natural antioxidants review - meat science

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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.

Antioxidant Market

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


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


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)

Oxidation

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 Antioxidants

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

)

Current Research

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



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



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


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)



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)


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


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)



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)



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

Thank you

natural antioxidants review - meat science

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