ISOTOPIC MARKING AND IDENTIFICATION OF LIQUIDS

Abstract

Method for isotopic identification, allowing, where appropriate, a liquid to be linked to a site of growth or harvest or a sub-product derived from a determined liquid, via analysis of concentration or of ratios of stable isotopes, and comparison to isotopic codes generated beforehand in a manner unique to a set of liquids issued from a site of growth, harvest or conversion. The invention also relates to a method that makes it possible to give a unique code to liquids of a site of growth, harvest or conversion, and to a computer making it possible to store the unique codes generated in memory, to generate unique codes for new liquids of a site of growth, harvest or conversion and to perform comparisons.

Claims

1. A method allowing a specific code of a place of origin to be applied to liquids, preferably wines or spirits, or to by-products of this liquid; method wherein the basic geographic signature (BGS) is provided of the liquid or by-product thereof, comprising: (i) the concentrations of at least 5, 6, 7, 8, 9, 10, 11, 12 or the entirety of the elements in group (3): Rb, Sr, B Li, Ca, Na, Mg, K, F, P, C1, As, Pb, Cd, (ii) the concentrations of at least 5, 10, 15, 20, 25, 30, or the entirety of the elements in group (2): Be, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Y, Zr, Nb, Mo, Rh, Pd, Ag, Sn, Sb, Te, I, Ba, Hf, Ta, W, Re, Ir, Hg, Ti, Si, and (iii) the concentrations of stable isotopes stables of at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 of the elements in this group (2); the method comprising the addition to this liquid having this BGS of a known quantity of at least 1 stable isotope of at least 1, 2 or 3 chemical elements of group (2), by means of which a liquid is obtained having a determined isotopic signature, with a modified isotope ratio compared with the BGS.

2. The method according to claim 1, wherein the BGS also comprises the concentrations of chemical elements of at least 2, 3, 4 or the 5 chemical elements in group (1): C, O, N, H, S.

3. The method according to claim 1, wherein the BGS comprises concentrations of stable isotopes of at least 1, 2 or 3 of the elements in group 2′) Al, Mn, Fe, Co, Cu, Zn, Mo, Sn, Ti, Si.

4. The method according to claim 1, wherein the addition is made to the liquid of a known quantity of at least 1 stable isotope of at least 1, 2 or 3 of the elements in group (2′) Al, Mn, Fe, Co, Cu, Zn, Mo, Sn, Ti, Si.

5. The method according to claim 3, wherein the BGS comprises the concentrations of at least 2 stable isotopes of at least 1, 2 or 3 of the elements Fe, Cu, Zn, Mo, Sn, Ti, Si.

6. The method according to claim 5, wherein, for the BGS, the concentrations are determined of at least 2 stable isotopes of at least 1 element from among Fe and Zn.

7. The method according to claim 6, wherein 56Fe and 57Fe, and/or 66Zn and 68Zn are measured and, via addition of isotope to the liquid, the concentration is varied of 56Fe and/or of 57Fe, and/or of 66Zn and/or of 68Zn.

8. The method according to claim 1, wherein the BGS comprises the concentrations of the elements Rb, Sr and B.

9. The method according to claim 1, wherein the BGS comprises the concentrations of the elements Li, Ca, Na, Mg, K, F, P, Cl, As, Pb, Cd.

10. The method according to claim 1, wherein the unique code is defined by an electronic computer as a function of the unique codes already generated and of the BGS of the liquid or its by-product, this electronic computer comprising a model (M) having in memory the unique codes already generated.

11. The method according to claim 10, wherein the BGS is measured of liquids or successive by-products, and each time a unique code is defined for the liquid or last-analysed by-product, this code differing from the unique codes previously defined and recorded in the model (M).

