ASTM D6866 For Biobased Products

Quantifying the Biobased Content
of Products Using ASTM D6866
Beta Analytic Inc.

4985 SW 74 Court
Miami, Florida 33155
Tel: 305-667-5167
Fax: 305-663-0964
Biobased Content Analysis using Radiocarbon Dating

ASTM D6866 is a standard method based on
radiocarbon dating techniques that
determine the age of fossils, artifacts, and
materials.

Topics
• Understanding Radiocarbon Dating
• ASTM D6866 Method
• Accuracy & Precision
• Results Report
• ASTM D6866 as QC Tool
• ASTM D6866 in Labeling Programs

Understanding Radiocarbon Dating
STEP 1: Ongoing formation and decay of

radiocarbon within the atmosphere
Nitrogen ( 14N ) + cosmic neutrons Radiocarbon ( 14C )
Radiocarbon immediately oxidizes Carbon Dioxide ( 14CO2 )
The radiocarbon immediately starts to decay (T1/2 = 5730 years)

14N +n 14C
“Constant” amount of
radiocarbon in the
14C Decay 14CO
2 atmosphere as CO2
(~ 14.7 dpm)

STEP 2: Radiocarbon is removed from the

atmosphere by plants
Plants take in the 14CO2

during photosynthesis
While alive, they have the same

radiocarbon content as the air
around them (equilibrium with the
atmosphere is maintained).
14CO 14C Decay

2 uptake

STEP 3: Disequilibrium begins upon “death”
Upon harvest – carbon uptake ceases
Radiocarbon within the plant is no

longer being replenished
The 14C Decay

continues
The plants are no longer in

equilibrium with the atmosphere
The “Radiocarbon Clock”

is set to zero and starts
ticking

Non-fossil
0 50,000 yrs Fossil

If it were 100%
petroleum derived
If it were 50% corn-based &

50% petroleum derived
0 50,000 yrs

ASTM D6866 Method
Method A Method C Method B

CO2 Absorption Benzene Synthesis AMS
(Accelerator Mass Spectrometry)
Routine by the 1970s Routine by 1960s Routine by the 1980s

SAMPLE SAMPLE SAMPLE
CO2
CO2 CO2
Lithium Carbide
Absorbed into Acetylene Reduced to

Counting Solution Graphite
Benzene
Increasing cost of analysis, Increasing price to manufacturer
LSC $25,000 AMS $1.5 - 3 million

ASTM D6866 Method
ADVANTAGES DISADVANTAGES
Low cost chemistry lab Very low precision (+/- 10 %)

CO2 ABSORPTION
Standard LSC detection High carbon content requirement
Rapid throughput
BENZENE Good precision (<= 2% absolute) High chemical overhead

Standard LSC detection
Rapid throughput
AMS Good precision (<= 2% absolute) High detector overhead

Very small sample requirements

ASTM D6866 Method
CO2 and BENZENE LABORATORIES

ASTM D6866 Method
AMS LABORATORY

Accuracy & Precision
A Test of Accuracy - Know n Ethanol Concentrations in Heptane

verified by Radiocarbon Dating
100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
0% 20% 40% 60% 80% 100%
% Ethanol per 14C % Ethanol per Chemistry

Variables that can be controlled in the lab:
• Quantitative combustion of all available carbon in the product
• The yield of carbon through the chemical conversions
• The methodology used: Method A, B, or C
• How long the sample is measured in the detector

Variables that can’t be controlled in the lab:
• The homogeneity of the biomass components within the product
• Component loss during manufacturing (“fractionation”)
• Collection parameters
• Storage parameters

Results Report
ASTM D6866 Report
Simple Visual Report
Easy Inter-comparison
Instinctively Obvious

Quality Control Tool
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 us that A, B, & C were
all the same product and an error must be present in the result for Product B
A B C
The 14C dating determined the biobased content & revealed a quality control issue.

