1. PREDICTING SHELF LIFE IN FOODS THROUGH OXIDATIVE STABILITY LINDSAY WARD APRIL 9, 2015

2. WHAT DETERMINES SHELF LIFE? The time period within which the food is safe to consume or has an acceptable quality to consumers When conducting a shelf life study, it is best to do so based upon the food product’s limiting factor Microbial activity Chemical or enzymatic activity Lipid oxidation, browning Moisture migration

3. ACCELERATED SHELF LIFE STUDIES Used for practical purposes to shorten the process of determining shelf life Deliberately increase the rate of deterioration Especially useful when the product is shelf stable Most studies pertain to chemical deterioration

4. PREDICTING SHELF LIFE THROUGH EXTRAPOLATION Select the kinetic factor for accelerating the deterioration process Addition of heat, enzymes, metals, etc. Use product deterioration data to extrapolate the kinetic model to predict shelf-life at actual storage conditions

5. Source: Understanding and Measuring the Shelf-Life of Foods

6. PREDICTING SHELF LIFE USING THE Q 10 VALUE Ratio of the shelf life of a product at temperatures 10 o C apart Shelf-life at T (°C) Q 10 = --------------------------- Shelf-life at (T (°C) + 10°C)

7. LIPID OXIDATION…WHAT IS IT? Lipid oxidation occurs due to a catalytic event Free Radicals Lipoxygenase Light Heat Leads to the formation of radicals and peroxides off flavors and odors Rancidity of the product

8. L.O. AS IT RELATES TO SHELF LIFE Lipid oxidation (chemical deterioration) is one of the most common limiting factors in a food product’s shelf life Monitoring lipid oxidation is a primary method to predict food product shelf life in accelerated studies elevated temperatures

9. ASLT METHODS FOR PREDICTING SHELF LIFE OXIDATIVE STABILITY Schaal Oven Test Active Oxygen Method Oxygen Bomb

10. SCHAAL OVEN TEST METHOD Accelerates oxidation by increasing temperature Samples placed in oven (~60 o C) Loosely capped test tubes Oxidation level commonly measured using the peroxide value Sensory (rancidity), G.C. to measure volatile compounds

11. ACTIVE OXYGEN METHOD Accelerates oxidation by increasing temperature and addition of air Sample placed in a test tube and incubated at ~98 o C oil bath Dry air bubbled into the sample continuously Peroxide values measured at different time points to determine oxidation

12. OXYGEN BOMB METHOD Oxidation accelerated by increasing temperature and the addition of oxygen and pressure Samples placed in a pressure vessel (“bomb”) Oxygen is pressurized into the vessel Vessel in incubated in an oil-bath (~99 o C) Lipid oxidation is determined by the decrease in oxygen pressure over time

13. DOWNSIDES TO ASLT METHODS Lipid oxidation reaction mechanism changes at high temperatures Physical and chemical changes in food system Extrapolations of the reaction to determine actual shelf life may not be as accurate Volatile antioxidants may be removed from food product due to addition of heat and oxygen

14. FREE RADICAL GENERATION ASSAYS Chemically induced radical generation through the addition of azo-initiators (R-N=N-R) 2,2′-azobis-(2,4-dimethylvaleronitrile) (AMVN) Allows for the use of lower acceleration temperatures More accurate actual shelf life predictions Balili and Pintauer, 2010

15. FREE RADICAL GENERATION ASSAYS…. Induction point (inflection point in curve) without free radical addition is >20 days Van Dyck, et al., 2005

16. …APPLICABLE FOR SHELF LIFE TESTING? Slopes of the curves calculated from the FRG-OB assay used to predict TBA max Used to indicate shelf life Results compared to non-accelerated shelf life study evaluated with TBARS Van Dyck, et al., 2005

17. REFERENCES ASTM D 942-02. Standard test method for oxidation stability of lubricating greases by the oxygen pressure vessel method. In Annual Book of ASTM Standards; ASTM International: West Conshohocken, PA, 2002. Balili, M. N. C.; Pintauer, T. 2010. Kinetic Studies of the Initiation Step in Copper Catalyzed Atom Transfer Radical Addition (ATRA) in the Presence of Free Radical Diazo Initiators as Reducing Agents. Inorganic Chemistry. 49(12): 5642-5649. Frankel, E. N.; Meyer, A. S. 2000. Review: The problems of Using One-Dimensional Methods to Evaluate Multifunctional Food and Biological Antioxidants. Journal fo the Science of Food and Agriculture. 80: 1925-1941. Li, H; Fa, Y.; Li, J.; Tang, L.; Hu, J.; Deng, Z. 2013. Evaluating and Predicting the Oxidative Stability of Vegetable Oils with Different Fatty Acid Compositions. Journal of Food Science. 78: 633- 641. Quinchia, L. A.; Delgado, M. A.; Valencia, C.; Franco, J. M.; Gallegos, C. 2011. Natural and Synthetic Antioxidant additives for Improving the Performance of New Biolubricant Formulations. Journal of Agricultural and Food Chemistry. 59: 12917-12924. Ragnarsson, J. O.; Labuza, T. P. 1977. Accelerated Shelf-life Testing for Oxidative Rancidity in Foods – A Review. Food Chemistry. 2: 291-308. Steele, Robert. 2004. Understanding and Measuring the Shelf-life of Food. Subramaniam, A.; Veazey, R. L.; Schober, A.; Rada, A.; Rong, Y.; van Sleeuwen, M. T.; Golding, R.; Zhang, S. 2013. Orange Oil Stability in Spray Dry Delivery Systems. Carbohydrate Polymers. 97: 352- 357. Van Dyck, S. M. O.; Verleyen, T.; Dooghe, W.; Teunckens, A.; Adams, C. A. 2005. Free Radical Generation Assays: New Methodology for accelerated Oxidation Studies at Low Temperature in Complex Food Matrices. Journal of Agricultural and Food Chemistry. 53: 887-892.

18. QUESTIONS?