Lipid Technology July 2013, Vol. 25, No.

7 151

DOI 10.1002/lite.201300288

Feature
Mitigation of 3-MCPD and glycidyl esters within
the production chain of vegetable oils especially
palm oil
Bertrand Matth
us, Frank Pudel
B.M. is Senior Scientist at Max Rubner-Institut, Institute for Safety and Quality of Cereals, Working Group for Lipid Research, Detmold,
Germany; E-mail: bertrand.matthaus@mri.bund.de
F.P. is Managing Director at Pilot Pflanzen
ltechnologie Magdeburg e.V., Magdeburg, Germany; E-mail: pudel@ppm-magdeburg.de

Summary
In 2007 the oil producing industry and the downstream food processing industry were worried by the announcement that fatty acid esters of
3-MCPD and later in 2008 that glycidyl esters have been found in different types of vegetable oils after processing. The reason for the
concern was that the German Federal Institute for Risk Assessment assumed in a first statement the complete degradation of the esters to
free 3-MCPD and glycidol both classified by the International Agency for Research on Cancer (IARC) as possible and probably,
respectively, carcinogenic to humans. In the meantime a lot of research has been done on these heat-induced compounds to mitigate their
formation during oil processing and today the content in vegetable oils could be remarkably lower if all approaches were implemented. This
paper summarizes the different mitigation strategies and shows their effect on lowering the amount of 3-MCPD and glycidyl esters in
refined vegetable oils.

Development of mitigation strategies pounds (input of inorganic or organic chlorine-containing com-

For the development of mitigation strategies to lower the con-
tent of the esters in refined oil three different approaches are
conceivable: avoidance and minimization of precursors in the
raw material, modification and extension of the refining process
and removal of the esters after refining. The most promising
way of mitigation is definitively to take care that the raw mate-
rial contains as little of the precursors as possible resulting in
raw material with a low capability for the formation of the
esters. For this approach knowledge of t the precursors involved
into the reaction is necessary.
Avoidance and minimization of precursors
Today it is known that a nucleophilic attack of chlorine-contain-
ing compounds on acylglycerols like triacylglycerols (TAG) and
diacylglycerols (DAG) via acyloxonium ion formation is responsi-
ble for the formation of 3-MCPD esters during the deodorization
step of refining [1]. Another important point is that different
types of vegetable oils have different capabilities to form the
esters (Figure 1). Thus, avocado oil, extra virgin olive oil, rape-
seed oil, soybean oil and palm kernel fat form only about 1 mg
3-MCPD and glycidyl esters per kg oil after heating at 2408C for
2 h, while the levels in palm oil, corn oil and coconut oil are
markedly higher at up to 14 mg/kg. Palm oil especially shows a
wide range in formation of the esters implying that different fac-
tors have influence on the formation. The reason for this great
variation might not only be different climate, soil and growth
conditions, but genotype, harvest technique and processing are
also considered to have a strong influence on the capability of
the crude oil to form 3-MCPD and glycidyl esters. These different
conditions influence the amount of chlorine-containing com-
pounds via salts in the soil or pesticides) and partial acylglycer-
ols in the oil which might act as precursors.
Since the 3-MCPD ester molecule contains a chlorine atom it is
clear that the presence of chlorine-containing compounds has a
strong influence on the formation of 3-MCPD esters. Results
with different types of chlorine donators indicate that chlorine-
containing compounds must be available in an organic form,
because otherwise a reaction with acylgylcerols would be diffi-
cult. Later Nagy et al. [2] showed that palm oil contains a huge
number of different organic chlorine-containing compounds
and several inorganic chlorides such as iron [II] and [III] chloride.
The content of water-soluble chloride in palm oil is between 1
mg/kg and 10 mg/kg.
Palm fruits can take up chlorine-containing compounds from
the environment and accumulate them in the plant while still
attached to the tree. Craft et al. [3] described a chlorine cascade
where inorganic chloride is transferred into lipophilic orga-
nochlorides during palm growth and maturation until fresh
fruit bunch (FFB) sterilization in the oil mill. Sources for the
uptake of inorganic chloride are saline soils, use of ferric chlor-
ide as coagulant in water treatment, potassium fertilizers,
ammonium chloride as nitrogen source or the use of empty fruit
bunches and palm oil mill effluent with the risk of an enrich-
ment of chloride ions within the plantation. Also several orga-
nochlorides for weed and pest control in the plantation are
potential sources for the introduction of chlorine-containing
compounds. While the use of water for the generation of strip
steam during deodorization has no effect as a source for chloride
the recycling of sterilization condensate and water from crude
oil washing enriches chloride in the processing and increases
the ability of the crude oil to form the esters during deodoriza-
tion.

