agilent - 3-mcpd - my
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Analysis of 3-MCPDand Glycidyl Estersin Palm Oil
Jimmy Wong
Marketing Program Manager
Gas Phase2nd June 2015
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Introduction
Free 3-MCPD (3-monochloropropane-1,2-diol or 3-
chloropropane-1,2-diol) is first identified on lipid hydrolyzedby HCl
In 2006, 3-MCPD esters were reported in edible oils,especially in refined oils but not in crude oils.
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Introduction
The critical step of refining may be the deodorization. In this
step mono-and di-glycerides, chloride ion and temperatureled to the formation of 3-MCPD monoesters and 3-MCPD
diesters
It is one of the food safety concerns for oils and fats industry
Hot topic in Europe especially among the refiners of oils and
fats
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Issue of concern
Dec 2007 German Risk Assessment Body (BfR) issued evaluationdietary on 3-MCPD esters
Exposure up to tolerable daily intake (TDI) of 3-MCPD esters was
anticipated in infant formula
Refined oils - highest amount, hence food products using them will
contain elevated amount 3-MCPD esters
Toxicity level is not yet available
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Possible formation oil refining process
Crude oil
Refined oil
Degumming
Bleaching
Phosphoric acidis added
Phosphoric acid
and gums
Gums/Clays and
phosphoric acid are
removed
Bleaching
clay
is addedFilter Press
Deodorisation
(Siew W.L., 2012)
3-MCPD esters occurs during the refining of edible crude oils
mostly at the deodorization step
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Formation mechanism hypothesis
Acylglycerol Cyclic acyl
oxonium ion
3-MCPD esters
R O
OOH
OR1
H+
-H2O
R
O
O
OR1
Cl-
O
OR1
O
Cl
R
3-MCPD
R = alkyl
R1 = H or COR
* International Life Sciences Institute (ILSI) Report, 2009
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Summary of method:AOCS Official Method Cd 29a:13
GC-MS Analysis
Derivatization of 2- and 3-MCPD and 3-MBPD with Phenylboronic acid (PBA)
Extraction of fatty acid methyl esters
Conversion of 2- and 3-MCPD esters and 3-MBPD esters into free form in acid methanolic solution
Conversion of GE to 3-MBPD monoesters in bromide salt
Add internal standards + THF
100 mg oil/fat sample
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Agilent GC Configuration
7890B GC Multimode inlet
5977B GCMSD
Extractor ion source Triple Axis detector
Monolithic Quartz Quadrapole
Mass Hunter software
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Chemicals and Reagents as per AOCS Cd29a-13
Standards
1. 1,2- Dipalmitoyl-3-chloropropanediol (PP-3-MCPD)
2. 1,3- Dipalmitoyl-3-Chloropropanediol( PP-2-MCPD
3. Pentadeuterated -1,2-Dipalmitoyl-3-chloropropanediol (PP-3-MCPD D-5)4. Glycidyl Palmitate (Gly-P)
5. Pentadeuterated Glycidyl Palmitate (Gly-P-d5)
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Reagents Preparation
Followed AOCS method- Below Screen shot
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Standards Preparation
Followed AOCS method- Below Screen shot
Calibration Stock solution:
1) 550ul of 3-MCPD stock and 550ul of 2-MCPD stock diluted to 10 ml with toluene-
55ug/ml ( Calib 1)
2) 1ml of Calib 1 to 10 ml with toluene 5.5ug/ml ( Calib 2)
3) 400ul of 3-MCPD-d5 to 10 ml with toluene 40ug/ml ( Calib ISTD)
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Standards Preparation- Continued
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Standards Preparation- Continued
Calibrationlevel
Calib 1(ul)
Calib 2(ul)
Finalconcentration
as 3-MCPD
(ug)
CalibISTD
(ul)
Final concentration as 3-MCPD-d5(ug)
Level 0 0 0 0 50 0.39
Level 1 0 25 0.03 50 0.39
Level 2 0 50 0.05 50 0.39
Level 3 0 100 0.10 50 0.39
Level 4 20 0 0.21 50 0.39
