Method for detecting origin of cosmetic-grade ethanol

Abstract

According to various aspects of the present disclosure, a method is provided for the traceability and source identification of cosmetic-grade ethanol. The method includes the step of measuring at least two stable isotope ratios.

Description

METHOD FOR DETECTING ORIGIN OF COSMETIC-GRADE ETHANOLCLAIM OF PRIORITY

[0001] This patent application claims the benefit of priority to French Application Serial No. 2403152, filed March 28, 2024, which is incorporated by reference herein in its entirety.BACKGROUND

[0002] Traditional ethanol employed in the perfume industry comes from agricultural crops such as sugar beet, com and sugar cane. In all cases, yeasts are used to ferment the sugars from the substrates and produce ethanol and byproducts. Subsequent separation from the yeast brew and distillation will ensure that the ethanol is extracted from all other nonvolatiles and volatile molecules alike. The result is a safe-to-use and more importantly neutral grade ethanol that can be used to formulate consumer products.

[0003] A different source of cosmetic-grade ethanol is synthetic ethanol. Synthetic ethanol is manufactured through a complex three stage process that ultimately produces a single grade of ethanol (DRAA - Double Rectified Absolute Alcohol) which is 99% pure.

[0004] Finally, the latest frontier in ethanol synthesis is carbon capture, whereby acetogenic bacteria are used to convert carbon emissions into ethanol. The potential for biologically fixating carbon that otherwise would end up in the atmosphere has great potential in reducing the impact of global warming. Since recently, ethanol has been produced industrially by fermenting carbon emissions (mainly carbon monoxide, carbon dioxide, and hydrogen) in tanks. Carbon emissions can be captured from industrial off-gases, cleaned up, compressed and injected into a fermentation tank. Acetogenic bacteria transform these off-gases into ethanol and by-products such as sulfur compounds. Further separation, distillation and dehydration produce a highly concentrated ethanol (>99%) to be used in the fuel industry. In order to produce a high purity alcohol for cosmetic and perfumery uses, further distillation steps (purification) are required. During the purification step, both heads, representing highly volatile materials, and tails, representing low volatile materials, are further reduced to achieve a neutral-grade alcohol. A crude-ethanol purification system may include a three-distillation column process. First an extractive distillation unit where water and ethanol are put in contact, and where low volatile impurities like acetaldehyde are removed. Then the purified ethanol from the extractive column may be fed into the rectifying column which has a series of trays, where the ethanol gets successively concentrated. A smallpart of heads can be removed from the top, whereas fossil oils (mainly propanol) are drawn off before the trays where the pure ethanol is concentrated. The final concentration of ethanol is achieved at this column. In the last step, a demethylizer column is used, whose task is to remove methanol.

[0005] Mitigating global warming to avoid environmental risks has become a strategic imperative for beauty companies reliant on natural resources to continue satisfying consumer demands. Consumers have become more sensitive to the environmental impact of the products they use and perceive climate change among the most important global issues today. Since ethanol can make up about 80% of a final cosmetic product, it is obvious that carbon capture ethanol represents an optimal ingredient to meet the consumer’s environmental expectations.

[0006] Against this background, there remains a need for a reliable method to enhance traceability and identification of cosmetic-grade ethanol, among others for quality control and for detecting counterfeit claims in commercial products.

[0007] In general terms, isotope fingerprint (or isotope signature) is the ratio of non- radiogenic stable isotopes, stable radiogenic isotopes, or unstable radioactive isotopes of particular elements in an investigated material. In isotope analysis the ratios of isotopes in a sample material are measured by isotope-ratio mass spectrometry against an isotopic reference material. The isotope fingerprints most commonly used in the food industry are 513C or13C / 12C, 515N or15N / 14N and 518O or18O / 16O.

[0008] On the other side, hydrogen isotope fingerprints are used for botanical origin detection of biofuels.SUMMARY OF THE INVENTION

[0009] The present invention is based on the observation that ethanol from different sources has a different isotope fingerprint.

