SSE eee ee FATS AND PROTEINS RESEARCH FOUNDATION, INC. FRED D. BISPLINGHOFF, D.V.M. Director Technical Services C/ OG: 7160 ESTERO BLVD, « APT. 908 FT. MYERS BEACH, FL 33931 AREA CODE 813 — 463-4744 June, 1992 No, 249 ANTIOXIDANTS Which ones are best for your petfood product? Eastman Chemical Company, Kingsport Tennessee Andreas M. Papas, PhD Consider this scenario: A grocery store customer buys some petfood and takes it home, A tail-vagging dog greets him at the back door and jumps up and down with anticipation. But when the container is opened, a strong, offensive, rancid odor gushes out and permeates the room. Nostrils stinging the customer wrinkles his nose in disgust and looks at the doy. The dog, whose tail is no longer wagg- ing, looks back with sad brovn eyes. The aggravated customer swears at the man- facturer, returns the container to the store, and vows to never purchase the same brand again! A likely scenario? Hardly, in fact a very rare one in recent years-thanks to antioxidants. Antioxidants prevent rancidity and help maintain the odor, flavor, texture and other qualities which together make what we call "freshness" of food. Antioxidants have definite advantages. ‘The question is, which ones are best for the individual circumstances? Different perspective ‘Today's petfood producers are looking at antioxidants from a different per- spective. In today's rapidly growing global market, the choice of antioxidant has legal, manufacturing and marketing implications. For example, regulatory approvals differ from country to country. Should the petfood manufacturer select an antioxidant system acceptable in all countries? 32Another consideration is consumer awareness of the antioxidants in petfoods. As with many issues today, consumers are expressing strong preferences, and these must be addressed. Why the need? Petfoods contain oils, animal fats and other 1ipid-1ike compounds such as vitamins A, D, E and K, flavorings, etc. Fats and oils have the potential to de- teriorate (oxidize). This deterioration can lead to: * Decreased palatability, * Destruction of nutrients and * Formation of toxic compounds. Antioxidants help prevent these negative developments. The deterioration of fats, oils and related compounds is @ three-stage chain reaction called lipid peroxidation (or autoxidation). The three stages are: initiation, propagation and termination. Initiation: In the first stage (initiation) of this reaction, a free radical (usually oxygen) attacks a polyunsaturated fatty acid and forms a fatty acid radical. Fac~ tors that accelerate the formation of radicals include: Heat Ultraviolet Light Metal ions (especially when the pH is high) Pigments and A high degree of unsaturation. Propagation Fatty acid radiceis react readily with oxygen to form peroxides. Peroxides react with other fatty acids to form hydroperoxides and new fatty acid radicals. ‘Thus, the rate of the reaction accelerates in a geometric manner (propagation) because each free radical produces a peroxide and a free radical. Termination ‘The propagation can become a runaway process unless it is stopped by anti- oxidants. Othervise it is terminated only when fatty acids are not available and peroxides combine to form inactive products (termination stage). Ultimately, the hyéroperoxides decompose into aldehydes, ketones, alcohols and acids. This decomposition produces the offensive rancid odor and destroys the flavor and taste of the food. More important, the results of this process are very harmful to the health of animals and humans. 33Not only do free radicals attack fats and oils, they also attack proteins and other molecules. The result: Formation of peroxides and other compounds harmful to health. Antioxidants break the chain reaction of rancidity by combining with free radicals to form molecules which are less reactive. Therefore, they stop free radicals from catalyzing the propagation of additional radicals. The process of fatty acid oxidation and the function of antioxidants are summarized in Figure 1. Synthetic antioxidants Commercial antioxidants are either synthetic or naturel (extracted from nat~ ural sources). Historically, synthetic antioxidants have been predominant in the market place, primarily due to their lower cost. An example of the relative