River sediment contains natural organic material, largely derived from allochthonous sources, meaning a source from outside the river. This is particularly important when regarding polycyclic aromatic hydrocarbons (PAHs), which can have sources hundreds of kilometers from a sampling point within the river catchment. In fact, every river can contain PAHs from a source other than that which is the focus of a remedial investigation, and consideration of this is very important. Presentation of the detection of PAHs in relation to guidelines is a requirement for regulatory purposes. However, if those PAHs are natural, or at least originate from a source that is unrelated to the investigation, why take responsibility for them? In order to determine the source of PAHs it is important to collect the right kind of samples (fine grained, highly organic sediment), analyse for the right kind of chemical package (include alkylated PAHs), and interpret the results using the right kind of techniques. This presentation will describe the correct, and incorrect use of environmental forensics techniques using example datasets from our work in Canadian oil spill response and US CERCLA investigations. It will focus on how to construct and interpret PAH fingerprints and ratios, and the use of statistics such as PCA. Environmental professionals involved in spill remediation or site monitoring will find this presentation applicable.

1. © 2018
Chemistry Matters Inc.
Making chemistry data meaningful
Whose PAH is this?
Envirotech 2018
Wednesday April 4, 2018
Phil Richards and Court D Sandau
Chemistry Matters Inc., Calgary, AB

2. © 2018
Chemistry Matters Inc.
Copyright Statement
All rights reserved. No part of this publication may be reproduced,
distributed, or transmitted in any form or by any means, including
photocopying, recording, or other electronic or mechanical methods,
without the prior written permission of Chemistry Matters Inc.
2Whose PAH is this? Envirotech 2018

3. © 2018
Chemistry Matters Inc.
Overview
3Whose PAH is this? Envirotech 2018
0%
10%
20%
30%
40%
50%
60%
70%
Percent (%)
Heavy Fuel Oil
0
100
200
300
400
500
600
700
800
900
1000
NAP C1 NAP C2 NAP C3 NAP C4 NAP
FLU C1 FLU C2 FLU C3 FLU
PHE/ANT
C1 PHE/ANT
C2 PHE/ANT
C3 PHE/ANT
C4 PHE/ANT
DBT C1 DBT C2 DBT C3 DBT C4 DBT
FLRN/PYR
C1 FLRN/PYR
C2 FLRN/PYR
C3 FLRN/PYR
C4 FLRN/PYR
BaA/CHR
C1 BaA/CHR
C2 BaA/CHR
C3 BaA/CHR
C4 BaA/CHR
Concentra)on (mg/kg)
RDR01
0
5
10
15
20
25
30
35
40
45
16-SA73 - 0 km
16-SA70 - 0 km
16-SA20 - 3.47 km
16-SA23 - 3.74 km
16-SA21 - 3.79 km
16-SA22 - 3.81 km
16-SA24 - 4.61 km
16-SA26 - 6.96 km
16-SA25 - 7.4 km
16-SA28 - 8.38 km
16-SA27 - 9.35 km
16-SA30 - 11.59 km
16-SA29 - 11.63 km
16-SA46 - 26.12 km
16-SA44 - 27.39 km
16-SA43 - 28.45 km
16-SA31 - 28.93 km
16-SA40 - 29.2 km
16-SA40 - 29.2 km
16-SA42 - 29.51 km
16-SA38 - 30.08 km
16-SA33 - 30.74 km
16-SA37 - 31.8 km
16-SA36 - 32.44 km
16-SA32 - 32.44 km
16-SA35 - 32.74 km
16-SA51 - 48.63 km
16-SA55 - 51.93 km
16-SA54 - 52.37 km
16-SA52 - 52.37 km
16-SA56 - 52.84 km
16-SA59 - 56.67 km
16-SA58 - 58.43 km
16-SA57 - 60.51 km
16-SA60 - 60.7 km
16-SA61 - 62.22 km
16-SA62 - 63.49 km
16-SA49 - 68.1 km
16-SA47 - 68.29 km
16-SA48 - 69.83 km
16-SA67 - 81.33 km
16-SA66 - 81.64 km
16-SA63 - 82.37 km
16-SA64 - 82.62 km
16-SA68 - 85.91 km
16-SA69 - 86.85 km
16-SA71 - 86.93 k
16-SA72 - 8
16-SA71
Sum PAH (mg/kg)
Bo/om Oil Samples
• Standard PAH analysis
• Extended PAH analysis
• Fingerprint graphs
• Diagnostic ratios
• Principle Component Analysis
• Source Apportionment