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152 July 2013, Vol. 25, No. 7
Figure 1. Ability of raw oils to form 3-MCPD and glycidyl esters during heating (2408C, 2h).
From these points it becomes clear that for the mitigation of
the formation of 3-MCPD esters either the enrichment of chlor-
ine-containing compounds in the fruits has to be avoided or
they have to be removed from the crude oil before further pro-
cessing. The reduction of chloride-containing compounds in the
crude oil can be achieved by washing the oil with polar solvents
like water or water/alcohol mixtures. Even more effective is the
removal of the reactive chlorine species by washing the pulp
during oil extraction in the oil mill instead of the crude palm oil
[3]. A general rule for an effective mitigation of 3-MCPD esters is
to remove chlorinated species as early as possible from the pro-
cess.
Other important precursors for the formation of the esters are
acylglycerols. While most vegetable oils are comprised of 88% to
96% triacylglycerols (TAGs), the content of diacylglycerols
(DAGs) is low for most oils with amounts ranging from 1–2%. Of
the major oils only palm oil contains DAGs ranging from 4% to
12% with a mean value of about 6.5%. That seems to be the rea-
son why palm oil is very susceptible to the formation of 3-MCPD
and glycidyl esters during the refining process.
Within a research project of the German industry a poor cor-
relation between the content of DAGs and the formation of the
esters for different kinds of oil from the industry has been
shown, but the addition of pure DAGs to a virgin rapeseed oil
with low ability for the formation of the esters resulted in a cor-
relation of R = 0.8. Additionally rapeseed oil from germinated
seeds with a higher content of DAGs shows a higher capability to
form 3-MCPD and glycidyl esters indicating that the quality of
the raw material strongly influences the formation of the esters.
Another important point is that there seems to be a limit to the
ability of oils to form the esters as this increases significantly
starting with a content of DAG > 4%. A particular case are so-
i 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Lipid Technology
called “DAG oils” comprising of 80% to 90% DAGs, because for
this type of oil there was a more than 10-fold increase in glycidyl
ester levels after processing compared with the common vegeta-
ble oils.
These observations show the importance of keeping the con-
tent of DAGs as low as possible before processing to avoid the for-
mation of 3-MCPD and glycidyl esters. A basic prerequisite to
achieve this aim is a careful selection and handling of the raw
material, especially palm fruits. With a high lipase activity in
ripe palm fruits a fast degradation of TAGs takes place resulting
in high amounts of DAGs depending on the time the lipases are
active. Therefore fast collection and sterilization of bunches
after harvest to inactivate the enzymes and no processing of
loose fruits together with bunches are important means to
reduce the formation of the esters during further processing.
Some companies in Malaysia demonstrated that optimizing and
shortening the time between harvesting and crude oil produc-
tion with sterilisation as crucial step to a few hours results in a
drastic reduction of the ability of palm oil to form 3-MCPD and
glycidyl esters during refining.
Modification and extension of the refining
process
Once the crude oil is available it is either possible to reduce the
content of precursors by washing the oil before further proces-
sing which can result in a reduction of the esters by 38% or the
conditions of the refining process have to be changed. Refining
is a multistep process carried out as physical refining, removing
free fatty acids during deodorization by distillation, or de-acidi-
ficaton by chemical refining using sodium hydroxide solution
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Lipid Technology
Figure 2. Formation of 3-MCPD and glycidyl esters during deodorization of crude palm oil at different temperatures.
during neutralization. Nowadays physical refining is preferred
because of environmental advantages resulting from the use of
fewer chemicals and the production of almost no sewage, but
also reduced refining losses resulting in higher oil yield. How-
ever during chemical refining lower deodorization tempera-
tures can be used because the major part of the free fatty acids is
already removed during neutralization.
The main point in the development of mitigation strategies
should be the avoidance of the formation of precursors during
