1111

Oxidative Stability of Blends and Interesterified Blends of Soybean

Oil and Palm Olein
W.E. Neff*, M.A. EI.Agaimy 1 and T.L. Mounts
USDA, ARS, NCAUR, Food Quality and Safety, Peoria, Illinois 61604

Improvement of oxidative stability of soybean oil by blend- Blends were prepared by directly mixing the appropriate
ing with a more stable oil was investigated. Autoxidation amount of PO with SBO to obtain SBO/PO blends of 9:1,
of blends and interesterified blends (9:1, 8:2, 7:3 and 1:1, 8:2, 7:3 and 1:1 (w/w). Other materials used in this study
w/w) of soybean oil and palm olein was studied with respect have been described previously (13).
to fatty acid composition, fatty acid location and triacyl- Interesterification. A 600-g sample of each blend was
glycerol composition. Rates of formation of triacylglycerol interesterified. The blend was heated to 70~ with stir-
hydroperoxides, peroxide value and volatiles were evalu- ring, and 0.5% sodium methoxide was added. The reac-
ated. The fatty acid composition of soybean oil was tants were stirred for 30 min and then quenched with 2%
changed by blending. Linolenic and linoleic acids decreased aqueous citric acid (20%) with stirring for 15 min. The pro-
and oleic acid increased. The triacylglycerol composition duct was filtered under vacuum through Celite 545. For
of blends and interesterified blends was different from that the oxidation study, the interesterified oil was dissolved
of soybean oil. Relative to soybean oil, LnLL, LLL, LLO, in diethyl ether and washed two times with distilled water;
LLP, LOO and LLS triacylglycerols were lowered and the ether layer was dried over anhydrous sodium sulfate,
POO, POP and PLP were higher in blends and interesteri- and the solvent was removed with a roto-evaporator.
fled blends (where Ln, L, O, P and S represent linolenic, Solid-phase extraction (SE) chromatography. Oil sam-
linoleic, oleic, palmitic and stearic acids, respectively}. In- ples (SBO, PO, blends and interesterified blends) were
teresterification of the blends leads to a decrease in POO stripped of non-TAG components by a previously reported
and POP and an increase in LOP. Linoleic acid concentra- silica SE chromatography procedure (15).
tion at triacylglycerol carbon-2 was decreased by blending FA analysis. FA composition was determined by capil-
and interesterification~ Rates of change for peroxide value lary gas chromatography (GC) of the methyl esters after
and oxidation product formation confirmed the improve- transmethylation of the SE-purified TAG. A 15-m sample
ment of soybean oil stability by blending and interesteri- was transmethylated by reaction with 5 mL of 0.5 N KOH
fication. But, blends were more stable than interesterified in methanol at 50~ for 30 min. The reaction mixture was
blends. Also, the formation of hexanal, the major volatile neutralized to pH 7 with dilute hydrochloric acid and ex-
of linoleate hydroperoxides of soybean oil, was decreased tracted with 5 mL petroleum ether/diethylether (1:1,
by blending and interesterification. vol/vol) and dried with 5 mL acetone azeotrope under
helium. Fatty acid methyl ester (FAME) samples were
KEY WORDS: Blend, interesterification,oxidative stability, palm analyzed by direct-injection capillary GC with an SP2380
olein, soybean oil, triacylglycerol. column (30 m, 0.25 mm i.d., and 0.2 ~m film thickness;
Supelco, Inc., Bellefonte, PA) in a Varian Gas Chroma-
Autoxidation is a chemical reaction whereby oxygen is tograph, Star 3400, equipped with a flame-ionization
added to unsaturated fatty acids in vegetable oils like soy- detector (Varian, Inc, Walnut Creek, CA). The column was
bean oil (SBO), with the ultimate production of compounds operated at 150~ with a hold for 35 rain and then pro-
such as shorter-chain alcohols, aldehydes and ketones, as grammed to 210 ~C at 3 ~C/min with helium head pressure
well as high-molecular weight polymers. The reaction has of 10 psi. The injector and detector temperatures were 240
major implications in the food industry because it causes and 280~ respectively. FA composition was obtained by
a disagreeable alteration in flavor and viscosity (1). chromatogram peak integration accomplished by com-
Efforts to improve SBO resistance to oxidation or ox- puter procedures (16}.
idative stability have involved partial hydrogenation, addi- TAG analysis. TAG molecular species analysis was per-
tion of synthetic antioxidants and metal inactivators (2-5), formed by a previously reported procedure of reverse-
and natural selection and induced mutation breeding to phase high-performance liquid chromatography (RP-
reduce the linolenic acid content (6-12). Als~ SBO stability HPLC) with flame-ionization detection (13).
has been improved through changes in triacylglycerol (TAG) Stereospecific analysis. Stereospecific analysis was by
composition and TAG fatty acid location (13,14). a lipolysis-GC procedure reported previously (13,
The present study reports the effects of chemical in- 15,17).
teresterification of SBO and palm olein {PO) blends on TAG TAG oxidation product (TAG-OX) analysis. RP-HPLC
composition and fatty acid (FA) location on the resulting (14) was performed in duplicate on each oxidized sample
oxidative stability. at 24, 48 and 72 h. The TAG-OX formed from LLnLn,
LLLn, LLL (LnLP and LnOP), LLO, LLP, LOO, LOP and
EXPERIMENTAL PROCEDURES PLP were monitored with ultraviolet (UV) detection at 235
nm for conjugated diene (where L = linoleic acid, P --
Materials. Refined, bleached and deodorized SBO was pur- palmitic acid; O -- oleic acid; Ln -- linolenic acid}. These
chased from a commercial sourc~ and PC) was obtained oxidation products were identified by matching peak
from Premier Edible Oils Corporation (Portland, Oregon). retention times with those of the standard oxidized TAGs.
*To whom correspondence should be addressed at USDA, ARS, Analysis of volatiles. Volatile analysis was performed
NCAUR, 1815 N. University St., Peoria, IL 61604. by the static headspace procedure (15). The volatiles moni-
1Visiting scientist from Oils and Fats Section, Food Technology tored (and their precursor FA) were pentane (L); propanal
Research Institute, AgricultureResearch Center, 9 Gamaa St., Giza, (Ln); pentanal (L); hexanal (L); 2-heptenal (L); 2,4-hepta-
Egypt. dienal (Ln) and nonanal (O).

