Quantifying the Biobased Content of Materials Using ASTM-D6866 - - PowerPoint PPT Presentation
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 /
ASTM-D6866-08
Standard Test Method for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples using Radiocarbon Analysis
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What is “Biobased” ? US Department of Agriculture’s definition:
ASTM-D6866 results are to be consistent with this definition Carbonates of natural mineral origin are to be excluded Mass of component is factored out Renewably Sourced Carbon Total Organic Carbon A single value is applicable across industries
Premise: Use less petroleum
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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.
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The Radiocarbon Cycle
Nitrogen + cosmic radiation
14C 14CO2
14C Decays
(T ½ ~ 5700 yrs) On-going Plant Respiration
Animals eat the plants Animals eat animals People eat the animals People eat the plants
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50,000 yrs
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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)
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50,000 yrs
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
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Complete pre-existing infrastructure
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Two practical methods of analysis
Routine by the 1980s Reduced to Graphite CO2 Plastic
Method B AMS
(Accelerator Mass Spectroscopy)
AMS
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Two practical methods of analysis
Routine by 1960s Acetylene Benzene Lithium Carbide Plastic CO2
Method C Benzene Synthesis
LSC
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100.0% 1.080239 1.069534
0.5% 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 0.4% 72.5% 0.775727 0.783491 0.003872 0.003892 0.003882 0.4% 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% 49.9% 0.533969 0.539313 0.002666 0.002679 0.002672 0.2% 44.1% 0.471467 0.476186 0.002354 0.002365 0.002359 0.2% 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% 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% 23.7% 0.251123 0.257454 0.003146 0.003185 0.003165 0.3% 20.9% 0.221177 0.227885 0.003329 0.003379 0.003354 0.3% 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% 14.4% 0.151868 0.157255 0.00267 0.002717 0.002693 0.3%
Typical Counting Errors (1 sigma - relative)
0.0% 0.1% 0.2% 0.3% 0.4% 0.5% 0.6% 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Biobased Content 1 S ig m a
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
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Reporting Easy Inter-comparison An “Easy” Visual Instinctively Obvious
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Ensure a representative sample is analyzed Consider the homogeneity of your product The reported result will be unique to the actual material analyzed All carbon components must be either fossil or contemporary (respiring carbon w/in last 10 years)
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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 2nd 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
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“This product contains 50% less petroleum carbon than our previous formulas”
50 % biobased also means 50% less petroleum carbon. – consider this in the marketing of your biobased products
MARKETING PERSPECTIVE
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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. 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 R&D or product development, generally one measurement is fine. An ASTM-D6866 analysis is routine, but complex – it is a “one of measurement”
LEGAL PERSPECTIVE – PRODUCT DEFENSE
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The manufacturer submitted 3 samples
Radiocarbon Dating Results were . . . 69 % Biobased Product A 78 % Biobased Product B 70 % Biobased Product C 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 B A C ASTM-D6866 determined the biobased content & revealed a quality control issue.
Working Examples : Surprises
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– Mandatory purchasing of biobased products by government agencies – Biobased minimums enforced for each product category – ASTM D6866 used to determine if products meet minimums
Two Programs:
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– 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
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