Final Results from the German FEI Research Pro ject ...aocs.files.cms-plus.com/ResourcesPDF/Vortrag-Rotterdam-1.pdf · Concerning 3-MCPD Esters and Related Compounds – Mitigation

Final Results from the German FEI Research Project jConcerning 3-MCPD Esters and Related Compounds

–Mitigation Strategies

Büh

rke/

PIX

ELI

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Mitigation Strategies

Bertrand Matthäus1, Anne Freudenstein1, Frank Pudel2, Tim Rudolph2,

hrod

t, V

eren

a N

., M

icha

el

1 Max Rubner-Institut2 Pilot Pflanzenöltechnologie Magdeburg e.V.

MRI – Max Rubner-Institut, MünsterMRI – Max Rubner-Institut, Detmold Bild

er: ©

Car

lo S

ch

November 2007: Statement of the Official Laboratory Stuttgart and the Federal

Basis for the German FEI-Project on 3-MCPD-EsterNovember 2007: Statement of the Official Laboratory Stuttgart and the Federal Research Center for Nutrition and Food, Münster

Toxicological Assessment on free 3-MCPDC i i i hi h d i l i i hCarcinogenic in high doses at animal experiments with ratsSCF did not assume genotoxicityIARC assesses 3-MCPD as possibly carcinogenic to humans (2B)Limit: 20 µg/kg for soy sauces and HVP (VO (EG) 1881/2006)

Statement Nr. 047/2007 of the German Federal Institute for Risk

Limit: 20 µg/kg for soy sauces and HVP (VO (EG) 1881/2006)TDI: 2 µg/kg BW (JECFA, EU, SCF)

Assessment, December 2007As it is not just individual products or products of individual manufacturers that are affected by the problems surrounding 3-MCPD fatty acid esters, alternative y p g ytechniques must, in principle, be developed for the production of refined fats and oils.

Euro Fed Lipid Congress 2011, Rotterdam

Investigations on the formation of 3-monochloropropane-1,2-diol fatty acid esters (3-MCPD esters) in vegetable oils and

development of minimization strategies

Clarification of the relationship between formation of 3-MCPD esters andAims

development of minimization strategies

Clarification of the relationship between formation of 3 MCPD esters and related compounds, process conditions and composition of involved components

Recommendations for the definition of processes resulting in mitigation of p g g3-MCPD esters and related compounds without impairing product quality

Removal of 3-MCPD esters and related compounds from the refined productp

Development of a direct method based on SIVA with LC-MS for the quantification of the esters

Max Rubner-Institut Pilot Pflanzenöl D h I i fü

Bundesforschungsinstitut für Ernährung und Lebensmittel

Deutsche


Max Rubner-Institut, Münster (MRI)

Pilot Pflanzenöl Magdeburg e.V.

(PPM)Deutsches Institut für

Lebensmitteltechnik e.V.Deutsche

Forschungsanstalt für Lebensmittelchemie

(DFA)

Mitigation strategy soil?

Raw material(removal of precursors)

fertilizer? genotype? Technique of harvest?p ) Technique of harvest? Time between ripeness and processing?

Refining(Changing of the

process)

Influence of degumming, neutralization, bleaching and deodorization

Introduction of additionals processing stepsprocess) Introduction of additionals processing steps

Product(Removal of the

)Euro Fed Lipid Congress 2011, Rotterdam

esters)

Capability of raw oils to form 3-MCPD esters and related compounds after heating (240 °C, 2h)

9

10

d

6

7

8

nd re

late

dm

g/kg

]

4

5

6

D-e

ster

s an

poun

ds [m

2

3

3-M

CPD

com

p

0

1

Avocado Olive Rapeseed Corn SoybeanSunflower Cocos PalmPalm


Avocado oil

Oliveoil

Rapeseedoil

Cornoil

Soybeanoil

Sunfloweroil

Cocosoil

Palm kernel

fat

Palm oil

Capability of different palm oils to form 3-MCPD esters and related compounds

14

16

ated

8

1012

rs a

nd re

las [

mg/

kg]

4

6

8

CPD

est

erom

poun

ds

0

24

3-M

C co

RegionA

RegionB

RegionC

RegionD

RegionE

Columbia Ghana Indonesia


Malaysia

Correlation between content of diacylglycerols and 3-MCPD esters and related compounds in different oils

20

25

mpo

unds

15

20

elat

ed c

omg]

10

ers a

nd re

[mg/

kg

5

MC

PD e

st

00 1 2 3 4 5 6 7 8 9 10

C t t f di l l l [%]

3-M


Content of diacylglycerols [%]

