This field study was presented at the October 2017 RemTech Conference in Banff, Alberta, Canada. The principles of the Canadian Biogenic Interference Calculation (BIC) Index were used to resolve false petroleum hydrocarbon exceedences in Peruvian organic rain forest soils.

1. October 2017 RemTech Conference, Banff, Alberta, Canada
Application of Canadian BIC Index Principles
to Resolve False Petroleum Hydrocarbon
Detections in Peruvian Rainforest Soils
Presented by: Francine Kelly-Hooper, PhD, Soils Scientist
CH2M HILL Canada
Authors:
V. UcarF. Kelly-Hooper J. Bishop J. Coffey
CanadaPeru
South
America

2. Historical Crude Oil Contaminationin
PeruvianRainforest Organic Peat/Turba Soils
Peru
South
America

3. 2015 Contaminated Site Study Overview
• 30 years of crude oil extraction activities contaminated a 721 hectare (ha)
rainforest area.
• 17,132 soil samples were analyzed for total petroleum hydrocarbons (PHC/TPH)
• Most of the 5,569 clean and contaminated peat soil samples exceeded Peruvian
PF3 (C28-C40) regulatory limit of 3000 mg/kg

4. What is Peat/Turba?
• Typically has >40% total organic carbon (TOC) content
Saturated Soil and
Decayed Plants
Thousands of
Years Peat/Turba
• Natural Biogenic Organic Compounds (BOCs) are often falsely detected as
Petroleum Hydrocarbons (PHCs)
Peat (English); Turba (Spanish)

5. Biogenic Organic Compounds are the BuildingBlocks of Life
 Natural carbon-based compounds biosynthesized by living organisms.
 BOC groups contain alkanes, lipids, carbohydrates, proteins, etc.

6.  However, background BOCs can be inadvertently
extracted as well.
 Peruvian and Canadian laboratories use organic hexane,
acetone and DCM solvents to extract PHC/TPH.
Why are Biogenic Organic Compounds Falsely Detected as PHC/TPH?
 Polar cleanups (e.g. silica gel) are used to reduce BOC
concentrations, but they can be ineffective if
oversaturated by highly organic materials such as peat
(>20% total organic carbon).

7. Peruvian Soil PHC/TPH Analysis Method
Adaptation of USEPA SW846 8015 Method
• Microwave extraction in acetone, hexane and dichloromethane solvents
• Silica gel cartridge cleanup of polar (biogenic) compounds
• PHC/TPH concentrations quantified by Gas Chromatography-Flame Ionization
Detector (GC-FID) on a 3 minute run
• Peruvian PF2 (C10-C28) regulatory limit 1,200 mg/kg
• Peruvian PF3 (C28-C40) regulatory limit 3,000 mg/kg
Peru
South
America

8. Does not Exceed Regulatory Limit Exceeds Regulatory LimitClean Peat Samples – Only PF3 exceedences; No PF2 exceedences
PeruSoil Data Examples: TrueandFalseExceedencesof
Regulatory Limitsin Cleanand ContaminatedPeatSoils
PF2 (C10-C28)
Reg. limit 1200 mg/kg
CLEAN Background Peat CONTAMINATED Peat
PF2(mg/kg)PF3(mg/kg)
PF3 (C28-C40)
Reg. limit 3000 mg/kg
62 Peat Samples

9. Source: Parish et al. 2008
Canadian
Peat
Peruvian
Peat
5%->10%<0.5% 0.5-5%
Same Carbon Distribution
Patterns Provided the Basis of
the Peru Study Approach
Peat Soils are Distributed Throughout the World

10. Does not Exceed Regulatory Limit Exceeds Regulatory Limit
PF2(mg/kg)PF3(mg/kg)
Clean Peruvian Peat
0
50
100
150
200
0
400
800
1200
1600
Clean Canadian Peat
C10-C28
C28-C40
C10-C16
C16-C34
F2(mg/kg)F3(mg/kg)
Comparison Of Peruvian and Canadian Clean Soil
Exceedences of Regulatory TPH/PHC Limits
32 Peat Samples 34 Peat and Mineral Samples

11. Does not Exceed Regulatory Limit Exceeds Regulatory Limit
Only heavy carbon ranges exceeded regulatory limits
PF2(mg/kg)PF3(mg/kg)
Clean Peruvian Peat
0
50
100
150
200
0
400
800
1200
1600
Clean Canadian Peat
C10-C28
C28-C40
C10-C16
C16-C34
Comparison Of Peruvian and Canadian Clean Peat
Exceedences of Regulatory TPH/PHC Limits

12. Resolution of Peruvian False Exceedences
through Canadian BIC Index Principles
 A calculationfor determining if biogenic interferences have caused organic (peat) samples to falsely exceed the Canadian
Council of Ministers of the Environment (CCME) F3 PHC 300 mg/kg F3 PHC soil guideline.
 [F2/(F2+F3b)] x 100
 <10% = false PHC exceedence
 >10% = true PHC exceedence
What is the Biogenic Interference Calculation (BIC) Index?
Pronounced “BIC” like the pen
 CCME Fractions: F2 (C10-C16), F3 (C16-C34), F4 (C34-C50); BIC Index Sub-fraction F3b (C22-C34)

