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Research/Analytical Purpose Adulteration (economical/food safety)
Authenticity (economical/quality)
Quality
Sensory…Analytical Instrumentation
Adulteration Nineteen Arrested Over Alleged Olive Oil Fraud
(Spain, Olive Oil Times)
Spanish Police Say Palm, Avocado, Sunflower Was Passed Off as Olive Oil (Spain, Olive Oil Times)
Two Plead Guilty in Olive Oil Fraud Scheme, Sentenced to Two Years in Jail (Spain, 2011, Olive Oil Times)
Toxic Oil Syndrome (TOS), Spain 1981
Economics At 10% adulteration (soybean oil), the producer saves
about $0.20/Kg……commodity pricing
Metric Ton of Olive Oil….@$2900
Metric Ton….$200
3 M Metric Tons in Spain
10% = 300,000 Metric Tons @ $60 million (in Savings)
Retail…10% oil (100 Kg) savings…$5000-10,000
Olive Oil (Extra Virgin) (Standards of Identity) Sterol composition and
content Fatty acid composition Saturated fatty acid content
in position 2 of the triglyceride
Unsaponifiable material Wax content Erythrodiol and uvaol ECN 42 content UV Light Absorbency Moisture and Volatiles Metal Traces
Hydrocarbons: stigmastadiene, stigmasta-3, 5 diene, and campesta-3, 5 diene
Trans fatty acid isomer Total aliphatic alcohols DNA characterization Color Aspect Free Acidity Peroxide Value Insoluble Impurities Flash Point
Olive Oil (Standards of Identity)
Halogenated Solvents
Additives
Heavy Metals & Pesticide Residues
Sensory
Olive Oil (IFSH Focus) Technology for Olive Oil
Authenticity & Adulteration
Rapid Technology for Olive Oil Quality (Sensory)
Collaborators
Agilent
Alpha Mos
AOCS
LC-MS/MS and QTOF GC-MS
ICP-MS
Electronic Nose (FID)
Statistical Analysis Software
Goal Rapid Techniques to relate to
sensory quality
(Rapid) Technology to confirm Authenticity and Adulteration
LC-QTOF Sample Prep and Chromatographic Parameters Method: 5 mL oil diluted with 5 mL hexane extracted twice with 10 mL
methanol, evaporated and reconstituted in 50% methanol in water. (Polar Fraction)
Chromatographic separation achieved on a Poroshell 120 EC-C18 2.7 µm column kept at 45oC
Gas temp was 325oC with a flow of 10 L/min
Nebulizer was 45 psig
Analysis was conducted in positive ionization mode
Injection volume 5 µL
The mobile phase was a gradient of 0.1% acetic acid in water and acetonitrile starting at 5% ACN and increasing to 100% ACN over 25 min with a post time of 3 min.
Oil Analysis Using QTOF Technology Chromatograms Produced Using MFE (Molecular Feature Extraction) and Contain Several Thousands of Compounds
Olive Oil from Palestine
Soybean Oil
Mass Profiler Professional MPP software allows multivariance statistical analysis of MS data
Data can be filtered based on set parameters and organized into entity lists.
Venn Diagram of Olive Oils and Olive Oils Overlap with Soybean
Specific entity lists can be displayed in many different ways. An example is A Venn diagram representing similarities and differences among various groups of samples.
ID Browser for Identification of Compounds included in Entity Lists
An entity list can be also identified based on available databases and libraries using the ID browser
Table of representative 38 compounds identified in EVOO. Over 200 compounds identified.
Name Formula Mass RT
12-amino-octadecanoic acid C18 H37 N O2 299.282 21.911
2-Oxo-4E-hexenoic acid C6 H8 O3 128.0478 1.657
Vanillin C8H8O3 152.0473 1.298
3,4-bis(methylene)-Hexanedioic acid C8 H10 O4 170.0577 1.657
2,3-Dihydroxy-3-methylvaleric acid C6 H12 O4 148.0733 4.995
Oleamide C18 H35 N O 281.2714 21.911
2,2-dimethyl-4-pentenoic acid C7 H12 O2 128.0831 8.676
(R)-3-methyl-2-oxo-Pentanoic acid C6 H10 O3 130.0628 3.276
2,2-dimethyl-3-butenoic acid C6 H10 O2 114.0691 3.919
2-Hydroxycinnamic acid C9 H8 O3 164.0465 10.404
3-oxo-4-pentenoic acid C5 H6 O3 114.031 3.61
(5R)-5-Hydroxyhexanoic acid C6 H12 O3 132.079 16.458
(R)-3-methyl-2-oxo-Pentanoic acid C6 H10 O3 130.0627 5.296