[0010] More specifically, the present invention is based on the observation that the most discriminant parameter between agricultural-derived ethanol and carbon-captured ethanol is 513CVPDB. However, in the case of synthetic ethanol, bigger differences are found with hydrogen isotope signature.FIGURES

[0011] Figure 1. 513CVPDB [%o]and (D / H) I[ppm] for different mixtures of Agricultural-derived and Carbon-captured ethanol.DETAILED DESCRIPTION

[0012] Reference will now be made in detail to certain embodiments of the disclosed subject matter. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.

[0013] Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise. Likewise, the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise.

[0014] In this document, the terms “a,” “an,” or “the” are used to include one or more than one unless the context clearly dictates otherwise. The term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. The statement “at least one of A and B” or “at least one of A or B” has the same meaning as “A, B, or A and B.” In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section.

[0015] In the methods described herein, the acts can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously withina single operation, and the resulting process will fall within the literal scope of the claimed process.

[0016] The term “about” as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range and includes the exact stated value or range. The term “substantially” as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. The term “substantially free of’ as used herein can mean having none or having a trivial amount of, such that the amount of material present does not affect the material properties of the composition including the material, such that about 0 wt% to about 5 wt% of the composition is the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than or equal to about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less, or about 0 wt%.

[0017] The carbon-emissions alcohol distillate is a product obtained by fermentation of a carbon-emissions gas stream as a feedstock. The carbon-emission gas stream can include CO, CO2, H2, or a mixture thereof. A common feedstock is syngas.

[0018] The overall gas fermentation process can be broadly divided into four steps: (1) accumulation or generation of syngas; (2) gas pretreatment; (3) gas fermentation in a bioreactor; and (4) product separation.Generation of Syngas

[0019] The versatility of acetogenic bacteria to ferment syngas of diverse compositions means virtually any carbonaceous materials can be gasified to generate the feedstock. When gasification is utilized, the carbonaceous material reacts with steam and air at an elevated temperature (600-1000 °C) and high pressure (>30 bar) to form syngas of variable composition (depending on input and process parameters). Although a small amount of energy input is required to heat the incoming feedstock to gasification temperature at the beginning of the process, at steady-state the process is self-sustaining. Excess heat generated from gasification can be used to generate steam for product distillation and / or electricity. Depending on the type of gasifier, the starting material may be subjected to drying, commination (size reduction), chipping, pelletization, torrefaction, pyrolysis and / or pulverization prior to gasification. Defined by how the reactor brings about contact with the feedstock and reactive gas, there are four main gasifier configurations: fixed / moving bed, fluidized bed, entrained flow, and transport flow. Fluidized bed gasifiers are currently themost commonly used biomass gasifiers due to their ease of up-scaling, isothermal operation conditions and high feedstock conversion efficiencies.Gas Pretreatment

[0020] In addition to the main constituents CO, H2, CO2, input gas streams can also contain impurities such as particulates, tar, aromatics grouped as benzene, toluene, ethylene, xylenes (BTEX) and naphthalene, sulfur compounds such as hydrogen sulfide (H2S), carbonyl sulfide (COS), and carbon disulfide (CS2), halogens such as chlorine and hydrogen fluoride (HF), and other potentially inhibiting gases such as ammonia (NH3), nitric oxide and nitrogen dioxide (NOX), acetylene, oxygen (O2), reactive oxygen species (ROS), and hydrogen cyanide (HCN). These are generated for example during the gasification process, pyrolysis or manufacturing and can be present in fluctuating quantities. A complete understanding of impurity species, their concentration fluctuations based on syngas input, process variables as well as installed treatment capacity is critical to maintain optimal productivity. In addition, monitoring impurity accumulation patterns within the fermentation is required to determine biological tolerance levels and the minimal inhibitory concentration (MIC) for designing economical treatment capacity. Understanding the effect of impurities could save treatment costs, however failure to do so can cause delays reaching full scale production capacity as shown in one large-scale syngas fermentation endeavor.

