Sequestrants as a Food Ingredient

Benjamin M Bohrer, University of Guelph, Guelph, ON, Canada

© 2019 Elsevier Inc. All rights reserved.

Glossary
Chelation a type of bonding of ions or molecules to metal ions; involves the formation or presence of two or more separate
coordinate bonds between a polydentate ligand and a single central atom.
Food additives substances (synthetically produced or naturally occurring) incorporated in the formulation of a food product
with the purpose to contribute in the processing, storage, preparation, or quality of foods.
Ligand a molecule, ion, or atom that is bonded to the central metal atom of a coordination compound.
Sequestrant a type of a food additive which improves the quality and stability of foods through the formation of chelate
complexes.

Overview

Sequestrants (chelating agents) offer food processors a valuable tool to be used to ensure integrity of whole and processed
foods. The reaction caused by sequestrants protects food products from chemical, oxidative, and enzymatic reactions that promote
deterioration during processing, storage, or preparation of foods through chelation. Sequestrants form chelate complexes with
polyvalent metal ions (i.e. copper, iron and nickel), which can serve a variety of purposes in maintaining food quality (Aamoth
and Butt, 1960). The term chelate comes from the Greek word “claw”, and they often resemble a claw with the metal ion clutched
between the pincers of the organic molecule (Bessman and Doorenbos, 1957). As a food additive that has been around and used
for over 75 years, the mechanistic action and purposes of sequestrants as a food additive are relatively well understood (Bessman
and Doorenbos, 1957; Albert and Serjeant, 1984). This book chapter will help readers understand the mechanistic action of
sequestrants, provide insight to common examples of sequestrants, and describe the use of sequestrants in foods.

Mechanistic Action of Sequestrants

The reaction of a sequestrant with metallic and alkaline ions causes new metal complexes to be formed. In the newly formed
complex, the metallic or alkaline ion is bound with a charged or uncharged electron donor referred to as the ligand (Damodaran
et al., 2007; Furia and Furia, 1972; Yoe, 1958). By definition, the sequestrant is the molecule with the ligand properties (binding
sites) that enable the newly formed metal complex to be formed (Furia and Furia, 1972).
Metal Ion þ Ligand ðsequestrantÞ ¼ Newly formed Metal Complex
Two general conditions must be satisfied for a sequestrant to be effective (Furia and Furia, 1972). First, the sequestrant must have
the proper steric and electronic configuration in relation to the metal ion that is being acted upon, and secondly the environmental
conditions (pH, ionic strength, solubility, etc.) must be conducive to the formation of the new complex.

Examples of Sequestrants

While a great number of sequestrants are known to be highly effective as metal complexing agents, a great concern of food
processors and government regulatory agencies continues to surface regarding their safety (Furia and Furia, 1972). Thus, most
sequestrants used in the food industry are naturally occurring substances such as polycarboxylic acids, hydroxycarboxylic
acids, polyphosphoric acids, amino acids, and various other macromolecules (Furia and Furia, 1972). Once safety and efficacy
are established, the other determining factors determining the usefulness of a sequestrant is the effect on product quality and
sensory attributes (color, flavor, etc.). Depending on the food product being manufactured, other considerations when choosing
a sequestrant includes the substrate capability and the particular metal(s) in the food matrix that warrants chelation. Common
examples of sequestrants in foods can be broken into three major categories, which will be discussed in the succeeding
subsections.

Ethylenediaminetetraacetic Acid
Likely the most commonly recognized of all sequestrants, EDTA is widely used with great success as a chelating agent in both food
and non-food applications (Yoe, 1958; Gardiner, 1976; Branen and Davidson, 2004). EDTA is colorless, water soluble solid that is
typically used in the food industry in a di-sodium salt form, a di-ammonium form, a chelated ferric sodium form, or a ferric

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252 Sequestrants as a Food Ingredient

ammonium salt form. EDTA contains six donor groups (hexadentate) and has the ability to bind six times, at two nitrogen positions
and at four oxygen positions (Fig. 1). Examples of food applications of EDTA salts include beverages (beer and malt beverages),
condiments (salad dressing and sauces), canned meats and seafoods, and many others (Table 1). Overall, EDTA forms very stable
complexes with most metal ions (particularly calcium and magnesium), and has been proven to be safe at low inclusion levels in
food products (Lanigan and Yamarik, 2002; Heimbach et al., 2000; Wedeen et al., 1983).