2-Octenedioic acid C8 H12 O4 172.0729 2.709
(5R)-5-Hydroxyhexanoic acid C6 H12 O3 132.079 15.79
2-keto-n-caprylic acid C8 H14 O3 158.0938 1.716
2,2-dimethyl-4-pentenoic acid C7 H12 O2 128.0825 10.621
Isovalerylglucuronide C11 H18 O8 278.1018 4.495
2E,4E,6E,8E-Decatetraenedioic acid C10 H10 O4 194.0573 14.721
11-amino-undecanoic acid C11 H23 N O2 201.1724 1.248
2-ethyl-3E-hexenoic acid C8 H14 O2 142.0984 1.949
12-amino-dodecanoic acid C12 H25 N O2 215.1878 2.166
6,8-dihydroxy-octanoic acid C8 H16 O4 176.1056 9.803
2,2-dimethyl-4-pentenoic acid C7 H12 O2 128.083 10.32
13-methyl-pentadecanoic acid C16 H32 O2 256.2393 0.931
10,12,14-octadecatrienoic acid C18 H30 O2 278.2254 20.984
3,4,5-Trimethoxycinnamic acid C12 H14 O5 238.0826 15.314
10-oxo-5,8-decadienoic acid C10 H14 O3 182.093 10.629
3,6-dioxo-decanoic acid C10 H16 O4 200.1035 10.629
2S-amino-pentanoic acid C5 H11 N O2 117.0795 6.372
5-oxo-7-octenoic acid C8 H12 O3 156.0798 11.306
(+)-catechin C15 H14 O6 290.0809 8.108
Tyrosol C8H10O2 138.0681 11.306
(+)-pinoresinol C20H22O6 358.1416 12.684
Syringic acid C9H10O5 198.0536 10.195
Caffeic acid C9H8O4 180.0423 9.752
Elenolic acid C11 H14 O6 242.0788 4.578
p-coumaric acid C9H8O3 164.0465 10.404
Name Formula Mass RT
12-amino-octadecanoic acid C18 H37 N O2 299.282 21.911
2-Oxo-4E-hexenoic acid C6 H8 O3 128.0478 1.657
Vanillin C8H8O3 152.0473 1.298
3,4-bis(methylene)-Hexanedioic acid C8 H10 O4 170.0577 1.657
2,3-Dihydroxy-3-methylvaleric acid C6 H12 O4 148.0733 4.995
Oleamide C18 H35 N O 281.2714 21.911
2,2-dimethyl-4-pentenoic acid C7 H12 O2 128.0831 8.676
(R)-3-methyl-2-oxo-Pentanoic acid C6 H10 O3 130.0628 3.276
2,2-dimethyl-3-butenoic acid C6 H10 O2 114.0691 3.919
2-Hydroxycinnamic acid C9 H8 O3 164.0465 10.404
3-oxo-4-pentenoic acid C5 H6 O3 114.031 3.61
(5R)-5-Hydroxyhexanoic acid C6 H12 O3 132.079 16.458
(R)-3-methyl-2-oxo-Pentanoic acid C6 H10 O3 130.0627 5.296
2-Octenedioic acid C8 H12 O4 172.0729 2.709
(5R)-5-Hydroxyhexanoic acid C6 H12 O3 132.079 15.79
2-keto-n-caprylic acid C8 H14 O3 158.0938 1.716
2,2-dimethyl-4-pentenoic acid C7 H12 O2 128.0825 10.621
Isovalerylglucuronide C11 H18 O8 278.1018 4.495
2E,4E,6E,8E-Decatetraenedioic acid C10 H10 O4 194.0573 14.721
11-amino-undecanoic acid C11 H23 N O2 201.1724 1.248
2-ethyl-3E-hexenoic acid C8 H14 O2 142.0984 1.949
12-amino-dodecanoic acid C12 H25 N O2 215.1878 2.166
6,8-dihydroxy-octanoic acid C8 H16 O4 176.1056 9.803
2,2-dimethyl-4-pentenoic acid C7 H12 O2 128.083 10.32
13-methyl-pentadecanoic acid C16 H32 O2 256.2393 0.931
10,12,14-octadecatrienoic acid C18 H30 O2 278.2254 20.984
3,4,5-Trimethoxycinnamic acid C12 H14 O5 238.0826 15.314
10-oxo-5,8-decadienoic acid C10 H14 O3 182.093 10.629
3,6-dioxo-decanoic acid C10 H16 O4 200.1035 10.629
2S-amino-pentanoic acid C5 H11 N O2 117.0795 6.372
5-oxo-7-octenoic acid C8 H12 O3 156.0798 11.306
(+)-catechin C15 H14 O6 290.0809 8.108
Tyrosol C8H10O2 138.0681 11.306
(+)-pinoresinol C20H22O6 358.1416 12.684
Syringic acid C9H10O5 198.0536 10.195
Caffeic acid C9H8O4 180.0423 9.752
Elenolic acid C11 H14 O6 242.0788 4.578
p-coumaric acid C9H8O3 164.0465 10.404
Blue=phenolic compounds Green=fatty acids
PCA Analysis of Italian (P) Greek (G) Olive Oils and Soybean Oil(B).
Cluster analysis based on five sensors with the highest discrimination power.
IFSH Direction Oxidation correlated to Analytical Methods
PV, FFA, …
Sensory correlated to Analytical Methods
Continue with Adulteration and Authenticity
ICP-MS
HS-GC-MS
Statistical Analysis
PCA
Mass Profiler Professional
IFSH Institute for Food Safety & Health (IFSH) Bedford Park, IL
National Center for Food Safety and Technology (NCFST)
At the Illinois Institute of Technology (IIT) Chicago
50:50 IIT:FDA
Collaborative Model of Industry:Academia:FDA
Food Safety…Chemistry, Process Engineering, Microbiology (molecular biology)
Nutrition (biological/clinical)
In existence for 23 years