ANTIOXIDANTS -Fish meal and Feed · Oxidative Stability & Shelf Life • Antioxidants are food additives used to extend the shelf of foods by delaying the onset of oxidation. •

ANTIOXIDANTS - Fish meal and Feed

David Prime

Vitablend Protection Business Unit.5th April 2018

BARENTZ – KEY FIGURES.

Barentz - Your Ingredients Partner. From Source to Solution.

2

Founded in

1953195319531953privately owned

Present in

60606060countries

>900>900>900>900employees

16.00016.00016.00016.000customers 4444

Divisions• Food & Nutrition

• Animal Nutrition

• Pharmaceuticals

• Personal & Home care 6666Global

production units

7777application centers

> > > > 1 1 1 1 billion Eurobillion Eurobillion Eurobillion Euro

2017turnover

Growing

>10>10>10>10%%%%annually

CONCEPT & APPLICATION CENTRES


3

AntioxidantSystems

Food

Pet Food

Aquaculture

Fish Oils

Personal care

NutritionalPremixes

Sport Nutrition

Clinical Nutrition

Infant Nutrition

NutritionalDrinks

FunctionalBlends

Meat & Fish

Bakery,

Natural Solutions

Health Solutions

Personal CareFormulations

Formulation Support

Lanolin Expertise

Center

Technical Support

Antioxidant Applications

Meat Applications

Skin Care Applications Synthetic

Natural

Vitamin based

Antioxidant classes

Aquaculture Cereals

Autoxidation – reaction is cyclic

Secondary products(Aldehydes, Ketones, Carboxylic acids, Hydrocarbons)

RH

ROOH

R.

ROO.

O2

RH(unsaturated fatty acid)

R.+H.

O2

R’+ H’ = free radicals ROO’ = peroxy radical ROOH = Lipid hydroperoxide

Oxidation Curve

• accelerated fast reaction

• Oxidation of fatty acids

�� formation of volatile

carboxylic acidsInduction period:

• Oxidation of fatty acids

�� peroxide formation

• no formation of volatile

carboxylic acids

Oxidative Stability & Shelf Life

• Antioxidants are food additives

used to extend the shelf of foods

by delaying the onset of oxidation.

• Unsaturated fats and oils are

particularly susceptible to oxidation

and their degradation products are

responsible for “rancid” off notes

and flavours.

• Antioxidants are also used to

improve the stability of colours,

flavours, vitamins and other

nutritive components such as long

chain polyunsaturated fatty acids.

Compounds formed during oxidation

Non volatile compounds

Volatile compounds

Initiation TerminationPropagation

PUFA source

Peroxides

Time

co

nce

ntr

atio

n

Oxidation Secondary

products

Oxidation primary products

OXIDATION - A FEED QUALITY ISSUE

Unsaturated Fatty Acid Source –Fish

meal oil

Light, O2Metal Catalyst

Oxidation -Peroxides,

Free Radicals

Volatile compounds

Protein

Amines

Cross linking

Off flavours and safety

Colour loss

Loss of ValuesTexture

modification

Vitamins (A, E)Omega 3

Pigments

Astaxanthin

Toxic compounds

OXIDATION IN FISH MEAL

Oxidation in meal and feed

• Nutritional loss (vitamins

especially)

• Astaxanthin loss (costly )

• Loss of Omega 3 (EPA / DHA)

• Oil quality (energy value)

• Protein quality (decreases on

exposure to oxidised oil)

OXIDATION AND LOSS OF OMEGA 3’S


10

0

5

10

15

20

25

30

35

40

50 Kg 1 Ton 50 Kg

30ppm

1 Ton

50ppm

50 Kg 1 Ton 50 Kg 1 Ton 50 Kg 1 Ton 50 Kg 1 Ton

EQ : 300 ppm EQ: 30-50ppm * BHT Solution 2000 ppmBHT Solution 4000 ppm Tocopherol Rosemary

Extract Blend

2000ppm

Tocopherol Rosemary

Extract Blend 4000

ppm

Om

eg

a 3

co

nte

nt

PU

FA

(g

/10

0g

Fa

tty

aci

ds)

Treatment

Change in Omega 3 content over 12 month period

Series1

Series3

Month

zero

Month

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SOURCE IMO IFFO ST/SG/AC.10/C.3/2016/82 SEP 2016

CURRENT SITUATION- EFSA

• suspending the authorisation of ethoxyquin as a feed additive

• Specific transitional measures for certain feed materials and related products

• a. the additive ethoxyquin and premixtures containing it, intended to be incorporated in the feed materials ….may continue to be placed on the market in accordance with the rules applicable before 28 June 2017 until 30 September 2019,

• b. feed materials referred to in point (a) produced with the additive ethoxyquinor with premixtures containing it may continue to be placed on the market in accordance with the rules applicable before 28 June 2017 until 31 December 2019;

• c. compound feed produced with the feed materials referred to in point (b) may continue to be placed on the market in accordance with the rules applicable before 28 June 2017 until 31 March 2020.