4. © 2018
Chemistry Matters Inc.
Example PAH dataset
4Whose PAH is this? Envirotech 2018
Whose PAH is this?
Forensic interpretation of PAH data
Source + History
(Where it came from + How it got here)
Guideline Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6
Naphthalene 0.0346 0.047 0.033 0.013 0.009 0.005 <0.005
2-Methylnaphthalene 0.0202 0.060 0.051 0.023 0.014 0.015 <0.005
Acenaphthylene 0.00587 <0.005 <0.005 <0.005 <0.005 0.006 <0.005
Acenaphthene 0.00671 <0.005 <0.005 <0.005 <0.005 0.022 <0.005
Fluorene 0.0212 <0.02 <0.02 <0.02 <0.02 0.04 <0.02
Phenanthrene 0.0419 0.11 0.05 0.02 0.02 0.23 0.19
Anthracene 0.0469 <0.004 <0.004 <0.004 <0.004 0.032 0.052
Fluoranthene 0.111 <0.01 <0.01 <0.01 <0.01 0.08 0.19
Pyrene 0.053 <0.01 0.01 <0.01 0.04 0.21 0.49
Benzo[a]anthracene 0.0317 <0.02 <0.02 <0.02 <0.02 0.07 0.14
Chrysene 0.0571 <0.05 <0.05 <0.05 <0.05 0.11 0.36
Benzo[a]pyrene 0.0319 <0.03 <0.03 <0.03 <0.03 0.04 0.05
Dibenzo[ah]anthracene 0.00622 <0.005 <0.005 <0.005 0.006 0.008 0.007
CCME ISQG FAL
13 PAHs

5. © 2018
Chemistry Matters Inc.
Fish tissue analysis
5
Analysis of fish muscle and liver tissue following release into river.
Sampling downstream of an urban center after spring thaw.
Substantial difference in naphthalene concentration – is this due to the release product?
0.00#
0.50#
1.00#
1.50#
2.00#
2.50#
3.00#
3.50#
4.00#
4.50#
2012#Upstream#
2012#Downstream#
2013#Upstream#
2013#Downstream#
2013#U/S#Side#channels#
2013#D/S#Side#channels#
Naphthalene)
Logng/glipidweight
Year 1 Year 2 Year 2a
Whose PAH is this? Envirotech 2018

6. © 2018
Chemistry Matters Inc.
Fish tissue analysis
6
0"
500"
1,000"
1,500"
2,000"
2,500"
3,000"
Naphthalene"
20Methylnaphthalene"
2,60Dimethylnaphthalene"
2,3,50Trimethylnaphthalene"
Acenaphthylene"
Acenaphthene"
Fluorene"
Phenanthrene"
10Methylphenanthrene"
Anthracene"
Fluoranthene"
Pyrene"
Benz[a]anthracene"
Chrysene"
Benzo[b]fluoranthene"
Benzo[j,k]fluoranthenes"*"
Benzo[e]pyrene"
Benzo[a]pyrene"
Perylene"
Dibenz[a,h]anthracene"
Indeno[1,2,30cd]pyrene"
Benzo[ghi]perylene"
Dibenzothiophene"
Lipid%normalized%concentra0on%(ng/g)%
PAH source is gasoline from urban centre, not release product.
Whose PAH is this? Envirotech 2018
0.00#
0.50#
1.00#
1.50#
2.00#
2.50#
3.00#
3.50#
4.00#
4.50#
2012#Upstream#
2012#Downstream#
2013#Upstream#
2013#Downstream#
2013#U/S#Side#channels#
2013#D/S#Side#channels#
Naphthalene)
Logng/glipidweight
Year 1 Year 2 Year 2a

7. © 2018
Chemistry Matters Inc.
Forensic fingerprints
0%
10%
20%
30%
40%
50%
60%
70%
Percent (%)
Heavy Fuel Oil
7
naphthalene benzo[ghi]perylene
• One bar per PAH (either as percentage or concentration)
• Structured based on physico-chemical properties – mol. weight
Whose PAH is this? Envirotech 2018

