hydrolysis of STPP to orthophosphate was complete after 1 day storage at 5 °C. Frederick et al. (1994) studied the effect of microbial growth of 95% lean beef, German (cooked) sausage containing either 0.5 or 1.0% phosphate (unspecified). Microbial growth was somewhat reduced in products containing phosphate plus 0, 10, or 20% added water, but was enhanced in the high fat control and the sample containing 35% added water. Hydrolysis of phosphate during the cook cycle or during frozen storage to orthophosphate may actually have been
a nutrient microbial growth. Phosphates have been patented as carcass wash treatments to either reduce or elimi- nate microbial contamination. Pathogen reduction has been of greatest interest due to recent outbreaks of foodborne illness.
Bender and Brotsky (1991) and Bender and Brotsky (1993a,b) patented processes for treating poultry carcasses and red meat (to control Salmonella and bacterial contaminants, respectively) with phosphates and, particularly, 8 to 12% TSP solutions. This is a very alkaline treatment (pH ca. 11–12). A second treatment includes a chealating agent (SAPP, acidic SHMP, EDTA, etc.), a fatty acid monoester, and a food grade surfactant (Andrews and Munson, 1995) and was described as being as effective or moreso than an 8% TSP wash. Various researchers have evaluated the efficacy of a variety of carcass washes and arrived at differing conclusions (Bautista et al., 1997; Lillard, 1994; Somers and Schoeni, 1994). Among factors in dispute are the carryover of an alkaline wash into either diluent peptone or plating media, poor adherence of bacteria when carcasses are artificially inocu-
Kim and Slavik (1994) determined that a 10% TSP wash to beef pieces resulted in effective removal of Escherichia coli and Salmonella typhimurium from the fat, but less so from the fascia. E. coli was determined to be more efficiently removed than S. typhimu- rium .
A disinfectant containing ethanol (8.7%), lactic acid (0.87%), and phosphoric acid (0.43%) for eliminating coliforms from blocks of kamaboko was described by Ueno et al. (1981). This work was expanded to include a group of organic acids (acetic, citric, tartaric gluconic, malic ascorbic, or phytic) to substitute for lactic when used in combina- tion with ethanol and phosphoric acid (Ueno et al., 1987). This formulation was described to be suitable for treating kamaboko, onion, cucumber, chicken eggs, chicken portions, Vienna sausage, ham, raw vegetables, noodles, and pasta. It was described as disinfecting
a kamabokolike crab cake after a contact time of 30 s (Ueno et al., 1984).