Australia adopted the Canadian petroleum hydrocarbon (TPH/PHC) soil standards in 2010. The Biogenic Interference Calculation (BIC) Index can be used to resolve false TPH/PHC detections caused by the presence of natural organic matter.

1. 1
Biogenic Interference Calculation (BIC) Index for
Eliminating False Exceedences of the Australian
National Environmental Protection Measure Screening
Soil Limits Due to Biogenic Interferences
December 2016 Webinar
Presented by: Francine Kelly-Hooper

2. Australian NEPM Adopted Canadian TPH Standards in 2010

3. Canadian Council of Ministers of the Environment (CCME)
Reference Method for the Canada-Wide Standard (CWS) for
Petroleum Hydrocarbons (TPH) in Soil
Methods can produce false positives
in uncontaminated organic materials
(e.g. organic soil, manure, etc.).

4. • The objective is to “capture” petroleum hydrocarbons. However,
background biogenic organic compounds (BOCs) are
inadvertently “captured” as well.
The problem is that the hexane and acetone solvents indiscriminately
extract all carbon from petroleum and biological sources.
• Silica gel is used to remove polar BOCs. However, soil samples
with >5% Total Organic Carbon (TOC) can overwhelm allowable
silica gel volumes, resulting in false F3 and F4 TPH detections.

5. Soil Extract
injection
F2, F3, F4
concentrations
quantified by
chromatogram
integrations
) ) ) ) ) ) ) )
ion flowflame detector
capillary column
carrier
gas line
Vaporizer
Oven
Flame Ionization
Detector
electronic
signal
GC-FID Analysis of Sample Extract

6. Soil Extract
injection
F2, F3, F4
concentrations
quantified by
chromatogram
integrations
) ) ) ) ) ) ) )
ion flowflame detector
capillary column
carrier
gas line
Vaporizer
Oven
Chromatograms are key
to TPH forensics
electronic
signal
GC-FID Analysis of Sample Extract
Flame Ionization
Detector

7. GC-FID Chromatogram Patterns for Different TPH Products and Natural organic
soil
F2 (C10-C16) F3 (C16-C34) F4 (>C34)
Bitumen
Engine Oil
Crude Oil
Diesel Fuel
Soil
UCM
UCM (Unresolved Complex Mixture)
• “UCM” refers to the hump shape in
a GC-FID chromatogram.
• Dominant UCMs are key
signatures of TPH chromatograms.
• UCMs are not dominant in
BOC chromatograms.
UCM
UCM
UCM

8. GC-FID Chromatograms
Important QA/QC and Forensics Tools
1) Identify Laboratory Contamination
2) Identify the Presence of Unusual TPH Products and Weathering
Patterns
3) Identify False Detections of TPHs due to the presence of natural
Biogenic Organic Compounds (BOCs).

9. 1) Laboratory Contamination - Case Study
min2 4 6 8 10 12 14
pA
10
12
14
16
18
20
22
Lab contamination
True
contamination
for diesel
contaminated
sample
Contaminated Lab Blank
min2 4 6 8 10 12 14
pA
10.5
11
11.5
12
12.5
Lab contamination
Soil sample collected from a diesel contaminated site
• Our QA/QC standards of practice requires that
laboratory reports include blank sample GC-FID
chromatograms.
CH2M Standard QA/QC
• We would request that our samples be re-analyzed
such that lab contamination would not affect detectable
TPH concentrations.

10. 2) Identify the Presence of Unusual TPH Products – Case Study
Soil sample with a highly weathered crude oil pattern
Soil sample with a slightly weathered diesel pattern
• The crude oil source originated from a crude oil pipeline break
CH2M’s Automated TPH Source Identification System
• The diesel originated from a fuel spill, which occurred during the cleanup of the
crude oil spill.
F2 F3 F4
14-Year Old Crude Oil Contaminated Site
• Different remediation plans were required to suit each TPH product
• We have programmed our software to automatically identify unusual TPH patterns
in large databases.
Site History
• The construction company was responsible for the cleanup of the diesel
contaminated area of the site.
• Project managers receive automated emails informing them of which samples
require forensics attention.

11. 3) Identify False Detections of TPHs Caused by the Presence
of Natural Biogenic Organic Compounds (BOCs)
CH2M’s Automated BOC Identification System
• We have automated our software to identify BOC
interferences
• Project managers receive automated emails informing them of which
samples require forensics attention.
BIC Index
Pronounced “BIC” like the pen

12. What is the BIC Index?
A calculation for determining if biogenic interferences have caused organic samples to falsely exceed the 300 mg/kg F3 ESL
• [F2/(F2+F3b)] x 100
• <10% = false TPH exceedence
• >10% = true TPH exceedence
➢ This simple calculation is based on 10 years of laboratory experiments and field data research
➢ It can only be applied to light TPH products that extend into the F2 range
➢ It can only be used by persons who are qualified to interpret GC-FID chromatogram patterns

