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Mineral oil in vegetable oils :

Laboratory and Industrial Issues

Florence LACOSTE, ITERG

DGF Symposium, 10 March 2016


Agenda

Mineral oil composition

EFSA Scientific Opinion on Mineral Oil Hydrocarbons in food

Methods of analysis

Standardization work (ISO & CEN levels)

Origin of the contamination

Examples of contamination

Effect of refining on the mineral oil contamination

FEDIOL code of practice for the management of mineral oil hydrocarbons in vegetable oils

Conclusion

2


Mineral oil (MO) composition

3

Naphtenes

Paraffins

Food grade

MOSH

65% à 85%

MOH

(C10 –C50)

MOAH

15 % à 35%Aromatics

(PAHs)

EFSA Journal 2012;10(6):2704

Technical grade


0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

Contaminated Sunflower oil (MOSH analysis)

Natural hydrocarbons

Mineral oil :unresolved complex mixture

Mineral oil (MO) composition

4

Chemical composition of MOH largelyunknown

Depending on the crude oil source and theprocess, MOH products composition canvary batch to batch

Number of isomers increases exponentiallywith the number of carbon atoms (numberof substances > 100 000)

unresolved complex mixture

Quantification of total MOSH and totalMOAH is achievable


CONTAM Panel conclusions:

Potential concern associated with the current exposure to MOSH in

Europe (white oils as release agents for bread and rolls, spraying of grains)

Exposure to MOAH through food considered to be of potential concern

because of its specific health risk

Total MOSH and MOAH should be separately determined

2 sub-classes to be distinguished: MOSH up to n-C16 & MOSH from n-C16

to n-C35

Mineral oil: EFSA Scientific Opinion

5

EFSA Journal 2012;10(6):2704


Principle of the methods :

First step : isolation of hydrocarbons by liquid chromatography or HPLC

Second step (optional) : extra purification and concentration in order to increase the sensitivity

Third step : gas chromatography analysis with FID detection

Critical points:

Integration of the hump & subtraction of the “natural hydrocarbons”

Quantification of hydrocarbons without loosing the volatile ones

Removal of interference compounds

Limit of quantification as low as possible

Mineral oil determination - Critical points

6


Ring test organised by a French producer

7 -

6 European laboratories using their own method + 1 reference Labo 8 different samples dispersion of the results (between 40 and 130 for sample H)

In 2010, it was stated that a reference method was needed

0

20

40

60

80

100

120

140

160

180

A B C D E F G H

Reference Lab

50

2010


Standardization : on-going work

8

ISO/TC34/SC11 CEN/TC275/WG13

EC requirement :

determination of mineral oil

method able to distinguish MOSH (MineralOil Saturated Hydrocarbons) and MOAH(Mineral Oil Aromatic Hydrocarbons)

crude and refined vegetable oils

foodstuffs on basis of vegetable oils

ISO work :

determination of saturated aliphatichydrocarbons in vegetable oils (MOSH)

crude and refined vegetable oils

pre-trial in 2012

collaborative study in 2013 & 2014

ISO 17780: 2015 for MOSH Method for MOSH & MOAHExpected publication : 07/2017


Fractionation of the sample by LC on silica gelimpregnated with AgNO3

Quantification with C18 (IS)

Injection of a reference standard blend (C10-C40) and a C48 standard

GC condition on an apolar column (15 m)

Double integration (subtraction of the peaksabove the hump)

Silica gel with AgNO3 18,5 g

Test portion 1 g

Elution with hexane 55 ml

ISO 17780 : MOSH determination

9

« mineral oil »

« natural hydrocarbons »


2013 Trial : 7 oil samples + 2 foodstuffs virgin olive O + huile minérale

refined pomace olive O

crude palm O + gasoil

refined grapeseed O

refined sunflower O

refined sunflower O + MOSH

crude soja O + MOSH

margarine & mayonnaise + MOSH

Laboratories : 39 participants from 12 pays

2012 Pre-trial : 2 oil samples virgin olive O + 50 ppm crude soja O +450 ppm

2014 Trial : 6 oil samples virgin olive O + MOSH

refined pomace olive O

refined rapeseed O

refined sunflower O + MOSH

crude soja O + MOSH

Laboratories : 21 participants from 9 pays

grapeseed (235 mg/kg)soja (90 mg/kg)

olive (50 mg/kg)pomace olive (163 mg/kg)

ISO 17780 : Validation

10


ISO 17780 : Validation

11

Mineral oil – 50 mg/kg spiked olive oil sample 2-2013 sample 4-2014

Spiking level (mg/kg) 50 50

Mean value (m) 52 52

Repeatability limit (r) 19,3 15,3

Reproducibility limit (R) 51,7 28,1

Horrat value 4,1 2,2

0

20

40

60

80

100

120

140

160

26 3 8 23 21 34 15 31 1 19 4 33 36 9 28 17 30 27 29 24 11 10 35 5 32 12 6 22 2 18 20 14