8. © 2018
Chemistry Matters Inc.
Forensic fingerprints
0%
10%
20%
30%
40%
50%
60%
70%
Percent (%)
Heavy Fuel Oil
0%
10%
20%
30%
40%
50%
60%
Percent (%)
Petroleum Tar; Lightly Weathered Pyrogenic
PAH Pattern; 3.00 mg
mg/kg
8
Can’t distinguish fuel oil from gas plant tar. Not very forensic!
(however, can use diagnostic ratios)
Whose PAH is this? Envirotech 2018

9. © 2018
Chemistry Matters Inc.
Extended PAH Analysis
Parent PAHs
17
Extended PAHs
50+
Naphthalene
C1-Naphthalenes
C2-Naphthalenes
C3-Naphthalenes
… …
…
9Whose PAH is this? Envirotech 2018

10. © 2018
Chemistry Matters Inc.
Interpretation of Parent PAH Data
PAH Data
Guideline Exceedances?
Fingerprint
Sources and
history
Diagnostic
Ratios
Statistical
Analysis
10Whose PAH is this? Envirotech 2018
0%
10%
20%
30%
40%
50%
60%
70%
Percent (%)
Heavy Fuel Oil

11. © 2018
Chemistry Matters Inc.
Interpretation of Extended PAH Data
PAH Data
Guideline Exceedances?
Fingerprint
Sources and
history
Diagnostic
Ratios
Statistical
Analysis
Environmental Forensics
11Whose PAH is this? Envirotech 2018
0
100
200
300
400
500
600
700
800
900
1000
NAP C1 NAP C2 NAP C3 NAP C4 NAP
FLU C1 FLU C2 FLU C3 FLU
PHE/ANT
C1 PHE/ANT
C2 PHE/ANT
C3 PHE/ANT
C4 PHE/ANT
DBT C1 DBT C2 DBT C3 DBT C4 DBT
FLRN/PYR
C1 FLRN/PYR
C2 FLRN/PYR
C3 FLRN/PYR
C4 FLRN/PYR
BaA/CHR
C1 BaA/CHR
C2 BaA/CHR
C3 BaA/CHR
C4 BaA/CHR
Concentra)on (mg/kg)
RDR01

12. © 2018
Chemistry Matters Inc.
Environmental Forensics
Fingerprint
Diagnostic
Ratios
Statistical
Analysis
Visual comparison of PAH data
Ratios selected for source or
weathering
Usually PCA… but can go much
further
12Whose PAH is this? Envirotech 2018

13. © 2018
Chemistry Matters Inc.
0%
5%
10%
15%
20%
25%
Percent (%)
Heavy Fuel Oil
Construction of PAH Fingerprints
Parent PAH
Alkylated PAHs
0%
10%
20%
30%
40%
50%
60%
70%
Percent (%)
Heavy Fuel Oil
Parent PAHs only Alkylated PAHs
13Whose PAH is this? Envirotech 2018

14. © 2018
Chemistry Matters Inc.
Forensic fingerprints
0%
10%
20%
30%
40%
50%
60%
70%
Percent (%)
Heavy Fuel Oil
0%
10%
20%
30%
40%
50%
60%
Percent (%)
Petroleum Tar; Lightly Weathered Pyrogenic
PAH Pattern; 3.00 mg
mg/kg
0%
5%
10%
15%
20%
25%
Percent (%)
Heavy Fuel Oil
0%
5%
10%
15%
20%
25%
30%
35%
Percent (%)
Petroleum Tar; Lightly Weathered Pyrogenic PAH Pattern; 3.00 mg
mg/kg
14Whose PAH is this? Envirotech 2018