Copyright 9 1994 by AOCS Press JAOCS, Vol. 71, no. 10 (October 1994)
1112

W.E. NEFF ET AL.

Oxidation of purified TAG. Purified TAG were oxidized from 0.6788 (for SBO) to 0.4107 (SBO/PO, 1:1). Blending
at 60 +_ 2~ in the d a r k in oxygen in a forced-air oven with PO would be expected to improve SBO stability due
(Precision Scientific Co., Chicago, IL). Samples (225 m g to predicted or calculated oxidative stability (13,18). The
each) were weighed into 20-mL vials, which were purged oxidizability is calculated as 0.2 [0%] + [L%] + 2
with oxygen and sealed. One sample of each TAG was (Ln%)/100 GC area percent composition (18). Also, the
prepared for each oxidation period (24, 48 and 72 h). After ratios of L and Ln to O decreased in blends. This too would
each period of oxidation, three 15-mg aliquots were re- be expected to improve SBO stability (13). Also, as with
moved from each sample for peroxide value (PV) deter- the blends, O increased and Ln, L, L/O, and Ln/O ratios
mination by a colorimetric ferric thiocyanate method decreased in interesterified products compared to SBO.
(13,15). Two 50-mg aliquots were removed for volatile head- This would be expected to improve stability of the pro-
space analysis, and one 50-mg aliquot was removed for ducts compared to SBO (13). As expected (Table 1), the
analysis of TAG-OX by RP-HPLC. Due to limited sample FA composition of TAG and calculated oxidizability of
amounts, each oxidation experiment was performed once. blends and interesterified blends were almost the same.
However, under the same conditions used in previous work TAG FA location for blends and interesterified blends.
(13), a soybean oil TAG standard had a coefficient of varia- Positional analysis d a t a for SBO, PO, their blends and in-
tion for APV of 5% or less for 20 oxidation experiments. teresterified blends are presented in Tables 2 and 3. Com-
This allowed valid comparisons of the d a t a between ox- parison of FA located at glycerol carbon-2 relative to
idation experiments. carbons-1 and-3 in the blends and their interesterified pro-
Experimental oxidative stability parameters. The perox- ducts revealed t h a t interesterification was successful in
ide change with oxidation time (APV) was determined from randomizing FA distribution. The data indicated t h a t for
linear regression (two-dimensional) of plots of PV vs. time these blends and m o s t interesterified blends (9:1, 8:2 and
for the oxidized TAG. The hydroperoxide formation rate 7:3; SBO/PO), L was greater t h a n O at b o t h glycerol
(ATAG-OX), a second measure of experimental oxidative carbon-2, -1 and -3. However, for the 1:1 blend and its in-
stability was determined from a linear regression of the teresterified blend, L and O at carbon-2 or -1 and -3 did
plot of TAG-OX [summation of c h r o m a t o g r a m peak areas not differ greatly. L at carbon-2 was the highest in SBO
(area counts) from the detector response for the above (69.3%) and was decreased by blending to 45.8% in blend
TAG-OX] vs. oxidation time. A linear regression plot of 1:1 due to the introduction of TAG with less L. Inter-
the sum of the gas chromatogram peak areas (area counts) esterification decreased L at carbon-2 to 31.2% for the 1:1
from the detector response for the above volatiles (ATV) interesterified blend. The O level at carbon-2 for the blends
vs. oxidation time was used as a third measure of ex- also was greater t h a n in interesterified blends, especially
perimental oxidative stability for the SBO/PO blends. blends 7:3 (37.1% vs. 29.8%) and 1:1 (45.5% vs. 32.7%). The
content of L at carbons-1 and -3 was greater in the 9:1
RESULTS AND DISCUSSION interesterified blend (49.9%) t h a n in SBO (45.4%). L de-
creased to 26.5% at carbons-1 and -3 in blend 1:1. B a s e d
FA composition of blends and interesterified blends. L is on previous studies, reduction of L content at carbon-2
the p r e d o m i n a n t FA in SBO (53.4%), whereas O followed should improve the oxidative stability of the blends and
by P were the major acids, FA, in PO (Table 1). Blending interesterified products of SBO and PO (13-15).
SBO with PO caused O to increase and L to decrease. Ln TAG composition for blends and interesterified blends.
was decreased from 7.0% in SBO to 3.8% in the 1:1 TAG composition d a t a for SBO, PO and their blends and
SBO/PO blend. The FA composition thus was changed by interesterified blends are presented in Table 4. The m a j o r
blending, and this decreased the calculated oxidizability TAG of SBO oil were LLO, LLL, LLP, LOP, LOO, LnLL,

