C/ C IRMS Analyses of Alcohol Beverages at the Alcohol and ... · 13C/12C IRMS Analyses of Alcohol...
Transcript of C/ C IRMS Analyses of Alcohol Beverages at the Alcohol and ... · 13C/12C IRMS Analyses of Alcohol...
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 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
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)
4.1
77 -
Eth
yl A
ceta
te 4
.392
- M
etha
nol
7.9
35 -
n-P
ropa
nol
9.1
79 -
iso-
Buta
nol
10.
086
- n-
Buta
nol
11.
111
- Ac
tive
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 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
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
0 100 200 300 400 500
δ13C
(‰) v
s. V
PDB
Sample Number
Pure SakéSaké with Added AlcoholSuspect SakéSaké with Other IngredientsRum Standard ValueVodka Standard ValuePure 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 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
Whiskey Authentication
0
100
200
300
400
500
600
700
-30 -25 -20 -15 -10 -5
Amyl Alcohols (g/100L) abs. EtO
H
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 on 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