Food Technology Fact Sheet: Edible Oil Quality

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FAPC-197

Robert M. Kerr Food & Agricultural Products Center

FOOD TECHNOLOGY FACT SHEET


Adding Value to OKLAHOMA
405-744-6071 • www.fapc.biz • fapc@okstate.edu

Edible Oil Quality


Nurhan Turgut Dunford
FAPC Oil/oilseed Specialist

Introduction Monitoring and maintaining edible oil quality are


Majority of the edible oils used for cooking, frying paramount importance to ensure safety of the product for
and food formulations are derived from plant sources, consumption. Although there is no official standard set
specifically from oilseeds such as soybean, canola, sun- for evaluating edible oil quality, FFA content, peroxide
flower seeds, cottonseed and peanuts. Edible vegetable value (PV) and p-anisidine value (AV) are commonly
oils are liquid at room temperature and comprised of used in industry to report edible oil quality. This fact
mainly triacylglycerides that are made up of three fatty sheet summarizes edible oil quality parameters used in
acids attached to a glycerol molecule through ester bonds industry and for research purposes.
(see fact sheet FAPC-196 Lipid Glossary). Physical,
chemical and nutritional properties of vegetable oils Quality Parameters
vary significantly depending on the type of fatty acids Free Fatty Acid Content
present in the oil. Unsaturated fatty acid content of Free fatty acids (FFA) are formed by the hydroly-
vegetable oils is significantly higher than that of animal sis of oils (triacylglycerides). They are not bound or
fats. Although high unsaturated fatty acid content makes esterified to a glycerol molecule. Crude oils and fats in
the oil healthier, highly unsaturated oils are prone to fast natural form, not refined, contain small amounts of FFA,
oxidation and quality deterioration during processing, which are usually removed during the refining process.
handling and storage. Vegetable oils also contain other FFA are not desirable in edible oils because when oils
compounds in minor amounts that affect their quality with high FFA content are used in foods, they lower the
and nutritional value. Phytosterols, tocopherols, waxes oxidative stability of the product, increase acidity and
are some of the minor components of vegetable oils (less lead to off-flavor formation. The standard methods for
than 1 percent of the oil). These compounds are not regu- determining FFA content of oils are American Oil Chem-
larly analyzed for oil quality evaluation purposes partly ists’ Society (AOCS) Ca-5a-40 [1] and European Union
due to the complexity of the analytical protocols and the Regulation No.2568/91 [2]. There are other analytical
need for expensive instruments for testing. methods, which are faster and suitable for small sample
Oil quality deteriorates by hydrolysis, oxidation sizes [3,4]. Chemical analysis kits and various automated
and polymerization of the oil. Hydrolysis increases the hand-held instruments also are available for analyzing
amount of free fatty acids (FFA), mono- and diacylglyc- FFA concentrations in oils [5].
erols and glycerols in oils. Oxidation produces hydro- Voluntary industry standard for FFA content in
peroxides and low molecular weight volatile compounds refined edible oil is ≤0.05 percent (based on oil weight).
such as aldehydes, ketones, carboxylic acids, and short In the food industry, frying oils with FFA content ex-
chain alkanes and alkenes. Dimers and polymers also are ceeding 2 percent are either discarded or fresh oil is
formed when oil is exposed to high temperatures during added to bring the FFA content down.
cooking and frying.

