Eur. J. Lipid Sci. Technol.
103 (2001) 117–122
Werner Zschau Bleaching of edible fats and oils IX
Süd-Chemie AG, Legal and analytical aspects of bleaching
Munich, Germany From the working group
“Technologies of industrial extraction
and processing of edible fats”
8.1 General
Bleaching is a technological process during refining of ed-
ible fats and oils which cannot be discussed without con-
sideration of other processes during refining as degum-
ming, neutralisation and deodorisation. All these process-
es within the refining have to be used to remove certain
naturally occurring or secondary by-products as well as
possible contaminants which have a negative influence
on organoleptic properties, shelf life and use of edible oils
for human consumption.
In Germany any treatments which are used in the produc-
tion of human food as defined by §1 “Lebensmittel-Be-
darfsgegenstände-Gesetz (LMBG)” have to fulfill the legal
requirements in §7 (1) LMBG. According to §4 of the hy-
giene act for human food (LMHV) everybody “who pro-
duces, treats or trades human food, ...” has to analyse
critical control points in the process and to assure that
proper safety measurements are set and monitored”. The
requirements in §4 LMHV correspond to those estab-
lished by the Codex-Alimentarius-Commission “Hazard
Analysis Critical Control Points” (HACCP) [111]. Chemical
and microbiological health risks due to food consumption
by the consumer should be recognisable. Furthermore
the likelihood of these risks is to be evaluated by fixation
of critical control points (CCP = Critical Control Points).
A direct human health risk does not occur by applying the
refining process or in particular the bleaching step. The
monitoring measures as far as this is concerned will be
restricted to the checking of process specific limit values
(minimum or maximum values).
8.2 Structural alterations of fats during
refining respectively bleaching
During the refining process fatty substances can be struc-
turally altered by various chemical reactions like hydroly-
Correspondence: Werner Zschau, Süd-Chemie AG, Osten-
rieder Str. 15, 85368 Moosburg, Germany. Phone +49-8761-
82 606, Fax: +49-8761-82 661; e-mail: w.zschau@sued-
chemie.de
© WILEY-VCH Verlag GmbH, 69451 Weinheim, 2001
117
sis, oxidation, dehydration, dimerisation, polymerisation
and interesterification. Depending on the process used,
its controlling and the quality of the crude material, a cer-
tain type of chemical reactions is dominating.
Update of the Expert Network of the DGF
Fig. 1. Protonation of conjugated fatty acids.
A major task of the bleaching step is the decomposition of
possibly existing hydroperoxides in order to improve the
stability of the refined product. Conjugated dienes and
trienes are formed by dehydration (Fig. 1) [112]. In the
past, the spectrophotometric proof of conjugated diene
and triene bonds was often used to check if a refining step
had been applied to virgin oils. This proof is not very spe-
cific and strictly speaking it is good only for bleached oils
if at all. The test depends on the type of oil and can
amongst other things be interfered by autoxidation prod-
ucts [113]. The addition of maleic anhydride influences
the formation of diene and triene peaks in the UV spec-
trum so that this proof can be manipulated [114].
For the analysis of virgin olive oil the EC 2472 [115] sug-
gests the analysis of the steradienes besides the determi-
nation of trans fatty acids. Virgin olive oil may show in
the sum of the trans-oleic acid-isomers a maximum value
of 0.05% and in the sum of trans linoleic acids and trans
linolenic acids a maximum value of 0.05%.
As gas chromatographic tests show, a statistically se-
cured distinction of cold-pressed and “steam washed” oil
(0.012–0.035% trans fatty acids) in contrast to refined
products (0.14–1.47% trans fatty acids) is on the basis of
the trans fatty acid content presently not possible [116].
“Steam washing” is an expression used for mild deodori-
0931-5985/2001/0202-0117 $17.50+.50/0
118 Zschau et al.
sation without altering fat components. Blending of virgin
oil with refined products or the “steam washing” of virgin
oil are not detectable by this method.
Analytically recognisable quantities of trans fatty acids
are being formed by deodorisation at more than 190 °C
only [117, 118]. At the bleaching step as well as at the
steam washing step due to the low thermal load at about
90 °C to 120 °C only a small quantity of non-conjugated
isomeric trans fatty acids is being formed. At the deodori-
sation step only geometric isomers of fatty acids are be-
ing formed, while position isomers arise only at higher
temperatures during distillative deacidification above
210 °C or by partial hydrogenation.
Products of dehydration of sterols as steradienes and di-
sterylethers are only formed at temperatures higher than
150 °C during deodorisation [119]. In the presence of an
