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CONFIDENTIAL. THIS DOCUMENT CONTAINS TRADE SECRET INFORMATION. DISCLOSURE, USE OR REPRODUCTION OUT-SIDE CARGILL AND INSIDE CARGILL, TO OR BY THOSE EMPLOYEES WHO DO NOT HAVE A NEED TO KNOW, IS PROHIBITED EXCEPT AS AUTHORIZED BY CARGILL IN WRITING.
(COPYRIGHT CARGILL INCORPORATED 2002. ALL RIGHTS RESERVED.)
Natural Antioxidants Review
James E. HaworthSr. Professional
Cargill Inc., Health and Food Technologies
Outline• Introduction•Antioxidant Market•Oxidation
•General mechanisms•Effects•Myoglobin degradation•Methods of evaluation
•Natural Antioxidants•Current Research
•Food research•Bioavailability
•Conclusions
Introduction
During processing, storage, and display, meat and poultry products are subjected to harsh environments that are ideal for oxidation, thus reducing overall product appeal. One way to combat these negative aspects is to add natural herbal flavorings and/or antioxidants (AO). Recent reported health issues surrounding synthetics have increased the interests of consumers to seek out products containing natural ingredients.
Observations:• TBHQ banned in Japan and Europe• Many synthetic antioxidants are regulated
and only allowed in foods at low levels • At or below 200 ppm on a fat basis
• Growth of natural antioxidants is increasing due to appeal of “Natural”
• Growth of natural heart-healthy foods is on the rise
Antioxidant Market
Key Food Applications for Antioxidants• Meat and Poultry• Spice & Condiments• Oils, Fats, and Margarines• Fish and Seafood• Snack Foods• Baked Goods• Other Applications
In 2002, the total European and US food antioxidant market was valued at $190.7 million.Document #3952-88, European and United States Food Antioxidants Markets, 2002, Frost & Sullivan, available at:www.frost.com
LowMediumMediumNew Product Development5
MediumMediumMediumGlobalization of the Antioxidant Industry4
MediumMediumMediumIncreased Concern About Food Safety3
HighHighMediumIncreased Consumption of Convenience Foods2
HighHighHighDemand for Natural Ingredients1
5-6 Years3-4 Years1-2 YearsDriverRank
Total Food Antioxidants Market: Market Drivers Ranked in Order of Impact(Europe and United States), 2003-2009
Source: Frost & Sullivan
Antioxidant Market Growth
Document #3952-88, European and United States Food Antioxidants Markets, 2002, Frost & Sullivan, available at:www.frost.com
5.9 – 9.6-3.7 – 4.2Herbal Extracts
-3.7 – 1.22.9 – 3.2Vitamin C
2.1 – 2.22.6 – 5.0Tocopherols (Vitamin E)
NA6.5 – 6.3TBHQ
5.1 – 2.31.6 – 1.1BHT
3.4 – 1.02.7 - 2.3BHA
EU Market Growth2000-2009 (%)
US Market Growth2000-2009 (%)
Antioxidant
Market Forecast (2000-2009)
Antioxidant Applications Breakdown
Document #3952-88, European and United States Food Antioxidants Markets, 2002, Frost & Sullivan, available at:www.frost.com
41%
11%
9%
8%
7%6%
18%
Meat and PoultrySpice and CondimentsOils, Fats, and MargarinesFish & SeafoodSnack FoodsBaked GoodsOther
55%
7%
6%
6%
7%
14%
5%
Herb Extracts; US Market by Applications for 2002
Herb Extracts; EU Market by Application for 2002
Antioxidant Applications Breakdown
Document #3952-88, European and United States Food Antioxidants Markets, 2002, Frost & Sullivan, available at:www.frost.com
72%
6%
13%
9%
Meat and Poultry
Fish & Seafood
Beverages
Other
65%
6%
14% 15%
Meat and Poultry
Oils, Fats, and Margarines
Spices and Condiments
Other
Vitamin E; EU Market by Applications for 2002
Vitamin C; EU Market by Application for 2002
Application Examples