12. An isotopic identification method allowing a liquid or by-product, preferably a wine or spirit, to be linked with a place of origin, the method comprising: a—in a sample of liquid or by-product, measuring: (i) the concentrations of at least 5, 6, 7, 8, 9, 10, 11, 12 or the entirety of the elements in group (3) Rb, Sr, B Li, Ca, Na, Mg, K, F, P, Cl, As, Pb, Cd, (ii) the concentrations of at least 5, 10, 15, 20, 25, 30, or the entirety of the elements in group (2): Be, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Y, Zr, Nb, Mo, Rh, Pd, Ag, Sn, Sb, Te, I, Ba, Hf, Ta, W, Re, Ir, Hg, Ti, Si, and (iii) the concentrations of stable isotopes of at least 2, 3, 4, 5, 6, 7, 8, 9 or 10 of the elements in this group (2); to obtain a profile of concentrations of elements and stable isotopes; b—comparing this profile with profiles recorded in a predefined model (M) having profiles in memory in the form of unique codes each specific to a type of liquid or by-product from a place of origin, each unique code having been previously generated by the model (M) with a variation in isotopes of elements; c—concluding that the liquid or derivative by-product to be identified has a profile substantially equal to a recorded code and hence indicating a place of origin, if after comparison the profile corresponds to a recorded profile, and on the contrary concluding that the liquid or derivative by-product does not come from any place of origin having a code recorded in the model, or that the liquid has been adulterated.

13. The method according to claim 12, wherein in a sample of the liquid or by-product, the concentrations are also measured of at least 2, 3, 4, or the 5 chemical elements in group (1): C, O, N, H, S.

14. The method according to claim 12, wherein the BGS comprises concentrations of stable isotopes of at least 1, 2 or 3 of the elements in group (2′): Al, Mn, Fe, Co, Cu, Zn, Mo, Sn, Ti, Si.

15. The method according to claim 12, wherein the addition is made to the liquid of a known quantity of at least 1 stable isotope of at least 1, 2 or 3 of the elements in group (2′): Al, Mn, Fe, Co, Cu, Zn, Mo, Sn, Ti, Si.

16. The method according to claim 14, wherein the BGS comprises the concentrations of at least 2 stable isotopes of at least 1, 2 or 3 of the elements Fe, Cu, Zn, Mo, Sn, Ti, Si.

17. The method according to claim 16, wherein, for the BGS, the concentrations are determined of at least 2 stable isotopes of at least 1 element from among Fe and Zn.

18. The method according to claim 17, wherein 56Fe and 57Fe, and/or 66Zn and 68Zn are measured, and via addition of isotope to the liquid the concentration is varied of 56Fe and/or of 57Fe, and/or of 66Zn and/or of 68Zn.

19. The method according to claim 12, wherein the BGS comprises the concentrations of the elements Rb, Sr and B.

20. The method according to claim 12, wherein the BGS comprises the concentrations of the elements Li, Ca, Na, Mg, K, F, P, Cl, As, Pb, Cd.

21. The method according to claim 12, comprising the use of an electronic computer in which there are recorded the unique codes specific to other liquids from at least one other place of origin, and/or in which the BGS is recorded of the liquid from a place of origin for comparison with the recorded profiles.

22. An electronic computer (2) that can be used to implement the isotopic identification method according to claim 12, comprising a programmable logic unit (3) and data recording medium (4) containing software instructions adapted, when executed by the logic unit (3), for implementing steps to compare a profile of concentrations or ratios of elements and stable isotopes in a sample of a liquid or by-product, in the form of concentrations (C2) or ratios (R2), with profiles recorded in the form of unique codes each one being specific to a place of origin, and to determine whether the liquid or by-product has a profile substantially equal to a recorded code and hence indicating a place of origin, or whether the liquid or by-product does not come from any place of origin having the code recorded in the model, or that the liquid has been adulterated; the data recording medium (4) having in memory the unique codes of at least one wine or spirit, this unique code representing a label of origin, a vineyard and/or a vintage and, for each wine or spirit, comprising the concentrations of at least 5, 6, 7, 8, 9, 10, 11, 12 or the entirety of the elements in group (3): Rb, Sr, B Li, Ca, Na, Mg, K, F, P, Cl, As, Pb, Cd, and at least 5, 10, 15, 20, 25, 30, or the entirety of the elements in group (2): Be, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Y, Zr, Nb, Mo, Rh, Pd, Ag, Sn, Sb, Te, I, Ba, Hf, Ta, W, Re, Ir, Hg, Ti, Si, and concentrations or ratios of isotopes of at least 1, 2 or 3 of the elements in group (2′): Al, Mn, Fe, Co, Cu, Zn, Mo, Sn, Ti, Si.

23. The method according to claim 3, wherein the BGS also comprises the concentrations of chemical elements of at least 2, 3, 4 or the 5 chemical elements in group (1): C, O, N, H, S.

