3 AUTOXIDATION SERIES OF DESTRUCTIVE CHEMICAL PROCESSES OCCURS IN ORGANIC MATERIALSCHANGES THE CHEMICAL NATURE OF AFFECTED MOLECULESINCREASINGLY FASTROOM TEMPERATURE REACTIONCAUSES RANCIDITY IN FATS, OILSSeries of destructive chemical process, it is important to mention that it is also irreversible.This reaction occurs mainly in organic materialsDue to the reaction, the chemical nature of molecules is changed. Vitamins for example will loose their activity.The auto oxydation is an increasingly fast reaction, which is already present within a few hours after mixing. In untreated raw materials, often the pericarp protects the material from oxydation (no oxygen), once it is grinded, protection has dissappeared.The reaction of autooxydation is a reaction which takes place at room temperature, this in contradiction to many other chemical reactions. Of coarse higher temperatures will increase the speed of the reaction.BIOTIN
4 Oxidation influenced by: Moisture: free water in raw material and feedCatalysts: metals promoting free radical formation,Light: promotes oxidationTemperature: increase oxidation also during coolingContact with air: improves peroxide formationEnzymes: lipase, lipoxygenaseTime: storage time, productionComplet reactions involved including all of the aboveMoisture is outside (humidity) also Aw, Humidity from steam during the process.Cataly mostly in premixes
8 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)
9 Effect of peroxides on broiler performances (49 days) University of Arkansas %caabb%Cabel, M. C., P. W. Waldroup, W. D. SHermer and D. F. Calabotta (1989), Poultry Science 67:
10 Effect of raw material quality on broiler performances (56 days) INTA (Argentina) %aaabaa%abSchang et al
11 The three stages of OXIDATION 1) Initiation phaseRH > R° H°Fat moleculeFree radical2) Propagation phaseR° O > ROO°ROO° RH > ROOH R°(peroxide)3) Termination phaseROO = peroxide= faster oxidationAim is to control the peroxide levels so want to stay in initial phaseperoxide is only an intermediate moleculeperoxide good indicator of oxidation /quality……. Snap shot onlyROO° + ROO° ---> stable end products(aldehydes, ketones, short chain fatty acids)
12 Oxidation Process involving Oxygen & lipids temp.CatalystsLightAirTimeFREERADICALSDamage criticalnutrientsLipidsFREERADICALSPEROXIDES+Oxygen formsReaction with cell membranesToxic for animalsDestruction of fat soluble vitaminsReduction of performancesPEROXIDESAldehydesKetonsRancidityReduction of feed intakeEn-products absorbed in the bodyStart of in vivo oxidation
13 The three stages of OXIDATION Peroxides value (meq)Polimers, oxidisedfat, acids, aldehidesketonesPeroxides, radicalswaterTherefore need to treat early because everything lost cannot be reversed, easier to stop/control reaction when reaction is slowInductionWhen there is dis -association of fat molecules and then reaction with oxygenOxidation Phasedis-association + direct reaction from peroxide on fat moleculePolimers, oxided fat, etc are all stable forms of lower energy value, also palatability issuesInduction Oxidation Termination period
14 Different antioxidants Free radical scavengers:Ethoxyquin, BHA, BHT, Propyl GallateChelators:Citric acid, phosphoric acidCombination of 2 Free radical scavengers best (except in aquaculture)Oxidation scavengersto absorb oxygen from air not really revealent for feedChelatorsTo bind metals so not so availableto promote free radicals but not bound for nutrition. Only use citric acid as literature good chelator , we know that phosphoric acid sometimes works sometimes increases sometimes no effect (Endox Kemin uses phosphoric..is a cheeper ingredient)
15 Differences between antioxidants Ethoxyquin:very stable, only feed grade, raw materialsGallates:very stable, regenerates ethoxyquin or BHA activityBHA:heat stable, mainly food and petfoodBHT:heat stability problem, repartition problem,readily broken down in premixes
16 Structures of commonly used synthetic antioxidants Butylated hydroxytoluene (BHT) Mol. Wt. 220Tertiary butylhydroquinone (TBHQ) Mol. Wt. 166Non allowed in UEEthoxyquin Mol. Wt. 217These all are relatively short chain compounds compared to fats and VitaminsLonger chain > reactivity and easier to oxidise (they are less stable)> number of bonds > reactivity and easier to oxidise (again less stable)When RH RO - + H+ The fat chain then has a -ve charge which for reasons that we don’t really understand makes it easier for O2 to attach and oxidise the molecule leading to the reduction in nutrient value ransidity etc.To stop this reaction anti-oxidant molecules (which are shorter chain so more stable) donate a H+ to reverse the Initial phase reaction this only helps DELAY oxidation as the RH RO - + H+ is a dynamic reaction.Propyl gallate Mol. Wt. 212Butylated hydroxyanisole (BHA) Mol. Wt. 180