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C O M M I S S I O N I M P L E M E N T I N G R E G U L A T I O N ( E U ) 2 0 1 7 / 9 6 2

SITUATION FOR FISH MEAL PRODUCERS

• Ethoxyquin was very cost effective. 80% of all fish meal factories use EQ*

• Ethoxyquin replacement is not possible at same cost efficiency. Very few approved options.

• Market is moving ahead of deadline to replace Ethoxyquin.

• Feed Producers - have little advice on preferred options.

• Producers of antioxidants are offering options but issue is broad based in time scale to cover.


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T H E M A R K E T I S I N R E A C T I V E M O D E

* Source IFFO -2015

STUDIES ON REPLACING EQ

• Study on self heating fish meal 12 months stability .

• Approval to EQ ; BHT; Tocopherols;

• fish meal shall contain at least

• 50 ppm (mg/kg) of ethoxyquin, (was 100ppm)

• 100 ppm (mg/kg) of BHT

• 250 ppm (mg/kg) of tocopherol based antioxidant

at the time of consignment.

No other AOX approved.


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I F F O R E P O R T T O S U B C O M M I T T E E O N T R A N S P O R T O F D A N G E R O U S G O O D S – N O V 2 0 1 6

0

50

100

150

200

250Maximum Temperature above which sampe will fail test 200 °C

Analytical methods: Oxidative stability tests

3 types of tests are available

•Oxidability test - Rancimat- often referred to as ;

•AOM (Active Oxygen Method)

•OSI (Oxidative Stability Index)

–volatile oxidation products (largely formic acid are carried by the

air current into the measuring vessel, where they are absorbed

(dissolve) in the measuring fluid (distilled water).

–By continuous measurement of the conductivity of this solution,

oxidation curves can be generated.

• Oxygen consumption test (Oxipres)

• Accelerated ageing tests ( e.g Autoxidation, photo oxidation,

chemical oxidation)

Oxygen consumption test: Oxipres

– sample is subsequently placed at elevated temperature and the oxygen pressure is monitored in time. When the induction time of a sample has passed a (steep) drop in oxygen pressure is observed.

– Test can be performed on complete food matrix (solid food, emulsion…)

– Test run at standard temp or multiple temp for extrapolation to real time

4

4.5

5

5.5

6

6.5

7

7.5

0 5 10 15 20 25 30 35 40 45 50 55 60 65 70Time (h)

Oxyg

en

pre

ssu

re (

bar)

control 500 ppm AOX 1 500 ppm AOX 31000 ppm AOX4 500 ppm AOX 2

VITABLEND FISH MEAL AND FEED

• All AOX added to provide 150 ppm active


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S T U D I E S P E R F O R M E D – F I S H M E A L A N A L O G U E *

0

1

2

3

4

5

6

7

8

Oxipres Hours at 80 °C

0

5

10

15

20

25

30

35

EQ BHA BHT PG NMT

relative active required to

achieve same as EQHours

* 16.1% fat, 80.1% wheat flour, 2.8% silica

Fish meal Ethoxyquin >> BHA > BHT > Tocopherol > PGFish oil Ethoxyquin > BHA > PG >> BHT > Tocopherol

STUDIES ON REPLACING EQ


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I F F O – O X I P R E S F I S H M E A L - 6 M O N T H S T O R A G E

0

1

2

3

4

5

6

7

8

9

10

Ethoxyquin BHT Solution

2 000ppm

BHT Solution

2 000ppm

BHT Solution

4000ppm

BHT Solution

4000ppm

Tocopherol

2000 ppm

Tocopherol

2000 ppm

Tocopherol

4000ppm

Tocopherol

4000ppm

Oxipres Hrs

SOURCE IMO IFFO ST/SG/AC.10/C.3/2016/82 SEP 2016

RELATIVE ACTIVE AOX USE TO EQ

Relative active dose to EQ to achieve same antioxidant capablity in Fish meal

Active Vitablend ** IFFO*

BHT 5.50 7.00

Tocopherols 7.00 6.5

BHA 2.00 NT


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D A T A : V I T A B L E N D A N D I F F O

** Source –Fish Meal analogue studies in Oxipres

* Source - IMO IFFO ST/SG/AC.10/C.3/2016/82 SEP 2016 –Mean of values

• A close correlation between two separate studies

• Fish source and freshness of meal to be considered.


