Biogenic Interference Calculation (BIC) Index for resolving false petroleum hydrocarbon detections in clean organic soils and compost

1. F2:F3b Ratio and BOC-Adjusted PHC F3 Mathematical
Approach to Resolving False Detections of Crude Oil and
Diesel Drilling Waste in Clean Soils and Compost
Francine Kelly-Hooper, PhD Thesis Presentation
Wednesday July 17, 2013
University of Waterloo

2. Discussion Items
Conclusions
Research objective
Experiment methods and results

3. Research Objective
To determine if gas chromatography flame ionization detector
(GC-FID) patterns can be used to quantitatively distinguish
petroleum hydrocarbons from biogenic organic compounds in
clean and contaminated soils and compost materials.

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

5. Biogenic and Petrogenic Hydrocarbon Sources
Biogenic: Plant and animal tissues, fluids, manure, sewage, etc.
Petroleum: Crude oil, diesel fuel, motor oil, waxes, mineral oils, etc.

6. CWS Classification of Petroleum Hydrocarbon
Sources by Carbon Number Range
Number of Carbons
F1
F2
F4
C10
C16
C6
C34
>C34
F4
C34
F1 F2
C10-C16 >
F3
C16-C34
C6-C10
Biogenic Compounds
(plant and animal sources)
Gasoline
Diesel/No. 2 Fuel Oil
Crude Oil
No. 6 Oil/Lube Oil/Heavy fuels, Tar, Asphalts

7. CCME Recommended Biological Interference Solutions (pg 22)
15.1 High Organic Carbon Soils
Document recommendation is to analyze and subtract natural
background concentrations from petroleum contaminated soil samples.
15.2 Soils Remediated With Manure
15.3 Soils Containing Partially Degraded Hydrocarbons

8. Obvious Central
Contamination
Boundary Zone
Minimal-Moderate
Contamination
Boundary Line????
Relevance to Spill Site Evaluations?
- F3 carbon ranges in uncontaminated peat can range from 700 mg/kg to 2000 mg/kg.
- CCME course soil criteria is 300 mg/kg and fine soil criteria is 1300 mg/kg

9. 2007: Crude Oil Spiked Peat Experiment
Spiked peat with crude oil to study biogenic vs petrogenic carbon
patterns over a 300 day period.

10. 2008: Diesel Spiked Manure Experiment
Spiked composted manure and sand with diesel oil and studied
biogenic vs petrogenic carbon patterns over a 300 day period.

11. 2009: Canadian background PHC survey of 34 sites
located in AB, BC & NF
Canadian Geologic Survey collected soils samples and shipped them
to ALS in Waterloo for PHC, PAH and grain size analysis.

12. 2009: Crude Oil Contaminated Peat Field Study
Applied laboratory experiment methods to delineate contaminated soil
boundary zone at a a 45-year old crude oil spill site in northern Alberta.
Reduced the original remediation zone by 45% at a cost savings of
$877,000.

13. List of Analytes
EPA priority PAHs & 1-, 2- methylnapthalenes
F2, F3, F4, F3a, F3b
Total Carbon, Total Organic Carbon, Total inorganic Carbon

14. %TOC
0
1000
2000
3000
0% 5% 10% 15% 20% 25% 30% 35% 40% 45%
F4(mg/kg)
0% exceeded F4
course or fine soil
criteria
0
400
800
1200
1600
F3(mg/kg)
6% exceeded F3
fine soil criteria
44% exceeded F3
course soil criteria
34 Clean Background Soils
0% exceeded F2
course/fine soil criteria
0
50
100
150
200
F2(mg/kg)
<20 method detection limit

15. F3a (C16-C22) and F3b (C22-C34) Distributions in Diesel
and Uncontaminated Peat
F3a F3b
F2 Total F3 F4
Carbon Number
C16C10 C22 C34
Clean
Peat
7% F3a
93%
F3b
11%
F3b
89%
F3a
F3b
63%
F3a
37%
Diesel
Diesel
Contaminated
Peat

16. F3a (C16-C22) and F3b (C22-C34) Distributions in Crude Oil
and Uncontaminated Peat
F3a F3b
F2 Total F3 F4
Crude +
Peat
Carbon Number
C16C10 C22 C34
Federated
Crude Oil
Peat Non-detectable F2
69%
F3b
31%
F3a
7%
F3a 93%
F3b
50%
F3b
50%
F3a