Phosphates
Phosphates are the naturally occurring form of the mineral phosphorus and the salt-forming anion of phosphoric acid.
Many different types of phosphate salts are approved for use including sodium phosphates, calcium phosphates, and potassium
phosphates (Table 2). Common food applications include processed meat products, ice cream, and frozen dairy products. With
particular inference to meat processing, phosphates offer multi-functional roles with direct effects on water retention and improved
binding properties (Sindelar, 2015). The meat industry has been attempting for several years to replace phosphates with
more “natural” ingredients to meet clean label requirements, yet no direct substitutes have been discovered nor are any complete
substitutes are being used at the present time.

Figure 1 The chemical structure of Ethylenediaminetetraacetic Acid (EDTA) with potential binding sites depicted with an asterisk (*).

Table 1 List of permitted EDTA substances permitted uses according to United States Food and Drug Administration (FDA) and Canadian Food
Inspection Agency (CFIA)

Name of compound Permitted uses

Calcium disodium EDTA Ale; Beer; Malt liquor; Porter; Stout

Unstandardized dressings; Unstandardized sauces; French dressing; Mayonnaise; Salad dressing
Potato salad; Unstandardized sandwich spreads
Canned shrimp; Canned tuna; Canned crabmeat; Canned lobster; Canned salmon
Margarine
Canned clams; Canned sea snails; Canned snails
Canned legumes except canned green beans, canned peas and canned wax beans
Unstandardized beverage concentrates, except unstandardized dairy beverage concentrates and unstandardized
alcoholic beverage concentrates
Pasteurized sous-vide potatoes
Beans; Beans with pork
Disodium EDTA Dressing and sauces
Unstandardized sandwich spreads
Canned legumes except canned green beans, canned peas and canned wax beans
Dried banana products
Aqueous suspensions of color lake preparations for use in coating confectionery tablets
Pasteurized sous-vide potatoes
Edible coating for sausages
Beans; Beans with pork

Information sourced from regulatory webpages of the United States Food and Drug Administration (FDA) and Canadian Food Inspection Agency (CFIA).
 Sequestrants as a Food Ingredient 253

Table 2 List of permitted phosphates with sequestration activity and their permitted uses according to United States Food and Drug Administration
(FDA) and Canadian Food Inspection Agency (CFIA)