15. © 2018
Chemistry Matters Inc.
Petroleum Source Types
0%
2%
4%
6%
8%
10%
12%
14%
16%
18%
Bitumen
0%#
2%#
4%#
6%#
8%#
10%#
12%#
14%#
16%#
Naphthalene#
C1#naphthalene#
C2#naphthalene#
C3#naphthalene#
C4#naphthalene#
Acenaphthene#
C1#acenaphthene#
Biphenyl#
C1#biphenyl#
C2#biphenyl#Fluorene#
C1#fluorene#
C2#fluorene#
C3#fluorene#
Phenanthrene/Anthracene#
C1#phenanthrene/anthracene#
C2#phenanthrene/anth.#
C3#phenanthrene/anth.#
C4#phenanthrene/anth.#
Dibenzothiophene#
C1#dibenzothiophene#
C2#dibenzothiophene#
C3#dibenzothiophene#
C4#dibenzothiophene#
Fluoranthene/Pyrene#
C1#fluoranthene/pyrene#
C2#fluoranthene/pyrene#
C3#fluoranthene/pyrene#
C4#fluoranthene/pyrene#
Benz(a)anthracene/Chrysene#
C1#B(a)A/chrysene#
C2#B(a)A/chrysene#
C3#B(a)A/chrysene#
C4#B(a)A/chrysene#
Benzofluoranthene/Benzopyrene#
C1#benzofluoranthene/benzopyrene#
C2#benzofluoranthene/benzopyrene#
Plains'Product'
0%#
5%#
10%#
15%#
20%#
25%#
30%#
NAP#
C1#NAP#
C2#NAP#
C3#NAP#
C4#NAP#
ACE#
C1#ACE#
BPH#
C1#BPH#
C2#BPH#
FLU#C1#FLU#C2#FLU#C3#FLU#PHE/ANT#
C1#PHE/ANT#
C2#PHE/ANT#
C3#PHE/ANT#
C4#PHE/ANT#
DBT#
C1#DBT#
C2#DBT#
C3#DBT#
C4#DBT#FLRN/PYR#
C1#FLRN/PYR#
C2#FLRN/PYR#
C3#FLRN/PYR#
C4#FLRN/PYR#B(a)A/CHR#
C1#B(a)A/CHR#
C2#B(a)A/CHR#
C3#B(a)A/CHR#
C4#B(a)A/CHR#
BFLRN/BPYR#
C1#BFLRN/BPYR#
C2#BFLRN/BPYR#
Diesel&Fuel&)&0%&
Diesel
Medium Crude
0%#
10%#
20%#
30%#
40%#
50%#
60%#
NAP#
C1#NAP#
C2#NAP#
C3#NAP#
C4#NAP#
ACE#
C1#ACE#
BPH#
C1#BPH#
C2#BPH#
FLU#
C1#FLU#
C2#FLU#
C3#FLU#PHE/ANT#
C1#PHE/ANT#
C2#PHE/ANT#
C3#PHE/ANT#
C4#PHE/ANT#
DBT#
C1#DBT#
C2#DBT#
C3#DBT#
C4#DBT#FLRN/PYR#
C1#FLRN/PYR#
C2#FLRN/PYR#
C3#FLRN/PYR#
C4#FLRN/PYR#B(a)A/CHR#
C1#B(a)A/CHR#
C2#B(a)A/CHR#
C3#B(a)A/CHR#
C4#B(a)A/CHR#
BFLRN/BPYR#
C1#BFLRN/BPYR#
C2#BFLRN/BPYR#
Gasoline
15Whose PAH is this? Envirotech 2018

16. © 2018
Chemistry Matters Inc.
Sample dataset
16
Sample Description Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6
Naphthalene 0.047 0.033 0.013 0.009 0.005 <0.005
2-Methylnaphthalene 0.060 0.051 0.023 0.014 0.015 <0.005
Acenaphthylene <0.005 <0.005 <0.005 <0.005 0.006 <0.005
Acenaphthene <0.005 <0.005 <0.005 <0.005 0.022 <0.005
Fluorene <0.02 <0.02 <0.02 <0.02 0.04 <0.02
Phenanthrene 0.11 0.05 0.02 0.02 0.23 0.19
Anthracene <0.004 <0.004 <0.004 <0.004 0.032 0.052
Fluoranthene <0.01 <0.01 <0.01 <0.01 0.08 0.19
Pyrene <0.01 0.01 <0.01 0.04 0.21 0.49
Benzo[a]anthracene <0.02 <0.02 <0.02 <0.02 0.07 0.14
Chrysene <0.05 <0.05 <0.05 <0.05 0.11 0.36
Benzo[a]pyrene <0.03 <0.03 <0.03 <0.03 0.04 0.05
Dibenzo[ah]anthracene <0.005 <0.005 <0.005 0.006 0.008 0.007
0
100
200
300
400
500
600
700
800
900
1000
NAP C1 NAP C2 NAP C3 NAP C4 NAP
FLU C1 FLU C2 FLU C3 FLU
PHE/ANT
C1 PHE/ANT
C2 PHE/ANT
C3 PHE/ANT
C4 PHE/ANT
DBT C1 DBT C2 DBT C3 DBT C4 DBT
FLRN/PYR
C1 FLRN/PYR
C2 FLRN/PYR
C3 FLRN/PYR
C4 FLRN/PYR
BaA/CHR
C1 BaA/CHR
C2 BaA/CHR
C3 BaA/CHR
C4 BaA/CHR
Concentra)on (mg/kg)
RDR01
Natural source
Whose PAH is this? Envirotech 2018
Instead of three exceedances, can now
demonstrate a fingerprint that is different to
that of the release product.