17. Measured Total F3 concentration in soil sample = 2,567 mg/kg
The maximum possible F3 concentration from crude oil
PHCs would be 272 mg/kg.
Formula
a + (a x b/c)
a = measured F3a concentration in soil sample is 128 mg/kg
b = measured %F3b distribution in federated crude oil source = 53%
c = measured %F3a distribution in federated crude oil source = 47%
128 mg/kg + (128 mg/kg x 0.53/0.47) = 272 mg/kg
Example BOC-Adjusted PHC F3 Calculation for Determining
Maximum Possible PHCs in a Crude Oil Contaminated Soil Sample
F3b
51%
F3a
49%
Measured F3a concentration in soil sample = 128 mg/kg

18. 13 Crude Oil Samples
%ofTotalF3Concentration
0
25
50
75
100
13 Fresh Crude Oil Samples 34 Uncontaminated 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

19. F2
Total F3
Carbon Number
C16C10 C22 C34
Peat
F2 = 10
mg/kg
F2:F3b Ratio
0.10 PHC Presence versus Absence Threshold Value
F3b = 1,000
mg/kg
F2:F3b Ratio
= 0.01
Crude +
Peat
F2 = 1,000
mg/kg
F3b = 2,000
mg/kg
= 0.50
Federated
Crude Oil
F2 = 1,000
mg/kg
F3b = 1,200
mg/kg
= 0.83
F3b

20. F3F2 F4
F3a
%F3a and %F3b
of F3 rangeF3b
F2:F3b
ratio
0.12
0.02
Carbon Number
C16C10 C22
C34 C50
92%
F3b
62%
F3b
BOC-
adjusted F3
230
mg/kg
370
mg/kg
in 2 out of 63 clean soil samples
Unusual
biogenic
F2 peak
Unusual
biogenic
F3a peak
Rare biogenic peaks in F2 and F3a ranges

21. 10
100
1000
10000
100000
300 mg/kg F3
course soil
guideline
0.10
Clean soils/
compost
PHC Absent
Contaminated soil/
compost
Contaminated
sand
F2:F3b Ratios and F3 Concentrations
Clean Peat/Compost, Diesel/Crude Oil Spiked Peat/Compost/Sand
0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60
0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60
1000
100000
10000
100
MeasuredF3
(mg/kg)(logscale)
PHC Present
F2:F3b Ratio
F2:F3b Ratio
0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.600.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60
10
300 mg/kg F3
course soil
guideline
BOC-adjustedPHCF3
(mg/kg)(logscale)

22. Is the F2:F3b ratio greater than 0.10?
No
Remediation/
management not
required
Yes
Does the BOC-adjusted PHC F3 concentration
exceed the F3 soil guideline?
Remediation/management not required
if biomarker and/or PAH analysis
determine that PHCs are absent in
sample
No
Remediation/
Management not
required
Yes
CWSPHC
–Tier1
CWSPHC
–Tier2
Decision Tree to Determine if a Soil Sample Location Requires
Remediation/Management Due to Diesel and/or Crude Oil Contamination
No
Remediation/Management
not required
Yes
Does the F3 concentration exceed soil guideline?
Remediation/
Management
required
Do the F2 and/or F4 concentrations exceed soil guidelines?
YesNo

23. Conclusions
The F2:F3b ratio of less than 0.10 indicated PHC absence in clean
soils/compost. The F2:F3b ratio of greater than or equal to 0.10
indicated PHC presence in diesel/crude oil spiked soils.
The measured F3 concentrations in all of the clean peat/compost
were above the 300 mg/kg course soil toxicity guideline. Most
(97%) of the BOC-adjusted PHC F3 concentrations did not exceed
the guideline.
Combination of these two calculation approaches resolved all of
the false F3 guideline exceedences.

24. Research Partners
Imperial Oil
ALS Laboratory Group
Canadian Association of Petroleum Producers, Petroleum
Technology Alliance of Canada
Husky Energy
Alberta Parks and Protected Areas Division
Environment Canada Oil Spills Research Centre
Natural Sciences and Engineering Research Council
Natural Resources Canada
Orphan Well Association
Geological Survey of Canada

25. Thank You to my Advisors
Dr. Andrea Farwell
Dr. D. George DixonPhD Supervisor:
PhD Advisory
Committee: Dr. Bruce Greenberg
Dr. Eric Grunsky
Dr. Mark Servos
Dr. Paul Sibley
Dr. Gladys Stephenson

26. Thank You