Stable isotope ratio analysis for verifying the authenticity of vegetal oils - Federica Camin, Luana Bontempo, Fondazione Edmund Mach (FEM), Via ...
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Stable isotope ratio analysis for verifying the
authenticity of vegetal oils
Federica Camin, Luana Bontempo,
Fondazione Edmund Mach (FEM), Via E. Mach 1, 38010, San Michele
all’Adige (TN), Italy
Vegetable edible
oils
- glycerides of fatty acids (mainly unsaturated) of vegetable origin,
small amounts of phosphatides, unsaponifiable constituents and
free fatty acids;
- obtained by mechanical procedures (virgin and cold pressed oils) or
by solvent extraction
- wide variety of food uses: commodities, condiment for salad or for
cooking, essential ingredients in processed food (pastries, cookies).
Production and price
• World 2011 production of edible vegetable oils (FAOSTAT data,
http://faostat3.fao.org/home/E): 150 million tonnes
• Different price: e.g. soybean oil: 677 US$ per metric ton whereas
extravirgin olive 4200 US$ per metric ton).
• EU Regulation 1169/2011: it is compulsory to specify the type of
vegetable oil present also in the case of blended vegetable oils used
in food products.
• commercial temptation to fraud: dilution with cheaper oils,
different geographical origin
Isotopo (iso+topos) = stesso posto
13 12 16 18
1H
C C O O
2H
Analisi dei rapporti tra isotopi stabili di
bioelementi:
Metodi ufficiali per la verifica di adulterazioni
anno metodo prodotto strumento Rapporto isotopico
1987 OIV vino, mosto SNIF-NMR D/H
1990 EU Reg 2676/90, encl. 8 vino, mosto SNIF-NMR D/H
1991 AOAC 998,12 miele IRMS 13C/12C
1993 ENV 12140, 13070 succhi di frutta e vegetali IRMS 13C/12C
1995 AOAC 995,17 succhi di frutta e vegetali SNIF-NMR D/H
1996 OIV 2/96 vino, mosto IRMS 18O/16O
1997 EU Reg 2676/90, 822/97 vino, mosto IRMS 18O/16O
1997 ENV 12141 fruit juice IRMS 18O/16O
2000 AOAC 2000.19 sciroppo d’acero SNIF-NMR D/H
2000 OIV 71/2000 vinegar SNIF-NMR, IRMS D/H, 13C/12C
2001 OIV 17/2001 vino, mosto IRMS 13C/12C
2003 EU Reg. 2676/90, 440/03 vino, mosto IRMS 13C/12C
2003 OIV MA-F-AS314-03 vino IRMS 13C/12C
succhi di frutta e vegetali,
2004 AOAC 2004,01 succo d’acero SNIF-NMR D/H
2006 AOAC 2006,05 vanillina SNIF-NMR D/H
2007 OIV-MA-AS312-07 vino IRMS 13C/12C
2011 EU Reg 584/2011 Grana Padano DOP IRMS D/H, 13C/12C, 15N/14N, 34S/32S
2013 EN 16466-1, 2, 3 aceto SNIF-NMR, IRMS D/H, 13C/12C, 18O/16O
2013 OIV 510, 511/2013 Aceto IRMS 13C/12C, 18O/16O
Stable isotope ratio analysis: factors of variability
(emissions, natural and industrial) (photosyntesis, specie)
[Agriculture]
biological
d13C
anthropogenic d15N
[Physiology]
Indicator function of d2H
[Environment] d34S
d18O climatological
(precipitation, evaporation)
geological
[Geography]
(rocks, soils)
H, C, O Stable isotope analysis in oil:
bulk and specific compound!
Bulk
Isotope
Analysis
Compound
Specific
Isotope
Analysis
glycerol, sterols, aliphatic acids, fatty acids
and n-alkanes
Compound-specific d13C and d2H analysis of fatty
acids
Methanol transesterification of oil triglycerides
Methanolic sodium hydroxide 2 M, 1 min
GC-c-IRMS and GC-Py-IRMS analyses
13C/12C and 2H/1H Isotopic Fingerprints
• Paolini et al.,Talanta 2017
• Bontempo et al., Food Chemistry
Internal accepted
standard
Peaks: Heneicosane (1), methyl palmitate (2), methyl stearate (3), methyl oleate (4), methyl linoleate (5)Extravirgin olive oil
• Since 1993 (Bianchi et al., 1993)
• Spangenberg et al, 1998 and 2001 (d13C bulk, d13C16:0, d13C18:1, FA
composition)d18O and d13C isoscapes and relative 95% confidence intervals (C.I.) for Italian extra virgin olive oils collected in 2011. (Chiocchini et al., FC, 2016)
DATABANK ICQRF-MIPAAF > 160 authentic (almeno 3 campioni per ognuna delle 43 DOP/IGP italiane), campionate dall’ICQRF (convenzione MIPAAF) Annuale dal 2001
Italian databank 2011 + TUNISIA
29
28
Abruzzo
27 Calabria
Campania
Emilia Romagna
26 TUNISIA, Sicilia, Friuli Venezia Giulia
Sardegna, Calabria, Lazio
Lazio (4)
O ‰ vs V-SMOW
Liguria
25 Lombardia
Marche
Molise
24 Puglia
Sardegna
18
Abruzzo, Campania, Emilia Sicilia
23 Romagna, FVG, Liguria, Toscana
Marche, Molise, Puglia, Trentino Alto Adige
Toscana, Umbria, Lazio Umbria
22 Veneto, TAA, Veneto
Lombardia
Tunisia
21
Camin et al.,
20 2016, Food
-175 -170 -165 -160 -155 -150 -145 -140 -135 -130 Chemistry
2
H ‰ vs V-SMOWTraceability model:
stable isotope + 1H-
NMR
ITALIA TUNISIA TUNISIA_LAMP class.error
ITALIA 177 0 0 0.00
TUNISIA 3 50 1 0.07
TUNISIA_LAMP 0 0 32 0.00
Camin et al.,
2016, Food
ChemistrySesame oil Addition of corn oil to sesam oil Sesam oil with different origin (Seo et al. J Am Oil Chem Soc, (Horacek et al., Plose one, 2015) 2010; Seol et al., J Food Science 2012)
Camelina sativa oil
d13C ‰
Hrastar et al., JAFC, 2009Sunflower oil
Kelly et al., RCM, 1997Conclusions
H, C, O stable isotope ratio analysis of bulk oil and components
Detection of dilution with other types of oil
Verification of the geographical originYou can also read