Name of compound Permitted uses

Calcium phosphate, monobasic
Calcium phosphate, tribasic
Potassium phosphate, monobasic
Potassium phosphate, dibasic
Potassium phosphate tetrabasic
Potassium tripolyphosphate
Sodium acid pyrophosphate
Sodium hexametaphosphate
Sodium phosphate,
monobasic and dibasic
Sodium potassium hexametaphosphate
Sodium potassium tripolyphosphate
Sodium pyrophosphate, tetrabasic
Sodium pyrophosphate, tribasic
Sodium tripolyphosphate
Calcium Phytate
Phosphoric acid
Unstandardized dairy products; Ice cream mix; Ice milk mix; Sherbert
Ice cream mix; Ice milk mix
Unstandardized foods; Injection or cover solution for the curing of poultry or poultry meat; Pumping pickle
for the curing of pork, beef and lamb cuts; Prepared meat; Solid cut meat and poultry; Meat tenderizers;
Ice cream mix; Ice milk mix; Sherbet
Injection or cover solution for the curing of poultry or poultry meat; Pumping pickle for the curing of pork,
beef and lamb cuts; Prepared meat; Solid cut meat and poultry; Meat tenderizers
Injection or cover solution for the curing of poultry or poultry meat; Pumping pickle for the curing of pork,
beef and lamb cuts; Prepared meat; Solid cut meat and poultry; Meat tenderizers; Canned seafood
Unstandardized foods; Injection or cover solution for the curing of poultry or poultry meat; Pumping pickle
for the curing of pork, beef and lamb cuts; Prepared meat; Solid cut meat and poultry; Meat tenderizers;
Canned seafood
Unstandardized foods; Injection or cover solution for the curing of poultry or poultry meat; Pumping pickle
for the curing of pork, beef and lamb cuts; Prepared meat; Solid cut meat and poultry; Meat tenderizers;
Canned seafood; Ice cream mix and milk mix
Unstandardized foods; Injection or cover solution for the curing of poultry or poultry meat; Pumping pickle
for the curing of pork, beef and lamb cuts; Prepared meat; Solid cut meat and poultry; Meat tenderizers;
Canned seafood
Unstandardized foods; Injection or cover solution for the curing of poultry or poultry meat; Pumping pickle
for the curing of pork, beef and lamb cuts; Prepared meat; Solid cut meat and poultry; Meat tenderizers;
Ice cream mix; Ice milk mix; Sherbet
Unstandardized foods; Injection or cover solution for the curing of poultry or poultry meat; Pumping pickle
for the curing of pork, beef and lamb cuts; Prepared meat; Solid cut meat and poultry; Meat tenderizers;
Canned seafood; Ice cream mix; Ice milk mix; Liquid whey products
Unstandardized foods; Injection or cover solution for the curing of poultry or poultry meat; Pumping pickle
for the curing of pork, beef and lamb cuts; Prepared meat; Solid cut meat and poultry; Meat tenderizers;
Canned seafood
Unstandardized foods; Injection or cover solution for the curing of poultry or poultry meat; Pumping pickle
for the curing of pork, beef and lamb cuts; Prepared meat; Solid cut meat and poultry; Meat tenderizers;
Ice cream mix; Ice milk mix; Sherbet
Unstandardized foods; Injection or cover solution for the curing of poultry or poultry meat; Pumping pickle
for the curing of pork, beef and lamb cuts; Prepared meat; Solid cut meat and poultry; Meat tenderizers
Unstandardized foods; Injection or cover solution for the curing of poultry or poultry meat; Pumping pickle
for the curing of pork, beef and lamb cuts; Prepared meat; Solid cut meat and poultry; Meat tenderizers
Glazed fruit
Mono- and di-glycerides

Information sourced from regulatory webpages of the United States Food and Drug Administration (FDA) and Canadian Food Inspection Agency (CFIA).

Citric Acid
Citric acid and other forms of citrate (derivatives of citric acid) occur naturally in citrus fruits (lemons, limes, oranges, etc.; Table 3). In
addition to the acidic properties that citric acid elicits in terms of flavor, preservation, and emulsification – citric acid and other forms
of citrate are fairly effective sequestrants by binding metals into water soluble complexes (Mehltretter et al., 1953; Soccol et al., 2006).

The Role of Sequestrants in Foods

Newly formed complexes formed by sequestrants exhibit unique properties in terms of their ability to function in a food matrix.
Sequestrants have been adopted as common food additives for a variety of purposes in foods; yet the major reason would be to
ensure product quality after extended periods of storage and/or shelf time. Sequestrants can contribute an important part in the
stabilization and sustainability of fat/oil quality. Sequestrants do not directly contribute to the inhibition of oxidation; however,
play a role in the delay of lipid oxidation by chelating trace metals that are pro-oxidant catalysts. Metal chelation slows or even
eliminates the ability for pro-oxidant activity of some metals in food products (Furia and Furia, 1972; Labuza and Dugan, 1971).
The synergistic effects of sequestrants and antioxidants have been established for a lengthy period of time in a variety of food
applications (Furia and Furia, 1972). Vitamins tend to be unstable components in food products, and sequestrants have been
used (along with antioxidants) for preventing and inhibiting the decomposition of oil soluble vitamins. The use of sequestrants
in produce prone to enzymatic browning (i.e. fruits, vegetables, potato, and dairy products) has been well-established for decades
(Furia and Furia, 1972).
254 Sequestrants as a Food Ingredient