[0021] Even with gas-fermenting microorganisms' abilities to grow in the presence of low levels of impurities, some impurities necessitate near complete removal from an operational, biological and / or product specificity perspective. Particulates can be removed by cyclone separators and filters. Tars can be condensed and removed by quenching hot syngas, or, alternatively, can be reformed by heating at 800-900°C using olivine, dolomite, and nickel compounds as catalysts, generating additional syngas.

[0022] Many contaminants including BTEX are lipophilic compounds that readily dissolve in the cytoplasmic membrane affecting membrane fluidity. Although polycyclic aromatics do not readily dissolve in aqueous phase, they can accumulate and negatively affect operations. Removal technologies for aromatics from gas are commercially available, and techniques to improve efficiency are still being reported. Ch's toxicity above microoxic levels is particularly critical during inoculation of a bioreactor, when little biomass has accumulated to withstand introduction of aerobic conditions. O2 can be tolerated in certain microoxic conditions. C. Ijungdahlii has been shown to detoxify O2 and ROS (likely via rubrerythrin and hydrogen peroxidases) and ethanol formation could actually be stimulated by exposure toO2 (likely due to changes in AOR activity and co-factor metabolism). O2 can be removed by passing the gas over various metal catalysts such as Pt, Pd, and Cu. Using biological coculture for O2 removal has also been described. Sulfur-containing impurities (e.g., H2S and COS) can poison the metal-based catalysts and require prior removal despite the microorganisms' ability to grow in their presence.

[0023] Acetylene, NOXand HCN are considered particularly troublesome as they are known to inhibit enzymes responsible for initial harvesting of energy from syngas. Cyanide binds to CODH, a key enzyme of the WLP. NO is a non-competitive inhibitor of hydrogenase activity while acetylene reversibly inhibits hydrogenases, which reduce ferredoxin for use in redox reactions. INEOS Bio has identified and reported HCN as a key contaminant that needs treatment from operation of their Vero Beach plant.Gas Fermentation

[0024] Treated syngas is next cooled and compressed then sparged into a bioreactor containing the gas-fermenting microorganisms in an aqueous medium. The fermenting microorganisms can be acetogenic bacteria or Ci-fixing microorganisms, which have been demonstrated to convert gases containing CO2, CO, and / or H2 into products such as ethanol and isopropanol.

[0025] For example, a microbial biomass including the acetogenic bacteria of CI- fixing bacteria comprises at least one suitable microorganism used as the biocatalyst of the fermentation process. For example, the microorganism may be selected from Escherichia coli, Saccharomyces cerevisiae. Clostridium acelohiilylicum. Clostridium heijerinckii. Clostridium sacchar butyr icum, Clostridium saccharoperbutylacetonicum, Clostridium bulyricum. Clostridium diolis. Clostridium kluyveri, Clostridium paslerianium. Clostridium novyi, Clostridium difficile, Clostridium ihermocellum, Clostridium cellulolylicum, Clostridium cellulovorans, Clostridium phytofermentans, Lactococcus laclis. Bacillus subtilis, Bacillus licheniformis, Zymomonas mobilis, Klebsiella oxyloca, Klebsiella pneumonia, Corynebacterium glutamicum, Trichoderma reesei, Cupriavidus necator, Pseudomonas putida, Lactobacillus plantar um, and Methylobacterium extorquens. In certain instances, the microorganism may be a Cl -fixing bacterium selected from Acetobacterium woodii, Alkalibaculum bacchii, Blautia producta, Butyribacterium methylotrophicum, Clostridium aceticum, Clostridium autoethanogenum, Clostridium carboxidivorans, Clostridium coskatii, Clostridium drake i, Clostridium formicoaceticum, Clostridium ljungdahlii, Clostridium magnum, Clostridium ragsdalei, Clostridium scatologenes,Eubacterium limosum, Moorella thermautotrophica, Moorella lhermoacelica, Oxobacter pfennigii, Sporomusa ovata, Sporomusa silvacetica, Sporomusa sphaeroides, and Thermoanaerobacter kiuvi. In a specific embodiment, the microorganism is a member of the genus Clostridium. In certain instances, the microorganism is Clostridium autoethanogenum.