acidic bleaching earth the formation of steradienes and
disterylethers is catalytically supported already at temper-
atures below 100 °C [120].
In 1967 and 1974 the Extraneous Substance Commission
of the German Research Association has laid down pro-
cessing parameters for the deodorisation of edible oils
[121]. According to the level of knowledge at that time, ed-
ible oils and fats do not take on health damaging charac-
teristics provided a temperature of 270 °C and a heating
period of 30 min is not exceeded in a continuous process.
Discontinuous heat bleaching of palm oil at a temperature
of 220 °C and a heating period of 3 h should not be ex-
ceeded.
Only upper limits for process parameters and no analyti-
cal limiting values have been recommended, because it
had not been known exactly which partial reactions – and
to what extent – could occur during the heating of edible
oils and fats [122].
In those days it has already been known that an isomeri-
sation of oleic acid to elaidic acid can occur occasionally
during the deodorisation, for example, of soybean oil
which leads to a turbidity of the deodorised oil after cool-
ing [123]. However, systematic investigations on possible
partial reactions have been done much later, whereby,
besides isomerisation reactions, a crosslinking of fat mol-
ecules has been observed as well as the formation of
oligomer triglycerides [124]. At the deodorisation of sun-
flower oil at a temperature of up to 220 °C a very slow in-
crease of trans fatty acids as well as of oligomer triglyc-
erides has been observed, which not even reached 1%
for both types of products after 5 h – other highly unsatu-
rated oils behave in a similar way. The formation of these
side products has been remarkable at 270 °C and
reached values of about 10% [121]. Also soybean oil has
been treated under similar extreme conditions of 240 °C
to 300 °C up to 3 h. In this case the formation of more than
Eur. J. Lipid Sci. Technol. 103 (2001) 117–122
5% trans fatty acids, more than 0.5% conjugated acids
and more than 1.5% polymerised products have been ob-
served at a temperature of 270 °C and higher [124]. Inter-
and intramolecular transesterifications of triglycerides in
sn-2-position have been detected, too [125]. When oils
are treated at an elevated temperature mainly the inter-
molecular formation of the unpolar dimer triglycerides be-
sides higher polar intramolecular oxidised monomer
triglycerides is observed [126].
The bleaching of edible fats and oils is usually conducted
at a temperature of 90 to 100 °C. For difficult-to-bleach
oils the temperature can even reach 120 °C (see para-
graph 2.3.1.) [127]. We can conclude that the above-men-
tioned temperature effects observed during deodorisation
cannot be applied to the bleaching step.
Activated bleaching earth has not only an adsorptive ef-
fect but acts also as a solid acid, a cation exchanger and
catalyst of various reactions (see chapter 2.2.) [127].
Over both ways, the corresponding hydroperoxides as
well as acid catalysed, the multiple unsaturated fatty
acids are being transformed to conjugated fatty acids
[128]. Through the intermediate formation of a me-
somerism stabilised cation a proton can be added much
more easily to a conjugated than to an isolated double
bond (Fig. 1) [129]. Therefore, conjugated fatty acids
have a higher reactivity. For a long time it had been as-
sumed that the formation of dimer fatty acids prosecutes
a Diels-Alder-reaction [130]. In more recent tests [131] a
cationic reaction mechanism was suggested which ex-
plains the formation of the aliphatic dimer fatty acids,
methyl branched isomeric stearic acids and cyclic
monomer fatty acids (Fig. 2). Obviously after protonisa-
tion of the unsaturated fatty acids a further fatty acid mol-
ecule is being accumulated. After deprotonisation multi-
ple-unsaturated dimer fatty acids can be formed, which
cyclize with increasing temperature and duration and
even form aromatic compounds.
For the formation of steradienes a similar mechanism has
to be assumed, as by acid catalysis at already 80 °C a
small quantity of sterols is dehydrated to the correspond-
ing steradienes. Through nucleophilic substitution the
corresponding disteryl ether is being formed (Fig. 3). The
formed amount of steradienes depends on the tempera-
ture and the acidity of the bleaching earth used. In the
presence of neutral reacting silicic acid (e.g. TriSyl®) no
considerable amount of stigmastadienes are formed.
The transformation of sesamolin to sesamol and sesamin
in the presence of acids and water has been described by
A. Kamal-Eldin et al. [132]. Sesamolin and sesamol have
a high antioxidant effect. Especially acidic bleaching
earths catalyse a number of disintegrating reactions of
natural ingredients which influence the usability of veg-
etable oils with regard to their heat stability [133].
Eur. J. Lipid Sci. Technol. 103 (2001) 117–122 Legal and analytical aspects of bleaching 119

