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©	2015		
Chemistry	Ma2ers	Inc. 1	AGAT	Science	and	Technology	Talks	2016	
Making	environmental	data	meaningful	
Use	of	Envi...
©	2015		
Chemistry	Ma2ers	Inc.
Acknowledgements	
2	
•  Phil	Richards,	MChem,	MRes,	PhD,	PChem	
	
	
•  AGAT	Laboratories	Lt...
©	2015		
Chemistry	Ma2ers	Inc.
Environmental Forensic Investigation
‘Forensics’ - the application of scientific knowledge ...
©	2015		
Chemistry	Ma2ers	Inc.
Birthplace of Environmental
Forensics
Exxon Valdez 1989
Term “Environmental Forensics”
coin...
©	2015		
Chemistry	Ma2ers	Inc.
Petroleum Hydrocarbons – A lot of
Compounds to Choose From
Unresolved Complex
Matter
Nelson...
©	2015		
Chemistry	Ma2ers	Inc.
Case	Study	#1	–	Phytogenic	vs.	Petrogenic	
Hydrocarbons	
•  Petroleum	release	in	peat	(bog/...
©	2015		
Chemistry	Ma2ers	Inc. 7	
Muskeg is a very rich organic environment > 50% TOC
PHC Fractions analysis cannot differ...
©	2015		
Chemistry	Ma2ers	Inc.
PHC	FracKons	Results	
8	AGAT	Science	and	Technology	Talks	2016	
PHC F3 – above guidelines i...
©	2015		
Chemistry	Ma2ers	Inc.
Source	Sample	
9	
F2 F3 F4
31000 210000 430000
Large	UCM		
no	prominent	peaks	
AGAT	Science...
©	2015		
Chemistry	Ma2ers	Inc.
Natural	Peat	
10	
F2 F3 F4
290 2300 800
Prominent	peaks	
Typical	paYern	for	peat	
AGAT	Scie...
©	2015		
Chemistry	Ma2ers	Inc.
Mixture	of	Source	Material	and	Natural	Peat	
11	
F2 F3 F4
320 3100 1300
Clear	mixture	of	so...
©	2015		
Chemistry	Ma2ers	Inc.
Biomarker	Analysis	
12	
Chemicals	found	in	petrogenic	hydrocarbons	and	not	found	in	
phytog...
©	2015		
Chemistry	Ma2ers	Inc.
Diagenesis	
Sterols	to	steranes	
13	
Cholestadienol	 Cholestane	
Diagenesis	
Plant	structur...
©	2015		
Chemistry	Ma2ers	Inc.
Source	Sample		
steranes	and	hopanes	
14	
C23,	C24,	C25,	C26	
tricyclic	terpanes	
Hopanes	
...
©	2015		
Chemistry	Ma2ers	Inc.
Biomarkers
in Site Samples
Petroleum	
Biomarker	
Standard	
Site									
Sample	
15	AGAT	Sc...
©	2015		
Chemistry	Ma2ers	Inc.
Peat	Sample		
fa2y	acids	and	alcohols	
16	
1.	Hexadecanoic	acid	(C16)	
2.	Octadecanoic	acid...
©	2015		
Chemistry	Ma2ers	Inc.
Peat	Sample		
sterols	
17	
Gamma-sitasterol	Ergosterol	
Cholestadienol	
Cyclolanostanol	
AG...
©	2015		
Chemistry	Ma2ers	Inc.
Plant	cell	structure	
18	
Sterols		
Fa2y	acids	 Fa2y	acids	
AGAT	Science	and	Technology	Tal...
©	2015		
Chemistry	Ma2ers	Inc.
•  Natural phytogenic hydrocarbons can
be above guidelines peatlands
•  Biomarker analysis ...
©	2015		
Chemistry	Ma2ers	Inc.
Case	Study	#2	–	Tracking	Odours	from	Oil	
and	Gas	AcKviKes	
•  DirecSve	60	requires	no	odou...