Lab

me

an v

alu

e (

mg/

kg)

Laboratories

Sample 2: 50 mg/kg spiked olive oil

0

20

40

60

80

100

120

140

160

20 12 14 10 7 9 13 16 15 1 11 19 4 8 5 2 6 17

Lab

me

an v

alu

e (

mg/

kg)

Laboratories

Sample 4: 50 mg/kg spiked virgin olive oil

Improvement of the precision data by selecting experienced laboratories


ISO 17780 : 2014 collaborative trial

12

Mineral oil - MOSH 1 2 3 4 5 6

Number of participating laboratories 20 20 20 20 20 20

Number of laboratories retained after elim. outliers 18 18 18 18 17 18

Spiking level (mg/kg) - - 100 50 25 -

Mean (m) 119 11 107 52 38 90

Repeatability standard deviation (sr) 4,4 3,1 3,7 5,5 2,7 4,9

Repeatability relative standard deviation (RSDr) 3,7% 28,1% 3,4% 10,5% 7,2% 5,4%

Repeatability limit (r) 12,4 8,7 10,3 15,3 7,6 13,7

Reproducibility standard deviation (sR) 14,8 8,2 11,2 10,0 9,6 9,2

Reproducibility relative standard deviation (RSDR) 12,4% 73,9% 10,4% 19,3% 25,7% 10,2%

Reproducibility limit (R) 41,4 22,9 31,2 28,1 27,0 25,6

sample 1-2014 pomace olive oil

sample 2-2014 refined rapeseed oil

sample 3-2014 spiked refined sunflower oil

sample 4-2014 spiked virgin olive oil = sample 2-2013

sample 5-2014 spiked refined sunflower oil

sample 6-2014 crude soybean oil

Scope Method applicable from 50 mg/kg


MOSH and MOAH Determination – 2014 trials

13

Determination of aliphatic and aromatic hydrocarbons in animal andvegetable fats and oils with on-line-HPLC-GC-FID analysis”

Principle of the method

Fractionation of MOSH & MOAH withHPLC/UV

On-line injection with large volume ofeach fraction followed by GC/FIDanalysis

Optional purification by LC on a Silica-ALOX column (to get rid of C23-C33 n-alkanes)

Optional clean-up by an epoxidationprocedure (to avoid interferences witholefinic substances )

Biedermann, Grob. Journal of Chromatography A, 1255 (2012) 56– 75


MOSH & MOAH - 2015 Collaborative study - Samples

14

sample matrix Spiking Mineral oil used Level of spiking Remarks

1 & 13 refined sunflower oil 1 none

2 & 16 crude soybean oil none

3 & 20 virgin olive oil noneEpoxidation

purification asked

4 & 17 refined sunflower oil 2 yes MOSH & MOAH (75:25) 110 mg/kg

5 & 19 refined sunflower oil 3 yes MOSH 20 mg/kgALOX purification

asked

6 & 11 refined sunflower oil 4 yes MOSH & MOAH (70:30) 150 mg/kg

7 & 15 refined olive pomace oil noneEpoxidation

purification asked

8 & 12 mayonnaise yes MOSH & MOAH (75:25) 150 mg/kg

9 & 18 palm oil yes MOSH & MOAH (75:25) 70 mg/kgEpoxidation

purification needed

10 & 14 margarine noneEpoxidation

purification needed


MOAH - 2015 Collaborative study – impact of the epoxidation step

15

refined olive pomace oil

palm oil

Palm oil and olive oil samples need an epoxidation step for the MOAH determination

For pomace olive oil samples with very long chain MOSH, part of the hump may be lost by incomplete elution


MOSH & MOAH - 2015 Collaborative study - Results

- Some of the participants reported data as “< LOQ” for MOAH in non-spiked oil- It was decided to use the value of the LOQ as the result for the calculation of the precision data

16

Sunflower 3 is Sunflower 1 spiked only with MOSH no difference in MOAH content expected Sunflower 1 : variations between 0 and 10 mg/kg for both MOSH or MOAH

Laboratories Laboratories



MOSH & MOAH - 2015 Collaborative study - Results

17

When samples are spiked (> 10 mg/kg), the dispersion of the laboratories is less important