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Synthetic

• BHA; E320

• BHT; E321

• TBHQ; E319

• Propyl Gallate; E310

• Ethoxyquin E324

Natural

• Natural Tocopherols E306;

• Rosemary extracts (No E Number in feed)

• Botanical extracts (no E number)…

Vitamin based

• Ascorbates (esp. Ascorbyl palmitate, E304

• Ascorbic acid E300)

• Vitamin E -

• DL-AlphaTocopherol; E307

VITABLEND ANTIOXIDANTS – ACTIVES FOR FEED

VITABLEND ANTIOXIDANTS – FORMULATION


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Choose Antioxidant

• Synthetic or Natural.

• Delay the lipid oxidation.

• Can be used synergistically.

• Maintain the quality of the foods .

• Offered in powder or liquid formats

• Oil or Water soluble

Add Chelator

• Citric acid

• Citric acid Mono glyceride esters.

• Work with the Antioxidant synergistically.

• Remove trace metals that act as pro-oxidants.

Add Carriers

• Emulsifiers , vegetable oils

• Ensure homogeneity of the Antioxidants

• Increase the solubility of the Antioxidants

• Ensure optimum effect of the Antioxidant.

Increasing Antioxidant capability

Natural antioxidants -

Demonstrated efficacy

Positive label acceptance

Global acceptance

Positive image

Not limited in use

GRAS status

Potential health benefits

Low volatility

Higher price c.w. Synthetics.

Possible undesired colour & flavour.

Possible GM / Allergen issue

Certain natural AOX’s not tested

extensively

Possible availability Issues.

Advantages Disadvantages

NATURAL TOCOPHEROLS

Natural Mixed Tocopherols

:

• Alpha tocopherol : 5-10%

• Beta tocopherol : < 5%

• Gamma tocopherol : 70-85%

• Delta tocopherol : 5-15%

• Delta and gamma homologues form the greater percentage of homologues. The In- vitro “ work horses “

Homologue breakdown

• Tocopherol origin: Soya (GM, IP) Sunflower, Rape seed oil.

• Tocopherol - is a mixture of 8 forms

(homologues) namely , Alpha (α ), Beta (β), Gamma (γ) and Delta (δ) Tocopherol and 4 tocotrienol homologues ( γ,δ,β,α).

• The mixed homologue natural tocopherols are referred to as “d (natural) mixed tocopherols” (E306).

• In- Vitro (non- Biological ) tocopherol is in the order

– delta> gamma> beta> alpha.

O

HO

R1

R2

R3

CH3

CH3

CH3CH

3

Natural Mixed Tocopherols

• Slightly viscous liquid.

• Soluble in fats and oils.

• Part of Vitamin E family.

• Activity: Delta>Gamma> Beta>Alpha.

• Temp stability> 200°C

• Main source is Soya bean oil.

• Typical specification 25 % mixed tocopherols as Toco PET IP

• Can be added QS

• Relatively expensive to EQ

• Options now on Sunflower and rape seed oil

• NON GM (IP)

• permanently non- allergen (EU)

Primary Antioxidants

• These terminate the free radical chain reaction by donating hydrogen. This stops the propagation cycle.

ROO� + (unsaturated lipid) AH �ROOH + A�

• Hindered phenolics - BHA, BHT , Tocopherols and gallates belong to this group.

• The close proximity of the tert –butyl group to the hydroxyl group in each case leads to the term “hindered Phenol”

• Natural Phenolics (Rosemary, Flavonoids) behave in same way.

Butylated Hydroxytoluene (BHT)

C(CH3)3C

OH

C(CH3)3

CH3

VITABLEND ANTIOXIDANTS – SOLUTIONS & INNOVATION


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• Non GMO Project

• Non Allergen

• Soya or SF origin options

• Non Chinese options

• HALAL and Kosher

• Powder or liquid forms

Tocopherols

• Non GMO

• Non allergen

• Deodorized versions

• Liquid or powderRosemary Extracts

• Ascorbyl Palmitate

• Ascorbyl Stearate

• DL Alpha TocopherolsVitamin basedsolutions

• Green Tea

• Other compounds

Botanicalextracts

Synergie of different

compounds

Carriers + emulsifers

Vitablend process

• Customer targets

• Regulations

• Customer process

• Matrix/oils

Tocoblend A/T/R

Vitablend 16X

Vitablend GTR

Tocoblend L/NAT

Active compounds

R&D - NPD Solution

VITABLEND ANTIOXIDANTS – MODELS AND METHODS


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Evaluation

Oil type?