Chicken breast (chicken breast with rib meat, water, partially hydrogenated soybean and corn oil, salt, seasoning [salt, roast chicken flavor {maltodextrin, autolyzed yeast extract, soy sauce (soybeans, wheat, salt), tapioca maltodextrin, chicken fat, dextrose, flavor), sugar, citric acid], rice starch, lemon phosphate [sodium phosphate, lemon juice solids], flavoring [natural extractives of rosemary, soybean oil, mono- and diglycerides, lecithin], lemon juice powder [corn syrup solids, lemon juice solids]), teriyaki sauce (water, sugar, soy sauce [water, soybeans, wheat, salt, alcohol, lactic acid, acetic acid], modified cornstarch, pineapple juice concentrate, salt, hydrolyzed soy protein, sherry wine, vinegar, hydrolyzed wheat protein, spice, caramel color, disodium inosinate, disodium guanylate)
Seasoned cooked ground beef [beef, seasoning (salt, dextrose, caramel color, yeast extract, hydrolyzed corn and soy protein, extractives of rosemary, flavor (maltodextrin, grill flavor (from beef fat), modified corn starch, corn syrup solids))], water, tomatoes (tomato paste, water), textured soy protein (caramel color added), modified corn starch; contains 2% or less of: sugar, salt spices, glucono delta lactone, dried onion, garlic, partially hydrogenated soybean and/or cottonseed oil, onion, wheat flour, erythorbic acid, caramel color, onion puree, dried chili pepper, garlic puree, autolyzed yeast extract, monosodium glutamate, paprika extract, color, soybean oil, carrageenan, sodium, benzoate, maltodextrin, onion juice, corn syrup, soy lecithin, mono and diglycerides, garlic juice, mixed tocopherols added to retain freshness, natural flavor, malic acid, corn oil, dextrose, dried garlic citric acid (to protect flavor), sulfiting agents
Mackerel, saccharides (sugar, syrup), miso, ginger, starch, salt, dextrin, vegetable oil and fat, agar, thickener (gua), antioxidants (rosemary extract, vitamin E, vitamin C)
Free Radical Mechanism
Initiation may be catalyzed by traces of metal or heme iron, light, reactive oxygen species (ROS), or byproducts from the propagation phase.
Oxidation is propagated by abstraction of an H from an allylic carbon, resulting in free radical species. Oxygen addition results in the formation of peroxy radicals.
Initiation Propagation
Edwin N. Frankel, Lipid Oxidation, §1, (1998)
Termination
Non radical or inactive products that do not initiate or propagate further reaction.
Chain-breaking antioxidants inhibit or retard lipid oxidation by interfering with either chain propagation or initiation by readily donating hydrogen atoms to lipid peroxyl radicals. Chelators may remove free metal before catalyzing oxidation.
Antioxidation
Lipid Oxidation
•Primary byproducts•Hydroperoxides
•Generally odorous compounds•Very unstable and catalyze further oxidation
•Secondary byproducts•Carbonyl compounds
•Volatile products causing flavor problems•High impact on flavor at minor concentrations•High formation rate
Negative Effects of Oxidation•Quality loss
•Negative color and texture changes•Warmed-over flavor
•Economic loss•Consumer acceptance
•Nutritional losses•Destruction of essential fatty acids•Vitamin loss
•Health risks•Growth retardation•Heart disease•Various forms of cancer
Myoglobin Oxidation
Fe +2 Fe +2
Fe +2
+O2 (oxygenation)
-O2 (reduced)
+O2
(oxi
dize
d)
-O2
(redu
ced)-O
2 (reduced)
+O2 (oxidized)
Jane Ann Boles and Ronald Pegg , Meat Color, Montana State University and Saskatchewan Food Product Innovation ProgramUniversity of Saskatchewan
il bl t htt // i l t d /D / t l ht
Myoglobin
•Levels in tissue varies•Species dependant (Beef, poultry, pork, etc.)