[0026] There are a multitude of variables to account for during gas fermentation. Bioreactor design, agitation, gas composition and supply rate, pH, temperature, headspace pressure, oxidation-reduction potential (ORP), nutrients, and amount of foaming in the bioreactor all can contribute to the goal of improving selectivity and yield of the desired product (e.g., ethanol and butanol) as discussed below.

[0027] One major obstacle immediately present in gas fermentation is the low solubility of the gaseous substrates and combined with an efficient transfer of their masses into the liquid media. CO, H2, and CO2 are soluble to approximately 28 mg / L, 1.6 mg / L, and 1.7 g / L (293 K, 1 atm), respectively, compared to 900 g / L for glucose, a prevalent substrate for traditional fermentations. As gas-fermenting microorganisms consume the gas, substrate availability can become rate-limiting. Increasing flow of the substrate gas can lead to decreased yields of product per mole of carbon fed to the reactor, making reactor design and operation crucial. Continuous stirred tank reactors (CSTR) offer excellent mixing and homogenous distribution of gas substrates to the microorganisms and are most commonly employed at laboratory scale. However, the high power per unit volume required to drive the stirrer renders commercial scale operation economically challenging. Therefore, other less energy-demanding bioreactor designs such as bubble column, loop, and immobilized cell columns and their specific volumetric mass-transfer coefficients (k r a) that describes the efficiency of which a gas can be delivered to a bioreactor have been investigated intensively and reviewed elsewhere.

[0028] Next to gas availability determined by reactor ki.a, the ratio and partial pressures of CO, H2, and CO2 also influence the product yield, production rate, and selectivity of a gas fermentation. CO and H2 are sources of electrons / reducing equivalents for reducing CO2 in the WLP and generating reduced products over acid products (e.g., ethanol vs. acetate). This product profile reflects the organism's requirement to maintain an internal energy balance that favors growth and is directly influenced by the gas composition and availability. As an example, productivity with C. Ijungdahlii was improved from 38.4 g / L / d at 1 atmosphere to 360 g / L / d at 6 atmospheres. Another strategy to control the product profile is lowering the pH of the fermentation culture. This pH change can lead to a (reversible) shiftfrom acidogenesis to solventogenesis allowing an increased production of ethanol and other highly reduced products.

[0029] Besides gas, medium composition also affects product yield and selectivity. Nutrient optimization has proven to be a process and species-specific requirement. Media optimizations have been conducted for many acetogens including C. autoethanogenum, C.vitamins and metals such as zinc, nickel, selenium, and tungsten, required as cofactors for certain enzymes in the central metabolism, are required for bacterial growth and affect product selectivity. For an industrial process it is critically important to keep media cost low, for example by eliminating yeast extract requirements, recycling nutrients and usage of industrial-grade bulk chemicals.Product Separation

[0030] Finally, product separation is required to separate the desired metabolic product (ethanol) from the fermentation broth. Distillation systems are common to separate lower boiling point products such as ethanol and acetone, but this is considered energy- intensive (and therefore potentially expensive), especially for low concentration products and products with high boiling points (e.g., butanediol). Other technologies to separate fermentation products from broth include liquid-liquid extraction, gas stripping, adsorption, perstraction, pervaporation, and vacuum distillation Each of these separation technologies has their own benefits and drawbacks, including potential fouling of membranes (perstraction and pervaporation) and substrate removal (gas stripping and liquid-liquid extraction). Liquidliquid extraction is also an option for removing acetate from the fermentation broth of gasfermenting acetogens.EXAMPLES

[0031] Various embodiments of the present disclosure can be better understood by reference to the following Examples which are offered by way of illustration. The present disclosure is not limited to the Examples given herein.Test Method 1 : Determining isotope fingerprints of ethanol

[0032] The analysis of stable carbon and hydrogen isotope ratios was done according to Elemental Analysis Isotope Ratio Mass-Spectrometry (“EA-IRMS”) and Specific Natural Isotope Fractionation studied by Nuclear Magnetic Resonance (SNIF-NMR) according toOIV-MA-BS-23 R2009 from the compendium of international methods of analysis of spirituous beverages of vitivini cultural origin.