17. © 2018
Chemistry Matters Inc.
PAH exceedances from background
17
Upstream
0
100
200
300
400
500
600
700
800
900
1000
NAP C1 NAP C2 NAP C3 NAP C4 NAP
FLU C1 FLU C2 FLU C3 FLU
PHE/ANT
C1 PHE/ANT
C2 PHE/ANT
C3 PHE/ANT
C4 PHE/ANT
DBT C1 DBT C2 DBT C3 DBT C4 DBT
FLRN/PYR
C1 FLRN/PYR
C2 FLRN/PYR
C3 FLRN/PYR
C4 FLRN/PYR
BaA/CHR
C1 BaA/CHR
C2 BaA/CHR
C3 BaA/CHR
C4 BaA/CHR
Concentra)on (mg/kg)
RDR01
Natural source
0"
0.05"
0.1"
0.15"
0.2"
0.25"
0.3"
CTRL"S/C"
LTM
3"
LTM
6"
Site"2"
Site"3"
LTM
11C"
LTM
13"
LTM
14"W
BASIN1"W
BASIN2"W
BASIN3"W
BASIN4"W
BASIN5"LTM
16(1)"LTM
16(2)"LTM
16(3)"LTM
16(4)"LTM
16(5)"
LTM
17"
LTM
18"
LTM
19"
LTM
20"
LTM
21"
ConcentraCon"(mg/kg"dry"weight)"
2KMethylKnaphthalene"
Whose PAH is this? Envirotech 2018
Downstream
Why evaluate background?
Demonstration of sources unrelated to release.

18. © 2018
Chemistry Matters Inc. 18
0
100
200
300
400
500
600
700
800
900
Concentration (mg/kg)
RDR15
0
500
1000
1500
2000
2500
Concentration (mg/kg)
RDR20
Whose PAH is this? Envirotech 2018
Highway Runoff
Weathered
Pyrogenic
Vehicular exhaust,
crank case oil drips,
wood preservatives

19. © 2018
Chemistry Matters Inc.
Sample dataset
19
0
100
200
300
400
500
600
700
800
900
Concentration (mg/kg)
RDR15
Sample Description Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6
Naphthalene 0.047 0.033 0.013 0.009 0.005 <0.005
2-Methylnaphthalene 0.060 0.051 0.023 0.014 0.015 <0.005
Acenaphthylene <0.005 <0.005 <0.005 <0.005 0.006 <0.005
Acenaphthene <0.005 <0.005 <0.005 <0.005 0.022 <0.005
Fluorene <0.02 <0.02 <0.02 <0.02 0.04 <0.02
Phenanthrene 0.11 0.05 0.02 0.02 0.23 0.19
Anthracene <0.004 <0.004 <0.004 <0.004 0.032 0.052
Fluoranthene <0.01 <0.01 <0.01 <0.01 0.08 0.19
Pyrene <0.01 0.01 <0.01 0.04 0.21 0.49
Benzo[a]anthracene <0.02 <0.02 <0.02 <0.02 0.07 0.14
Chrysene <0.05 <0.05 <0.05 <0.05 0.11 0.36
Benzo[a]pyrene <0.03 <0.03 <0.03 <0.03 0.04 0.05
Dibenzo[ah]anthracene <0.005 <0.005 <0.005 0.006 0.008 0.007
Highway Runoff
Scary set of exceedances!
Highway bridges can offer easy access for
sampling, but take care to sample upstream
of bridges.
Whose PAH is this? Envirotech 2018