2015 Collaborative study – MOSH – Precision data

18

Sample1 &

13

2 &

16

3 &

20

4 &

17

5 &

19

6 &

11

7 &

15

8 &

12

9 &

18

10 &

14

Number of laboratories 12 12 12 12 12 12 12 12 12 12

Number of laboratories retained after eliminating

outliers12 12 12 11 11 10 10 12 11 11

Number of outliers (laboratories) 0 0 0 1 1 2 2 0 1 1

MOSH mean value, mg/kg 4,0 190,3 6,0 80,9 21,4 101,3 196,6 101,9 53,9 5,0

Repeatability standard deviation, mg/kg 1,1 6,1 1,7 4,1 2,0 1,8 7,5 2,5 3,4 0,2

Repeatability relative standard deviation (RSDr), % 28% 3% 29% 5% 9% 2% 4% 2% 6% 4%

Repeatability limit r, mg/kg 3,1 17,2 4,9 11,6 5,5 5,2 21,1 6,9 9,6 0,5

Reproducibility standard deviation, mg/kg 3,0 26,0 3,0 9,7 3,9 13,7 30,9 8,8 12,2 3,5

Reproducibility relative standard deviation (RSDR), % 75% 14% 50% 12% 18% 14% 16% 9% 23% 70%

Reproducibility limit R, mg/kg 8,4 72,9 8,4 27,1 11,0 38,3 86,6 24,7 34,2 9,8

Application limit fixed at 10 mg/kg for MOSH with the method as described

sample 1 refined sunflower oil

sample 2 crude soybean oil

sample 3 virgin olive oil

samples 4-5-6 refined sunflower oil

sample 7 refined olive pomace oil

sample 8 mayonnaise

sample 9 palm oil

sample 10 margaribe


2015 Collaborative study – MOAH – Precision data

19

Sample1 &

13

2 &

16

3 &

20

4 &

17

5 &

19

6 &

11

7 &

15

8 &

12

9 &

18

10 &

14

Number of laboratories 12 12 12 12 12 12 12 12 12 10

Number of laboratories retained after eliminating

outliers11 12 11 10 11 12 11 12 11 9

Number of outliers (laboratories) 1 0 1 2 1 0 1 0 1 1

MOAH mean value, mg/kg 2,0 1,6 1,7 29,3 4,2 50,7 44,7 36,1 11,4 2,4

Repeatability standard deviation, mg/kg 0,7 0,5 0,5 1,6 0,3 5,6 2,5 3,2 1,0 1,3

Repeatability relative standard deviation (RSDr), % 36% 29% 33% 6% 7% 11% 6% 9% 9% 53,4%

Repeatability limit r, mg/kg 2,0 1,3 1,5 4,6 0,8 15,7 7,0 9,0 2,9 3,5

Reproducibility standard deviation, mg/kg 1,9 1,3 1,3 6,6 2,7 15,6 23,0 7,4 1,9 3,6

Reproducibility relative standard deviation (RSDR), % 94% 81% 79% 23% 64% 31% 51% 20% 17% 152%

Reproducibility limit R, mg/kg 5,2 3,7 3,7 18,5 7,5 43,6 64,3 20,7 5,4 10,0

Application limit fixed at 10 mg/kg for MOAH with the method as described

sample 1 refined sunflower oil

sample 2 crude soybean oil

sample 3 virgin olive oil

samples 4-5-6 refined sunflower oil

sample 7 refined olive pomace oil

sample 8 mayonnaise

sample 9 palm oil

sample 10 margaribe


Origin of the contamination

20

Crop

Storage

Crushing

Meal Crude oil

Plant protection

Environmental pollution (air, soil)

Diesel or lubricant leakage

Mineral oil

See

ds

Technical oils used in the oil mill

Transport

Treatment of the seeds (anti-dusting)

Transport in contaminated containers

Diesel or lubricant leakage


Multiple sources of mineral oil

21

EFSA Journal 2012;10(6):2704

The quality of the mineral oils, in terms of molecular mass range and MOAH content, differs for the sources.


Anti-dusting agent

22

White mineral oil may be safely used in food in USA (21 CFR 172.878) As a dust control agent for wheat, corn, soybean, barley, rice, rye, oats, and sorghum Applied at a level of no more than 200 mg/kg of grain.