Level 5 30 0 0.31 50 0.39
Level 6 70 0 0.72 50 0.39
Level 7 90 0 0.93 50 0.39
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MethodColumn Used- DB-1 , 30m x 0.25, 0.25mm FT capillary column
GC Conditions:
1. Injection Volume 1.0 ul
2. Inlet temperature- 250 deg C
3. Injection Mode- Pulsed splitless
4. Inlet Flow- 0.8 ml/min constant Flow
5. Oven Programming- 80C (1 min), from 80C to 170C at 10C/min, from 170C to 200C at
3C/min, from 200C to 300C at 15C/min, 15 min at 300C
MS Conditions
1. Transfer line temperature: 300C
2. Ion source temperature: 230C3. Quadrupole temperature: 150C
4. Ionization mode: EI, SIM mode
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Method Continued
Parameters for SIM (Selected Ion Monitoring) mode:
1. Phenylboronic derivative of 3-MCPD (m/z) 147 (quantifier ion); 196, 198 (qualifier ions);
2. Phenylboronic derivative of 2-MCPD (m/z) 196 (quantifier ion); 198 (qualifier ion);
3. Phenylboronic derivative of 3-MCPD-d5 (m/z) 150 (quantifier ion for 3-MCPD); 201
(quantifier ion for 2-MCPD); 203 (qualifier ion);
4. Phenylboronic derivative of 3-MBPD (m/z) 147 (quantifier ion); 240 (qualifier ion);
5. Phenylboronic derivative of 3-MBPD-d5 (m/z) 150 (quantifier ion); 245 (qualifier ion).
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6x10
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
3
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
4
4.1
4.2
4.3
4.4
+SIM(147.1)SIM9Dec2015-C-Cal8.D
phenylboronic derivative of 3-MCPD
phenylboronic derivative of 3-MBPD
Countsvs.AcquisitionTime(min)
10.3 10.4 10.5 10.6 10.7 10.8 10.9 11 11.1 11.2 11.3 11.4 11.5 11.6 11.7 11.8 11.9 12
Overlay of Cal 0, Cal 1, Cal 2, Cal 3, Cal 4, Cal 5, Cal 6, Cal 7 & Cal 8 of AOCS Method Cd 29a-13
Chromatogram of 3-MCPD & 3-MBPD
m/z 147
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Chromatogram of 2-MCPD
m/z 196
Overlay of Cal 0, Cal 1, Cal 2, Cal 3, Cal 4, Cal 5, Cal 6,
Cal 7 & Cal 8of AOCS Method Cd 29a-13
5x10
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.82.9
3
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
4
4.1
4.2
4.3
4.4
4.5
+SIM(196.1)SIM9Dec2015-C-Cal8.D
phenylboronic derivative of 2-MCPD
Countsvs.AcquisitionTime(min)
10.3 10.4 10.5 10.6 10.7 10.8 10.9 11 11.1 11.2 11.3 11.4 11.5 11.6 11.7 11.8 11.9 12
phenylboronic derivative of 3-MCPD
Overlay of Cal 0, Cal 1, Cal 2, Cal 3, Cal 4, Cal 5, Cal 6, Cal 7 & Cal 8 of AOCS Method Cd 29a-13
m/z 196
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Chromatogram
6x10
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
+SIM(147.1)SIM9Dec2015-C-Cal8.D
phenylboronic derivative of 3-MCPD
phenylboronic derivative of 3-MBPD
5x10
0
1
2
3
4
5
6
7
8
9
+SIM(150.1)SIM9Dec2015-C-Cal8.D
phenylboronic derivative of 3-MCPD-d5
phenylboronic derivative of 3-MBPD-d5
5x10
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
+SIM(196.1)SIM9Dec2015-C-Cal8.D
phenylboronic derivative of 2-MCPD
Countsvs.AcquisitionTime(min)
10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9 11 11.1 11.2 11.3 11.4 11.5 11.6 11.7 11.8 11.9
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3-MCPD- Linearity plot
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2-MCPD- Linearity plot
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Glycidyl Esters
Gly-9Levels,9LevelsUsed,9Points,9PointsUsed,0QCs
RelativeConcentra
-0.2 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6
RelativeR
esponse
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5=1.390515*x+0.010148R^2=0.99884432Type:Linear,Origin:Ignore,Weight:None
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Agilent Food Contamination Resource
http://www.agilent.com/about/features/food-contamination.html
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THANK YOU!
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