the processing. Even if it was successful to supply palm fruits
with low amounts of precursors during the further steps of the
refining process there are still some pitfalls which may increase
the content of precursors. The use of acid during degumming
could activate the formation of 3-MCPD ester precursors, while
degumming in general results in a reduction of 3-MCPD and gly-
cidyl esters during further processing. An additional neutraliza-
tion step reduces the ability of crude palm oil to form the esters
by lowering the acidity of the oil before deodorization, and by
removal of potential precursors from the oil during washing the
neutralized oil with water to eliminate the soapstock. By the use
of potassium hydroxide and sodium hydroxide, respectively a
45% and 35%, respectively, lower ability of the oils to form the
esters was found in comparison to untreated oil. During bleach-
ing Ramili et al. [4] found a good correlation between the con-
tent of 3-MCPD esters in refined oil and the acidity of bleaching
earth for acidic and water degumming (0.9759 and 0.9351,
respectively). The recommendation from this finding was to use
natural bleaching earths and acid activated bleaching earths
with more neutral pH-value. Residual mineral acids can be
removed by comprehensive washing procedures. In smaller
amounts the amount of activated bleaching earth (0.7 and 1.5%,
respectively) seem to have no significant effect on the formation
of the esters during the deodorization step, while using 3% of
bleaching earth instead of 1% before deodorization of water-
degummed palm oil at 2508C results in a lower ability of the oils
to form the esters possibly by absorbance of some 3-MCPD ester
precursors from the oil. The results suggest that neutral clays in
i 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
July 2013, Vol. 25, No. 7 153
amounts as high as economically acceptable are recommended
for the bleaching process.
The most crucial step during processing is deodorization
because the formation of 3-MCPD and glycidyl esters is a heat-
induced reaction and an increase of the temperature results in
an increase of the contaminants in the resulting oil. While the
amount of 3-MCPD esters remained between 2 and 4 mg/kg at a
temperature ranging from 1808C to 2708C, for glycidyl esters a
nearly exponential increase can be found for temperatures
higher than 2408C (Figure 2). Destaillats et al. [5] showed that a
temperature of 2008C is crucial for the formation of glycidyl
esters from DAGs. The formation of 3-MCPD esters takes place in
the early stage of the heating period and requires only minimal
heating.
The strong temperature dependency of the formation of glyci-
dyl esters opens up new promising opportunities to reduce the
formation of the esters during deodorization by lowering the
temperature. In that case the temperature load of the sample
should be as low as possible while simultaneously maintaining
the oil quality as expected by the processing industry and the
consumer. In the last years different possibilities have been sug-
gested such as dual deodorization which combines a short term
deodorization at a higher temperature with a long term deodor-
ization at a lower temperature or vice versa. A combination of
120 minutes at 2008C in a first step with 5 minutes at 2508C in a
second step results in a reduction of the amounts of 3-MCPD and
glycidyl esters to one third, 3-MCPD esters alone were two thirds
lower than for the conventional deodorization. At 2708C the
reduction rate was much higher, dual deodorization with 2008C
for 120 min in a first step and 2708C for 5 min in a second step
achieved nearly 80% reduction of 3-MCPD and glycidyl esters in
comparison to a deodorization at 2708C for 90 min (Figure 3).
Another possibility to reduce the temperature load during
deodorization is short-path distillation used for the distillation
of heat sensitive compounds. The application of this technology
results in palm oils with more than 90% lower amounts of 3-
MCPD and glycidyl esters in comparison to conventional deodor-
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154 July 2013, Vol. 25, No. 7
Figure 3. Effect of conventional and dual deodorisation of palm oil on the formation of 3-MCPD and glycidyl esters.
ization, but the resulting oil has the characteristic red color of
crude palm oil which may not be suitable for all applications.
On the other hand for many industrial applications the color of
the oils does not really matter and in comparison to conven-
tional refined palm oil the red palm oil is high in valuable caro-