•Age (Veal vs. beef)
•Gender•Physical activity/stress•Muscle to muscle (Beef sirloin vs. brisket)
Actions• React with peroxyl radicals
– Donation of electrons or hydrogen
Primary Antioxidants
Examples of primary antioxidants• Tocopherols• Tocotrienols• Carnosic acid• Carnosol
• Rosmarinic acid• Gallic acid• Carotenoids
Examples of secondary antioxidants• Citric acid• Phosphoric acid• Ascorbic acid• Flavones• Inositol
• Lecithin• Ascorbyl palmitate (Naturally
derived)• Erythorbic acid (Naturally derived)
Secondary AntioxidantsActions• Reduce rate of oxidation• Chelate/bind metals• Scavenge oxygen• Decompose unstable hydroperoxides• Absorb UV radiation• Deactivate singlet oxygen• Regeneration of primary antioxidants
Shelf Life Determination• Colorimeter (Minolta or Hunter a-values)• Thiobarbituric acid reactive substances (TBA or TBARS)• Peroxide value (PV)• Metmyoglobin formation• Human sensory panels• GC/MS
•GC/MS olfactory•GC analysis of volatiles
• Active oxygen method (AOM)• Fluorescence methods• Oxidative stability index (OSI)• Rancimat• Oxygen bomb • Conjugated dienes
Natural Sources• Herbs and spices
• Rosemary, oregano, sage, tea
• Seeds/grains• Soybeans, corn, sunflower, cocoa,
sesame, oats, canola
• Fruits• Strawberries, apples, nuts, peppers,
blueberries, grapes, olives, palm
• Vegetables• Tomatoes, spinach, peppers, carrots
• Tubers• Turmeric rhizomes, potato
• Others• Marigolds, liquid smoke, honey, wine,
seaweed
• Flavonoids• Tocopherols/Tocotrienols• Phenolics• Polyphenols• Catechins• Carotenoids• Tannins• Etc.
Common Natural AntioxidantsCOOH
OH
OH
HO
Gallic acid
OO
HO OH
HC
CH2OH
OH
Ascorbic acid
C COOHHO
COOH
COOH
Citric acid
CH3CH3
CH3
CH3O
OH
OH
OH
Carnosic Acid Carnosol
CH3CH3
CH3
CH3O
OH
OH
O
RosemanolCH3CH3
CH3
CH3O
O
OH
OH
OHO
OH
R2
R1
CH3
CH3CH3CH3CH3
CH3
Tocopherols
O
OOH
HO
OH
GenisteinCapsaicin
NH
CH3
CH3H3CO
HO
O
Why the Efficacy of Some Naturals?
RFI Ingredients web site: http://www.rfiingredients.com/antioxidants.htm
Free Radical
Free Radical
Free Radical
Not All Extracts Are Created EqualCarnosic Acid Levels Over One Year in Rosemary
0
5
10
15
20
25
30
35
40
45
50
1 3 5 7 9 11
Month
Carnosic acid level (mg/g)Temperature (oC)Sunshine (Hours)
P.J. Hildago, J.L Ubera, M.T. Tena, and M. Valcarcel, “Determination of the Carnosic Acid Content in Wild and Cultivated Rosmarinus officinalis”, J. Agric. Food Chem., (1998), 46, p2624-2627
Synergistic Effects
• 1+1=3• Mixing primary antioxidants
• Different antioxidants for different radical pathways
• Lipophilic and hydrophilic mix
• Combining primary and secondary antioxidants• Regeneration, emulsification, chelation
• Primary antioxidants work on stopping oxidation, while secondary antioxidants enhance primary functions or inhibit catalysts
Synergistic Effects of Two Primary AOsSardine Oil Model System
0
100
200
300
400
500
600
700
800
900
1000
0 10 20 30 40 50 60 70
Storage Days
PV (m
eq/K
g)
Control
Alpha-tocopherol (700 PPM)