Plant protection

23

Minutes

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Mill

ivol

ts

0

50

100

150

200

250

300

350

400

450

Mill

ivol

ts

0

50

100

150

200

250

300

350

400

450

TRACE GC-Channel 1

Vegefix

Retention Time

Name

TRACE GC-Channel 1

Oviphyt

Paraffinic white oils are used for plant protection for:

- winter and spring insecticide treatment (pome fruit, stone fruit),

- adjuvant for herbicide spray (beetroot, rapeseed)


Contamination during transport

24

1999: diesel in crude palm oil 2008: mineral oil in crude sunflower oil

36343230282624222018161412108642

17 000

16 000

15 000

14 000

13 000

12 000

11 000

10 000

9 000

8 000

7 000

6 000

5 000

4 000

3 000

2 000

1 000

0

C5

C6

C7

C8

C9

C1

0

C1

1

C1

2

C1

3

C1

4

C1

5

C1

6

C1

7

C1

8

C2

0

C2

2

C2

4

C2

6

C2

8

C3

0

C3

2

C3

4

C3

6

C3

8

C4

0

C4

2

C4

4

C4

6

C4

8

C5

0

C5

2

C5

4

C5

6

C5

8

C6

0

C6

2

C6

4

C6

6

C6

8

RT [min]

ech ITERG1114.DATAN-Paraff ines-1067.DATA

µV

Sample prepared by ITERG (saponification of 15 g + purification on silica gel)

IFP analysissimulated distillation

White MO included in the EU list of previous cargoes


Contamination with mineral oil during crushing

25

Hexane recovery plant: absorption tower where mineral oil absorbs residual hexane in air before being exhausted to the air


Contamination with thermal heating fluid

26

Minutes

0 2 4 6 8 10 12 14 16 18 20 22

Millivolts

0

100

200

300

400

500

600

700

800

Millivolts

0

100

200

300

400

500

600

700

800TRACE GC-Channel 1

613 B

Retention Time

Minutes

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

Mill

ivo

lts

-50

0

50

100

150

200

250

300

350

400

Mill

ivo

lts

-50

0

50

100

150

200

250

300

350

400

1

3.2

08

TRACE GC-Channel 1

6114

Name

Retention Time

Pressed Walnut oil Contaminated Refined walnut oil

MOSH < 50 mg/kg MOSH = 372 mg/kg

Natural hydrocarbons

2009 : contamination of walnut oil with a food grade thermal heating fluid during refining process


Migration from packaging

27

2014 : contaminated sample with a high boiling fraction of paraffin oil (POSH)coming from the low-density-polyethylene-bottles (food grade bottle)

Extraction with hexane of a new bottle

Mineral oil used to spike the oil

Bottled oil


Effect of deodorization on mineral oil

28

Wagner, Neukom, Grob, Moret, Populin, Conte, Mitt. Lebensm. Hyg. 92, 499–514 (2001)

Crude oil with 2 types of mineral paraffins:- one centered at n-C22- one from C28 to beyond C40

Deodorization completely removed:- MOSH up to C23- about 50% of C25 alkanes.

Step of the processMOSH content

(mg/kg)

Crude oil 50

Neutralized soap 40

After bleaching 55

After deodorization 14


Effect of deodorization on mineral oil

29

Wagner, Neukom, Grob, Moret, Populin, Conte, Mitt. Lebensm. Hyg. 92, 499–514 (2001)

1200 mg/kg 230 mg/kg

350 mg/kg 250 mg/kg

4 samples of deodistillates:- A : mineral paraffins (C16 - C33)

centered at C23 - B : diesel or heating oil (C9-12) +

mineral paraffins (C20 - C40) centered at C29

- C & D : mineral paraffins (C16 - C33) centered at C23 + PAO (C34;C41)

poly-alpha-olefins (PAO): synthetic base oils used for high grade motor oils or as food-compatible technical oils.

Number of analysed samples of deodistillates

28

MOSH min (mg/kg) 120

MOSH max (mg/kg) 6 800

MOSH mean value (mg/kg) 650


FEDIOL Recommendations

FEDIOL code of practice for the management of mineral oil hydrocarbonspresence in vegetable oils and fats intended for food uses (24 February 2016)

Prevention in vegetable oil and fat crushing and refining plants

Only lubricants suitable for incidental contact with food to be used

Mineral oil used as absorber in the hexane recovery system free from MOAH

Steam used for heating in processing installations

Control of possible sources of MOH contamination in the supply chain

Transport in bulk of oils: thermal heating fluids not used in direct heating systems

Spraying of white mineral oil as anti-dusting: monitoring of MOH levels in soybean

oils and verification of the absence of MOAH

Monitoring scientific developments and next steps

More precise identification of the possible entry sources of MOH

Exploration of the MOH mitigation strategies through refining

30


Conclusion

Mineral oil hydrocarbons are present at different levels in nearly all foods, including in vegetable oils (EFSA)

MOAH fraction may be both mutagenic and carcinogenic (EFSA)

There is a potential concern associated to the background exposure to MOSH (EFSA)

no EU legislation regulating the limits of MOH in vegetable oils

Standardized method for MOSH published in 2015

Standardized method MOSH & MOAH soon available with application limits at 10 mg/kg

Mineral oil may be introduced at different stages of the vegetable oil and fat production

Total removal of mineral oil during refining seems very difficult

31

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32

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