TABLE 1

Calculated Oxidizability (OX)a, Fatty Acid Composition b and Ratios of Linoleic (L) and Linolenic
(Ln) Acid to Oleic (0) Acid for Soybean Oil (SBO), Palm Olein (PO) and Their Blends
and Iuteresterified Blends
Fatty acid area percent
OX 14:0 16:0 18:0 18:1 18:2 20:0 18:3 L/O Ln/O
SBO 0.679 -- 10.0 4.2 25.4 53.4 -- 7.0 2.10 0.28
Blend (SBO/PO)
9:1 0.618 -- 13.2 4.2 27.5 49.2 -- 6.0 1.79 0.22
8:2 0.562 -- 16.7 4.3 29.1 44.5 -- 5.6 1.53 0.19
7:3 0.517 0.4 18.2 4.5 30.5 41.0 0.4 5.1 1.34 0.17
1:1 0.411 0.6 23.8 4.6 34.0 33.0 0.3 3.8 0.97 0.11
Interesterified
9:1 0.627 0.2 12.8 4.1 26.9 49.1 0.3 6.5 1.83 0.24
8:2 0.571 0.3 15.9 4.2 28.6 45.0 0.3 5.8 1.58 0.20
7:3 0.519 0.4 18.4 4.2 30.4 41.0 0.4 5.2 1.35 0.17
1:1 0.409 0.6 24.1 4.4 34.2 32.8 0.3 3.7 0.96 0.11
PO 0.132 1.3 40.0 4.6 41.7 12.4 -- -- 0.30 --
aOX, Oxidizability = [(0.02 (0%)) + L% + 2 (Ln%)]/100 (Ref. 18).
bSee Experimental Procedures section for conditions for gas chromatography analysis of fatty acid
composition.

JAOCS, Vol. 71, no. 10 (October 1994)

 1113

OXIDATIVE STABILITY OF BLENDS AND INTERESTERIFIED BLENDS

TABLE 2

Fatty Acid Composition and Ratios of L and Ln Acids to O on Glycerol Carbon-2 for SBO, PO
and Their Blends and Interesterified Blends a
Fatty acid area percent
14:0 16:0 18:0 18:1 18:2 20:0 18:3 L/O Ln/O
SBO -- -- -- 24.6 69.3 -- 6.2 2.82 0.25
Blend (SRO/PO)
9:1 -- 1.3 0.3 28.9 63.9 -- 5.6 2.21 0.20
8:2 -- 2.2 0.4 32.8 59.5 -- 5.2 1.81 0.16
7:3 -- 3.3 -- 37.1 55.0 -- 4.6 1.48 0.13
1:1 -- 4.9 0.7 45.5 45.8 -- 3.1 1.01 0.07
Interesterified
9:1 0.3 14.1 5.3 26.3 47.6 0.4 6.0 1.81 0.23
8:2 0.5 15.2 4.7 28.9 45.2 0.3 5.2 1.56 0.18
7:3 0.9 20.0 6.7 29.8 38.2 -- 4.4 1.29 0.15
1:1 0.8 26.0 5.6 32.7 31.2 0.4 3.4 0.95 0.10
PO 0.6 9.2 1.1 66.7 22.4 -- -- 0.34 --
aSee Experimental Procedures section for analysis conditions for fatty acid composition at glycerol carbon-2.
See Table I for abbreviations.