20. © 2018
Chemistry Matters Inc.
Sample dataset
20
Sample Description Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6
Naphthalene 0.047 0.033 0.013 0.009 0.005 <0.005
2-Methylnaphthalene 0.060 0.051 0.023 0.014 0.015 <0.005
Acenaphthylene <0.005 <0.005 <0.005 <0.005 0.006 <0.005
Acenaphthene <0.005 <0.005 <0.005 <0.005 0.022 <0.005
Fluorene <0.02 <0.02 <0.02 <0.02 0.04 <0.02
Phenanthrene 0.11 0.05 0.02 0.02 0.23 0.19
Anthracene <0.004 <0.004 <0.004 <0.004 0.032 0.052
Fluoranthene <0.01 <0.01 <0.01 <0.01 0.08 0.19
Pyrene <0.01 0.01 <0.01 0.04 0.21 0.49
Benzo[a]anthracene <0.02 <0.02 <0.02 <0.02 0.07 0.14
Chrysene <0.05 <0.05 <0.05 <0.05 0.11 0.36
Benzo[a]pyrene <0.03 <0.03 <0.03 <0.03 0.04 0.05
Dibenzo[ah]anthracene <0.005 <0.005 <0.005 0.006 0.008 0.007
Fingerprint consistent with upstream source
Fingerprint consistent with highway source
None of these exceedances are
attributable to the release.
Whose PAH is this? Envirotech 2018

21. © 2018
Chemistry Matters Inc.
Whose PAH is this?
21Whose PAH is this? Envirotech 2018
• Sample background (upstream / upwind…)
• Analyze for alkylated PAH data
0"
500"
1,000"
1,500"
2,000"
2,500"
3,000"
Naphthalene"
20Methylnaphthalene"
2,60Dimethylnaphthalene"
2,3,50Trimethylnaphthalene"
Acenaphthylene"
Acenaphthene"
Fluorene"
Phenanthrene"
10Methylphenanthrene"
Anthracene"
Fluoranthene"
Pyrene"
Benz[a]anthracene"
Chrysene"
Benzo[b]fluoranthene"
Benzo[j,k]fluoranthenes"*"
Benzo[e]pyrene"
Benzo[a]pyrene"
Perylene"
Dibenz[a,h]anthracene"
Indeno[1,2,30cd]pyrene"
Benzo[ghi]perylene"
Dibenzothiophene"
Lipid%normalized%concentra0on%(ng/g)%
Unexpected sources
0
100
200
300
400
500
600
700
800
900
1000
NAP C1 NAP C2 NAP C3 NAP C4 NAP
FLU C1 FLU C2 FLU C3 FLU
PHE/ANT
C1 PHE/ANT
C2 PHE/ANT
C3 PHE/ANT
C4 PHE/ANT
DBT C1 DBT C2 DBT C3 DBT C4 DBT
FLRN/PYR
C1 FLRN/PYR
C2 FLRN/PYR
C3 FLRN/PYR
C4 FLRN/PYR
BaA/CHR
C1 BaA/CHR
C2 BaA/CHR
C3 BaA/CHR
C4 BaA/CHR
Concentra)on (mg/kg)
RDR01
0
500
1000
1500
2000
2500
Concentration (mg/kg)
RDR20
Background PAH sources
Highway sources
0%
2%
4%
6%
8%
10%
12%
14%
16%
18%
0%#
5%#
10%#
15%#
20%#
25%#
30%#
NAP#
C1#NAP#
C2#NAP#
C3#NAP#
C4#NAP#
ACE#
C1#ACE#
BPH#
C1#BPH#
C2#BPH#
FLU#C1#FLU#C2#FLU#C3#FLU#PHE/ANT#
C1#PHE/ANT#
C2#PHE/ANT#
C3#PHE/ANT#
C4#PHE/ANT#
DBT#
C1#DBT#
C2#DBT#
C3#DBT#
C4#DBT#FLRN/PYR#
C1#FLRN/PYR#
C2#FLRN/PYR#
C3#FLRN/PYR#
C4#FLRN/PYR#B(a)A/CHR#
C1#B(a)A/CHR#
C2#B(a)A/CHR#
C3#B(a)A/CHR#
C4#B(a)A/CHR#
BFLRN/BPYR#
C1#BFLRN/BPYR#
C2#BFLRN/BPYR#
Diesel&Fuel&)&0%&
Product type