effectiveness of synthetic antioxidants is shown in Figure 2, Regulatory considerations are sumarized in Table 1. Synthetic antioxidants include: BAA. Butylated hydroxyanisole (BHA) is effective in vegetable oils. It main- tains its potency during processing (good carry-through). Because it is volatile, it can be used in packaging materials. It is almost universally approved for human and animal use. BAT. Butylated hydroxytoluene (BHT) and BHA have similar properties. When used together, a synergistic effect is achieved. BHT is almost universally approved for both human and animal food. Although its status may be reviewed again. Ethoxyquin Ethoxyquin is effective in animal fats and vegetable oils and has good carry- through properties. Recently there has been some consumer concern about its safety (Phillips, 1989). Only extremely limited uses are permitted for human foods. Its use for animal feeds, however, is widely approved. It is significant that ethoxyquin levels are regulated as parts per million in complete feed vs. in the fat or oil portion. The net effect is that higher levels of ethoxyquin are allowed compared with other antioxidants. PG Propyl gallate (PG) is effective in vegetable oils and is synergistic with BHA and BHT. It is heat sensitive at 148°C(299‘F) or above and has poor carry~ through properties. It forms color complexes with metal ions if they are not chelated. It forms color complexes vith metal ions if they are not chelated. It is approved for both human and animal use in the US, Canada, Japan, and many European Countries. 347 ‘Tertiary bulylhydroquinone (TBHQ) is very effective in most fats and oils bat is particularly effective in vegetable oils. It has good carry-through and does not form color complexes with metals. While it is approved for both human and animal use in the US, it has not been approved in Canada, by the European Economic Community, Japan and some other countries. Natural antioxidants Changing consumer preferences have focused attention on natural antioxidants. Natural antioxidants include: d-alpha-tocopherol. Natural source vitamin E, d-alpha-tocopherol, is the best biological antioxidant for animal and human tissues. Mixed tocopherols. Netural tocopherol antioxidants exist in four forms: d-alhpa-, @-bete-, d-gramms—, and d-deita-tocopherol. They are extracted commercially from vegetable oilseeds, primarily soybeans. Recommended usage levels are 100-300 ppm of the fat or oil portion of the food (Dougherly, 1988). Mixed tocopherols are effective antioxidants for lard, tallow, poultry fat, and other animal products. They are synergistic with other natural antioxidants such as ascorbic and citric acids. Odor and taste is slight and they have good carry-through. ‘They are approved for human and animal food in most countries. However, the cost of tocopherols may be higher than some synthetic antioxidants. Iecithin. Lecithin, a common emulsifier, is a veak antioxidant. Citric acid and ascorbic acid. Citric and ascorbic aciés are water-soluble. Because rancidity occurs primarily in fats and oils, the fat-soluble antioxidants are more important ones. In foods with high pH or high content of metel ions, combinations of citric and/or ascorbic acids with tocopherols produce better efficancy. Deciding on an antioxidant Selection of antioxidants should be based on: [] type of fat or oil, (1 cost, (] Efficacy, [1 carry through, [] Base of use, [] consistency, [] Stabinity, 35[] Safety, [] Discoloration tendencies, (1 Odor [] Regulatory considerations and [] customer preference. Consumer preferences and the globalization of markets are now becoming strong considerations. Regulations for the use of antioxidants in human and animal foods in the United tates, Canada, and the European Economic Community are summarized in Table 1. Al~ though synthetic antioxidants are limited in use in Japan, they approved for use in petfoods (except for TRHO). FDA and USDA regulation require that antioxidants, whether added directly or indirectly, mst be identified on the label. These regulations also require a statement of the purpose, indicating why they were added. Effective synthetic antioxidants for petfoods include BAA, BHT, ethoxyguin, and ‘TBHQ. Combinations of BHA with BH? and/or propyl gallate or TSHQ are