©	2015		
Chemistry	Ma2ers	Inc.
Potential Sources
•  Source	samples	collected	near	various	operators	in	the	region	
•  Comp...
©	2015		
Chemistry	Ma2ers	Inc.
VOCs
0"
0.05"
0.1"
0.15"
0.2"
0.25"
0.3"
0.35"
0" 1" 2" 3" 4" 5" 6"
NMHC%(ppm)%
Methane%(pp...
©	2015		
Chemistry	Ma2ers	Inc.
C6-ratio
1"
2"
3"
4"
5"
6"
7"
8"
9"
10"
11"
12"
397"
14"
15"16"17"
18"
19"
20"
25" 26"
a"
b...
©	2015		
Chemistry	Ma2ers	Inc.
Butane isomers
1"
2"
3"
4"5"
6"
7"
8"
9" 10"
11"
12"
14"
15"
16"
17"
18"
19"
20"
21"
22"
23...
©	2015		
Chemistry	Ma2ers	Inc.
Better interpretation?
Diagnostic ratios are indicators for only 2 chemicals.
But, we can d...
©	2015		
Chemistry	Ma2ers	Inc.
PCA
1"
2"
3"
4"
5"
6"
7" 8"
9"
10"
11"
12"
13"
14"
15"
16"
17"
18"
19"
20"
21"
22"
23"
24"
...
©	2015		
Chemistry	Ma2ers	Inc.
R&D for a Solution
•  Working with laboratories and
industry to develop new forensics
appro...
©	2015		
Chemistry	Ma2ers	Inc.
•  Routine air monitoring of VOCs provides valuable data to
potentially determine sources
•...
©	2015		
Chemistry	Ma2ers	Inc.
Case	Study	#3	–	PAHs	in	Sediments	
•  Sediments	in	waterways	serve	as	sinks	to	PAHs	
•  Run...
©	2015		
Chemistry	Ma2ers	Inc.
Fingerprint Graphs
0%#
2%#
4%#
6%#
8%#
10%#
12%#
NAP#
C1#NAP#
C2#NAP#
C3#NAP#
C4#NAP#
ACE#
...
©	2015		
Chemistry	Ma2ers	Inc.
Oil Types
0%#
2%#
4%#
6%#
8%#
10%#
12%#
14%#
16%#
18%#
NAP#
C1#NAP#
C2#NAP#
C3#NAP#
C4#NAP#...
©	2015		
Chemistry	Ma2ers	Inc.
Product Types
0%#
2%#
4%#
6%#
8%#
10%#
12%#
14%#
NAP#
C1#NAP#
C2#NAP#
C3#NAP#
C4#NAP#
ACE#C...
©	2015		
Chemistry	Ma2ers	Inc.
Petrogenic / Pyrogenic
0%#
5%#
10%#
15%#
20%#
25%#
30%#
35%#
NAP#
C1#NAP#
C2#NAP#
C3#NAP#
C...
©	2015		
Chemistry	Ma2ers	Inc. 34	
Fluoranthene Pyrene
10 1
1 10
Pyrogenic
Petrogenic
•  Formed within different environme...
©	2015		
Chemistry	Ma2ers	Inc.
Double	RaKo	Plots	to	DisKnguish	Source	
35	
0.0#
0.2#
0.4#
0.6#
0.8#
1.0#
1.2#
1.4#
0.0# 0....
©	2015		
Chemistry	Ma2ers	Inc.
Principle Components Analysis
A double ratio plot is good for 4 compounds.
But, we can do b...
©	2015		
Chemistry	Ma2ers	Inc.
!4#
!2#
0#
2#
4#
6#
8#
!6# !4# !2# 0# 2# 4# 6# 8# 10# 12# 14#
PC2$
PC1$
Oil#Product#
Upstre...
©	2015		
Chemistry	Ma2ers	Inc.
