13 C/ 12 C IRMS Analyses of Alcohol Beverages at the Alcohol and - - PowerPoint PPT Presentation

13C/12C 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

Alcohol and Tobacco Tax and Trade Bureau

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

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

13C/12C IRMS Analyses

• f Alcohol Beverages
• Probing fermented versus distilled

character or markers of beverage alcohol

• Determining agricultural sources of

alcohol in sakés

• Differentiating between bourbons and
• ther types of whiskeys
• Determining natural versus artificial

carbonation in wine

Probing Fermented Versus Distilled Character or Markers of Beverage Alcohol

Alcohol and Tobacco Tax and Trade Bureau

Fermentation Products

• Naturally produced

during fermentation:

– Methanol, acetaldehyde, ethyl acetate – Fusel oils

• n-propanol
• iso-butanol
• n-butanol
• amyl alcohol
• Detected using GC

– DB-WAX column, 30m x 0.53 mm, 1 µm film thickness – Hydrogen carrier gas

2.5 5 7.5 10 12.5 pA 100 200 300 400 500 600 FID1 A, (ALS031109\2009-03-11ALS\003B0401.D) 4.177 - Ethyl Acetate 4.392 - Methanol 7.935 - n-Propanol 9.179 - iso-Butanol 10.086 - n-Butanol 11.111 - Active Amyl 11.791

Alcohol and Tobacco Tax and Trade Bureau

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

Neat Wine

n-Propanol (37 ppm) Isobutanol? Unknown? Co-elution? n-Butanol? Amyl Alcohol (122 ppm) Unknowns

Alcohol and Tobacco Tax and Trade Bureau

Grape Wine Results

Alcohol and Tobacco Tax and Trade Bureau

Repeatability Issue

Determining Agricultural Sources of Alcohol in Sakés

Alcohol and Tobacco Tax and Trade Bureau

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

Plant Type δ 13C values (‰)* Examples

C3 (95% of plants are C3)

• 30 to -23

rice, barley, grape, sugar beet, molasses made from sugar beet, coconut, palm, peanut, plum, potatoes, rye, soybean, sunflower, wheat C4 (1% of plants are C4)

• 10

sugar cane, corn, millet, sorghum, molasses made from sorghum CAM

• 18 to -12**

vanilla, agave, cactus, pineapple

Photosynthesis and Carbon Isotopes

* These ranges are approximations. **Results in this range can also indicate a mixture of C3 and C4 plant origin alcohols.

• Different photosynthetic pathways lead to different

13C/12C ratios detectable by IRMS

Alcohol and Tobacco Tax and Trade Bureau

HS-GC-IRMS 13C/12C

• f 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

Example Chromatogram

Alcohol and Tobacco Tax and Trade Bureau

Sake Results

• 30.00
• 28.00
• 26.00
• 24.00
• 22.00
• 20.00
• 18.00
• 16.00
• 14.00
• 12.00
• 10.00

100 200 300 400 500

δ13C (‰) vs. VPDB Sample Number

Pure Saké Saké with Added Alcohol Suspect Saké Saké with Other Ingredients Rum Standard Value Vodka Standard Value Pure Saké/Added Alcohol Cutoff Line

Differentiating between Bourbons and Other Types of Whiskeys

Alcohol and Tobacco Tax and Trade Bureau

Bourbon Whiskey

Standard of Identity

Bourbon whiskey is whisky produced at not exceeding 160° proof from a fermented mash

• f 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

Whiskey Authentication

100 200 300 400 500 600 700

• 30
• 25
• 20
• 15
• 10
• 5

Amyl Alcohols (g/100L) abs. EtOH

δ13C(‰)

Straight Bourbon and Tennesse Canadian Irish Blended Scotch Single Malt Scotch

Determining Natural Versus Artificial Carbonation in Wine

Alcohol and Tobacco Tax and Trade Bureau

Tax Implications

• Sparkling Wines

– > 0.392 g CO2 / 100 mL

• Naturally Sparkling

– $3.40 / wine gallon

• Artificially Carbonated

– $3.30 / wine gallon

• Hard Cider

– Still wine

• $0.226 / wine gallon

– Naturally Sparkling

• $3.40 / wine gallon

– Artificially Carbonated

• $3.30 / wine gallon

Alcohol and Tobacco Tax and Trade Bureau

Ring Study

Sponsor

• MOU Partner DGCCRF

France’s General Directorate for Competition Policy, Consumer Affairs, and Fraud Control

– Francois Guyon, coordinator

• Inter-Laboratory ring test
• n CO2 ᵟ13C Ratio

Determination In Sparkling Beverages, published Feb. 2013 Participants

Alcohol and Tobacco Tax and Trade Bureau

Ring Study Results

Alcohol and Tobacco Tax and Trade Bureau

Database Results

Alcohol and Tobacco Tax and Trade Bureau

Thank You

• www.ttb.gov
• Any questions?
• Thank you!

Acknowledgements: Armen Mirzoian whiskey authentication Abdul Mabud and Jeffrey Ammann resources and support