Gertz and Mezouari [134] (see Tabs. 1 and 2) have treat- various temperatures with different types of bleaching
ed and deodorised sunflower oil as a high linoleic oil and earth. If oils are deodorised only, the grade of isomeriza-
olive oil as an oil rich in oleic acid on laboratory scale at tion at a constant time and temperature was depending

Fig. 2. Intermolecular formation of dimerised and cyclic linoleic acid.

Fig. 3. Acid-catalysed dehydration of sterols during bleaching.

120 Zschau et al. Eur. J. Lipid Sci. Technol. 103 (2001) 117–122

Tab. 1. Artefact formation during the deodorisation of olive oil and sunflower oil.
Sample Treatment C18:1 trans C18:2 trans C18:3 trans Polymers Stigmastadiene
Triglycerides
[g/100g] [g/100g] [g/100g] [g/100g] [mg/kg]
Sunflower oil steam washing, 0.02 0.05 0.00 0.08 <0.05
120 °C
Sunflower oil deodorised, 0.03 0.05 0.00 0.26 <0.05
3 h, 140 °C
Sunflower oil deodorised, 0.02 0.06 0.04 0.42 <0.05
3 h, 170
Sunflower oil deodorised, 0.02 0.06 0.07 0.90 0.20
3 h, 200 °C
Sunflower oil deodorised, 0.04 0.70 0.05 1.01 11.00
3 h, 260 °C
Olive oil native, not steam – – – <0.03 <0.05
washed
Olive oil deodorised, n.n 0.02 – 0.13 <0.05
3 h, 140 °C
Olive oil deodorised, 0.05 0.02 0.02 0.33 <0.05
3 h, 170 °C
Olive oil deodorised, 0.03 0.01 – 0.42 0.15
3 h, 260 °C
Olive oil deodorised, 0.15 0.26 0.03 0.56 0.89
3 h, 260 °C

only on the kind of oil. An increase of trans fatty acids has
been observed only above 200 °C, whereas dimeric
triglycerides have already been formed at temperatures
above 100 °C.
A considerable amount of stigmastadiene as the main
substance of the steradienes has only been detected at a
temperature higher than 200 °C. A completely different
picture results when both oils are treated with different
types of bleaching earth and TriSyl®, a silicagel, at various
temperatures. During the bleaching steradienes are al-
ready formed at temperatures around 80 °C in the pres-
ence of acid bleaching earth. The content of dimeric