Influence of polar compounds and diacylglycerols on the formation of 3-MCPD esters and related compounds

6.0Diacylglycerol Polar compounds from palm oil

ound

s

4.0

5.0R² = 0.9092

ted

com

po

3.0

4.0R² = 0.9259

s and

rela

t[m

g/kg

]

1.0

2.0

PD e

ster

s

0.0

1.0

0 5 10 15 20

3-M

C


0 5 10 15 20Diacylglycerols or polar compounds [%]

Influence of polar compounds and diacylglycerols on the formation of 3-MCPD esters and related compounds

60

70 12Diacylglycerols

3-MCe

fatty

50

60

8

10Free fatty acids

3-MCPD esters and related compounds

CPD

esters and

free

30

406

rs and rela[m

g/kg]

cylg

lyer

ols

acid

s [%

]

20

30

2

4

ated comp

nt o

f Dia

c a

0

10

0

2

pounds Con

ten


crude palm oil "model oil" polar fraction

Mitigation strategy soil?

Raw material(removal of precursors)

fertilizer? genotype? Technique of harvest?p ) Technique of harvest? Time between ripeness and processing?

Refining(Changing of the

process)

Influence of degumming, neutralization, bleaching and deodorization

Introduction of additionals processing process)steps

Product(Removal of the

)Euro Fed Lipid Congress 2011, Rotterdam

esters)

Impact of refining on the formation of 3-MCPD esters and related compounds

Bleaching

crude oil5.6 52.1

40.55

6

7

poun

ds 50

60. 3-MCPD esters and related compounds

Phospholipids

DegummingBleaching

-45%

este

rs a

nd re

late

d un

ds [m

g/kg

]

degumming3.9

3.43.9

3.327.4

33.4

11.9

1

2

3

4

5

3-M

CPD

est

ers

and

rela

ted

com

p[m

g/kg

]

10

20

30

40

Phos

phol

ipid

s [m

g/10

0g]-41%

crude palm oil240°C, 2 h

crude palm oil1% Tonsil 4191 FF

240°C, 2 h

3-M

CPD

eco

mpo

u

neutralisation0

crude palm oil240°C, 2h

crude palm oil20% water240°C, 2h

crude palm oil5 % water240°C, 2h

crude palm oil5 % water + 0.2% phosphoric acid

240°C, 2h

crude palm oil5 % water+ 0.3%

citric acid,240°C, 2h

0

Source: A. Schwaf, Diploma thesis, 2009

50glycidyl esters 3-MCPD esters

bleaching

d d i ti

5,6

3,13,64

5

6

7

d re

late

d co

mpo

uund

s g/

kg]

Neutralisation

-45% -36%

mg/

kg]

25

30

35

40

45

50

deodorization

Refined oil

3,1

0

1

2

3

crude palm oil crude palm oil

3-M

CPD

est

ers a

nd [mg

crude palm oil

Con

tent

[m

5

10

15

20

25


Refined oilcrude palm oil240°C, 2 h

crude palm oilKOH, 240°C, 2h

crude palm oilNaOH, 240°C, 2h

1 2 4

180

1 2

210

4 1 2

240

4 1 2

270

4

0time [h]

temperature [°C]

Amount of bleaching earth during bleaching6

ompo

unds

5

d re

late

d co

g/kg

]

3

4

D e

ster

s and [mg

2

3

3-M

CPD

0

1

degummed: 0.2 % H2O bleached: 1 % BE;

deodorized: 250 °C 60 min

Crude palm oil deodorized: 250 °C, 60 min

0degummed: 0.2 % H2O

bleached: 3 % BE;deodorized: 250 °C 60 min


deodorized: 250 C, 60 min deodorized: 250 C, 60 min

Influence of temperature and time of washing7

s

5

6

com

poun

ds

- 38 %

4

5

nd re

late

d c

mg/

kg]

2

3

D e

ster

s an [m

13-M

CPD

no washing

Temperature [°C]Duration [min]

0605

805

8020

1005

10010

10020


Simulation of deodorisation by heating at 240 °C for120 min

Addition of diacetin during deodorisation

6

7

unds

5

ted

com

pou

- 47 %- 30 %

3

4

rs a

nd re

lat

[mg/

kg]

- 49 %

2

MC

PD e

ster

Tonsil 215 FF Tonsil 118 FF0

1

Tonsil 215 FF Tonsil 118 FF

3-M


Tonsil 215 FF250°C, 120 min

Diacetin

Tonsil 118 FF 250°C, 120 min

Diacetin



Köstrolith during deodorisationed

910

3-MCPD esters and related compounds 3-MCPD estersan

d re

late

[mg/

kg]