Quality Control Tool
The manufacturer submitted 2 samples
Radiocarbon Dating Results were:
Product A 96 % Biobased
(19% difference)
Product B 77 % Biobased
After the analyses, the manufacturer informed us that Product B was

Product A diluted with water and sold under a different name.
Their formulator’s investigation revealed Product B contain 2 petroleum derivatives,
TEA-99 and a Polyol, with a total fossil C contribution to the product of ~ 20 %.
The correct biobased contents were identified and the marketing of Product B
has to be reconsidered.

ASTM D6866 in Labeling Programs
USDA BioPreferred Program
~ Preferred Procurement Program for US Federal Agencies and their Contractors
~ Voluntary Labeling Program for the broad scale consumer marketing of biobased
products
Both programs need biobased content certification.

ASTM D6866 in Labeling Programs
Other Programs Requiring Biobased Content Certification
• EcoLogo (Canada) standard for hand sanitizers (CCD-170)
• Vinçotte (Belgium) OK Biobased Eco-label System
• Sustainable Biomaterials Collaborative's BioSpecs specific to food service ware

Key Points and Considerations
Radiocarbon Dating works for comparing biobased content between products
Basic assumption : all carbon in the product is either present day or fossil
ASTM D6866 also provides an added quality control measure.
Accuracy relies heavily on homogeneity and quantitative extraction of all

available carbon.
http://www.betalabservices.com/biobased.html

ASTM D6866 For Biobased Products

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Quantifying the Biobased Content

of Products Using ASTM D6866

Beta Analytic Inc.

Biobased Content Analysis using Radiocarbon Dating

Biobased Content Analysis using Radiocarbon Dating

Biobased Content Analysis using Radiocarbon Dating

STEP 1: Ongoing formation and decay of

Nitrogen ( 14N ) + cosmic neutrons Radiocarbon ( 14C )

Radiocarbon immediately oxidizes Carbon Dioxide ( 14CO2 )

The radiocarbon immediately starts to decay (T1/2 = 5730 years)

Biobased Content Analysis using Radiocarbon Dating

STEP 2: Radiocarbon is removed from the

Plants take in the 14CO2

While alive, they have the same

14CO 14C Decay

Biobased Content Analysis using Radiocarbon Dating

STEP 3: Disequilibrium begins upon “death”

Upon harvest – carbon uptake ceases

Radiocarbon within the plant is no

The 14C Decay

The plants are no longer in

The “Radiocarbon Clock”

Biobased Content Analysis using Radiocarbon Dating

0 50,000 yrs Fossil

Biobased Content Analysis using Radiocarbon Dating

If it were 50% corn-based &

Biobased Content Analysis using Radiocarbon Dating

Method A Method C Method B

Routine by the 1970s Routine by 1960s Routine by the 1980s

Absorbed into Acetylene Reduced to

Increasing cost of analysis, Increasing price to manufacturer

LSC $25,000 AMS $1.5 - 3 million

Biobased Content Analysis using Radiocarbon Dating

Low cost chemistry lab Very low precision (+/- 10 %)

BENZENE Good precision (<= 2% absolute) High chemical overhead

AMS Good precision (<= 2% absolute) High detector overhead

Biobased Content Analysis using Radiocarbon Dating

CO2 and BENZENE LABORATORIES

Biobased Content Analysis using Radiocarbon Dating

Biobased Content Analysis using Radiocarbon Dating

A Test of Accuracy - Know n Ethanol Concentrations in Heptane

% Ethanol per 14C % Ethanol per Chemistry

Biobased Content Analysis using Radiocarbon Dating

Variables that can be controlled in the lab:

• Quantitative combustion of all available carbon in the product

• The yield of carbon through the chemical conversions

• The methodology used: Method A, B, or C

• How long the sample is measured in the detector

Biobased Content Analysis using Radiocarbon Dating

Variables that can’t be controlled in the lab:

• The homogeneity of the biomass components within the product

• Component loss during manufacturing (“fractionation”)

Biobased Content Analysis using Radiocarbon Dating

ASTM D6866 Report

Simple Visual Report

Biobased Content Analysis using Radiocarbon Dating

The manufacturer submitted 3 samples

Biobased Content Analysis using Radiocarbon Dating