[0033] The carbon isotope ratio (513C) is reported according to Vienna Pee Dee Belemnite (VPDB) standard ( “Reference and intercomparison materials for stable isotopes of light elements’", International Atomic Energy Agency, 1995) as

[0034] The deuterium isotope ratio is reported as D / H of ethanol isotopomer I (CH2D CH2OH) and II (CH3CHDOH) in parts per million (ppm). R is equal to 2(D / H)II / (D / H)I, which expresses the relative distribution of deuterium in molecules I and II.

[0035] The reported stable isotope ratios represent the mean value of the sample’s replicate analysis (n>2), accepted when the standard deviation of the sample’s replicate analysis per stable isotope ratio is for 513CVPDB <0.4 (D / H)I <1,1 (D / H)II <3,2.Test Method 2: Sensory testing - Degree of Difference

[0036] At the testing facility, samples of the compositions and the controls are applied to glass slides. Twenty-seven external panelists screened & trained were recruited for this evaluation. After five minutes, slides are presented randomized, coded with three-digit numbers. Panelists start the evaluation with an identified reference: the standard alcohol formula. Then, they receive either a control sample (blind reference) or the test sample. They were asked to rate the degree of difference with the identified reference. Difference from control was evaluated from 0 - 10 scale, where 0 = no difference and 10 = very large difference. Statistical analysis was with Duncan’s post hoc analysis. Twelve fragrance compositions from varying olfactive families were used for the test.Test Method 3: Ethanol Olfactive Evaluation and Shelf-Life evaluation

[0037] At least 3 expert evaluators were selected for these experiments. Panelists are asked to give a score on a scale of 1 to 5 for changes in the perceived olfactive profile change for the test compositions versus the controls according to the odor grading scale, where 1 = total difference in the olfactive profile from the control, and 5 = unchanged olfactive profile. Blotters are dipped in the samples and immediately after they are given to the evaluators. Eleven commercial fragrance products from varying olfactive families were used for the test. For ethanol evaluation, the control samples were internal ethanol standards approved due toits neutral-grade quality. For shelf-life evaluation, the control sample is the same sample that was kept refrigerated at 4 °C.Example 1 : Comparison of purified carbon-captured ethanol vs. agricultural-based ethanol standards

[0038] The purified carbon-captured ethanol was compared by olfactive evaluation on blotter against agricultural-derived standards that were previously approved for fragrance use. Furthermore, evaluations were done on an undenatured and denatured carbon-captured ethanol to understand if there was any difference. Results can be seen below in Table 1 showing that overall, purified carbon-captured ethanol is comparable to both internal standards. Repeating comments indicate that the carbon-based ethanol is perceived having less lift and being less dusty, indicating lower pungency. Some of the notes associated with agri cultural -derived ethanol like woody, sweetness, earthy and cardboard are also absent. These results show that the purification process was efficient in removing the unpurified carbon-captured ethanol off-notes.Table 1. Olfactive evaluation of purified carbon-captured ethanol compared to two agricultural-derived ethanol standards

[0039] To evaluate if any off-note residues remained after ethanol evaporation, a olfactive degree of difference between traditional agricultural-derived ethanol and carbon- captured ethanol. Twelve commercial fragrances from different families were evaluated by a panel of sensory experts (Table 2). For all twelve candidates, no significant difference was detected between those composed with agricultural-derived ethanol or carbon-captured ethanol.Table 2. Degree of difference of Carbon-Captured Ethanol vs. Standard Ethanol from Agricultural OriginExample 2: Effect on shelf life of the carbon-captured ethanol-containing fragrances vs. reference products containing agricultural-derived ethanol

[0040] Impurities can have an impact on fragrances beyond the initial olfactive signature if their presence contributes to catalyzing degradation reactions of the fragrance or reacts with the fragrance.