particulary effective, especially when citric acid is included. ‘The natural antioxidants of choice are mixed tocopherols, especially in com bination with citric acid ané/or ascorbic acids. References Burton, G.W. and M.G. Traber, 1990. Vitamin E: Antioxidant activity, bio- Kinetics and bioavailability, Annu Rev. Nutr. 10:357-382. Dougherty dr., M.E. 1988. Tocopherois as food antioxidants. Cereals Foods World 33:222-223. Hidiroglou, N. L.F. Laflanme and L.R. McDowell, 1988. Blood plasma and tissue concentrations of vitamin E in beef cattle as influenced by supplementation of various tocopherol compounds. J. Anim. Sci. 66:3227-3234, Hidiroglou, N. ER. McDowell and R. Pastrana, 1988. Bioavailability of various vitamin E compounds in sheep. Internat. J. Vit. Nutr. Res. 58: 189-197. Papas, A.M., R.C. Cambre, §.B. Citino, D.J. Baer and G.R. Wooden, 1990. Species differences in the utilization of vitamin E. Proceedings, 1990 annual Conference of American Association of Zoo Veterinarians. Phillips, T., 1989. Ethoxyguin, fact and fiction. Petfood industry, Novenber/ December, 1989. 36Antioxidant action Synergism Efficacy {tee radical ame Antioxidant Hydroperoxide R-0-OH @ : ©) +R Figure 1. The process of fatty acid oxidation and the function of antioxidants. fr O, Peroxide 0-0-" ‘Tocopherol, 0.01%! Ciirie acid, 6.005% ‘Tocopherol, 0.01% Control: 150 200 250 300 350 Storage stability (Pays at room temperature to reach a peroxide value of 20 meqjkg) Figure 4. The synergistic effect of cltric acid on antioxidant performance of mixed tocopherols. = Poulry fat TeHOS 0.02% Etioxyquin, 0.10% PG, 0.02% BHT, 0.02%, BHA, 0.02% Control a0 ‘AON stability (Hrs fo reach a peroxide velue of 20 meqika) Figure 2. Performance of synthetic antioxidants. Performance varies considerably ‘with type of fat oF ol, presence of metals and addition of synergists. AOM stands for ‘active oxygen method. The percentages {o the right of each antioxidant refer to the level used as a percentage of the poultry tat. 37Pros and cons Synthetic vs. natural BAe cena tocar ave been precornant primary Jdue to thelr lower cost. However, reeant changas in consumer preter- fences have focused attention on natural antioxidants. | tere ate general considerations for deciding between synthetic and natural antioxidants ‘Cost, Nafural antioxidants tend to be more expensive to use (50% and up) than synthelte ones. The difference varies considerably with each application. Eificacy. Performance of antioxidants varies considerably with type of fat oro, presence ol metals and addition of synergists. Mixed tocophe- rols are more elective for animal fas than vagetable ols. Regulatory status, Natural antioxidants enjoy almost universal ac- copiance. Some synthetic antioxidants Ike gellates and TBHO, are not 1s widely accepted (see Table 1, above). ‘Odor and color. Some synthetic antioxidants such es BHT and etho- xyquin may impart an odor to petiood. Gallates ‘can affect the color. Naural tocopherols do not affect the color or odor of peticads. ‘Customer preference. Some express strong preference for exclusion of some or ail synthetic antioxidants, . riloaldana, Note: USDA regulllans apply fr aome uses Inthe US. For athoxyquin, US Const Guard ‘aguiations apply for iskmaal, Other rogulationa may apply inather counties. ‘rtionont United Sates ‘Canede ‘European Community (EG) depen HAS ‘mi rn e2s1e8 “Table xt Pert WB: page 67-49 E20 ‘Approved LUnittion 200 ppm by Limitation same as US. Uso evel extsblished by weight nat oF el portion Individual counties ot ood ro Born eas emai ‘approved ‘Unita 200 ppm by Use vel established by ‘weight fat oro potion Invi! countries of ood Ethonguir Bi OrR srasa0 BSOEEC “Approved Limtaton same es us Propy gatate ‘2 CFR 184.1660, ‘TableXI Pa W,PaSTSOA, ESO Approved, ‘Umitaion 200 ppm by —_Limatlon same a8 US ~~ Use evel extabishod by 5 melghtin tat ool potion —~ “Inalldual counties : ol food as i yy at cn 72105 Noteppreved ae f . Limitation 200 ppm by : ‘lh nf al peten oltood g ‘sss ocophrela 2LCFRVG2a050 TAMER Pant, T2page oTSIB EDO Approved S Unita fective oval" Sames a US, manviacturinpractlos tha US, combinalons of ndoxGies mand wit one estrk ar permlted 1200 pp Goa af ft oral portions TBH ray be oreo copra op meena orm oe a lament oiertronramttelari ta]