TABLE 3

Fatty Acid Composition and Ratios of L and Ln Acids to O on Glycerol Carbons-1 and -3 for SBO, PO
and Their Blends and Interesterified Blends a
Fatty acid area percent
14:0 16:0 18:0 18:1 18:2 20:0 18:3 L/O Ln/O
SBO -- 15.0 6.3 25.9 45.4 -- 7.4 1.76 0.29
Blends (SBO/PO)
9:1 -- 19.1 6.1 26.8 41.8 -- 6.2 1.56 0.23
8:2 -- 23.9 6.2 27.2 37.0 -- 5.8 1.36 0.21
7:3 0.5 25.6 6.8 27.2 34.0 0.6 5.4 1.25 0.20
1:1 0.9 33.3 6.5 28.2 26.5 0.5 4.1 0.94 0.15
Interesterified
9:1 0.1 12.2 3.6 27.2 49.9 0.3 6.8 1.84 0.25
8:2 0.3 16.3 3.9 28.4 45.0 0.3 6.0 1.59 0.21
7:3 0.2 17.7 3.0 30.7 42.4 0.5 5.5 1.38 0.18
1:1 0.5 23.1 3.7 34.9 33.6 0.3 3.8 0.97 0.11
PO 1.7 55.4 6.4 29.2 7.4 -- -- 0.25 --
aSee Experimental Procedures section for analysis conditions for fatty acid composition at glycerol carbons-1
and -3. See Table 1 for abbreviations.

LnLO, LnLP, L O S (S = s t e a r i c acid) a n d OOO. For PO, LOO a n d L O P (13), for t h e p r o d u c t from b l e n d 1:1
the m a j o r TAG were POP, POO, LOP, PLP, SOP' L L P a n d SBO/PO. T h e P O O a n d P O P were 12.8 a n d 15.3% for t h e
S O 0 . B l e n d i n g of P O a n d S B O [SBO/PO, 9:1, 8:2, 7:3 a n d b l e n d a n d decreased to 9.1 a n d 7.0% i n t h e i n t e r e s t e r i f i e d
1:1 (w/w)], decreased L n L L , LLL, LnLO, LLO, LLP' LOO p r o d u c t , respectively.
a n d LLS, w h e r e a s LOP' POO, P L P a n d P O P were in- Oxidative stability of blends and interesterified blends.
creased as P O i n c r e a s e d i n t h e blend. For b l e n d 1:1, LLL, E x p e r i m e n t a l o x i d a t i v e s t a b i l i t y of SBO, P O a n d t h e i r
LLO a n d L L P c o n t e n t s decreased, c o m p a r e d to SBO, from b l e n d s a n d interesterified b l e n d s were d e t e r m i n e d accord-
15.6 to 8.3, 15.8 to 8.4 a n d 12.4 to 7.9%, respectively; a n d i n g to APV, hTAG-OX a n d h T V m e t h o d s u s e d p r e v i o u s l y
POP, P O O a n d P L P i n c r e a s e d from 0.6 to 15.3, 2.9 to 12.8 (13-15).
a n d 1.7 to 5.7%, respectively. T h u s , t h e more oxidizable PV a n d h P V r e s u l t s for SBO, PO, b l e n d s a n d inter-
T A G s i n S B O oil decreased, a n d t h e more o x i d a t i v e l y esterified b l e n d s are g i v e n i n Table 5. T h e s e r e s u l t s show,
s t a b l e T A G s i n c r e a s e d (13). as predicted b y oxidizability (Table 1), t h a t P O is t h e m o s t
D a t a i n Table 4 show t h e r e m a r k a b l e decrease in L L L s t a b l e a n d S B O is t h e l e a s t stable. T h e b l e n d s a n d in-
for interesterified b l e n d s c o m p a r e d to the physical blends. teresterified b l e n d s all were more s t a b l e t h a n SBO, a n d
LOO a n d L O P i n c r e a s e d in i n t e r e s t e r i f i e d b l e n d s com- each blend, except for 1:1, was more s t a b l e t h a n i t s cor-
p a r e d to blends, w i t h t h e g r e a t e s t i n c r e a s e o c c u r r i n g in r e s p o n d i n g i n t e r e s t e r i f i e d p r o d u c t . However, b l e n d s a n d
b l e n d 1:1 (SBO/PO). T h e s e T A G s were 5.2 a n d 10.4% i n interesterified b l e n d s h a d t h e s a m e FA c o m p o s i t i o n (Table
b l e n d 1:1 a n d increased to 9.5 a n d 17.2% in the interesteri- 1). T h i s i n d i c a t e d t h a t , in a d d i t i o n to F A c o m p o s i t i o n ,
fled p r o d u c t , respectively. However, t h e decrease i n L L L TAG c o m p o s i t i o n a n d FA l o c a t i o n a t glycerol have a n ef-
a n d increase i n LOO a n d L O P o c c u r r e d w i t h a s h a r p fect o n o x i d a t i v e s t a b i l i t y (13,14).
decrease i n P O O a n d POP, w h i c h are more s t a b l e t h a n T h e TAG-OX c o m p o s i t i o n for the b l e n d s oxidized i n ox-

JAOCS, Vol. 71, no. 10 (October 1994)

1114

W.E. NEFF E T AL.