24. The method according to claim 14, wherein in a sample of the liquid or by-product, the concentrations are also measured of at least 2, 3, 4, or the 5 chemical elements in group (1): C, O, N, H, S.

Description

[0186] The invention will now be described in more detail with the aid of embodiments taken as nonlimiting examples and with reference to the appended drawings.

[0187] FIG. 1 is a schematic of an assembly with electronic computer able to be used to implement the invention.

[0188] FIG. 2 is a flow chart of a method allowing a unique code to be applied to liquids.

[0189] FIG. 3 is a graph extract showing, for different wines and spirits, the concentrations of the chemical elements B, Na, Mg, Al, Ca, Mn, Cu, Rb and Sr, and of the isotopes 56Fe, 57Fe, 66Zn and 68Zn, obtained by mass spectrometry. The interest of the graph is not the precise measured values but the fact that it shows that the values vary from one product to another.

[0190] FIG. 4 is a graph showing the variations of the ratio 68Zn/67Zn in a wine as a function of 68Zn doping. X-axis: DDG is the name of the wine followed by indication of % doping with 68Zn. Y-axis: mass spectrometry value.

[0191] FIGS. 5 to 7 are MS graphs showing the trend in the isotope ratios 54Fe/56Fe, 57Fe/54Fe and 57Fe/56Fe with or without correction of interference between 54Cr and 54Fe, on samples of DDG wine, and as a function of performed isotopic doping (variation in the concentration of an isotope in relation to its reference natural abundance).

[0192] FIGS. 8 to 10 are MS graphs showing the trend in the isotope ratios 54Fe/56Fe, 57Fe/54Fe and 57Fe/56Fe, in samples of DDG wine, as a function of performed isotopic doping. Zn—Fe and de DZn-Fe are combinations of tracers (unique codes) allowing the demonstration that it is possible to mark/encode the same liquid with a different combination within the same range of values.

[0193] In FIGS. 5 to 10, the crosses are sometimes superimposed fully or partially over the black circles, which accounts for the fact that the circles are not or are only scarcely visible, but they are indeed present underneath the overlying cross.

EXAMPLES

Example 1: Description of a Computerized Assembly for Managing and Defining Isotopic Codes

[0194] The assembly 1 comprises a programmable electronic computer 2 provided with a programmable logic unit 3, a data recording medium 4 and a data exchange interface 5 linked together via an internal data bus. The electronic computer 2 also comprises a man-machine interface 6.

[0195] For example, the unit 3 comprises a programmable microprocessor or microcontroller. The medium 4 here has a memory module e.g. of FLASH or EEPROM technology, or a magnetic hard disk. The medium 4 contains software instructions adapted to implement steps of the method in FIG. 2 when these instructions are executed by the computing unit 3.

[0196] The man-machine interface 6 here comprises a display screen, a data entry tool such as a keyboard and a loud speaker. As a variant, the man-machine interface 6 can be of different configuration.

[0197] For example, the electronic computer 2 is a micro-computer or mobile communication device such as a tablet or telephone. It can also be a remote computer server, accessible via the internet or a dedicated computer network. In this case, the interface 6 can be omitted and replaced by a dedicated communication interface e.g. a computer, communication device such as a tablet or television which fulfils the same functions as this interface 6 but is physically separate from the electronic computer 2.

[0198] In particular, the computer 2 is programmed to implement a predefined model M, for example by means of executable instructions stored in the medium 4.

[0199] The model M particularly allows the applying to liquids or derivative by-products of a unique isotopic code specific to a place of origin, and optionally at even finer levels of granularity (e.g. label of origin, type of vine, type of production and optionally batch), this code being based on the type, the concentrations or ratios of stable isotopes of chemical elements. In addition, the model (M) can when needed verify the relating of a liquid with a determined place of origin, via analysis of concentrations or ratios of stable isotopes, allowing determination of a profile of concentrations or ratios of these stable isotopes, in particular using mass spectrometry, and comparison with the unique codes recorded in the model (M).

[0200] The data used by the model M can be stored in the medium 4 and/or stored in a dedicated database accessible by the computer 2.