!4#
!2#
0#
2#
4#
6#
8#
!6# !4# !2# 0# 2# 4# 6# 8# 10# 12# 14#
PC2$
PC1$
Oil#Product#
Upstre...
©	2015		
Chemistry	Ma2ers	Inc.
•  PAH fingerprints and marker compounds can identify
multiple sources
•  Use of patterns, ...
©	2015		
Chemistry	Ma2ers	Inc.
12C-2378-
TCDD
in Serum
Using cryo-focusing and HRMS, can achieve 540 ag 2378-
TCDD, assumi...
©	2015		
Chemistry	Ma2ers	Inc.
Where	is	Science	Going?	
41	
Genomic Testing
AGAT	Science	and	Technology	Talks	2016	
Microa...
©	2015		
Chemistry	Ma2ers	Inc.
Conventional GC Analysis
Unresolved Complex
Matter
Nelson et al. Environmental Forensics, 7...
©	2015		
Chemistry	Ma2ers	Inc.
Two-Dimensional
Gas Chromatography
Nelson et al. Environmental Forensics, 7:33–44, 2006
AGA...
©	2015		
Chemistry	Ma2ers	Inc.
40 60 80 100 120 140 160 180 200 220 240
500
1000
93
77
39 12167 10750 136
Peak True - samp...
©	2015		
Chemistry	Ma2ers	Inc.
Local Supply of Shell Diesel
AGAT	Science	and	Technology	Talks	2016	 45
©	2015		
Chemistry	Ma2ers	Inc.
Middle East Crude Oil Investigation
Alkyl	Phenanthrenes/Anthracenes
Alkyl	Naphthalenes
Alky...
©	2015		
Chemistry	Ma2ers	Inc.
2D-GC Chromatogram
Gasoline sample
Soil sample
Arson	InvesKgaKon	
AGAT	Science	and	Technolo...
©	2015		
Chemistry	Ma2ers	Inc.
Comparison of Gasolines
Esso
Shell
48© 2015
Chemistry Matters Inc.
©	2015		
Chemistry	Ma2er...
©	2015		
Chemistry	Ma2ers	Inc. 49	
Conclusions	
•  Environmental	Forensics	can	be	used	
to	help	determine	the	source	of	mo...
©	2015		
Chemistry	Ma2ers	Inc.
Thank you for your attention
Contact Info:
Chemistry Matters Inc.
Court Sandau
Cell: 403.66...
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Enviromental Forensics Petroleum Releases 2016

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Presentation provides overview of different case studies that used environmental forensics to investigate sources of petroleum releases. Case studies include biomarker analysis to aid in identifying phytogenic and petrogenic hydrocarbons, volatile organic compounds for emission source apportionment and polycyclic aromatic hydrocarbons (PAHs) in sediments.

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Enviromental Forensics Petroleum Releases 2016

  1. 1. © 2015 Chemistry Ma2ers Inc. 1 AGAT Science and Technology Talks 2016 Making environmental data meaningful Use of Environmental Forensics for Petroleum Releases Defining what is yours and what isn’t Court D. Sandau, PhD, PChem January 29, 2016 – AGAT Science and Technology Talks
  2. 2. © 2015 Chemistry Ma2ers Inc. Acknowledgements 2 •  Phil Richards, MChem, MRes, PhD, PChem •  AGAT Laboratories Ltd. AGAT Science and Technology Talks 2016
  3. 3. © 2015 Chemistry Ma2ers Inc. Environmental Forensic Investigation ‘Forensics’ - the application of scientific knowledge and analysis for public discussion/debate OR potential litigious issues “The application of scientific methods used to identify the origin and timing of a contaminant release” AGAT Science and Technology Talks 2016 3
  4. 4. © 2015 Chemistry Ma2ers Inc. Birthplace of Environmental Forensics Exxon Valdez 1989 Term “Environmental Forensics” coined in Dr. Robert Morrison’s first book since it was used in a peer reviewed publication. 4 AGAT Science and Technology Talks 2016