13. What is the BIC Index?
A calculation for determining if biogenic interferences have caused organic samples to falsely exceed the 300 mg/kg F3 ESL
• [F2/(F2+F3b)] x 100
• <10% = false TPH exceedence
• >10% = true TPH exceedence
➢ This simple calculation is based on 10 years of laboratory experiments and field data research
➢ It can only be applied to light TPH products that extend into the F2 range
➢ It can only be used by persons who are qualified to interpret GC-FID chromatogram patterns

14. References (additional papers are in-progress)

15. Data Set #1: 300-Day Crude Oil Spiked organic soil - PhD Experiment
Clean organic soil and sand were spiked with crude oil and studied for biogenic vs petrogenic carbon distributions over time.

16. Data Set #2: 300-Day Diesel Spiked Compost - PhD Experiment
Compost and sand were spiked with diesel drilling invert and studied for biogenic vs petrogenic carbon
distributions over time.

17. Data Set #3: Background TPH survey of 34 sites located in Alberta, BC and Newfoundland
Canadian Geological Survey collected 34 background soil samples for the biogenic vs
petrogenic carbon distribution study

18. Data Set #4: Orphan Well Association Field Validation Site
The OWA collected 55 samples from a 35-year old crude oil
contaminated Alberta organic soilland for the biogenic vs petrogenic
carbon distribution study.

19. What are biogenic organic compounds (BOCs)?
➢ BOCs are carbon-based compounds, which are naturally biosynthesized by living organisms.
➢ BOC groups containing C, H and O include: lipids, carbohydrates, proteins and nucleic acids.
➢ BOC hydrocarbon groups containing only C and H include n-alkanes.
The Building Blocks of Life

20. Examples of BOCs from Natural Sources
https://www.google.ca/search?q=australian+soil+map&safe=strict&biw=1093&bih=528&tbm=isch&imgil=4gQdjFs
EFDqxtM%253A%253BD0mCRSwyCwurNM%253Bhttp%25253A%25252F%25252Fwww.asris.csiro.au%25252F

21. Examples of BOCs from Human Activities
Livestock Manure
http://www.thefuturescentre.org/signals-of-change/4726/flying-cows-australian-cattle-board-747-china
Biosolids
http://www.awa.asn.au/AWA_MBRR/Communities/Australian_and_New_Zealan
d_Biosolids_Partnership/AWA
https://www.google.ca/search?safe=strict&hl=en&site=imghp&tb
m=isch&source=hp&biw=1093&bih

22. Comparison of Background Soil Survey Results to
NEPM ESLs

23. NEPM HSLs and ESLs for F1 – F4 TPH
➢ False exceedences only occur in the F3 range. HSLs for vapor intrusion do not include F3
(only F1 and F2 are assessed as volatile;
➢ BIC Index eliminates false exceedences of all direct contact HSLs, ESLs and
Management Limits, including the most stringent 300 mg/kg ESL for F3 TPH.
F3

24. 34 Background Soil Samples: Alberta, BC, Newfoundland
0
400
800
1200
1600
F3(mg/kg)
Comparisons of F2, F3, F4 Concentrations to Most Stringent NEPM ESLs,
Coarse Soil, Urban Residential and Public Open Space
16 samples (47%) exceeded F3 coarse
soil levels300 mg/kg
0
50
100
150
200
F2(mg/kg) 0 samples exceeded F2 coarse soil levels150 mg/kg
%TOC
0
1000
2000
3000
0% 10% 20% 30% 40%
F4(mg/kg)
0 samples exceeded F4 coarse
soil levels
2800 mg/kg

25. 0
400
800
1200
1600
F3(mg/kg)
16 samples (47%) exceeded
F3 coarse soil level300 mg/kg
0
50
100
150
200
F2(mg/kg)
0 samples exceeded
F2 course soil standards150 mg/kg
%TOC
0
1000
2000
3000
0% 10% 20% 30% 40%
F4(mg/kg)
0 samples exceeded F4
course soil standards
2800 mg/kg
34 Background Soil Samples: Alberta, BC, Newfoundland
Only F3 exceeded the ESLs
Comparisons of F2, F3, F4 Concentrations to Most Stringent NEPM ESLs,
Coarse Soil, Urban Residential and Public Open Space

26. But there is a light at the end of the tunnel!

27. Non-detectable F2
Detectable F2
Detectable F2
F3a (C16-C22) and F3b (C22-C34) Distributions in Diesel and Clean Organic Soil
F3a
F2
C10-C16
Total F3 F4
>C34
Carbon Number
C16C10 C22 C34
Organic
Soil
7% F3a
93%
F3b
11%
F3b
89%
F3a
F3b
63%
F3a
37%
Diesel
Diesel
Contaminated
Organic Soil
F3b
(C16-C22) (C22-C34)