6789

PD e

ster

s m

poun

ds

3456

3-M

CP

com

123

Percentage Köstrolith0

0 % 2.5 % 5 % 10 %


Crude palm oil; deodorisation: 250 °C 2 h

Comparison between one and two step deodorisation

161820

3-MCPD esters and related compounds3-MCPD esters

[mg/

kg]

10

1214

Con

tent

68

10

024

200°C120 min270°C

270°C5 min200°C

250°C5 min

200 °C

250°C10 min200°C

200°C120 min250°C

200°C120 min250°C

250 °C90 min

270°C90 min

1. step

2. step

0


5 min120 min120 min 120 min5 min 10 minStarting material: Palm oil, bleached with 1,5 % Tonsil Optimum 215

Comparison between short chain destillation and industrial desodorisation

1112 3-MCPD esters and related compounds 3-MCPD esters

g/kg

]

89

10

onte

nt [m

g

567

Co

345

012


Red palm oil after short chain destillation Industrial deodorised palm oil

Red palm oil3-MCPD esters and related compounds 3-MCPD esters

elat

ed

g]

3 MCPD esters and related compounds 3 MCPD esters

3

4es

ters

and

reou

nds [

mg/

kg

2

3-M

CPD

eco

mpo

1

Crude palm oil gently neutralised

Crude Palm oil, gently neuralised; heat-bleached:

220°C, 2h

0 Crude palm oilContent = 0Content= 0

Rancimat (120°C)

[h]

Peroxide value

[mmol O2]Free fatty

acids3-MCPD esters and related compounds

[mg/kg]Anisidine

value

Palm oil gently neutralised 13 2 0 8 0 4 0 6 1


Palm oil, gently neutralised 13.2 0.8 0.4 0 6.1Palm oil, industrial refined 8.4 2.2 0.7 5.8 8.4

Recommendations for the production of palm oil low in 3-MCPD esters and related compounds In General Deodorization is the important step for the formation of 3-MCPD esters

and related compounds The other refining steps reduce the capability of the oils to form 3-MCPD

esters and related compounds during deodorization Measures of mitigation Measures of mitigation Reducing the temperature during deodorization as low as possible Introduction of a washing step before refining Addition of diacetin, citric acid or Köstrolith during deodorisation Use of a two-step deodorization Use of a short-chain destillation Use of a short chain destillation Optimization of the pre-processing of palm fruits with short time of

storage between ripeness and processing Choice of raw material with low contents of precursors


Choice of raw material with low contents of precursors


and related compounds Still openDefinition of quality parameters for the raw material The other refining steps reduce the capability of the oils to form 3-MCPD

esters and related compounds during deodorization Measures of mitigation

q y pOptimization of the different stepsRealization into industrial facilities Measures of mitigation Reducing the temperature during deodorization as low as possible Introduction of a washing step before refining Addition of diacetin, citric acid or Köstrolith during deodorisation Use of a two-step deodorization Use of a short-chain destillation Use of a short chain destillation Optimization of the pre-processing of palm fruits with short time of





and related compounds Still openDefinition of quality parameters for the raw material The other refining steps reduce the capability of the oils to form 3-MCPD

esters and related compounds during deodorization Measures of mitigation

q y pOptimization of the different stepsRealization into industrial facilities Measures of mitigation Reducing the temperature during deodorization as low as possible Introduction of a washing step before refiningA new project was applied at the Addition of diacetin, citric acid or Köstrolith during deodorisation Use of a two-step deodorization Use of a short-chain destillation

Research Association of the German Food Industry

Use of a short chain destillation Optimization of the pre-processing of palm fruits with short time of




Acknowledgment

Dr. J.-P. Krause, PPMDr. P. Fehling, PPMDr. P. Fehling, PPM

Chr Böhme MRIChr. Böhme, MRIDr. K. Vosmann, MRIPetra Weitkamp, MRIA d S h f WWU Mü t MRI

Bundesforschungsinstitut für Ernährung und Lebensmittel

Andrea Schwaf, WWU Münster, MRIN. Schumacher, FH Münster, MRI

The presented work was supported by the FEI (Research Association of the German Food Industry),the AiF and the Ministry of Economics and Technology


the AiF and the Ministry of Economics and Technology. AiF-Project No.: BG 16004

Documents

Final Results from the German FEI Research Pro ject ...aocs.files.cms-plus.com/ResourcesPDF/Vortrag-Rotterdam-1.pdf · Concerning 3-MCPD Esters and Related Compounds – Mitigation