[0201] For example, the interface 6 is adapted to acquire input data e.g. in the form of digital or analogue signals or in the form of data structures such as values of accumulation rates AR and/or measurements of concentrations C2 and/or ratios R2 of stable isotopes. These data can also be transmitted to the computer 2 via the interface 6.

[0202] FIG. 2, in connection with FIG. 1, schematically describes one embodiment of the method for applying a unique code. MS is used to determine the BGS of the original liquid at step 101, the data are sent to the computer 2 e.g. via the interface 6.

[0203] The computer has in memory the unique codes which have been generated for other places of origin, this knowledge being identified at step 103 in FIG. 2.

[0204] By cross-referencing the data obtained at steps 101, 102 and 103, the computer at step 104 generates an isotope addition formula, which at the time of bottling or packaging, will allow liquids to be obtained having the unique code.

[0205] The addition method can be tested and the data held in the computer 2 for correlation between this operation and the obtaining of a stable isotope ratio of an element in a liquid or derivative by-product at the time of bottling or packaging. Adjustments (of content in particular) can be made to obtain usable isotope ratios i.e. with significant MS-measurable differences at the time of bottling or packaging.

[0206] The computer generates the composition of the isotope addition, to which the user has access via the interface 6 for example.

[0207] As a variant, the feed can be determined in advance and the computer gives the user the composition of the isotope addition.

Example 2: Application to a Red Wine Vineyard

[0208] Reference is made to FIGS. 1 and 2.

[0209] The BGS is determined of a liquid from a place of origin at step 101, the data are sent to the computer 2, for example via the interface 6. Samples of liquids are taken and analysed. The ratios of the stable isotopes of the following elements are determined (prior analyses determined the presence thereof at the place of cultivation, harvesting or processing, for example via mass spectrometry (MS) analysis on the liquid itself or on run-off water, soil, vegetation (vines, fruit trees . . . ): [0210] these 26 elements: Li, Be, B, F, Na, Mg, Al, Ca, Cr, Mn, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Mo, Rh, Pd, Ag, Cd, Te, Ba, Ti, Pb, Si, [0211] these 15 rare earths: La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.

[0212] The MS measurements in the invention in general, and in this particular example, can be performed with available methods, in particular: [0213] Inductively Coupled Plasma Mass Spectrometry (ICP-MS), [0214] Multicollector-Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS) [0215] Isotope-ratio mass spectrometry (IRMS). [0216] LA-ICP/MS (Laser Ablation) [0217] Laser Induced Breakdown Spectroscopy (LIBS).

[0218] The AR is known or can be calculated at step 102 by marking the liquids over a cycle with determined ratios of the stable isotopes of the indicated elements, followed by bottling or packaging, sampling the liquids or derivative by-products and MS analysis. The data are sent to the computer 2 e.g. via the interface 6.

[0219] The computer has in memory the unique codes which were generated for other places of origin, this knowledge is identified at step 103 in FIG. 2.

[0220] By cross-referencing the data obtained at steps 101, 102 and 103, the computer at step 104 generates an isotope addition formula and a treatment method which, at this place of origin, will allow liquids on bottling or packaging to have the unique code.

[0221] The addition method can be tested and the data held in the computer 2 for correlation between this method and the obtaining of a ratio of stable isotopes of an element at the time of bottling or packaging. Adjustments (of content in particular) can be made to obtain usable isotope ratios i.e. with significant MS-measurable differences at the time of bottling or packaging.

[0222] The computer generates the isotope addition composition and/or treatment method (operational process to be followed by the operator at the place of origin), which are accessible to the user via the interface 6 for example.

[0223] As a variant, the addition method can be determined in advance, and the computer provides the user with the composition of the isotope addition.

[0224] For liquids, it is therefore possible to define a method wherein the isotope addition forms the aqueous requirement in the week preceding bottling or packaging, step 105.