  5. 5. © 2015 Chemistry Ma2ers Inc. Petroleum Hydrocarbons – A lot of Compounds to Choose From Unresolved Complex Matter Nelson et al. Environmental Forensics, 7:33–44, 2006 Straight chained alkanes PAHs Biomarkers The rest AGAT Science and Technology Talks 2016 5 VOCs
  6. 6. © 2015 Chemistry Ma2ers Inc. Case Study #1 – Phytogenic vs. Petrogenic Hydrocarbons •  Petroleum release in peat (bog/fen) •  Former oil well, residual hydrocarbon impacts –  Previous remedial work; admixing of soil •  Client seeking reclamaSon cerSficate 6 AGAT Science and Technology Talks 2016
  7. 7. © 2015 Chemistry Ma2ers Inc. 7 Muskeg is a very rich organic environment > 50% TOC PHC Fractions analysis cannot differentiate natural hydrocarbons (phytogenic) from petroleum hydrocarbons (petrogenic). AGAT Science and Technology Talks 2016
  8. 8. © 2015 Chemistry Ma2ers Inc. PHC FracKons Results 8 AGAT Science and Technology Talks 2016 PHC F3 – above guidelines in background areas.
  9. 9. © 2015 Chemistry Ma2ers Inc. Source Sample 9 F2 F3 F4 31000 210000 430000 Large UCM no prominent peaks AGAT Science and Technology Talks 2016
  10. 10. © 2015 Chemistry Ma2ers Inc. Natural Peat 10 F2 F3 F4 290 2300 800 Prominent peaks Typical paYern for peat AGAT Science and Technology Talks 2016
  11. 11. © 2015 Chemistry Ma2ers Inc. Mixture of Source Material and Natural Peat 11 F2 F3 F4 320 3100 1300 Clear mixture of source and peat chemicals AGAT Science and Technology Talks 2016
  12. 12. © 2015 Chemistry Ma2ers Inc. Biomarker Analysis 12 Chemicals found in petrogenic hydrocarbons and not found in phytogenic hydrocarbons. o  Terpanes – prokaryotes (archaea and bacteria) o  Steranes – eukaryotes (plants and animals) AGAT Science and Technology Talks 2016
  13. 13. © 2015 Chemistry Ma2ers Inc. Diagenesis Sterols to steranes 13 Cholestadienol Cholestane Diagenesis Plant structural membrane chemical Oil biomarker Diagenesis – low pressure and low temperature change in deposited sediment as it undergoes solidificaSon. AGAT Science and Technology Talks 2016
  14. 14. © 2015 Chemistry Ma2ers Inc. Source Sample steranes and hopanes 14 C23, C24, C25, C26 tricyclic terpanes Hopanes AGAT Science and Technology Talks 2016
  15. 15. © 2015 Chemistry Ma2ers Inc. Biomarkers in Site Samples Petroleum Biomarker Standard Site Sample 15 AGAT Science and Technology Talks 2016
  16. 16. © 2015 Chemistry Ma2ers Inc. Peat Sample fa2y acids and alcohols 16 1. Hexadecanoic acid (C16) 2. Octadecanoic acid (C18) 3. Eicosanoic acid (C20) 4. Docosanoic acid (C22) 5. Tetracosanoic acid (C24) 6. Hexacosanol (C26) 7. Octacosanol (C28) 8. Decacosanol (C30) 1 2 3 4 5 6 7 8 AGAT Science and Technology Talks 2016
  17. 17. © 2015 Chemistry Ma2ers Inc. Peat Sample sterols 17 Gamma-sitasterol Ergosterol Cholestadienol Cyclolanostanol AGAT Science and Technology Talks 2016
  18. 18. © 2015 Chemistry Ma2ers Inc. Plant cell structure 18 Sterols Fa2y acids Fa2y acids AGAT Science and Technology Talks 2016