tenes, tocopherols, tocotrienols and phytosterols because of the
gentle processing.
A promising modification of the refining process is the addi-
tion of additives before or during the deodorization step with
the aim
* to prevent the formation of the 3-MCPD esters by addition of
0.5% to 2.5% (v/v) of either ethanol or glycerol to refined
bleached palm oil [6]
* to prevent the formation of 3-MCPD and glycidyl esters by ad-
dition of potassium hydrogen carbonate or sodium bicarbo-
nates before deodorization (1 to 5 mmol/kg)
* to destroy 3-MCPD esters by addition of K
strolith in amounts
ranging from 1% to 10% during deodorization
* to offer diacetin as a competing molecule for the reaction
with the chlorine-donating agent before evaporating during
deodorization.
In laboratory scale or bench-top deodorization experiments
these approaches were very successful and reduction rates from
about 30% (addition of either ethanol or glycerol) to 50% (addi-
tion of diacetin) and 66% (addition of carbonates) were achieved.
Removal of the esters after refining
The third approach to reduce the content of the esters in the
ready-to-sell product is the removal of the esters after the refin-
ing process. Strijowski et al. [7] described the successful applica-
tion of calcinated zeolite and a synthetic magnesium silicate to
reduce the content of glycidyl esters in refined palm oil. While
calcinated zeolite reached the total reduction effect at 608C, the
activation of magnesium silicate required temperatures of 808C.
The application of calcinated zeolite enabled a spontaneous
reduction of the esters after addition whereas the reduction
i 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Lipid Technology
after addition of magnesium silicate required at least 60 min-
utes to reach similar results. Another approach to remove glyci-
dyl esters from refined oil was shown by Shimizu et al. [8] by
treatment with activated bleaching earth resulting in a com-
plete removal of glycidyl palmitate from glycerol dioleate by
transformation of the ester to glycerol monopalmitate, glycerol
palmitate oleate and glycerol dipalmitate. An enzymatic degra-
dation of 3-MCPD esters in refined oils by converting 3-MCPD
esters in a biphasic system into free 3-MCPD by Candida antarc-
tica lipase A followed by the conversion of the free 3-MCPD into
glycerol via treatment with halohydrin dehalogenase from
Arthrobacter sp. AD2 and an epoxide hydrolase from Agrobacter-
ium radiobacter AD1 was described by Bornscheuer and Hesseler
[9].
Recommendations
Five years after the first announcement of 3-MCPD and glycidyl
esters in refined vegetable oils several approaches for a remark-
able reduction of the content of the esters are now available and
could be used by industry. An individual or combined applica-
tion of the presented opportunities can be recommended:
– Optimization of the palm fruit growing, harvesting and pre-
processing in the oil mill and selection of crude oil with low
contents of precursors.
– Optimization of oil extraction processes, avoiding the forma-
tion of lipophilic organochlorines from hydrophilic ones.
Introduction of an additional washing step prior to refining.
– Neutralization prior to deodorization to avoid lower pH va-
lues.
– The use of chemical refining appears to be the better option
for lower contents of 3-MCPD esters and related compounds,
in comparison to the commonly established physical refining.
– Use of natural bleaching earths and acid activated bleaching
earths with more neutral pH-value in high dosages.
– Addition of alcohols, diacetin, carbonates or bicarbonates be-
fore deodorization.
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Lipid Technology
– Application of short-path distillation instead of deodoriza-
tion.
– Reduction of the temperature load during deodorization, e. g.
by dual deodorization with different temperature profiles.
– Post treatment of fully refined oils by appropriate adsorbents
or enzymes.
The authors thank Mrs. A. M
ller for her skilful assistance. They are
also grateful to Dr. K. Vosmann and Mrs. P. Weitkamp for the analysis
of the 3-MCPD esters and related compounds by GC-MS.
The authors wish to thank OVID and FEDIOL for supplying the oils
for the investigations.
The presented work was done within the research project No. 17059
BG of the Research Association of the German Food Industry (FEI)
financed in the foundation program of industrial research from the
Federal Ministry of Economy and Technology by the AiF.
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July 2013, Vol. 25, No. 7 155
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