TABLE 4

Triacylglycerol (TAG) a Composition of SBO, PO and Their Blends (B) (SBO/PO) and Iuteresterified Blends (I)b
TAG area percent
B I B I B I B I
TAG SBO PO 90:10 90:10 80:20 80:20 70:30 70:30 50:50 50:50
LnLnLn 0.1 . . . . . . . . .
LnLnL 0.8 -- 0.9 0.7 1.0 0.6 0.9 0.3 0.7 0.4
LnLL 6.6 -- 6.4 4.8 5.6 3.9 5.1 2.7 3.4 1.3
LnLnO 0.4 -- 0.4 0.5 0.3 0.5 0.2 0.5 0.3 0.5
LLL 15.6 -- 15.4 10.9 12.6 9.0 12.2 5.9 8.3 2.9
LnLO 5.6 -- 4.0 5.7 4.7 4.9 3.5 4.4 2.4 2.7
LnLP 3.6 -- 3.6 3.7 3.1 3.6 2.9 3.5 2.2 2.7
LLO 15.8 0.4 14.2 18.3 13.1 14.8 11.2 13.2 8.4 9.0
LnOO 1.1 -- 1.0 1.2 0.8 1.6 1.0 1.3 0.4 1.2
LLP 12.4 2.5 12.1 11.4 11.0 11.8 10.1 11.4 7.9 8.9
LnOP 2.0 0.7 1.4 2.2 1.5 2.3 1.3 2.7 1.2 3.1
LOO 8.2 1.6 8.0 9.3 7.2 9.3 6.5 9.8 5.2 9.5
LLS 2.7 -- 2.9 2.3 2.6 1.8 1.7 1.7 1.6 1.9
LOP 9.5 11.2 9.5 12.3 9.8 14.0 10.2 16.0 10.4 17.2
PLP 1.7 9.9 2.7 3.0 3.4 4.1 4.0 5.4 5.7 7.0
OOO 3.2 2.7 3.0 1.7 3.2 2.2 3.3 2.4 3.4 3.2
LOS 3.3 -- 2.7 3.5 2.3 3.3 1.9 3.1 2.0 2.4
POO 2.9 25.3 4.7 3.0 7.1 4.6 9.4 5.8 12.8 9.1
SLP 1.5 -- 1.1 1.6 1.3 1.7 1.0 1.9 1.5 1.9
POP 0.6 34.4 3.0 1.5 6.1 2.7 9.2 3.9 15.3 7.0
PPP 0.1 0.5 0.1 0.0 0.1 0.1 0.2 0.2 0.5 0.4
SO0 0.9 2.4 0.9 0.6 0.9 0.7 1.2 0.8 1.5 1.1
SLS 0.3 -- 0.1 0.2 0.1 0.1 0.0 0.0 0.2 0.0
SOP 0.4 5.6 0.7 0.6 1.2 0.8 1.5 1.1 2.3 1.8
PPS 0.1 0.2 0.1 0.2 0.1 0.3 0.1 0.5 -- 0.8
SOS 0.1 0.1 0.2 0.1 0.1 0.2 0.1 0.2 -- 0.4
PSS 0.I 0.6 0.3 0.2 0.2 0.2 0.0 0.2 -- 0.3
SSS 0.1 0.1 0.1 0.1 0.1 0.1 0.2 0.1 0.3 0.1
Unknown 0.4 1.8 0.7 0.9 0.8 1.2 1.1 1.1 1.8 3.4
aDetermined by reverse-phase high-performance liquid chromatography with flame-ionization detection. See Experimental Procedures
section for details.
bp and S are palmitic and stearic acids, respectively. See Table 1 for other abbreviations.

y g e n for u p t o 72 h a t 6 0 ~ is p r e s e n t e d in Table 6. T h e s e TABLE 5