Oklahoma Cooperative Extension Service • Division of Agricultural Sciences and Natural Resources
Acid value compounds is conducted by high-performance size ex-
Acid Value is an important indicator of vegetable clusion chromatography, which allows the separation
oil quality. Acid value is expressed as the amount of and quantification of polymeric compounds, dimers,
potassium hydroxide (KOH, in milligrams) necessary oxidized triacylglycerides, mono- and diacylglycerides
to neutralize free fatty acids contained in 1 g of oil. The and FFA [7]. The standard method for analyzing total
standard method for determining acid value is AOCS polar content (TPC) in frying oils is the AOCS Cd 20-
Cd 3d-63 [1]. 91 [1]. As the name implies, this method determines the
total polar compounds in the oil, not the individual polar
Peroxide Value compounds.
Peroxide value (PV) is an index used to quantify Regulations in some countries specify that oils
the amount of hydroperoxides present in fats and oils. should contain less than 25–27 percent TPC.
Hydroperoxides, which are shown to be toxic to humans,
are the primary oil oxidation products formed during the TBARS
initial stages of oxidation. The standard method for PV This is one of the oldest tests used for evaluating
determination is AOCS Cd 8-53 [1]. Although Fourier lipid oxidation in foods. When heated under acidic con-
transform infrared (FTIR) and near-infrared (FT-NIR) ditions, thiobarbituric acid (TBA) reacts with a number
spectroscopy methods developed for PV measurement of compounds including nucleic acids, amino acids,
have the advantages of analytical speed and automation, proteins, phospholipids and aldehydes to produce a pink
the instruments used for these tests are quite expensive chromophore that can be measured by UV or fluores-
and require extensive calibration [6]. Evaluating oil qual- cence detection. These substances are termed TBARS
ity based on only PV can be misleading. Because low (thiobarbituric acid reacting substances). The extent of
PV does not necessarily indicate low level of oxidation, lipid oxidation is reported as TBA value, which corre-
it could be due to the advanced level of oil oxidation sponds to milligram of malonaldehyde equivalents per
during which primary oxidation products are converted kilogram of sample or micromoles of malonaldehyde per
to secondary oxidation product (see the section for an- gram of sample [8,9]. It is recommended other tests such
isidine value) lowering PV but increasing AV of the oil. as PV and AV also should be used when evaluating lipid
Hence, both PV and AV should be used for oil quality quality in complex food systems due to the limitations
evaluation (see totox value). of TBARS method. The standard method for analyzing
Refined oils usually have PV of <1 meq/kg. Oils are TBA value is the AOCS Cd 19-90 [1].
considered oxidized when PV > 3 meq/kg.
Conjugated Dienes
p-Anisidine Value Oxidation of polyunsaturated fatty acids results in an
p-Anisidine value (AV) is a measure of the secondary increase in the ultraviolet absorption of the product due
oxidation products that are formed by breakdown of the to conjugate formation. Measurement of the content of
primary oxidation products during extensive oxidation. conjugated dienes at 234 nm and conjugated trienes at
The secondary oxidation products are mainly aldehydes 268 nm is a quick physical method, which may be helpful
such as 2,4-dienals and 2-alkenals. AV is strongly cor- to assess the oxidative stability of vegetable oils [10].
related with overall oil odor intensity. The standard
method for AV content determination in oils is the AOCS Unsaponifiable Matter
Cd 18-90 [1]. Unsaponifiable matter (USM) fraction of vegetable
Refined oils should have AV of <5. oils naturally contains hydrocarbons, terpene alcohols,
sterols, tocopherols and other phenolic compounds,
Polar Compounds which may act as oxidation inhibitors. Vegetable oils
Presence of polar compounds in oil is one of the typically contain 0.5-2.5 percent USM while some others
best indicators of heated oil quality. Polar compounds have higher amounts, 5-6 percent. USM of edible oils
consist of dimeric and higher polymeric triacylglycer- is used for their characterization and authentication of
ides formed through thermal polymerization of triacyl- the products. The standard method for analyzing USM
glycerides, monomeric oxidized products, mono- and is the AOCS Ca 6b-53 [1].
diacylglycerides and FFA formed through hydrolytic
cleavage of triacylglycerides. The analysis of the polar
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Phospholipids Totox value
Phospholipid is a common name for lipids contain- Totox value is used as an empirical assessment of
ing phosphoric acid or other phosphorus-containing oxidative deterioration based on PV and AV of an oil.
acids in ester form such as glycerophospholipids (e.g.
phosphatidic acid, phosphatidylcholine, phosphatidyl- Totox value = 2 x PV + AV
ethanolamine) or sphingophospholipids (e.g. sphingo-