Rosemary (700 PPM)
Alpha-tocopherol (350 PPM)/Rosemary (350 PPM)
Xin Fand, Shun Wada, “Enhancing the Antioxidant Effect of alpha-tocopherol with Rosemary in Inhibiting Catalyzed Oxidation Caused by Fe2+ and Hemoprotein”, Food Research International, Vol. 26, (1993), P. 405-411
Polar Paradox • Hydrophilic antioxidants are more active in bulk
lipid systems• Lipophilic antioxidants present greater activity in oil
in water systems
Edwin N. Frankel, Lipid Oxidation, §8, (1998)
Lipophilic antioxidantHydrophilic antioxidant
Water
LipidWater
Lipid
Adding emulsifiers can improve the effectiveness of antioxidants
Increase Interaction w/Emulsifiers
Internal Cargill, Inc. Data OSI (Oxidative Stability Index) Cond., 150 ml air/min., 110oC
0
5
10
15
20
25
30
Control Lecithin (5000 PPM) Mixed Tocopherols(300 PPM)
MixedTocopherols/Lecithin
(300 PPM/5000PPM)
CommercialRosemary prod.
(1000 PPM)
CommercialRosemary
prod./Lecithin (1000PPM/5000 PPM)
Antioxidnat Treatment
OSI
She
lf Li
fe (H
ours
)
Cooked Turkey-Direct Addition
• Cooked turkey rolls were tested
• Water soluble rosemary was added at 0 PPM, 100 PPM, 250 PPM, and 500 PPM
• Packaged on polystyrene trays and over-wrapped with PVC stretch film and stored in the dark @ 4oC
• Tested at 0, 1, 2, 3, 5, 7, 10, and 13 days for TBARS and color (a-values)
L. Yu, L. Scanlin, J. Wilson, G. Schmidt, “Rosemary Extracts as Inhibitors of Lipid Oxidation and Color Change in Cooked Turkey Products During Refrigerated Storage”, Food Chemistry and Toxicology, Vol. 67, No. 2, 2002, p 582-585
Cooked Turkey-Direct Addition
L. Yu, L. Scanlin, J. Wilson, G. Schmidt, “Rosemary Extracts as Inhibitors of Lipid Oxidation and Color Change in Cooked Turkey Products During Refrigerated Storage”, Food Chemistry and Toxicology, Vol. 67, No. 2, 2002, p 582-585
0
5
10
15
20
25
30
0 2 4 6 8 10 12 14
Storage Time (Days)
TBA
RS
(mg
MD
A/K
g m
eat)
Control100 PPM Rosemary250 PPM Rosemary500 PPM Rosemary
Cooked Turkey-Direct Addition
L. Yu, L. Scanlin, J. Wilson, G. Schmidt, “Rosemary Extracts as Inhibitors of Lipid Oxidation and Color Change in Cooked Turkey Products During Refrigerated Storage”, Food Chemistry and Toxicology, Vol. 67, No. 2, 2002, p 582-585
10
11
12
13
14
15
16
17
18
19
20
0 2 4 6 8 10 12 14
Storage Time (Days)
Col
or (a
-val
ue)
Control100 PPM Rosemary250 PPM Rosemary500 PPM Rosemary
Beef Patties-Direct Addition
• Uncooked beef patties were tested
• Contained cayenne, red sweet peppers, lycopene-rich tomato pulp, or extract of tomato (Lyc-O-Mato™)
• Packaged in MAP packaging and stored at 2oC
• Tested for color and TBARS on days 0, 2, 8, 12, 16, and 20
Armida Sanchez-Escalante, Gaston Torrescano, Djamel Djenane, Jose Antonio Beltran, and Pedro Roncales, “Stabilisation of Color and Odour of Beef Patties by Using Lycopene-Rich Tomato and Peppers as a Source of Antioxidnats”, Journal of the Science of Food and Agriculture, Vol. 83, 2003, p 187-194
Beef Patties-Direct Addition