13. Contamination Experiments
2007-2010
Contaminated Site Studies
2005-2017
Clean Background Soil Surveys
2007-2015
Biogenic Interference Calculation (BIC) Index
Research & Development History
Developed Through 7-Year PhD Study

14. Publications

15. Non-detectable
F2
Detectable
F2
Detectable
F2
Clean Soils Have Negligible F2 (C10-C16) and High F3b (C22-C34)
F2 Total F3 F4
Crude + Peat
Carbon Number
C16C10 C22 C34
Clean Peat
69%
F3b
31%
F3a
F3a F3b
(C16-C22) (C22-C34)
Crude Oil
50%
F3b
50%
F3a
7%
F3a 93%
F3b
Primary BIC Index Principle:

16. F2
Carbon Number
C16C10 C22 C34
F2 = 10
mg/kg
F3b = 1,000
mg/kg
= 1%
F2 = 1,000
mg/kg
F3b = 2,000
mg/kg = 33%
F3b
F2 = 1,000
mg/kg
F3b = 1,200
mg/kg
= 45%
Guideline not
Exceeded
Guideline
Exceeded
Guideline
Exceeded
Example of BIC Index Calculation for Crude Oil PHCs
Crude + Peat
Clean Peat
Crude Oil
[F2/F2+F3b] x 100

17. Comparison of Canadian and
Peruvian GC-FID
Chromatograms
Canada

18. Carbon Range
C40C10
PF2 (C10-C28) PF3 (C28-C40)
C28
Peru
Alberta Canada
PeruverusCanadianSamples– SimilarCleanPeatGC-FIDPatterns
Less defined due to
3 minute run time
More defined due to
18 minute run time

19. PeruversusAlberta Samples– SimilarWeatheredCrudeOil Patterns
Carbon Range
C40C10
PF2 (C10-C28) PF3 (C28-C40)
C28
Peru
Less defined due to
3 minute run time
More defined due to
18 minute run time
Alberta Canada

20. Carbon Range
C40C10 C28
PeruversusAlberta Samples– SimilarCrudeOil ContaminatedPeatGC-FID Patterns
Peru
Less defined due to
3 minute run time
More defined due to
18 minute run time
PF2 (C10-C28) PF3 (C28-C40)
Alberta Canada

21. Challenges of Applying Canadian
BIC Index to Peruvian Peat Samples
 Different Canadian and Peruvian carbon ranges and regulatory limits
 Electronic chromatograms were essential to finding the correct Canadian
BIC Index F3b sub-fraction carbon range.
 Electronic chromatograms were not available for the Peruvian samples.
CH2M developed an alternative graphics software technique for
calculating false exceedences of Peruvian regulatory limits.

22. Peru Results
Peru Results

23. GC-FID Chromatogram
C40C10 C28
PF2 PF3
Regulatory LimitsCarbon Numbers
Peru ResultsHighly Contaminated Peat
PF2 and PF3 Concentrations
PF2 PF3

24. C10 C28
PF2 PF3
C40
Regulatory LimitsCarbon Numbers
Peru ResultsHighly Contaminated Peat
PF2 PF3
Reference
Crude Oil
Overlay
GC-FID Chromatogram
PF2 and PF3 Concentrations

25. C40C10 C28
PF2 PF3
Carbon Numbers
Subtracted peat
concentration from
total PF2 and PF3
concentrations
Regulatory Limits
PF2 and PF3 Concentrations
PF2 PF3
Total Concentration
Petrogenic Concentration
Peru ResultsContaminated Peat
True Exceedences of Regulatory Limits
GC-FID Chromatogram

26. Peru Results
GC-FID Chromatogram
C40C10 C28
PF2 PF3
Carbon Numbers
Regulatory Limits
PF2 and PF3 Concentrations
PF2 PF3
Clean Peat

27. C40C10 C28
PF2 PF3
Carbon Numbers
Reference Crude
Oil Overlay
GC-FID Chromatogram
Regulatory Limits
PF2 and PF3 Concentrations
PF2 PF3
Clean Peat

28. C40C10 C28
PF2 PF3
Carbon Numbers
GC-FID Chromatogram
Regulatory Limits
PF2 and PF3 Concentrations
PF2 PF3
Total Concentration
Petrogenic Concentration
False Exceedence of PF3 Regulatory Limit
Peru ResultsClean Peat
Subtracted peat
concentration from
total PF2 and PF3
concentrations

29. 1,199 (22%) of 5,568 contaminated soil samples were identified as
falsely exceeding the F3 regulatory limit due to background peat
#ofSamples
True PF3 Limit Exceedence
False PF3 Limit Exceedence
Peru ResultsSummary of All Results

30. Thank You
Francine Kelly-Hooper
f.kellyhooper@ch2m.com
519-502-3122