Quantifying the Biobased Content of Materials Using ASTM-D6866 ASTM-D6866-08 Standard Test Method for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples using Radiocarbon Analysis Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
What is “Biobased” ? Premise: Use less petroleum Renewably Sourced Carbon US Department of Agriculture’s definition: Total Organic Carbon � ASTM-D6866 results are to be consistent with this definition � Mass of component is factored out � A single value is applicable across industries � Carbonates of natural mineral origin are to be excluded Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
Nature has embedded a “carbon tracer” related to the carbon source Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
Radiocarbon ( 14 C, carbon-14 ) It’s a naturally occurring isotope. It’s in all recent plant and animals . It’s absent in petrochemicals. ASTM D6866 measures it. Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
Radiocarbon is a ubiquitous in all living things. But it doesn’t stick around. It decays away at a known rate such that after being removed from a respiring system, it’s all gone by 50,000 years. Ergo….petroleum, petrochemicals, coal,and natural gas don’t have any radiocarbon whereas biomass and plant feedstocks do. Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
The Radiocarbon Cycle Nitrogen + cosmic radiation 14 C Decays 14 C (T ½ ~ 5700 yrs) 14 CO 2 On-going Plant Respiration Animals eat the plants People eat the animals People eat the plants Animals eat animals Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
0 50,000 yrs Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
ASTM-D6866 is a standardization of radiocarbon dating methods used by archaeologists to determine the age of fossils. Methods that have been in use for 60 years (mature technology) Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
If it were 100% petroleum derived If it were 50 % corn-based & 50% petroleum derived Regardless of the percentage of total carbon in the product 0 50,000 yrs Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
and being a mature industry . . . � Expertise � Laboratories � Well known sources of error � Supply Lines � Venders � Instrumentation � Raw materials Complete pre-existing infrastructure Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
Two practical methods of analysis Method B AMS (Accelerator Mass Spectroscopy) Routine by the 1980s Plastic CO 2 Reduced to AMS Graphite Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
Two practical methods of analysis Method C Benzene Synthesis Routine by 1960s Plastic CO 2 Lithium Carbide Acetylene Benzene LSC Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
Precision 100.0% 1.080239 1.069534 -0.00537 -0.00534 -0.00535 0.5% Typical Counting Errors (1 sigma - relative) 93.0% 0.995033 1.004992 0.004967 0.004992 0.00498 0.5% 87.4% 0.934986 0.944344 0.004667 0.004691 0.004679 0.4% 82.1% 0.878563 0.887357 0.004386 0.004408 0.004397 0.6% 0.4% 72.5% 0.775727 0.783491 0.003872 0.003892 0.003882 0.4% 0.5% 64.0% 0.684927 0.691783 0.003419 0.003436 0.003428 0.3% 56.5% 0.604756 0.610809 0.003019 0.003034 0.003026 0.3% 0.4% 49.9% 0.533969 0.539313 0.002666 0.002679 0.002672 0.2% a m 44.1% 0.471467 0.476186 0.002354 0.002365 0.002359 0.2% ig 0.3% 1 S 38.9% 0.416282 0.420448 0.002078 0.002088 0.002083 0.2% 34.4% 0.366185 0.372623 0.003205 0.003233 0.003219 0.3% 0.2% 30.3% 0.323323 0.329008 0.00283 0.002855 0.002842 0.3% 26.8% 0.285123 0.290859 0.002854 0.002882 0.002868 0.3% 0.1% 23.7% 0.251123 0.257454 0.003146 0.003185 0.003165 0.3% 0.0% 20.9% 0.221177 0.227885 0.003329 0.003379 0.003354 0.3% 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% 18.4% 0.195288 0.201211 0.002939 0.002983 0.002961 0.3% 16.3% 0.172001 0.178102 0.003024 0.003077 0.003051 0.3% Biobased Content 14.4% 0.151868 0.157255 0.00267 0.002717 0.002693 0.3% Total Combined Error based on USDA Program Testing Data is ~ 2-3 % absolute (Methods B and C) Analytical error on 14C /12C ratio = 0.1 – 0.6 % RDS ASTM-D6866 cites +/- 3 % absolute error on each result Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
Reporting An “Easy” Visual Easy Inter-comparison Instinctively Obvious Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
Considerations in using ASTM-D6866 things to remember All carbon components must be either fossil or contemporary (respiring carbon w/in last 10 years) The reported result will be unique to the actual material analyzed Ensure a representative sample is analyzed Consider the homogeneity of your product Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
Considerations in using ASTM-D6866 things to remember If carbonates of natural mineral origin account for > 3% of the total carbon in the product, it must be subtracted out of the “Biobased Content”. This is going to require a 2 nd analysis of the same material Just about anything with carbon in it can be analyzed Difficult materials : high alkalinity, high acidity, high sulfur, high water content – let the lab know Knowing the % biobased content of each component, the % carbon within each component, and the fraction of the component within the product, you can predict the biobased content Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
Considerations in using ASTM-D6866 things to remember MARKETING PERSPECTIVE 50 % biobased also means 50% less petroleum carbon. – consider this in the marketing of your biobased products “This product contains 50% less petroleum carbon than our previous formulas” � Immediately understood by the public � Positive public image and reception � Brings value to your assemblers, distributors and retailers Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
Considerations in using ASTM-D6866 things to remember LEGAL PERSPECTIVE – PRODUCT DEFENSE An ASTM-D6866 analysis is routine, but complex – it is a “one of measurement” If you are doing R&D or product development, generally one measurement is fine. If you are submitting materials to the USDA’s BioPreferred Program or other certification, we recommend 2 per material for better credibility and averaging. If you are doing any kind of product discovery, product market protection, or purpose otherwise that may entail commercial or legal repercussions, we recommend 3-4 analyses per material. Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
Working Examples : Surprises The manufacturer submitted 3 samples Radiocarbon Dating Results were . . . Product A 69 % Biobased Product B 78 % Biobased Product C 70 % Biobased After the analyses, the manufacturer informed the lab that A, B, & C were all the same product and an error must be present in the result for Product B A B C ASTM-D6866 determined the biobased content & revealed a quality control issue. Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
USDA BioPreferred Program Two Programs: • Federal Procurement – Mandatory purchasing of biobased products by government agencies – Biobased minimums enforced for each product category – ASTM D6866 used to determine if products meet minimums • BioPreferred Label – Starting early 2010 – Consumer product label – 51% or higher (unless category has minimum in procurement program) – Biobased % listed on label – ASTM D6866 used to determine % More information: www.biopreferred.gov Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
WWW.BETALABSERVICES.COM Beta Analytic Limited Beta Analytic Inc. The London BioScience 4985 SW 74 Court Innovation Centre Miami, Florida 33155 2 Royal College Street USA London NW10NH United Kingdom Tel: (1) 305 662 7760 Fax: (1) 305 663 0964 Tel: (44) 207 617 7490 Info@betalabservices.com Fax: (44) 207 160 5350 Info@betalabservices.com Verification of Biogenic Carbon / Carbon-neutral CO 2 www.betalabservices.com
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