myelin). Although these compounds (also called gum Conclusions
because of their gummy consistency in oil) have some Commonly used edible oil industry voluntary quality
health benefits and surfactant/emulsifier properties, they parameters are FFA, PV and AV. National Oil Proces-
need to be separated from crude oil during the refining sors Association (NOPA) and American Oil Chemists’
process, which is referred to as degumming. Otherwise, Society (AOCS) provide laboratory services that include
they impart a cloudy appearance and precipitate out of AOCS methods, certified reference materials, quality ref-
the oil during storage creating a unpleasant solid residue erence materials and consulting. The AOCS Laboratory
at the bottom of the containers and adversely affect the Proficiency Program (LPP), formerly the Smalley Check
functionality of refined oils, i.e. cause foaming during Sample Program, is the world’s most extensive and re-
frying. The phospholipid content of oils is commonly spected collaborative proficiency testing program for oil-
measured as phosphorous (AOCS Ca 19-86), which can seeds, oilseed meals, and edible oils and fats. More than
be converted to phospholipids by using conversion fac- 500 chemists who participate in this program use AOCS
tors calculated by using the phospholipid composition or similar standard methods for sample analyses and then
and the molecular weight of individual phospholipids compare their results with the test results generated at
present in the oil. The standard method for analyzing other laboratories using the same methods and samples
phospholipids is the AOCS Ca 12b-92 [1]. and verify their quality control practices (http://www.
Refined oils have about 30 mg/kg phosphorous, aocs.org/LabServices/content.cfm?ItemNumber=841).
while super degummed oils contain less than 10 mg/
kg phosphorous. References
1. AOCS (2004) Official Methods and Recommended
Color Practices. American Oil Chemists’ Society, Cham-
The color of crude and refined vegetable oils is an paign, IL.
important factor in the determination of their market 2. Comission E Determination of the Free Fatty Acids
value. Removal of color pigments, which are extracted in European Commission Regulation (EED) No.
along with the oil from the seeds during the extraction 2568/91. Official Journal of the European Communi-
process, is achieved during the oil refining referred to as ties L 248 (5.9.91):6
bleaching. The color compounds in the oil mainly consist 3. Mahesar SA, Sherazi STH, Khaskheli AR, Kandhro
of carotenoids, chlorophyll, gossypol and related com- AA, Uddin S (2014) Analytical approaches for the
pounds. Chlorophyll is a sensitizer of photo-oxidation assessment of free fatty acids in oils and fats. Anal
and promotes oil oxidation in the presence of light and Methods 6:4956-4963
decreases the oxidative stability of oils. Chlorophyll 4. Lowry RR, Tinsley IJ (1976) Rapid Colorimetric
also acts as a catalyst poison during oil hydrogenation Determination of Free Fatty Acids. J Amer Oil Chem
process. The color of the edible oils also can be an issue Soc 53 (4):470-472
for food formulations adversely affecting the color of the 5. Perkins EG, Erickson MD (1996) Deep Frying, Chem-
final product which incorporated. Lovibond is the most istry, Nutrition, and Practical Applications. AOCS
common method (AOCS Wesson Cc 13b-45 and ISO Press, Champaign, IL
Cc 13e-92) used to determine color of the commercial 6. Li H, van de Voort FR, Ismail AA, Cox R (2000)
oils [1]. In Lovibond method color is expressed as red Determination of peroxide value by fourier transform
and yellow components. In general, fully refined oil may near-infrared spectroscopy. J Amer Oil Chem Soc 77
be 0.8 R (red) and 8.0 Y (yellow). Frying oils often are (2):137-142. doi:10.1007/s11746-000-0023-7
discarded when their Lovibond red color increases from
1.5-3.5 to 20-30.

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7. Dobarganes MC, Velasco J, Dieffenbacher A (2000) 9. Tarladgis BG, Pearson AM, Jun LRD (1964) Chemis-
Determination of polar compounds, polymerized and try of the 2-thiobarbituric acid test for determination
oxidized triacylglycerols, and diacylglycerols in oils of oxidative rancidity in foods. II.—formation of the
and fats: results of collaborative studies and the stan- tba-malonaldehyde complex without acid-heat treat-
dardized method (Technical report). Pure and Applied ment. Journal of the Science of Food and Agriculture
Chemistry, vol 72. doi:10.1351/pac200072081563 15 (9):602-607. doi:10.1002/jsfa.2740150904
8. Tarladgis B, Pearson AM, Dugan LR, Jr. (1962) The 10. St. Angelo A, Ory R, Brown L (1975) Comparison
chemistry of the 2-thiobarbituric acid test for the de- of methods for determining peroxidation in processed
termination of oxidative rancidity in foods. I. Some whole peanut products. Journal of the American
important side reactions. J Am Oil Chem Soc 39 Oil Chemists’ Society 52 (2):34-35. doi:10.1007/
(1):34-39. doi:10.1007/BF02633347 BF02901817

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