  19. 19. © 2015 Chemistry Ma2ers Inc. •  Natural phytogenic hydrocarbons can be above guidelines peatlands •  Biomarker analysis can differentiate phytogenic vs. petrogenic materials •  Conclusive assessment and remediation tool •  Definitive Closure •  Cost/Time Efficient •  Everyone Wins •  Lab - good science •  Consultant - sound decisions •  Client - closure and assurance •  Site - minimal disturbance in a peatland Case Study #1 - Conclusions 19 AGAT Science and Technology Talks 2016
  20. 20. © 2015 Chemistry Ma2ers Inc. Case Study #2 – Tracking Odours from Oil and Gas AcKviKes •  DirecSve 60 requires no odours off-lease •  Open venSng of CHOPS faciliSes in area as well as other types of producSon •  Use staSsScal analysis to determine potenSal sources 20 AGAT Science and Technology Talks 2016
  21. 21. © 2015 Chemistry Ma2ers Inc. Potential Sources •  Source samples collected near various operators in the region •  Compared to samples from air monitoring trailers during odourous event •  Odourous events were triggered samples from one of the two monitoring staSons •  No events associated with source samples in original publicaSon of results AGAT Science and Technology Talks 2016 21
  22. 22. © 2015 Chemistry Ma2ers Inc. VOCs 0" 0.05" 0.1" 0.15" 0.2" 0.25" 0.3" 0.35" 0" 1" 2" 3" 4" 5" 6" NMHC%(ppm)% Methane%(ppm)% Trailer"986" Hours"Surrounding" Triggered"Samples" 0" 0.05" 0.1" 0.15" 0.2" 0.25" 0.3" 0.35" 0" 50" 100" 150" 200" 250" 300" 350" 400" NMHC% Wind%Direc.on% Con.nuous%NMHC%Data%Plo6ed%with%Wind%Direc.on% Trailer"986" Hours"Surrounding" Triggered"Samples" Correlation between various VOCs. (methane, NMHCs, TRS, SO2). Wind direction data indicates general origin from the oilfield (multiple parties) Triggered Samples Other Samples AGAT Science and Technology Talks 2016 22
  23. 23. © 2015 Chemistry Ma2ers Inc. C6-ratio 1" 2" 3" 4" 5" 6" 7" 8" 9" 10" 11" 12" 397" 14" 15"16"17" 18" 19" 20" 25" 26" a" b" c" d" e" g" h" j" E" F" G" H" I" J" K" L" M" A" B" N" O" Q" R" 0.1" 1" 10" 100" 0.1" 1" 10" 100" 1000" 10000" 100000" 1000000" cyclohexane*/*benzene* benzene*concentra0on*(ppbv)* PotenHal"Source"Facility"(AE)" Field"Sample"(AE)" Three"Creeks"Trailer"Sample" Petrogenic Combustion benzene cyclohexane AGAT Science and Technology Talks 2016 23
  24. 24. © 2015 Chemistry Ma2ers Inc. Butane isomers 1" 2" 3" 4"5" 6" 7" 8" 9" 10" 11" 12" 14" 15" 16" 17" 18" 19" 20" 21" 22" 23" 24" 25" 26" a" b"c" d" e" f" g" h" i" j" E" F" G" H" I" J" K" L" M" A" B" N" O" P" Q" R" 0.05" 0.5" 5" 0.1" 1" 10" 100" 1000" 10000" 100000" 1000000" 10000000" 100000000" i"butane)/)n"butane)ra,o) n"butane)concentra,on)(ppbv)) PotenJal"Source"Facility"(AE)" Field"Sample"(AE)" Three"Creeks"Trailer"Sample" Petrogenic Combustion n-butane i-butane AGAT Science and Technology Talks 2016 24
  25. 25. © 2015 Chemistry Ma2ers Inc. Better interpretation? Diagnostic ratios are indicators for only 2 chemicals. But, we can do better… we can develop analysis to consider variability within all chemicals – Principle Components Analysis (PCA) A multi-variate statistical analysis that can be used as an exploratory data analysis technique AGAT Science and Technology Talks 2016 25