17 Triple Mode of ActionEUROTIOX1.Citric acid forms reversible bonds with metal pro-oxidantsin the premix and feed to inhibit them from initiatingoxidation2. Ethoxyquin blocks oxidation by donating hydrogen ionsto free and peroxy radicals formed during the onsetand propagation stages3. Propyl gallate restores and potentiates ethoxyquin activityup to 3 times by donating hydrogen ions from its 3 activesites to oxidised (spent) ethoxyquin molecules
18 Efficacy of synthetic antioxidants BHT <ETQ<BHA<gallate($30) for cost of material Gallate 20x more expensive than BHTData above is independent workSlide to show why we use our combination of ETQ and GalateDaysStability test in mixed fat - Dr. M. Coelho (1995)
23 Effect of citric acid on soya oil stability Metal chelatingEffect of citric acid on soya oil stabilityTrail was done by adding metals to oilWith citric reduced oxidation so less peroxideMustakas et Al. (1984)17
24 Inhibition of Initiation by Chelation of Copper OOCCH2CCOOOHOHOCu+++ Cu++HOCCOOHCH2COOHCitric AcidCu Citrate complex with divalent cation, forming two five-membered rings
25 Eurotiox 32-Premix Comparative granulometry Physical characteristics VIP after getting the right ingredients and ratiosbecause citric cannot use limestone as some other competitors are doingneed small homog. Particles, cannot be re-active with other ingredientsParticle size class ( Mesh, mm) - Sieve analysis by industrial lab, Belgium, July 1996
26 EUROTIOX unique antioxidant complex ETHOXYQUIN- high purity (% mono)- high stabilityPROPYL GALLATE-highly effective- EtQ regenaratorTwo very potent free radical scaven-gersOnlyprovensynergismVeryeffectiveeconomicalcomplexstablemicro-pearled+CITRIC ACID-metal scavengerMaximumprotectionat lowdosage+UNIQUE CARRIER- high absorption- free-flowing- impr. stability+ALUMINIUM bag-protected2320
31 EUROTIOX 32 Premix in premixes and concentrates Vitamin premix: 50g/tonVitamin and traces premix: 100 g/tonVitamin and traces and choline chloride: 200 g/tonHigher dosages are required in case proteins are present.
34 Dosage of EUROTIOX L 32 Raw material For one month protectionFor Two Months ProtectionFor Three Months ProtectionFor Four Months ProtectionVegetable oil (crude)75150200300Palm oil (crude)Rice Bran oil (crude)Rice Bran oil(Refined)Sunflower oil(crude)100400Copra oil (crude)Soya oil (crude)Fish oil (crude)Poultry fatLardTallow3570135Mixed fatMBM306090120Rice Bran(14-16% Fat)Full Fat Soy BeanSource: communication AVITECH
35 Vitamin recovery test against oxidation (Vitamin A in a vitamin mineral premix) HPLC assay - 6 months testing period March ‘95-Sep ‘95EUROTIOX 32-Premix - 45 g/ton45 g/t EUROTIOX 32200, g/t ETQ-66%ControlVerlies van 450 naar 300 is toch nog steeds hoog, vandaar dosering naar 100 g. Wel blijkt duidelijk dat 45 g/Eurotiox vergelijkbaar is met 200 g Ethoxyquin.
36 Vitamin recovery test against oxidation (Vitamin A and E in a Broiler premix) HPLC assay - 3 months testing period - Netherlands - Oct ‘96/ Feb ‘97EUROTIOX 32-Premix - 20 g/ton89.4% Vitamin Erecovered after 3 months94.5% Vitamin Arecovered after 3 monthsPeriode beperkt over 3 maanden, dit is in praktijk dikwijls te kort.No significant loss of Vitamin A & E during a 3 month periodVitamin A & E analytical detection test by HPLC performed by an independentlaboratory (SERLABO) in the Netherlands.
37 Vitamin A Stability in Premix Eurotiox 32 premix EUROTIOX 32-Premix - 20 and 30 g/tonPeriode van 1 maand, in praktijk te weinigIndependant laboratory - HPLC analysis.
38 Vitamin A Stability comparative test Broiler feed - March 1997 EUROTIOX 32-PremixAt 25 g/ton, EUROTIOX provides the best VITAMIN A protection of all products testedProject with large industrial company(Broiler integration) in Philippines. Vitamin detectionanalysis performed by an independent laboratory (SERLABO) in the Netherlands.
39 Vitamin recovery test (Vitamin A in a vitamin mineral premix) HPLC assay - Broiler premix from Thailand - Independent laboratory Holland - Sep 99EUROTIOX 32-Premix - 20 g/tonPdt N125 g/tonEUROTIOX20 g/tonControlPdt K125 g/tonPeriode van 14 dagen, in praktijk te weinig
42 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.
43 Eurotiox 32 Premix in meat and bone meal (poultry origin) CONTROL WITHOUT OXIPRESSCONTROL WITH OXIPRESSCONTROL WITH OXIPRESS PPM EUROTIOX 32 PREMIXCrude fat (g/kg)121.2105.4115.6Metaboliseble Energy (MJ/kg)11.1310.2210.95
44 Eurotiox 32 Premix in meat and bone meal (poultry origin) -1.6%-8.1%
46 Eurotiox 32 Premix in meat and bone meal (Poultry origin) Conclusions:Oxidation is responsible for loss of nutrients, mainly energyEUROTIOX 32 PREMIX is able to prevent nutrient losses due to oxidation.
47 Effect of EUROTIOX 32 PREMIX on energy values (kcal/kg) of MBM (ruminant origin) Source: Trial AO 002: INDIA
48 Eurotiox 32 Premix versus competitor in feed (8% fat) Competitor = ENDOX C
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