d a t a s h o w t h a t L L L , LLO, L L P a n d P L P r e m a i n e d t h e
Oxidative Stability of SBO, PO and Their Blends
a b u n d a n t T A G - O X in blends, e v e n w h e n t h e b l e n d w as
and Interesterilied Blends Measured by Oxidative
1:1. However, e v e n t h o u g h L L P T A G - O X d e c r e a s e d as a Stability Parameter Peroxide Value (PV}a
r e s u l t of b l e n d i n g {from 12.6% in S B O to 7.9% in b l e n d
1:1), t h e L L P T A G - O X i n c r e a s e d as t h e P O c o m p o s i t i o n Time (h)
i n c r e a s e d in t h e blend. PV (meq/kg) APVb (PV/h,
T h e T A G - O X of i n t e r e s t e r i f i e d b l e n d s is p r e s e n t e d in Product 0 24 48 72 meq/kg/h)
Table 7. D a t a in t h e t a b l e s h o w t h a t LLP, L L O a n d P L P SBO 0.2 7.0 16.5 33.2 0.45
T A G - O X were t h e a b u n d a n t T A G - O X . A s n o t e d before Blends (SBO/PO)
f r o m t h e T A G c o m p o s i t i o n of t h e b l e n d s a n d i n t e r e s t e r i - 9:1 0.6 5.3 10.8 18.3 0.25
8:2 0.4 4.9 9.9 16.8 0.23
fled b l e n d s (Table 4), t h e L L P a n d L L O in t h e t w o pro- 7:3 0.2 3.4 7.0 11.4 0.15
d u c t s were s o m e w h a t lower t h a n in SBO, especially a t 1:1. 1:1 0.3 2.3 4.4 7.2 0.10
T h a t m a y be w h y b l e n d s a n d i n t e r e s t e r i f i e d b l e n d s were Interesterified
m o r e s t a b l e t h a n S B O (Tables 5-7) (13,14}. However, com- 9:1 0.8 8.0 17.0 31.4 0.42
p a r i n g b l e n d s t o t h e i r i n t e r e s t e r i f i e d p r o d u c t s , t h e lower 8:2 0.5 6.6 14.3 26.3 0.35
c o n t e n t of L L O a n d L L P a n d h i g h e r P O O a n d P O P in 7:3 0.5 4.8 10.9 17.5 0.24
1:1 0.3 2.9 5.8 8.1 0.11
blends, in part, m i g h t ex p la in w h y blends were m o r e s t a b l e PO 0.1 0.4 0.6 0.9 0.01
t h a n interesterified blends (13,14). T h i s o b s e r v a t i o n is SUl>
p o r t e d by t[rAG-OX (Table 6), w h i c h w a s 28.0 for S B O a n d aSee Experimental Procedures section for PV determination and ox-
idation conditions. See Table 1 for other abbreviations.
d e c r e a s e d to 13.9, 11.4, 2.6 a n d 2.0 d e t e c t o r area c o u n t s / h bAPV is the rate of change of PV with oxidation time. See Ex-
for b l e n d s 9:1, 8:2, 7:3 a n d 1:1, r e s p e c t i v e l y , hTAG-OX in perimental Procedures section for hPV determination.
t h e i n t e r e s t e r i f i e d b l e n d s (Table 7) w a s lower t h a n in S B O
b u t h i g h e r t h a n in e a c h c o r r e s p o n d i n g b l e n d (Table 6).
T h e c o m p o s i t i o n of t h e m a j o r v o l a t i l e s a f t e r o x i d a t i o n 8. T h e d a t a show t h a t h e x a n a l , p e n t a n e , p r o p a n a l ,
for 72 h a t 6 0 ~ in t h e d a r k f r o m SBO, P O a n d t h e i r 2 - h e p t e n a l a n d 2 , 4 - h e p t a d i e n a l were t h e m a j o r v o l a t i l e s
b l e n d s a n d i n t e r e s t e r i f i e d b l e n d s are p r e s e n t e d in Table from oxidized SBO. M a j o r volatiles f r o m P O were pentane,

JAOCS, Vol. 71, no. 10 (October 1994)

 1115

O X I D A T I V E S T A B I L I T Y OF B L E N D S A N D I N T E R E S T E R I F I E D B L E N D S

TABLE 6

Composition of the Oxidized Triacylglycerols (TAG-OX) in SBO, PO and Their Blends After 24, 48 and 72 H Autoxidation a
TAG-OX area percent
SBO 9:1 (SBO/PO) 8:2 (SBO/PO) 7:3 (SBO/PO) 1:1 (SBO/PO) PO

TAG-OX 24 48 72 24 48 72 24 48 72 24 48 72 24 48 72 24 48 72
LLLn 0.4 3.8 6.5 1.9 2.6 4.7 2.5 4.7 5.1 1.3 3.0 1.4 0.0 2.1 3.3 -- -- --
LLL 9.8 16.8 22.9 8.8 12.3 19.3 9.8 14.5 18.9 5.8 9.8 15.4 4.2 9.8 13.0 -- -- --
LnLO + LnLP 0.8 1.0 1.4 5.3 1.3 1.2 1.6 0.7 1.3 1.8 1.6 1.0 0.9 1.3 1.4 -- -- --
LLO 17.5 20.4 22.0 13.7 17.2 18.5 19.4 21.0 18.7 18.9 16.8 21.9 19.9 18.9 21.8 -- -- --
LLP 22.9 17.1 12.2 28.8 30.7 16.9 36.5 23.8 17.3 33.0 28.7 21.9 39.0 35.5 26.9 14.7 13.9 4.0
LO0 7.8 9.7 8.2 11.5 6.9 8.8 6.3 5.2 7.4 6.2 8.8 4.6 8.6 7.9 5.5 7.9 13.0 5.1
LLS 11.3 9.6 8.2 7.6 3.7 7.5 7.4 8.2 60.0 1.3 3.3 7.1 2.3 3.1 8.7 -- -- --
LOP 12.9 11.9 7.7 9.7 12.4 9.1 7.7 11.9 10.3 14.8 13.5 11.1 9.5 8.6 9.9 31.8 24.3 10.6
PLP 16.6 9.7 10.9 12.7 12.9 14.0 8.8 10.6 14.6 16.9 15.5 13.2 15.6 12.7 9.5 45.6 48.8 80.5
ATAG-OXb 28.0 13.9 11.4 2.6 2.0 0.2
(detector area
c o u n t s per h)
aTAG-OX formation with oxidation time determination by reverse-phase high-performance liquid c h r o m a t o g r a p h y with ultraviolet detec-
tion of oxidized T A G conjugated diene at 235 nm. See E x p e r i m e n t a l Procedures section for analysis and oxidation conditions. See Tables
1 and 4 for other abbreviations.
bATAG-OX is rate of TAG-OX formation with respect to oxidation time of 72 h. See E x p e r i m e n t a l Procedures section for ATAG-OX
determination.