Example 3: Application to Wines Including Champagnes and Spirits

[0225]

TABLE-US-00001 Code Label of origin Year Colour Alcohol CR Côtes du Rhône 2016 Red 13.5° B1 Bordeaux 2015 Red 12.5° B2 Côte de Bourg 2016 Red 13.0° Château Lallibarde (Bordeaux) M Muscadet Sèvre et 2016 White 12.0° Maine-sur-Lie AR Alsace Riesling 2016 White 12.0° BA Bourgogne Aligoté 2016 White 12.0° DG1-2 Domaine des 2015 Red 13.0° Gardes R1-2 Tain l'Hermitage — Red 12.0° CM Champagne — Champagne 12.0° Mercier CBN Champagne — Champagne 12.5° Alexandre Bonnet PSM Cognac V.S — Cognac 40.0° Prince St Mérac VCC Viognier, Caprice 2016 White 13.0° de Clairmont

[0226] Using mass spectrometry, with ICP/MS ICAP RQ spectrometer, and for each product in the above Table, the concentrations were determined of the chemical elements present, namely B, Na, Mg, Al, K, Ca, Mn, Fe, Cu, Zn, Rb, Sr, Li, Be, Sc, Ti, V, Cr, Co, Ni, Ga, Ge, As, Se, Y, Zr, Nb, Mo, Pd, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, W, Hg, TI, Pb, Bi, Th, U.

[0227] C, H, O, N, S can be additionally analysed for dating of the production.

[0228] In these winegrowing products, it can be seen that rare earths are practically non-existent. Su

[0229] Among the elements Al, Mn, Fe, Co, Cu, Zn, Mo, Sn, Ti, Si, analysis first concerned Fe and Zn. Measurement was performed under conditions allowing measurement of concentrations of the isotopes 56Fe, 57Fe, 66Zn and 68Zn. The presence of these stable isotopes in all the samples and the distribution thereof allows the envisaged varying of the concentration of one in relation to the other and hence their ratios, in particular the ratios 56Fe/57Fe and 66Zn/68Zn, or the ratios of these Zn isotopes in relation to the majority isotope (64Zn) in natural abundance.

[0230] The graph in FIG. 3 is an extract of the data obtained. The differences in concentration can be seen according to analysed product.

[0231] Variation in concentrations or ratios can be obtained in particular: [0232] By adding the isotope of which the concentration is to be increased. [0233] By adding the majority natural isotope. [0234] By adding a mixture of isotopes in natural abundance. Or [0235] By adding a mixture of isotopes depleted of the majority isotope.

[0236] A 1.sup.st series was conducted to define the best procedures for preparing samples, based on analytical measurements of isotope ratios. The samples were white and red wines, Champagne, and a Cognac.

[0237] These marking tests were first performed on separate 10 ml wine samples, then reproduced on bottles. 68Zn isotope marking was applied to obtain a variation (doping) of 30% o and higher, as a function of the initial Zn concentration. The samples were solely diluted, or mineralised and diluted before analysis. The dilution factor was approximately 20 and Zn concentration close to 50 ppb.

TABLE-US-00002 Tests 68ZN 0.95 ppm Results Results Results in solution Volume 68/67Zn Volume 68/67 68/66 BA Alsace 59.8 μl 39.4‰ 48.2 μl 37.7‰ Riesling (48.262) M Bourgogne 56.8 μl 28.9‰ 60.2 μl 27.0‰ Aligoté (60.168) AR Muscadet 47.0 μl 26.8‰ 60.2 μl 26.1‰ (60.168) CR Côtes du 50.0 μl 31.4‰ 60.2 μl 30.8‰ Rhône (60.168) B1 Bordeaux 1 59.4 μl 29.7‰ 60.2 μl 28.1‰ (60.168) B2 Bordeaux 2 57.0 μl 28.4‰ 55.8 μl 28.7‰ (55.786) CM Champagne 33.4 μl 29.4‰ 26.9 Mercier (33.419) CBN Champagne 31.0 μl 29.4‰ 29.1 A. Bonnet (31.082) R1 Tain 1 61.8 μl 27.0‰ 26.9 (61.754) R2 Tain 2 68.6 μl 30.4‰ 30.1 (68.554) DDG1 Domaine des 49.4 μl 33.7‰ 30.9 Gardes 1 (49.344) DDG2 Domaine des 43.8 μl 26.8‰ 25.9 Gardes 2 (43.807) PSM Cognac 10.8 μl 92.5‰ High Eth = Prince St (10.861) Low [Zn] = Méran High ‰

[0238] Dilution of Wine Samples (without Mineralisation) for Analysis of Zn Isotope Ratios