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
0 2 4 6 8 10 12 14 16 18 20 22
Storage Time (Days)
TBA
RS
(mg
MD
A/K
g M
eat)
ControlRed Sweet Pepper (20g/Kg)Cayenne Pepper (20g/Kg)Lycopene-Rich Tomato Pulp (15g/Kg)Lycopene-Rich Tomato Pulp (50g/Kg)Lyc-O-Mato (550mg/Kg)Lyc-O-Mato (2g/Kg)
Armida Sanchez-Escalante, Gaston Torrescano, Djamel Djenane, Jose Antonio Beltran, and Pedro Roncales, “Stabilisation of Color and Odour of Beef Patties by Using Lycopene-Rich Tomato and Peppers as a Source of Antioxidnats”, Journal of the Science of Food and Agriculture, Vol. 83, 2003, p 187-194
Beef Patties-Direct Addition
0
5
10
15
20
25
30
0 2 4 6 8 10 12 14 16 18 20 22
Storage Time (Days)
Col
or (a
-val
ue)
ControlRed Sweet Pepper (20g/Kg)Cayenne Pepper (20g/Kg)Lycopene-Rich Tomato Pulp (15g/Kg)Lycopene-Rich Tomato Pulp (50g/Kg)Lyc-O-Mato (550mg/Kg)Lyc-O-Mato (2g/Kg)
Armida Sanchez-Escalante, Gaston Torrescano, Djamel Djenane, Jose Antonio Beltran, and Pedro Roncales, “Stabilisation of Color and Odour of Beef Patties by Using Lycopene-Rich Tomato and Peppers as a Source of Antioxidnats”, Journal of the Science of Food and Agriculture, Vol. 83, 2003, p 187-194
Beef Tallow Applications
0
10
20
30
40
50
60
70
80
Beef Tallow BHA BHT TBHQ Ethoxyquin Mixed Tocopherols
Antioxidant Treatment (150 PPM)
OSI
She
lf Li
fe (H
ours
)
Internal Cargill, Inc. data OSI conditions -110oC with 150ml air/min., n=3
Active Antioxidant Packaging
M.E. Moore, I.Y. Han, J.C. Acton, A.A. Ogale, C.R. Barmore, and P.L. Dawson, “Effects of Antioxidants in Polyolefin Film on Fresh Beef Color”, Journal of Food Science, Vol. 68 Nr. 1, 2003, p99-104
• Active packaging tested on fresh eye of round steaks that were allowed to “bloom” prior to packaging
• 25mm dia., 0.25mm thick LDPE discs were compounded with various antioxidants
• Control, BHA, BHT, rosemary, and delta-tocopherols were tested @ 1000 PPM
• Discs placed on steaks and over wrapped with PVC
• Stored in the dark @ 4oC until sampled
• Tested for color (a-value) on days 0, 1, 2, 3, 4, 5, 6, 7, 8, and 9
Active Antioxidant Packaging
M.E. Moore, I.Y. Han, J.C. Acton, A.A. Ogale, C.R. Barmore, and P.L. Dawson, “Effects of Antioxidants in Polyolefin Film on Fresh Beef Color”, Journal of Food Science, Vol. 68 Nr. 1, 2003, p99-104
LDPE/Antioxidant Meat Packaging Films
Antioxidants added @ 1000 PPM
5
7
9
11
13
15
17
0 1 2 3 4 5 6 7 8 9 10
Storage (Days)
Col
or (a
-val
ue)
Control disk
BHA (1000 PPM)
BHT (1000 PPM)
Rosemary Extract (1000 PPM)
Delta-tocopherol (1000 PPM)
Bioavailability of Rosemary Phenolics
• 12 dog study, 6 dogs control, 6 dogs tested
• Control dogs were given 0.5g placebo capsules
• Tested dogs were given 0.5g rosemary extract
• Blood samples were taken @ 0, 3, and 6 hours
• HPLC was used to detect carnosic acid and carnosol in the samples
J. Greaves, J. Haworth, J. Mann, Kemin Ind. Proceedings from the 2000 Petfood Forum "Breakthroughs in Natural Antioxidants”
Kemin Ind. HPLC data Standard
