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EUROTIOX. AUTOXIDATION. SERIES OF DESTRUCTIVE CHEMICAL PROCESSES OCCURS IN ORGANIC MATERIALS CHANGES THE CHEMICAL NATURE OF AFFECTED MOLECULES INCREASINGLY FAST ROOM TEMPERATURE REACTION CAUSES RANCIDITY IN FATS, OILS. BIOTIN. Oxidation influenced by:.
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AUTOXIDATION • SERIES OF DESTRUCTIVE CHEMICAL • PROCESSES • OCCURS IN ORGANIC MATERIALS • CHANGES THE CHEMICAL NATURE OF AFFECTED MOLECULES • INCREASINGLY FAST • ROOM TEMPERATURE REACTION • CAUSES RANCIDITY IN FATS, OILS BIOTIN
Oxidation influenced by: Moisture:free water in raw material and feed Catalysts: metals promoting free radical formation, Light:promotes oxidation Temperature:increase oxidation also during cooling Contact with air:improves peroxide formation Enzymes:lipase, lipoxygenase Time: storage time, production
Aldehydes from Fat Autoxidation Frankel, 1984
THE INFLUENCE OF OXIDISED FAT ON THE MICRO-FLORA IN BROILERS(11 DAYS)
TOXIC METABOLITES OF FAT OXIDATION Shorten small intestine villi length FROM: Poul. Sci. Abstracts (1994) Vol. 73, Suppl. 1, pg 47. Reduce nutrient adsorption
Autoxidation and Animal production • Reduced Egg production in laying hens (72%) (Voreck & Kirehgessner, 1981) • Autoxidation products are cancernogenic(Morita et al., 1983) • Even low increase in Peroxide Value (>7 meq/kg) has a significant effect on Feed Conversion Ratio (Cabel et al., 1988) • Rancid Feed has an impact on the gastro-intestinal Structure, Cell proliferation and intestinal Microflora (Shermer et al., 1995) • Oxidised vegetable oil in Broiler feed reduces growth rate (5%) (Engberg et al 1996) • Rancid fish oil induced anaemia in Mink, reduced iron absorption (Borsting et al., 1994)
Effect of peroxides on broiler performances (49 days)University of Arkansas + 4.78 % c a ab b - 6.29 % Cabel, M. C., P. W. Waldroup, W. D. SHermer and D. F. Calabotta (1989), Poultry Science 67: 1725-1730
Effect of raw material quality on broiler performances (56 days)INTA (Argentina) - 10.69 % a a a b a a + 6.43 % a b Schang et al. - 1987
The three stages of OXIDATION 1) Initiation phase RH -----> R° + H° Fat molecule Free radical 2) Propagation phase R° + O2 ----> ROO° ROO° + RH ----> ROOH + R° (peroxide) 3) Termination phase ROO° + ROO° ---> stable end products (aldehydes, ketones, short chain fatty acids)
Oxidation Process involving Oxygen & lipids temp. Catalysts Light Air Time Damage critical nutrients FREE RADICALS Lipids FREE RADICALS PEROXIDES + • Reaction with cell membranes • Toxic for animals • Destruction of fat soluble vitamins • Reduction of performances Oxygen forms Aldehydes Ketons • Rancidity • Reduction of feed intake • En-products absorbed in the body • Start of in vivo oxidation PEROXIDES
The three stages of OXIDATION Peroxides value (meq) Polimers, oxidised fat, acids, aldehides ketones Peroxides, radicals water Induction Oxidation Termination period
Different antioxidants Free radical scavengers: Ethoxyquin, BHA, BHT, Propyl Gallate Chelators: Citric acid, phosphoric acid
Differences between antioxidants Ethoxyquin: very stable, only feed grade, raw materials Gallates: very stable, regenerates ethoxyquin or BHA activity BHA: heat stable, mainly food and petfood BHT: heat stability problem, repartition problem, readily broken down in premixes
