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13 C/ 12 C IRMS Analyses of Alcohol Beverages at the Alcohol and Tobacco Tax and Trade Bureau (TTB) Amanda Smith, Alcohol and Tobacco Tax and Trade Bureau June, 2014 TTB Mission TTBs mission is to collect the taxes on alcohol,


  1. 13 C/ 12 C IRMS Analyses of Alcohol Beverages at the Alcohol and Tobacco Tax and Trade Bureau (TTB) Amanda Smith, Alcohol and Tobacco Tax and Trade Bureau June, 2014

  2. TTB Mission • TTB’s mission is to collect the taxes on alcohol, tobacco, firearms, and ammunition; protect the consumer by ensuring the integrity of alcohol products; and prevent unfair and unlawful market activity for alcohol and tobacco products. Alcohol and Tobacco Tax and Trade Bureau

  3. IRMS Systems IRMS #1 • CE Elantech EA • Trace Ultra GC • LEAP Autosampler • GCCIII and ConFlo IV • Delta V Plus IRMS IRMS #2 • Gasbench II • Trace Ultra GC • TriPlus Autosampler • GC Isolink • ConFlo IV • Delta V Plus IRMS Alcohol and Tobacco Tax and Trade Bureau

  4. 13 C/ 12 C IRMS Analyses of Alcohol Beverages • Probing fermented versus distilled character or markers of beverage alcohol • Determining agricultural sources of alcohol in sakés • Differentiating between bourbons and other types of whiskeys • Determining natural versus artificial carbonation in wine Alcohol and Tobacco Tax and Trade Bureau

  5. Probing Fermented Versus Distilled Character or Markers of Beverage Alcohol

  6. Fermentation Products • Detected using GC • Naturally produced during fermentation: – DB-WAX column, 30m x 0.53 mm, 1 µm film – Methanol, thickness acetaldehyde, ethyl – Hydrogen carrier gas acetate FID1 A, (ALS031109\2009-03-11ALS\003B0401.D) – Fusel oils pA 11.111 - Active Amyl 4.392 - Methanol 600 • n-propanol 9.179 - iso-Butanol 500 • iso-butanol 400 • n-butanol 4.177 - Ethyl Acetate 7.935 - n-Propanol 300 10.086 - n-Butanol • amyl alcohol 200 100 11.791 Alcohol and Tobacco Tax and Trade Bureau 2.5 5 7.5 10 12.5

  7. Distilled Scotch 935.48 sec -30.88 + 0.13‰ not detected not detected 698.27 sec -31.81 + 0.20‰ 556.36 sec -24.85 + 0.19‰ 485.09 sec = backflush bump. Headspace ethanol = -27.34 + 0.06‰ Alcohol and Tobacco Tax and Trade Bureau

  8. Neat Wine Amyl Alcohol (122 ppm) Isobutanol? Unknowns Unknown? Co-elution? n-Propanol n-Butanol? (37 ppm) Alcohol and Tobacco Tax and Trade Bureau

  9. Grape Wine Results Alcohol and Tobacco Tax and Trade Bureau

  10. Repeatability Issue Alcohol and Tobacco Tax and Trade Bureau

  11. Determining Agricultural Sources of Alcohol in Sakés

  12. Collect the Revenue • Saké is taxed as a beer – $18 per barrel (31 US liquid gallons) • Saké which contains alcohol produced by distillation is taxed as a distilled spirit – $13.50 per proof gallon • 7 times higher tax rate per US liquid gallon for a 15% ABV saké Alcohol and Tobacco Tax and Trade Bureau

  13. Photosynthesis and Carbon Isotopes • Different photosynthetic pathways lead to different 13 C/ 12 C ratios detectable by IRMS δ 13 C values (‰)* Plant Type Examples rice , barley, grape, sugar beet, C3 molasses made from sugar beet, (95% of plants -30 to -23 coconut, palm, peanut, plum, potatoes, are C3) rye, soybean, sunflower, wheat C4 sugar cane , corn, millet, sorghum, (1% of plants -10 molasses made from sorghum are C4) CAM -18 to -12** vanilla, agave, cactus, pineapple * These ranges are approximations. **Results in this range can also indicate a mixture of C3 and C4 plant origin alcohols. Alcohol and Tobacco Tax and Trade Bureau

  14. HS-GC-IRMS 13 C/ 12 C of Ethanol • Standards – Rum and Vodka standardized in relation to Vienna-Pee Dee Belemnite (VPDB) • Rum: -10.98 ‰, C4 • Vodka: -27.53‰, C3 • Samples – Alcohol beverages, above ~20% ABV are diluted to ~20% with water – 200 µL in a 2 mL autosampler vial, triplicate headspace injections (standards and samples) Alcohol and Tobacco Tax and Trade Bureau

  15. Example Chromatogram Alcohol and Tobacco Tax and Trade Bureau

  16. Sake Results -10.00 -12.00 Pure Saké -14.00 δ13C ( ‰) vs. VPDB Saké with Added Alcohol -16.00 Suspect Saké Saké with Other Ingredients -18.00 Rum Standard Value Vodka Standard Value -20.00 Pure Saké/Added Alcohol Cutoff Line -22.00 -24.00 -26.00 -28.00 -30.00 0 100 200 300 400 500 Sample Number Alcohol and Tobacco Tax and Trade Bureau

  17. Differentiating between Bourbons and Other Types of Whiskeys

  18. Bourbon Whiskey Standard of Identity Bourbon whiskey is whisky produced at not exceeding 160° proof from a fermented mash of not less than 51 percent corn and stored at not more than 125° proof in charred new oak containers. 27 CFR § 5.22 Alcohol and Tobacco Tax and Trade Bureau

  19. Whiskey Authentication 700 Straight Bourbon 600 and Tennesse 500 Amyl Alcohols (g/100L) abs. EtOH 400 Single Malt Scotch 300 200 Irish Blended Scotch 100 Canadian 0 -30 -25 -20 -15 -10 -5 δ13C(‰) Alcohol and Tobacco Tax and Trade Bureau

  20. Determining Natural Versus Artificial Carbonation in Wine

  21. Tax Implications • Hard Cider • Sparkling Wines – Still wine – > 0.392 g CO 2 / 100 mL • $0.226 / wine gallon • Naturally Sparkling – Naturally Sparkling – $3.40 / wine gallon • $3.40 / wine gallon • Artificially Carbonated – Artificially Carbonated – $3.30 / wine gallon • $3.30 / wine gallon Alcohol and Tobacco Tax and Trade Bureau

  22. Ring Study Sponsor Participants • MOU Partner DGCCRF France’s General Directorate for Competition Policy, Consumer Affairs, and Fraud Control – Francois Guyon, coordinator • Inter-Laboratory ring test on CO 2 ᵟ 13C Ratio Determination In Sparkling Beverages, published Feb. 2013 Alcohol and Tobacco Tax and Trade Bureau

  23. Ring Study Results Alcohol and Tobacco Tax and Trade Bureau

  24. Database Results Alcohol and Tobacco Tax and Trade Bureau

  25. Thank You • www.ttb.gov • Any questions? • Thank you! Acknowledgements: Armen Mirzoian whiskey authentication Abdul Mabud and Jeffrey Ammann resources and support Alcohol and Tobacco Tax and Trade Bureau

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