28. Non-detectable F2
Detectable F2
Detectable F2
F3a (C16-C22) and F3b (C22-C34) Distributions in Crude Oil and Clean Organic Soil
F2
C10-C16
Total F3
F4
>C34
Crude +
organic
soil
Carbon Number
C16C10 C22 C34
organic
soil
69%
F3b
31%
F3a
F3a F3b
(C16-C22) (C22-C34)
Federated
Crude Oil
50%
F3b
50%
F3a
7%
F3a 93%
F3b

29. 13 Crude Oil Samples
%ofTotalF3Concentration
0
25
50
75
100
13 Fresh Crude Oil Samples 34 Background Soil Samples
34 Soil Samples
0
25
50
75
100
%ofTotalF3Concentration
F3a (C16-C22) F3b (C23-C34)F3a (C16-C22) F3b (C23-C34)
Median
F3b
93%
F3a 7%
F3b
51%
F3a
49%
Median
1 2 3 4 5 6 7 8 9 10 11 12 13

30. F2, F3, F4, F3a, F3b Carbon Distributions in TPH Products and Clean Organic Soil
F3a F3b
F2 F3 F4
Bitumen
Engine Oil
Crude Oil
Diesel Fuel
Organic Soil 7%
F3a 93%
F3b
F3a
89%
F3b
11%
53%
F3b
47%
F3a
6%
F3a
94%
F3b
14%
F3a
86%
F3b
High
F3a
High
F3a
Low
F3a
Low
F3a
Low
F3a

31. F3a F3b
F2 F3 F4
Bitumen
Engine Oil
Crude Oil
Diesel Fuel
Organic Soil 7%
F3a 93%
F3b
F3a
89%
F3b
11%
53%
F3b
47%
F3a
6%
F3a
94%
F3b
14%
F3a
86%
F3b
High
F3a
High
F3a
Low
F3a
Low
F3a
Low
F3a
• Clean soils and heavy TPH products have the same non-detectable
F2 and high F3b carbon range patterns
• The BIC Index cannot be used for heavy TPH products
F2, F3, F4, F3a, F3b Carbon Distributions in TPH Products and Clean Organic Soil

32. Carbon Number
C16C10 C22 C34
Clean
Organic
Soil
Diesel
Diesel
Spiked
organic soil
69%
33%
F2
F2 = 823
mg/kg
F3b = 371
mg/kg
F2 = 613 mg/kg F3b = 2,816
mg/kg
F2 = 10 mg/kg F3b = 1,395
mg/kg
F3b
= F3 Level
Exceeded
[F2/F2+F3b] x 100
1%
= F3 level not
Exceeded
= F3 level
Exceeded
Total F3
BIC Example: Diesel and organic soil False Exceedence < 10% >True Exceedence

33. F2
Total F3
Carbon Number
C16C10 C22 C34
Clean
Organic
Soil
F2 = 10
mg/kg
F3b = 1,000
mg/kg
1%
Crude Oil
Spiked
Organic soil
F2 = 1,000
mg/kg
F3b = 2,000
mg/kg 33%
F3b
Crude Oil
F2 = 1,000
mg/kg
F3b = 1,200
mg/kg
45%
= F3 Level Not
Exceeded
= F3 Level
Exceeded
= F3 Level
Exceeded
BIC Example: Crude and organic soil False Exceedence < 10% >True Exceedence

34. No Yes
Does the GC-FID chromatogram image have an obvious
Unresolved Complex Mixture (UCM) petrogenic pattern?
No
Heavy TPH may be present (e.g. engine oil, asphalt,
etc). Do not proceed with the evaluation.
Indicates false exceedance
of F3 ESL
BIC Index Decision Tree for Identifying False Exceedences of F3 ESLs
Indicates true exceedance
of F3 ESL
Is the Biogenic Interference Calculation >10%?
Yes
Pre-screening criteria: only include samples that meet these criteria
1) F2 concentration is less than laboratory method detection limit (<20 mg/kg)
2) F3 concentration exceeds the 300 mg/kg ESL, F4 concentration does not exceed any ESLs
3) The released TPH product(s) must extend into the light F2 (C10-C16) carbon range (e.g. diesel, crude oil, etc.)
4) A qualified person must confirm that the GC-FID chromatogram does not have a heavy TPH pattern (e.g. asphalt, bitumen, motor oil, etc.).

35. BIC Index Statistical Probability Test Results
The BIC Index is a highly conservative/cautious tool.
0% likelihood of missing true exceedences.
10% likelihood of missing false exceedences.

36. Next Steps?
➢ CH2M is currently expanding the BIC Index to include heavy TPHs (e.g.
asphalt, bitumen, motor oil, etc.) as well.
➢ CH2M is continuing to develop our automated data management system
for flagging unusual TPH patterns and false TPH detections.

37. 37 Presentation Title
Thank You
Francine Kelly-Hooper, PhD
Senior Soils Scientist
5195 023 122
Francine.Kellyhooper@ch2m.com