TABLE-US-00003 0.5 M HNO3 + In Samples Wine 1 Measured (50 ppb in 10 ml) (ml) ppb concentration CM 0.899 9.101 ~51 ppb CBN 0.966 9.034 ~56 ppb R1 0.486 9.514 ~58 ppb R2 0.438 9.562 ~53 ppb DDG1 0.609 9.391 ~53 ppb DDG2 0.686 9.314 ~52 ppb PSM 2.765 7.235 Ethanol interference
0.5 M HNO.sub.3+In 1 ppb is the combination of an acid preparation composed of HNO.sub.3+an inorganic acid In (of HCL type in very small amount 1 ppb)

[0239] Results:

[0240] The marked samples were compared with their reference samples (non-marked wines) following the equation:

[00001]${\delta }_{\mathrm{Zn}}^{68}=\left[\frac{\left(68/{67}_{\mathrm{Marked}\mathrm{wine}}\right)}{\left(68/{67}_{\mathrm{Reference}\mathrm{Wine}}\right)}-1\right]*1000$

[0241] The analyses obtained with and without mineralisation globally showed the same results. Two test sessions were conducted. By default, liquids in principle do not need mineralisation for analysis, but to show the viability and coherency of results, we nevertheless verified liquid samples after mineralisation via an acid-based chemical preparation such as HNO.sub.3, HCL, H.sub.2O.sub.2 . . . ) allowing full solubility of the elements still present in the liquid.

[0242] 2.sup.nd series of tests performed on bottles:

[0243] These analyses were performed to test the mixing of a drop (14.8 μl) of marked solution in a bottle of wine and Champagne (75 cl). 68Zn isotopic marking was applied to obtain a variation of 30% o and higher.

TABLE-US-00004 Red wine test Champagne test Domaine des Gardes Brut de Noirs, A. Bonnet Zn concentration 1141.4 ng/ml 517.5 ng/ml Volume 250 14.8 μl 9.4 μl ppm .sup.68Zn .sup.68Zn quantity 3.516 μg 2.215 μg Wine (for 0.609 ml (50 ppb) 0.966 ml (50 ppb) dilution 10 ml) Sampling .sup.68Zn/.sup.67Zn δ.sup.68Zn Sampling .sup.68Zn/.sup.67Zn δ.sup.68Zn Natural 4.8786 4.8921 Glass 1 +10 min 4.9373 12.03‰ +15 min 5.6028 145.28‰  Glass 2 +10 min 4.9348 11.52‰ +15 min 5.0626 34.85‰ Glass 3 +10 min 4.9334 11.23‰ +15 min 5.0098 24.06‰ Glass 4 +2 h 5.0424 33.58‰ +1 h 4.9838 18.74‰ Last mixing +2 h 5.0606 37.31‰ +1 h 4.9819 18.36‰

[0244] 3.sup.rd series of tests: Measurement of standard deviation on unique codes

[0245] Analyses of isotopic ratios with ICP-MS can show variations in standard deviation over several analyses. To create a differentiating unique code, we tested several codes for the isotope ratios Zn, DZn (Zn depleted of one isotope) and Fe. These tests were performed on 10 ml aliquots of the same wine DDG1 for variations (doping) of 3, 5, 8, 10, 12, 15 and 30% o.

TABLE-US-00005 .sup.68Zn for 10 ml (0.5 .sup.68Zn for 10 .sup.68Zn for 75 measured Measured Zn .sup.68Zn tracer ppm) ml cl δ.sup.68Zn %.sub.o concentrations 0%.sub.o 46.27 ng/ml (0.41%) 3%.sub.o 9.4 μl  4.69 ng  351.57 ng 2.80 45.30 ng/ml (9,375) (0.48%) 5%.sub.o 15.6 μl  7.81 ng  585.96 ng 4.46 45.66 ng/ml (15.625) (0.60%) 8%.sub.o 25 μl 12.50 ng  937.53 ng 8.95 45.40 ng/ml (0.68%) 10%.sub.o 31.2 μl 15.63 ng 1171.91 ng 9.67 45.39 ng/ml (31.251) (0.72%) 12%.sub.o 37.6 μl 18.75 ng 1406.30 ng 12.36 46.01 ng/ml (37.50) (0.79%) 15%.sub.o 47.0 μl 23.44 ng 1757.87 ng 16.35 46.15 ng/ml (46.87) (0.99%) 30%.sub.o 46.88 ng 3515.73 ng

[0246] See FIG. 4.