0 hour
6 hour
3 hour
Carnosol Carnosic Acid
J. Greaves, J. Haworth, J. Mann, Kemin Ind. Proceedings from the 2000 Petfood Forum "Breakthroughs in Natural Antioxidants”
Bioavailability of Rosemary Phenolics
Bioavailability of Vitamin E, Rosemary, and Sage Phenolics
C. J. Lopez-Bote, J. I. Gray, E. A. Gomaa, C. J. Flegal “Effect of dietary administration of oil extracts from rosemary and sage on lipid oxidation in broiler meat” British Poultry Science (1998) 39: 235–240
• 96 Hubbard male broilers• Feed contained the following antioxidants
• Control (10 PPM α-tocopherol acetate)• 500 PPM rosemary or sage extracts• 200 PPM α-tocopherol acetate
• White meat tested for TBARS in three storage situations• Samples stored in polystyrene try with PVC over
wrap under fluorescent lighting
C. J. Lopez-Bote, J. I. Gray, E. A. Gomaa, C. J. Flegal “Effect of dietary administration of oil extracts from rosemaryand sage on lipid oxidation in broiler meat” British Poultry Science (1998) 39: 235–240
Refrigerated storage, 4oC (Uncooked)
0
0.1
0.2
0.3
0.4
0.5
0.6
0 1 2 3 4 5 6 7 8 9 10
Storage (Days)
TBA
RS
(mg
MD
A/K
g m
eat)
ControlVitamin ERosemarySage
Bioavailability of Vitamin E, Rosemary, and Sage Phenolics
C. J. Lopez-Bote, J. I. Gray, E. A. Gomaa, C. J. Flegal “Effect of dietary administration of oil extracts from rosemaryand sage on lipid oxidation in broiler meat” British Poultry Science (1998) 39: 235–240
Refrigerated storage, 4oC (Cooked @ 70oC for 30 min.)
0
2
4
6
8
10
12
14
0 1 2 3 4 5
Storage (Days)
TBA
RS
(mg
MD
A/K
g m
eat)
ControlVitamin ERosemarySage
Bioavailability of Vitamin E, Rosemary, and Sage Phenolics
C. J. Lopez-Bote, J. I. Gray, E. A. Gomaa, C. J. Flegal “Effect of dietary administration of oil extracts from rosemary and sage on lipid oxidation in broiler meat” British Poultry Science (1998) 39: 235–240
Frozen storage, -20oC (Uncooked ***No fluorescent lighting)
0
0.2
0.4
0.6
0.8
1
1.2
0 1 2 3 4 5
Storage (Months)
TBA
RS
(mg
MD
A/K
g m
eat)
ControlVitamin ERosemarySage
Bioavailability of Vitamin E, Rosemary, and Sage Phenolics
Cold Storage Needs?
Beef cold storage at all time high• Beef cold storage on Sept. 30, 2002 was at 495
million lbs, up 29% from prior year
• Pork cold storage on Sept. 30, 2002 was at 478 million lbs, up 30% from prior year
• Poultry cold storage on Sept. 30, 2002 was at 1.512 billion lbs, up 28% from prior year
Steve Kay, “Leftover a barrel”, Meat and Poultry, December 2002, p48-54
USDA est. total meat and poultry production at 84 billion lbs for 2003
Conclusion• Market growth of synthetics is decreasing, while natural
antioxidant growth is increasing
• Oxidation can be best controlled by a combination of protective measures
• Positive results can be obtained by the direct addition of natural antioxidants to meat systems
• Natural antioxidants can be used to supplement feed with impressive shelf life results
• The concept of “Natural” is increasingly important to the consumer