Application area?

Process?

Test

Rancimat

Oxipres

Other?

Apply

Process

Feedback loop

Feedback loop

Synergie of different

compounds

Carriers + emulsifers

Vitablend process


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VITABLEND ANTIOXIDANTS – ANALYTICAL SUPPORT

Analytical procedures .

• All analytical tests are performed to the

highest standards with the latest up to date

methods employed. Special unique

techniques can be considered on request.

All techniques are routinely employed

using internal standards and /or duplicate

samples to ensure accuracy, validity and

precision.

• The laboratory is equipped to cover

analysis on all types of feeds, oils, fats and

solid food ,feed or personal care matrixes.

• If you have a particular requirement or

question please contact us via your

Vitablend or Barentz representative.

VIT-ASSURANCE

Vitablend Antioxidant

Analytical Laboratory

ANALYTICAL METHODS

Analytical method Objective & Method Pros / cons

Sensorial Analysis consumer panel judges samples of product

according to senses of taste (smell, sight &

mouth feel) -

• Highly sensitive results

• Costly / heavy organization

• Low reproducibility (panel)

• Long preparation

Peroxide Value Determine the concentration of hydro peroxides

(primary oxidation compounds) in lipids

• Cheap and easy to repeat

• Characterize primary oxidation steps

(not linked to off flavours)

• Reproducibility may be difficult

Anisidine Value Test the apparition of secondary oxidation

compounds in fats and oils including non volatile

compounds.

• Good for long chain PUFA

• Measure hidden oxidation

• Good measure of non-volatile

• TOTOX = 2 PV + 1 AnV

Hexanal Determine the volatile oxidation products as

markers of flavour development in oxidised oils

or food

• Very specific method

• Very sensitive

• Good correlation with flavor score

• Require highly sophisticated

equipment and personnel

TBA value Determines the concentration of secondary

oxidation compounds of polyunsaturated lipids-

Thiobarbituric acid (TBA) reacts with

malondialdehyde (MDA) & secondary products .

• Easy and rapid . Good sensitivity

• Fairly specific to long chain PUFA.

• Protocol control is difficult

Analytical methods: testing of compounds formed

During oxidation

Non volatile compounds

Volatile compounds

Initiation TerminationPropagation

PUFATESTS: P.V or Conjugated dienes

Time

co

nce

ntr

atio

n

Secondary productsPrimary products

TESTS: TBARS

ANISIDINE

TESTS: HEXANAL

OXIDATION IN FISH MEAL

• SNP Trial –PERU

• Validate BHA as Potential

replacer to EQ;

Future and Focus

• Ethoxyquin Replacement.

• Spontaneous combustion (IMO & SNP Studies Options)

• Astaxanthin loss (feed Industry)

• Oxidative Shelf life studies

• Consumer awareness.

• Increase in “ Naturalness” and Organic.

• Synthetic Antioxidants are less preferred

• Cleaner label drive.

Vitablend activity

ANTIOXIDANTS IN HIGH IRON FISH FEED

• Vitablend sceened using the Oxipres on a received meal mix, to determine

which antioxidant blends work well in a meal mix high in iron.

• The tests were performed on a standard Mikrolab Oxipres set at 80°C and 5 bar

of oxygen has been applied at the start of the analysis.


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D E T A I L S O F T E S T

# Viitablend code Sample name Addition level (ppm)

1 -Control 0

2 16001109xxxVitaPet BT 750

3 6293xToco-PET IP 1500

4 -2017031 blend 4 1000

5 -2017031 blend 6 1000

6 6345xToco-PET RE 10-10 1500

7 -Ethoxyquin 150

8 6292xVita-Pet 24-8-8 625

ANTIOXIDANTS IN HIGH IRON FISH FEED

Blend

Ingredient (%) VitaPet BT Toco-PET IP 2017031 blend

4

2017031 blend 6 Toco-PET RE 10-

10

Ethoxyquin Vita-Pet 24-8-8

Vitablend code 16001109xxx 6293x - - 6345x - 6292x

Natural mixed

tocopherols IP x x x x

Propyl gallate x x x

Rosemary extract x

Ascorbyl palmitate x

BHA x x

Citric Acid x

BHT x

Ethoxyquin x


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Documents

ANTIOXIDANTS -Fish meal and Feed · Oxidative Stability & Shelf Life • Antioxidants are food additives used to extend the shelf of foods by delaying the onset of oxidation. •