[0041] Table 3 shows the effect on shelf life of the carbon-captured ethanol- containing fragrances and the reference products containing agricultural-derived ethanol. Most compositions degrade in a similar manner, when compared against their standards. When comparing products containing both ethanol origins, evaluators perceived seven out of twelve formulas as better for those containing carbon-emissions-based ethanol, whereas five were equivalent. Further analyses to explain those differences were done by quantifying the oxidative markers with GC-MS. In the case of composition 1,5, 6, 9, 11, and 12, the levels of Diethylacetal Acetaldehye (“DEAA”) were reduced in ranges from 42-75% for those formulas containing carbon-emissions-based ethanol. Additionally, the level of BHT, a well- known antioxidant added in fragrances, remained 32% and 24% higher in composition 5 and 6 respectively, indicating less oxidation. DEAA is a product generated by reactions in ethanol which brings a moldy, grappa note - considered unpleasant. In the case of composition 6, even though expert panelists considered it comparable olfactively, the slightly yellower aspect in the sample formulated with agri cultural -derived ethanol and higher oxidative markers after 3 weeks and 8 weeks (data not shown), indicated more oxidation. Similar results were found for composition 9 where samples formulated with agricultural ethanol were slightly pinker, and more oxidized after 3 weeks and 8 weeks. Other oxidation markerslike Galaxidone, and Linalool Oxide, present at higher quantities in the products formulated with the agricultural-derived ethanol, are product of oxidation.Table 3. Evaluation of olfactive character over shelf life and oxidative markersExample 3: Identification of Ethanol Origin by Isotope Ratio

[0042] The carbon and deuterium isotope ratios were analyzed for ethanol samples from different origins.

[0043] The results in Table 4 show that carbon-captured, synthetic, and agricultural- derived ethanol have distinct carbon and deuterium isotopes ratios. The most discriminant parameter is 513CVPDB between carbon-captured ethanol and the other ethanol origins. However, in the case of synthetic ethanol and the rest of the alcohol origins, bigger differences are found in (D / H)I and (D / H)II. To our knowledge, this is the first time that carbon-captured ethanol is analyzed using isotope ratio measurements.Table 4. Isotope signature of ethanol samples from different originsExample 4: Calculation of percentage of carbon-captured ethanol inside a mixture

[0044] In order to understand if carbon-captured ethanol can be detected at low levels in a mixture, the isotope ratio of several known mixtures of a C3-plant ethanol and carbon- captured ethanol were analyzed. From the results of Table 5 and Figure 1, the more carbon- captured ethanol there is in a mixture, the higher the values of (D / H)I whereas the opposite happens to 513C. Linear regression lines could be drawn for these two, showing a similar prediction ability in terms of R2-value. This however is greatly influenced by the 100% carbon-captured ethanol sample, since mixtures are skewed towards the lower percentages of carbon-captured ethanol in samples. When removing this sample, 513C is a better predictor (R2=0.965) versus (D / H)I (R2=0.898). These results show it is possible to detect the percentage of carbon-captured in a mixture from 1%. (D / H)II was the least discriminant predictor, followed by R [2x (D / H)II / (D / H)I],Table 5 Isotope Ratio for different mixtures of Agricultural-derived and Carbon-captured ethanol

Claims

CLAIMS1. A method for the traceability and source identification of cosmetic-grade ethanol, the method comprising the step of measuring at least two stable isotope ratios.

2. The method of embodiment 1, wherein the stable isotope ratios are 1) 513C and 2) (D / H)I.

3. The method of any of embodiments 1 or 2, wherein if 513C is in the range of about - 32 to about -50 %o, most preferably from -40 to -45 %o, relative to the VPDB standard and (D / H)I is less than 120 ppm, the ethanol is of carbon-capture origin.

4. The method of any of embodiments 1 or 2, wherein if 513CVPDB is in the range of about -32 to about -50 %oVPDB, most preferably from -40 to -45 %oVPDB, and (D / H)I is less than 110 ppm, the ethanol is of carbon-capture origin.

5. The method of any of embodiments 1 or 2, wherein if 513C and / or (D / H)I used to predict the amount of carbon-captured ethanol in a mixture of ethanol’s from different origins.

6. The method of embodiment 3, wherein if (D / H)Iis higher than about 120 ppm the ethanol is of synthetic origin.

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