Isotopic and elemental data f tracing for i the h origin i i off European p olive oils Federica Camin Camin, Roberto Larcher Larcher, Giorgio Nicolini Nicolini, Luana Bontempo, Daniela Bertoldi, Matteo Perini, Claus Schlicht, Antje Schellenberg, Freddy Thomas, Katharina Heinrich, Susanne Voerkelius, Micha Horacek, Henriette Ueckermann, Heinz Froeschl, Bernhard Wimmer, Gerhard, Heiss, Malcolm Baxter, Andreas Rossmann, Jurian Hoogerwerff
FEM-IASMA, Reasearch and Innovation Centre, via E. Mach 1, 38100 San Michele all’Adige (TN), Italy
EC Regulament n° 182/2009
Compulsory origin labelling for virgin and extravirgin i i olive li oil il
Increasingg demand for analytical y methods and statistical tools to verify claims of origin
Isotope ratios of bioelement and elemental profile
air humidity, temperature
Evapotraspiration of leaf water: D/H, 18O/16O
climate air humidity and soil moisture status,, irradiance, temperature
OLIVES OLIVE OIL processing i
Diffusion of CO2 through the stomata: 13C/12C H 2O
SOURCE WATER adsorption D/H Li Mg Mn Na Ca …
18O/16O
Geology, pedology of soil, climate: MINERAL PROFILE
Latitude, elevation, distance from the sea sea, temperature and amount of precipitation: D/H 18O/16O D/H,
Sampling sites 267 olive oils 314 surface waters Geographical characteristics (latitude, longitude, g , distance from the sea, altitude) Geological characteristics (shale/clay, limestone, acid id magmatic) ti )
Trentino Toscana Carpentras Chalkidiki
Algarve Barcelona
Climatic characteristics (temperature, RH, amount of precipitation)
Sicilia
Lakonia
Climatic characteristics: -mean values of 5 months temperature ((°°C), -mean values of 5 months relative humidity (%) -5 months total amount of rainfall (mm)
http://www.meteotrentino.it, Arco (TRE); http://www.ilmeteo.it/, Sesto Fiorentino (TOS); http://www.ilmeteo.it/, Assoro/Enna, (SIC); http://www7.ncdc.noaa.gov/, Faro/Almanacil (ALG); http://www7.ncdc.noaa.gov/, Carpentras (CAR); the Servei Meteorològic de Catalunya, Barcelona (BAR); the Hellenic National Meteorological Service, Mikra (CHA)*; the Hellenic National Meteorological Service, Kalamata/Gythi (LAK)*; http://www wunderground com http://www.wunderground.com. *through prof. Michael Komaitis (Agricultural University of Athens, Greece)
Sta able Isotope Ratiio An naly ysis
Commodity
Standard deviation of repeatibility (‰)
Standard deviation of reproducibility (‰)
δ C 13
oil
, 0,1
0,1 ,
δ O 18
oil water
0,4 0,1
0,6* 0,2
δD
oil water t
1 1
2 2
*after normalization
TE analysis: 15 g oil + 15 ml 6.7% H2O2, 1% HNO3 and 0.2% HCl vortex
ultrasonic bath bath, 5 min centrifugation 3500 rpm rpm, 5 min min.
Filtration of aqueous phase with Polyvinylidene Fluoride (PVDF, 0.45 mm, 33mm) filter
ICP MS ICP-MS
Method’s performances DETECTION LIMIT: Calculated as 3 times the standard deviation of the signal of the blank samples samples, extracted and analysed ten times ACCURACY: ACCURACY Calculated as the mean recovery on a natural oil spiked with 1 g of NIST 2387 “Peanut butter” or of SPEX s-23 “Mineral oil”
Certified Elements
R%
Zn Mn Ca Mg K Na
82 84 90 92 95 101
NIST 2387 “Peanut butter”
Certified Elements
R%
B Na Mg Al K Ca V Mn Ni Cu Zn Mo Cd Ba Pb
88 80 67 53 92 84 63 71 65 61 68 66 71 65 67
SPEX s-23 “Mineral oil”
element / isotope Li / 7 B / 11 Na / 23 Mg / 26 Al / 27 K / 39 Ca / 40 V / 51 Mn / 55 Co / 59 Ni / 60 Cu / 63 Zn / 66 Ga / 71 Se / 78 Rb / 85 Sr / 88 Mo / 98 Cd / 111 Cs / 133 Ba / 137 La / 139 Ce / 140 Nd / 143 Sm / 147 Eu / 151 Yb / 171 Lu / 175 Tl / 205 Pb / 208 U / 238
DL
ug/kg
0.008 0.17 20 4 3 20 25 0 007 0.007 0.2 0.002 1 0.10 6 0.001 0.014 0.001 0.3 0.050 0.005 0.001 0.12 0.0020 0.0050 0.004 0.0010 0.0002 0 0004 0.0004 0.0200 0.0040 0.1 0.001
% sample >DL 6 28 8 92 4 98 100 0 64 34 16 68 42 0 0 98 32 0 0 0 34 48 34 24 22 6 8 0 0 38 50
SIR correlations: SIR 18 δ O
δD
0,82
0,62
-0,80
0,13
-0,75
0,67
0,38
0,64
0,02
0,56
signific.