Table 3 List of permitted citric acids and derivatives with sequestrant activity and their permitted uses according to United States Food and Drug
Administration (FDA) and Canadian Food Inspection Agency (CFIA)

Name of compound Permitted uses

Citric acid Pumping pickle, cover pickle, and dry cure employed in the curing of preserved meat or preserved
meat by-product
Unstandardized foods
Frozen seafood (clams, crab, crustaceans, fish, lobster, marine mammals, minced fish, molluscs,
shrimp; Prepared fish or prepared meat; Preserved fish or preserved meat; Other Frozen marine
invertebrates
Ammonium citrate, monobasic or dibasic Unstandardized foods
Calcium citrate Unstandardized foods
Sodium citrate Unstandardized foods
Ice cream mix; Ice milk mix; Pumping pickle, cover pickle and dry cure employed in the curing of
preserved meat or preserved meat by-product; Sherbet
Frozen clams; Frozen crab; Frozen crustaceans; Frozen fish; Frozen fish fillets; Frozen lobster; Frozen
marine mammals; Frozen minced fish; Frozen molluscs; Frozen shrimp; Glaze of frozen fish;
Prepared fish or prepared meat
Stearyl citrate Margarine

Information sourced from regulatory webpages of the United States Food and Drug Administration (FDA) and Canadian Food Inspection Agency (CFIA).

Another key role that sequestrants have is their ability to aid in water retention during processing and product storage
(Shults et al., 1972; Hellendoorn, 1962; Thorarinsdottir et al., 2001). This example may be observed to the greatest extent
with the use of phosphates in processed meat products. Phosphates are a common ingredient in many processed meat products
and have direct roles on sensory attributes and processing techniques that are implemented in the meat industry. Similar to
the chelation in metals found in water, phosphates may also chelate divalent cations in meat. A classical theory claims that
phosphates bind divalent cations away from the protein cross-bridges, allowing the protein structure to unravel and hold
more water through capillary activity (Knipe, 1983). Some research even suggests that phosphates may only affect free cations
with limited to no effects on cations already bound to proteins (Knipe, 1983). The cation chelation by alkaline phosphates
protects cooked meats from “warmed-over” flavors, while also stabilizing cured color, and improving retention during thawing
of frozen products (Knipe, 1983).

Conclusions

Sequestrants provide food processors a valuable tool in the food additive toolbox with a wide range of purposes and uses. The
integrity of whole and processed foods can be improved with sequestrants with particular inference on slowing of lipid oxidation
and improvement of water retention properties. In general, sequestrants approved for use in food products are considered to be safe
and effective at inclusion levels established by governing agencies such as the United States Food and Drug Administration and the
Canadian Food Inspection Agency.