22. © 2018
Chemistry Matters Inc.
Diagnostic Ratios
22
Distinguishing features based on physical chemistry.
Whose PAH is this? Envirotech 2018
Sulfur content – Exxon Valdez (1989)
Phenanthrene
Dibenzothiophene
Pyrogenicity – Fraser River (2002)
Pyrene
Fluoranthene

23. © 2018
Chemistry Matters Inc.
0"
0.2"
0.4"
0.6"
0.8"
1"
1.2"
1.4"
1.6"
0" 0.2" 0.4" 0.6" 0.8" 1" 1.2"
C4#DBT'/'C4#Phen'
C3#DBT'/'C3#Phen'
Dibenzothiophene'/'Phenanthrene'Diagnos8c'Ra8os'Plot'
Oil"Product"
Upstream"of"Spill"
Diagnostic Ratios
Often crude can be distinguished from natural sources based on sulfur content
Product A
Natural Background
23Whose PAH is this? Envirotech 2018

24. © 2018
Chemistry Matters Inc.
0"
0.2"
0.4"
0.6"
0.8"
1"
1.2"
1.4"
1.6"
0" 0.2" 0.4" 0.6" 0.8" 1" 1.2"
C4#DBT'/'C4#Phen'
C3#DBT'/'C3#Phen'
Dibenzothiophene'/'Phenanthrene'Diagnos8c'Ra8os'Plot'
Oil"Product"
Upstream"of"Spill"
Impacted"Area"
Other"Areas"
Diagnostic Ratios
Partially Impacted Samples
Unimpacted Samples
24Whose PAH is this? Envirotech 2018

25. © 2018
Chemistry Matters Inc.
!4#
!2#
0#
2#
4#
6#
8#
!6# !4# !2# 0# 2# 4# 6# 8# 10# 12# 14#
PC2$
PC1$
Oil#Product#
Upstream#of#Spill#
Downstream#of#Spill#
Spill Oil
Non-impacted Area
Other Areasx
25Whose PAH is this? Envirotech 2018
Principle Component Analysis
Statistical technique for
looking at the whole
dataset.
Samples with PAHs
from Spill Oil
Samples with only
background PAHs

26. © 2018
Chemistry Matters Inc. 26Whose PAH is this? Envirotech 2018
Source Apportionment
• Demonstration of sources.
• Quantify amount of PAHs due to each source.
0
5
10
15
20
25
30
35
40
45
16-SA73 - 0 km
16-SA70 - 0 km
16-SA20 - 3.47 km
16-SA23 - 3.74 km
16-SA21 - 3.79 km
16-SA22 - 3.81 km
16-SA24 - 4.61 km
16-SA26 - 6.96 km
16-SA25 - 7.4 km
16-SA28 - 8.38 km
16-SA27 - 9.35 km
16-SA30 - 11.59 km
16-SA29 - 11.63 km
16-SA46 - 26.12 km
16-SA44 - 27.39 km
16-SA43 - 28.45 km
16-SA31 - 28.93 km
16-SA40 - 29.2 km
16-SA40 - 29.2 km
16-SA42 - 29.51 km
16-SA38 - 30.08 km
16-SA33 - 30.74 km
16-SA37 - 31.8 km
16-SA36 - 32.44 km
16-SA32 - 32.44 km
16-SA35 - 32.74 km
16-SA51 - 48.63 km
16-SA55 - 51.93 km
16-SA54 - 52.3
16-SA5216
Sum PAH (mg/kg)
Bo/om Oil
Source A
Source B

27. © 2018
Chemistry Matters Inc.
Conclusions
• Tabulation of detects or exceedances may be misleading.
• There are many PAH sources other than a released product.
• PAH data should make sense.
• Make sure you collect sufficiently powerful analytical data.
• Forensic techniques show sources and histories.
27Whose PAH is this? Envirotech 2018

28. © 2018
Chemistry Matters Inc.
Thank you for your attention
Contact Info:
Chemistry Matters Inc.
Court Sandau
Cell: 403.669.8566
Email: csandau@chemistry-matters.com
www.chemistry-matters.com
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Whose PAH is this? Envirotech 2018 28