[0247] Compared with the natural abundances of Zn, the 68ZnCl2 marker is highly enriched with 68Zn and depleted of isotopes 64, 66, 67 and 70 of Zn.

[0248] For the 67Zn/66Zn isotope ratio, the marker is non-observable. In the error bars, the results are the same.

[0249] For the 68Zn/67Zn isotope ratio, the values differ as a function of 68Zn marking. The two first values correspond to the DDG1 wine sample without marking. In the error bars, it will be easier to differentiate the 3‰ marking from the reference sample (not marked) with MC-ICP-MS.

[0250] Results of 57Fe Isotope Marking:

[0251] The isotopes analysed for our tests were 54Fe, 56Fe and 57Fe. 58Fe was not monitored on account of interference with 58Ni. 54Fe was also interfered by 54Cr.

[0252] For the 54Fe/56Fe ratio, the 57Fe isotope is not present and all the marking tests (5-10-15-20-25-30) can have the same error values. This is the case when the correction (54Cr) is applied to 54Fe. Without correction, these ratios have higher and differing values on account of the 54Ni signal.

[0253] Correction has no impact on the 57Fe/56Fe ratio. As with the Zn isotope ratios, distinguishing on 57Fe marking is possible for variations in marking of 5‰. For marking of 30‰ and higher, the error for Fe concentration is 1.5% RSD (Relative Standard Deviation, mean of isotopes 54, 56 and 57). For analysis of concentration, 56Fe is the recommended isotopic analysis, but 57Fe can also be analysed.

[0254] See FIGS. 5 to 10.

[0255] Both tests with the same DDG1 sample and the same quantity of marker allowed validation of reproducibility.

[00002]${\delta }_{\mathrm{Fe}}^{57}=\left[\frac{\left(57/{56}_{\mathrm{Marked}\mathrm{wine}}\right)}{\left(57/{56}_{\mathrm{Reference}\mathrm{Wine}}\right)}-1\right]*1000$

[0256] Example of Marking and Unique Encoding of Domaine Des Gardes (One 10 ml Sample and One 75 cl Bottle).

TABLE-US-00006 .sup.57Fe for 10 .sup.57Fe for 10 .sup.57Fe for 10 .sup.57Fe for 10 ml ml ml ml δ.sup.57Fe (%.) Tracer (4 ppm) (4 ppm) (4 ppm) (4 ppm) (mean)  3%. DGG1  10.4 μl  1.245 ng  93.406 ng (0.20%)  2.98 ± 1.30  5%.DGG1  17.4 μl  2.076 ng 155.676 ng (0.20%)  3.19 ± 1.14  8%. DGG1  27.8 μl  3.321 ng 249.082 ng (0.37%)  6.37 ± 0.11 10%. DGG1  34.6 μl  4.151 ng 311.352 ng (0.35%)  5.96 ± 4.40 12%. DGG1  41.6 μl  4.982 ng 373.622 ng (0.58%) 10.10 ± 0.08 15%. DGG1  52.0 μl  6.227 ng 467.028 ng (0.63%) 10.99 ± 0.42 30%. DGG1 103.8 μl 12.454 ng     9 ng (1.50%) 26.26 ± 0.10

[0257] By comparing the analyzed/measured mass spectrometry values with the data stored in the database of the unique codes, we can precisely determine the place of origin of a wine. Analysis of enriched or depleted Zinc markers and of Iron markers allows the origin to be obtained with precision on a local scale, whilst minimizing the number of analyses to be performed.

[0258] With regard to corrections and isotopic interferences, it is possible to proceed in the two following manners: [0259] Choice of a highly sensitive mass spectrometer, e.g. HR-ICP/MS Triple Quad combined with the use of helium.

[0260] The multi-element capacity and low detection limits of inductively coupled mass spectrometers, (ICP-MS) are major assets for the analysis of metals in trace form. However, the existence of polyatomic interferences can hamper this type of determination. The use of ICP-MS with a collision/reaction cell (CRC) allows such interference to be eliminated. Reactive gases are generally added but the use of a collision gas such as helium offers news prospects for the simultaneous elimination, with a single set of conditions, of all interferences in complex matrixes and of variable composition. [0261] Preparation of an isotopic chemical separation allowing solely the elements to be analyzed to be isolated/retained. This preparation varies according to the elements used.