TABLE 7

Composition of TAG-OX in Interesterified Blends (SBO/PO) After 24, 48 and 72 H Autoxidation a

9:1 (SBO/PO) 8:2 (SBO/PO) 7:3 (SBO/PO) 1:1 (SBO/PO)
TAG-OX 24 48 72 24 48 72 24 48 72 24 48 72
LLLn 3.2 3.1 4.9 1.9 3.5 4.2 1.6 2.4 3.1 1.5 2.5 2.6
LLL 10.0 10.0 17.5 6.4 14.9 18.1 4.0 7.8 11.4 1.6 4.2 4.9
LnLO + LnLP 0.8 0.8 1.7 0.8 0.8 1.1 0.5 0.6 0.9 0.3 0.6 0.6
LLO 15.4 15.5 22.4 13.4 19.9 20.8 16.8 16.3 19.1 7.8 14.3 15.7
LLP 20.6 20.1 12.1 21.6 15.6 10.9 18.5 14.3 10.7 17.8 11.1 10.3
LOO 8.1 8.1 8.5 7.8 9.1 10.8 6.4 7.6 9.4 5.9 5.0 7.5
LLS 14.9 15.2 12.8 16.7 13.6 10.6 22.5 20.2 19.3 28.3 24.4 21.7
LOP 12.3 12.3 9.1 13.8 7.7 6.6 15.2 13.2 9.3 16.5 13.4 10.9
PLP 14.7 14.8 11.0 17.7 15.0 16.9 16.6 17.5 17.0 20.3 24.6 25.6
ATAG-OX
(detector area
counts/h) 16.4 15.1 9.9 5.5
aSee Experimental Procedures section for TAG-OX, oxidation conditions and ATAG-OX determination. See
Tables 1 and 6 for other abbreviations.

TABLE 8

Volatile Decomposition of SBO, PO and Their Blends and Interesterified Blends at 72 h Autoxidation a
Volatile area percent
Blend Interesterified
Volatile SBO 9:1 8:2 7:3 1:1 9:1 8:2 7:3 1:1 PO
Pentane 24.1 26.8 23.7 27.4 26.3 23.3 24.3 28.3 28.0 28.8
Propanal 15.7 18.1 17.9 16.1 14.1 19.6 19.3 17.5 13.2 --
Pentanal 6.2 7.9 9.6 8.7 10.2 8.5 9.1 7.8 8.8 11.2
Hexanal 26.6 12.3 13.1 12.4 13.2 14.0 12.5 13.1 13.7 16.2
c, t-2-Heptenal 14.1 20.0 22.3 20.7 20.8 21.2 21.2 18.6 21.3 15.6
2,4-Heptadienal 10.3 13.0 11.5 12.3 12.1 11.8 11.9 12.3 11.0 --
Nonanal 2.9 1.8 1.9 2.4 3.3 1.7 1.7 2.5 4.0 28.1
ATVb 0.60 0.25 0.25 0.16 0.11 0.34 0.37 0.09 0.06 0.02
(detector area
c o u n t s per h)
aVolatile composition from t h e r m a l decomposition of oxidized samples determined by static headspace g a s
c h r o m a t o g r a p h y . See E x p e r i m e n t a l Procedures section for analysis and oxidation conditions. See Tables
1 and 5 for other abbreviations.
bATV is the rate of volatile formation from s a m p l e s oxidized to 72 h. See E x p e r i m e n t a l Procedures section
for 5TV determination.