Triple Mode of Action EUROTIOX 1.Citric acid forms reversible bonds with metal pro-oxidants in the premix and feed to inhibit them from initiating oxidation 2.Ethoxyquin blocks oxidation by donating hydrogen ions to free and peroxy radicals formed during the onset and propagation stages 3.Propyl gallate restores and potentiates ethoxyquin activity up to 3 times by donating hydrogen ions from its 3 active sites to oxidised (spent) ethoxyquin molecules
Efficacy of synthetic antioxidants Days Stability test in mixed fat - Dr. M. Coelho (1995)
Antioxidant Activity of BHA, Propyl Gallate and Heterodimers T. Kurechi and A.Kunugi, J. American Oil Chem. Soc. 60:33 (1983)
Metal chelating Effect of citric acid on soya oil stability Mustakas et Al. (1984)
COO CH2 O CH2COOH C CH2 COO C O HO HOCCOOH + Cu++ Cu++ OOC CH2 C OH O C CH2COOH O CH2 COO Inhibition of Initiation by Chelation of Copper Citric Acid CuCitrate complex with divalent cation, forming two five-membered rings
Eurotiox 32-PremixComparative granulometry Particle size class ( Mesh, mm) - Sieve analysis by industrial lab, Belgium, July 1996
EUROTIOX unique antioxidant complex ETHOXYQUIN - high purity (% mono) - high stability PROPYL GALLATE -highly effective - EtQ regenarator Two very potent free radical scaven-gers Only proven synergism Very effective economical complex stable micro- pearled + CITRIC ACID -metal scavenger Maximum protection at low dosage + UNIQUE CARRIER - high absorption - free-flowing - impr. stability + ALUMINIUM bag -protected
EUROTIOX ANTIOXIDANT PROGRAM Vitamins, Pigments protection in premixes & feed Preventing rancidity in fat, oils, bone meals EUROTIOX 32-Premix EUROTIOX L-32
EUROTIOX Dosage in feed and raw materials
EUROTIOX 32 Premix in feed • Eurotiox 32 Premix at 20 - 25 g/t in Feed with < 4% fat and < 1 month storage time • + 5 g/t for each 2% fat increase • + 5 g/t for each month storage increase
EUROTIOX 32 Premix in premixes and concentrates • Vitamin premix: 50g/ton • Vitamin and traces premix: 100 g/ton • Vitamin and traces and choline chloride: 200 g/ton • Higher dosages are required in case proteins are present.
Vitamin recovery test against oxidation (Vitamin A in a vitamin mineral premix)HPLC assay - 6 months testing period March ‘95-Sep ‘95 EUROTIOX 32-Premix - 45 g/ton 45 g/t EUROTIOX 32 200, g/t ETQ-66% Control
Vitamin A Stability comparative testBroiler feed - March 1997 EUROTIOX 32-Premix At 25 g/ton, EUROTIOX provides the best VITAMIN A protection of all products tested Project with large industrial company(Broiler integration) in Philippines. Vitamin detection analysis performed by an independent laboratory (SERLABO) in the Netherlands.
Eurotiox 32 Premix in meat and bone meal (poultry origin) • Trial set-up: • A control sample (no anti-oxydant added) and a treated sample (150 ppm Eurotiox 32) was incubated in the OXIPRESS. • The OXIPRESS was running until the control sample was completely oxidised. • Both samples were analysed on their nutritional value and compared to a control sample which was not put in the OXIPRESS at all.
Eurotiox 32 Premix in meat and bone meal (poultry origin) -1.6% -8.1%
Eurotiox 32 Premix in meat and bone meal (Poultry origin) • Conclusions: • Oxidation is responsible for loss of nutrients, mainly energy • EUROTIOX 32 PREMIX is able to prevent nutrient losses due to oxidation.
Effect of EUROTIOX 32 PREMIX on energy values (kcal/kg) of MBM (ruminant origin) Source: Trial AO 002: INDIA