Tab. 2. Influence of the bleaching of the formation of steradienes and polymeric triglycerides.
Sample Laboratory Bleaching* Polymers Stigmastadiene
Triglycerides
[g/100g] [mg/kg]
Sunflower oil 90 °C, 20 min, no Bleaching Earth 0.05 0.02
Sunflower oil 120 °C, 20 min, no Bleaching Earth 0.14 0.02
Sunflower oil 150 °C, 20 min, no Bleaching Earth 0.20 6.00
Sunflower oil 90 °C, 20 min, 0,5% Bleaching Earth Südchemie Type 210 0.18 0.66
Sunflower oil 120 °C, 20 min, 0,5% Bleaching Earth Südchemie Type 210 0.20 6.00
Sunflower oil 150 °C, 20 min, 0,5% Bleaching Earth Südchemie Type 210 0.46 88.90
Sunflower oil 90 °C, 20 min, 0,5% Bleaching Earth Südchemie Type 314 0.21 0.27
Sunflower oil 120 °C, 20 min, 0,5% Bleaching Earth Südchemie Type 314 0.24 1.30
Sunflower oil 150 °C, 20 min, 0,5% Bleaching Earth Südchemie Type 314 0.48 9.82
Sunflower oil 90 °C, 20 min, 0,5% Silicagel (TriSylTM) 0.07 0.03
Sunflower oil 120 °C, 20 min, 0,5% Silicagel (TriSylTM) 0.09 0.03
Sunflower oil 150 °C, 20 min, 0,5% Silicagel (TriSylTM) 0.35 0.06
* not followed by deodorisation
Eur. J. Lipid Sci. Technol. 103 (2001) 117–122
triglycerides increases slightly in proportion to the tem-
perature. A big alteration of the trans fatty acid content
cannot be detected during the deodorisation.
If bleaching tests at these temperatures are conducted
with a constant amount of bleaching earth (0.5%) of dif-
ferent activity respectively acidity, the steradienes respec-
tively stigmastadiene content increases considerably with
increasing activity of the bleaching earth. With neutral sil-
ica gels like TriSyl® which are frequently used as adsor-
bent for the removal of phospholipids and other mucilagi-
nous substances, no alteration of the sterols has been ob-
served. The increase of steradienes respectively the con-
tent of stigmastadiene depends on the type of oil, e.g. on
its sterol content and from the activity of the bleaching
earth. The stigmastadiene content is, therefore, not nec-
essarily the specific criterion for a successful bleaching
step (Tab. 3) [135].
Tab. 3. Steradiene content of refined vegetable oils.
Oil (refined) Stigmastadiene Total Steradienes
[mg/kg] [mg/kg]
Soybean oil 23.4 61.8
Safflower oil 5.8 9.2
Corn oil 134.8 200.8
Sunflower oil 22.0 34.2
Peanut oil 7.7 15.6
8.3 Accentuated remarks for the
designation of vegetable oils and fats
The descriptions in chapter 7 concerning the deodorisa-
tion [136] needs to be revised because of some legal
changes. On December 20, 1997, the revised version of
the guidelines for edible fats and oils was published in
Federal Gazette [137]. The guidelines of the German
book on food (see §33 LMBG) are basically not a legal
norm. As a valuable expert’s opinion they describe the
production, treatment and/or other essential characteris-
tics of food which are of importance for the food chain.
Whereas the description “virgin” was clearly defined for
olive oil only according to EG VO 2472/97 [115], the ap-
propriate definition in the principles for edible fats and oils
from 1987 was changed to the effect that all virgin oils are
produced from non-preheated raw material by pressing
only without heat supply. Virgin oils are washed only but
not deacidified, bleached or deodorised. Non-refined edi-
ble oils are produced in the same way as virgin oils. They
can be washed and/or treated with water steam without
altering fat components, dried and filtered. They are nei-
ther deacidified nor bleached. Fractionated or winterised
fats can be produced from non-refined as well as refined
fats and are to be marked accordingly.
Legal and analytical aspects of bleaching 121
In the assessment characteristics the guiding principles
for edible fats [137] differentiate between remarks which
point to a particular production or to a particular treatment
or better non-treatment. Edible oils produced without heat
supply under particularly careful conditions, whose raw
material shows a particular good quality, can be labelled
as “non-refined – cold-pressed” respectively “virgin –
cold-pressed”. Instead of “cold-pressed” the indication
“first pressing” can be chosen. The disintegration of the
seeds by crushing, milling, rolling respectively flocculating
with a ripple- or smooth-surfaced roll are pure mechanical
processes for the production of virgin oils. Often a thermal
treatment and conditioning of the seed is necessary in or-
der to increase the flow-ability of the oil, to eliminate
bacterias, fungi and enzymes (e.g. myrosinase), to co-
agulate proteins, to inactivate poisonous materials such
as gossypol and to adjust the product moisture. For the
conditioning temperatures from 80 to 110 °C are being
recommended for retention time of 20 to 30 min. In these
cases or after roasting of the seed the oil cannot be de-
fined as “virgin” or “cold-pressed” due to the pretreatment.
8.4 Evaluation and recommendation
In general one can say that the content of nonpolar dimer-
ic triglycerides according to DGF uniformity method C-III
3d(99) increases proportional to the temperature. It is
practically independent of the type of oil and can be
regarded, therefore, as the main criterion for a thermal
treatment in the course of the refining process. The analy-
sis of the trans fatty acids and of the steradienes respec-
tively stigmastadiene can give further insights into the
type of refining step like bleaching.
In the EC 2472/97 [115] limiting values for stigmastadiene
and trans fatty acids are laid down for virgin olive oil.
These can only partially be transferred to other oils. The
proof of a raffinate or its blending into a virgin or steam
washed oil can therefore only be succeeded by means of
applying various criteria in order to assess the kind and
amount of the refining step. Native oils which have
been gained only mechanically at temperatures below
70–80 °C show none respectively only traces of dimerised
triglycerides (< 0.03%) [138]. The determination of lower
amounts of dimerised triglycerides (< 2% ) is made after a
previous separation of nonpolar triglycerides by means of
HPLC-GPC [139].
Non-refined, steam washed oils show a content of dimer-
ic triglycerides of up to 0.1% whereas fully refined prod-
ucts show more than 1%.
Stigmastadiene in deodorised oil can only be found in
traces (Tab. 1). In fully refined products stigmastadiene
122 Zschau et al.
values of 200 mg/kg are found (average: 40–50 mg/kg)
(Tabs. 2 and 3).
According to the guidelines for edible fats and oils [137]
oils are considered as “pure” if they do not contain more
than 3% of other oils, be they native or refined. The rea-
son for this is the fact that there do not exist seeds which
are 100% pure and that during the manufacturing process
(refining, bottling) a blending with other oil is technically
not always avoidable.
For this reason a stigmastadiene value of 0.15 mg/kg
respectively a content of up to 0.05% dimerised triglyc-
erides can not be regarded for the legal assessment of
virgin vegetable oils.
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