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1116

W.E. NEFF E T AL.

nonanal, hexanal and heptenal. These volatiles also were interesterified products was countered by decreased POO
found as major components in blends and interesterified and POP, which are known to improve oxidative stability
blends. Pentane production was not greatly affected by (13). However, the blends and interesterified products were
blending or interesterification; its concentration made up still more stable than SBO.
24.1% of SBO volatiles and ranged from 23-28% in the
blends and interesterified blends. Hexanal, the major ACKNOWLEDGMENTS
volatile derived from L, was found in the same amount This research was conducted with the support and cosponsorship
(about 13%) in blends and interesterified blends, whereas of San Diego State University Foundation (San Diego, CA) and IN-
volatiles from SBO contained 26.6% hexanal. This reduc- TSOY/University of Illinois (Urbana, IL). We are grateful to Wilma
tion in hexanal content was apparently due to the lower Rinsch for oxidation experiments and static headspace analysis of
content of L acid at carbon-2 (Table 2). These results are volatiles and to Ray Hollowayfor gas chromatography of FA methyl
in agreement with those reported by Frankel et al. (19) esters.
for volatile studies of L and mixed L and Ln TAG. Pro-
panal and 2-heptenal increased to approximately the same REFERENCES
level in blends and interesterified blends. In regard to ox- 1. Frankel, E.N., in Handbook of Soy Oil Processing and Utiliza-
idative stability, measured by volatile generation, SBO tion, edited by D.R. Erickson, E.H. Pryde, O.L. Brekke, T.L.
had the lowest stability, with a hTV of 0.60 detector area Mounts and R.A. Falb, American Oil Chemists' Society, Cham-
counts/h. paign, 1980, p. 229.
2. Warner, K., T.L. Mounts and W.F. Kwolek,J. Am. Oil Chem. Soc.
Comparison of hTV of blends to that of their interesteri- 62:1483 {1985}.
fled products showed t h a t blends 9:1 and 8:2 were more 3. Snyder, J.M., E.N. Frankel and K. Warner, Ibid. 63:1055 {1986}.
stable than their interesterified products. This is in a g r e e 4. Warner, K., E.N. Frankel, J.M. Snyder and W.L. Porter, J. Food
ment with results from APV and ATAG-OX. But, for Sci. 51:703 (1986}.
blends 7:3 and 1:1, the hTV indicates that they were less 5. Frankel, E.N., K. Warner and K.L. Moulton, J. Am. Oil Chem.
stable with respect to volatile generation than their in- Soc. 62:1354 {1985}.
6. Smouse, T.H., in Flavor Chemistry of Fats and Oils, edited by
teresterified products. T.H. Smouse, and D. Min, American Oil Chemists' Society,Cham-
The results presented here indicate t h a t the oxidative paign, 1985, p. 85.
stability of SBO can be improved by blending and in- 7. Mounts, T.L., K. Warner, G.R. List, R. Kleiman, W.R. Fehr, E.G.
teresterification of SBO and PO. Blending and inter- Hammond and J.R. Wilcox,J. Am. Oil Chem. Soc. 65:624{1988}.
esterification lead to decreased Ln and L and increased 8. Hammond, E.G., W.R. Fehr and H.E. Snyder, Ibid. 4~.33 {1972}.
O. Also, L decreased at carbon-2 on the glycerol moiety. 9. Hammond, E.G., and W.R. Fehr, Ibid. 61:1713 {1984}.
10. Anonymous, I N F O R M i:186 {1990}.
The decrease in L at carbon-2 in blends was accompanied 11. Scowcroft, W.R., Ibid. 1:945 {1990}.
by an increase of O at carbon-2, which may be partly 12. Haumann, B.F., Ibid. 1:1002 {1990}.
responsible for better stability of blends compared to in- 13. Neff, W.E., E. Selke, T.L. Mounts, W. Rinsch, E.N. Frankel and
teresterified blends (13,15). Also, blends had less L at M.A.M. Zeitoun, J. Am. Oil Chem. Soc. 69:111 {1992}.
glycerol carbon-l(3). The total FA composition of blends 14. Neff, W.E., T.L. Mounts, W.M. Rinsch and H. Konishi, Ibid.
and interesterified blends were about equal, as expected. [email protected] (1993}.
15. Neff, W.E., T.L. Mounts, W.M. Rinsch, H. Konishi and M. E1-
However, the TAG composition of the blend was different Agaimy, Ibid. 71:1101 {1994}.
from that of its interesterified blend. LnLL, LLL, LLO, 16. Butterfield, R.O., W.K. Rohwedder, E.D. Bitner, J.O. Ernst, J.D.
L L P and LLO were lower and POP, POO and P L P were Wolf and H.J. Dutton, Prog. Lipid Res. 17.'93 (1978}.
higher in both blends and products. However, POO and 17. Neff, W.E., M.A.M. Zeitoun and D. Weisleder, J. Chromatogr.
P O P in interesterified blends were less than in blends. 58~.353 (1992}.
These noted differences in TAG composition may, in part, 18. Cosgrove,J.P., D.F. Church and W.A. Pryor, Lipids 22:299 {1987}.
19. Frankel, E.N., E. Selke, W.E. Neffand K. Miyashita, Ibi& 27.'442
explain why the blends were more stable than the in- (1992}.
teresterified blends. T h a t is, the effect of the decrease in
LLL, which is known to decrease oxidative stability, in [Received February 28, 1994, accepted June 21, 1994]

JAOCS, Vol. 71, no. 10 (October 1994)