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Final Results from the German FEI Research Project jConcerning 3-MCPD Esters and Related Compounds
–Mitigation Strategies
Büh
rke/
PIX
ELI
O
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
Euro Fed Lipid Congress 2011, Rotterdam
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
Euro Fed Lipid Congress 2011, Rotterdam
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
Euro Fed Lipid Congress 2011, Rotterdam
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
Euro Fed Lipid Congress 2011, Rotterdam
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
Euro Fed Lipid Congress 2011, Rotterdam
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
Euro Fed Lipid Congress 2011, Rotterdam
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
Euro Fed Lipid Congress 2011, Rotterdam
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
Euro Fed Lipid Congress 2011, Rotterdam
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
Euro Fed Lipid Congress 2011, Rotterdam
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
Euro Fed Lipid Congress 2011, Rotterdam
Tonsil 215 FF250°C, 120 min
Diacetin
Tonsil 118 FF 250°C, 120 min
Diacetin
Tonsil 215 FF 250°C, 120 min
Tonsil 118 FF 250°C, 120 min
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 %
Euro Fed Lipid Congress 2011, Rotterdam
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
Euro Fed Lipid Congress 2011, Rotterdam
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
Euro Fed Lipid Congress 2011, Rotterdam
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
Euro Fed Lipid Congress 2011, Rotterdam
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
Euro Fed Lipid Congress 2011, Rotterdam
Choice of raw material with low contents of precursors
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 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
storage between ripeness and processing Choice of raw material with low contents of precursors
Euro Fed Lipid Congress 2011, Rotterdam
Choice of raw material with low contents of precursors
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 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
storage between ripeness and processing Choice of raw material with low contents of precursors
Euro Fed Lipid Congress 2011, Rotterdam
Choice of raw material with low contents of precursors
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
Euro Fed Lipid Congress 2011, Rotterdam
the AiF and the Ministry of Economics and Technology. AiF-Project No.: BG 16004
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