References

Aamoth, H.L., Butt, F.J., 1960. Maintaining food quality with chelating agents. Ann. N. Y. Acad. Sci. 88 (1), 526–531.
Albert, A., Serjeant, E.P., 1984. Chelation and the Stability Constants of Metal Complexes. In the Determination of Ionization Constants. Springer, Netherlands, pp. 176–191.
Bessman, S.P., Doorenbos, N.J., 1957. Chelation. Ann. Internal Medicine 47 (5), 1036–1041.
Branen, J.K., Davidson, P.M., 2004. Enhancement of nisin, lysozyme, and monolaurin antimicrobial activities by ethylenediaminetetraacetic acid and lactoferrin. Int. J. Food
Microbiol. 90 (1), 63–74.
Damodaran, S., Parkin, K.L., Fennema, O.R., 2007. Fennema’s Food Chemistry, fifth ed. CRC Press, Cleveland, Ohio, pp. 814–816.
Furia, T.E., 1972. Sequestrants in Foods. In: Furia, T.E. (Ed.), CRC Handbook of Food Additives, second ed. CRC Press, Cleveland, Ohio, pp. 271–294.
Gardiner, J., 1976. Complexation of trace metals by ethylenediaminetetraacetic acid (EDTA) in natural waters. Water Res. 10 (6), 507–514.
Heimbach, J., Rieth, S., Mohamedshah, F., Slesinski, R., Samuel-Fernando, P., Sheehan, T., Dickmann, R., Borzelleca, J., 2000. Safety assessment of iron EDTA [sodium iron
(Fe 3þ) ethylenediaminetetraacetic acid]: summary of toxicological, fortification and exposure data. Food Chem. Toxicol. 38 (1), 99–111.
Hellendoorn, E.W., 1962. Water-binding capacity of meat as affected by phosphates. 1. Influence of sodium chloride and phosphates on water retention of comminuted meat at
various pH values. Food Technol. 16 (9), 119.
Knipe, C.L., 1983. Use of phosphates in sausage. In: Proceedings of the Third Annual Sausage and Processed Meats Short Course, pp. 105–108.
Labuza, T.P., Dugan Jr., L.R., 1971. Kinetics of lipid oxidation in foods. Crit. Rev. Food Sci. Nutr. 2 (3), 355–405.
Lanigan, R.S., Yamarik, T.A., 2002. Final report on the safety assessment of EDTA, calcium disodium EDTA, diammonium EDTA, dipotassium EDTA, disodium EDTA, TEA-EDTA,
tetrasodium EDTA, tripotassium EDTA, trisodium EDTA, HEDTA, and trisodium HEDTA. Int. J. Toxicol. 21, 95–142.
Mehltretter, C.L., Alexander, B.H., Rist, C.E., 1953. Sequestration by sugar acids. Industrial Eng. Chem. 45 (12), 2782–2784.
Shults, G.W., Russell, D.R., Wierbicki, E., 1972. Effect of condensed phosphates on pH, swelling and water-holding capacity of beef. J. Food Sci. 37 (6), 860–864.
 Sequestrants as a Food Ingredient 255

Sindelar, J.J., 2015. Impacts of removing functional non-meat ingredients in processed meat products and exploring possible alternatives. In: Reciprocal Meat Conference 2015
Proceedings, pp. 48–51.
Soccol, C.R., Vandenberghe, L.P., Rodrigues, C., Pandey, A., 2006. New perspectives for citric acid production and application. Food Technol. Biotechnol. 44 (2).
Thorarinsdottir, K.A., Arason, S., Bogason, S.G., Kristbergsson, K., 2001. Effects of phosphate on yield, quality, and water-holding capacity in the processing of salted cod (Gadus
morhua). J. Food Sci. 66 (6), 821–826.
Wedeen, R.P., Batuman, V., Landy, E., 1983. The safety of the EDTA lead-mobilization test. Environ. Res. 30 (1), 58–62.
Yoe, J.H., 1958. The analytical uses of ethylenediaminetetraacetic acid. J. Am. Chem. Soc. 80 (10), 2600.

Further Reading

Aamoth, H.L., Butt, F.J., 1960. Maintaining food quality with chelating agents. Ann. N. Y. Acad. Sci. 88 (1), 526–531.
Furia, T.E., 1972. Sequestrants in foods. In: Furia, T.E. (Ed.), CRC Handbook of Food Additives, second ed. CRC Press, Cleveland, Ohio, pp. 271–294.
Taylor, R.J., 1980. Food Additives. John Wiley & Sons, Hoboken, New Jersey, pp. 49–50.

Relevant Websites

http://www.jhbiotech.com/plant_products/chelation.htm – JH Biotech.
https://chem.libretexts.org/Core/Inorganic_Chemistry/Coordination_Chemistry/Properties_of_Coordination_Compounds/Ligands/EDTA – Inorganic Chemistry.
https://www.canada.ca/en/health-canada/services/food-nutrition/food-safety/food additives/lists-permitted/12-sequestering-agents.html – Health Canada Services.
https://www.fda.gov/food/ingredientspackaginglabeling/foodadditivesingredients/ucm091048.htm#abb – Food Ingredients Packaging.
https://oradix.com/content/6-24-benefits-of-chelation – Oradix.