  26. 26. © 2015 Chemistry Ma2ers Inc. PCA 1" 2" 3" 4" 5" 6" 7" 8" 9" 10" 11" 12" 13" 14" 15" 16" 17" 18" 19" 20" 21" 22" 23" 24" 25" 26" A" B" C" D" E" F" G" J"I" H" K" L" M" 93" 92" 91" 0" 1" 2" 3" 4" 92" 91" 0" 1" 2" 3" 4" 5" 6" Principle)Component)2) Principle)Component)1) Poten?al"Source"Facility"(AE)" Three"Creeks"Trailer"Sample" Combustion Toluene-rich sourcePetrogenic AGAT Science and Technology Talks 2016 26
  27. 27. © 2015 Chemistry Ma2ers Inc. R&D for a Solution •  Working with laboratories and industry to develop new forensics approach for source apportionment •  Using 2D-GC-TOFMS we can: •  Detect unlimited numbers of VOCs •  Detect very low concentrations of VOCs •  Identify every compound with full scan mass spectrometry and library matches •  Provides un-paralleled fingerprinting capabilities to determine source AGAT Science and Technology Talks 2016 27
  28. 28. © 2015 Chemistry Ma2ers Inc. •  Routine air monitoring of VOCs provides valuable data to potentially determine sources •  Need to use the right marker compounds and statistical analysis techniques •  More data could provide better fingerprinting (future of environmental forensics) Case Study #2 - Conclusions 28 AGAT Science and Technology Talks 2016
  29. 29. © 2015 Chemistry Ma2ers Inc. Case Study #3 – PAHs in Sediments •  Sediments in waterways serve as sinks to PAHs •  Runoff from mulSple sources make paYern assessment difficult 29 AGAT Science and Technology Talks 2016 •  Expanded suite of alkylated and parent PAHs helps with idenSficaSon of sources Days Weeks Months Years BTEX Alkanes Biomarkers PAHs
  30. 30. © 2015 Chemistry Ma2ers Inc. Fingerprint Graphs 0%# 2%# 4%# 6%# 8%# 10%# 12%# 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# Bunker'C')'0%' Naphthalene C1-Naphthalenes C2-Naphthalenes C3-Naphthalenes … … … 30 AGAT Science and Technology Talks 2016
  31. 31. © 2015 Chemistry Ma2ers Inc. Oil Types 0%# 2%# 4%# 6%# 8%# 10%# 12%# 14%# 16%# 18%# 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# K1A$Source+ 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' Light Crude Light PAHs dominant Nice bell-shaped patterns Bitumen Heavy PAHs dominant Mixed patterns 31 AGAT Science and Technology Talks 2016
  32. 32. © 2015 Chemistry Ma2ers Inc. Product Types 0%# 2%# 4%# 6%# 8%# 10%# 12%# 14%# 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# No.$5$Fuel$Oil$,$0%$ 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%& 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 Diesel Fuel Oil 32 AGAT Science and Technology Talks 2016
  33. 33. © 2015 Chemistry Ma2ers Inc. Petrogenic / Pyrogenic 0%# 5%# 10%# 15%# 20%# 25%# 30%# 35%# 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# EPRI%Study%PAHs%.%Petroleum%Tar%% 0%# 2%# 4%# 6%# 8%# 10%# 12%# 14%# 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# No.$5$Fuel$Oil$,$0%$ Petrogenic Bell-shaped family groups Oil products Pyrogenic scree-shaped family groups Combustion products 33 AGAT Science and Technology Talks 2016
  34. 34. © 2015 Chemistry Ma2ers Inc. 34 Fluoranthene Pyrene 10 1 1 10 Pyrogenic Petrogenic •  Formed within different environments •  Both have similar responses in the environment (biological decomposition rate) (water solubility) •  FLRN – kinetically favoured, PYR – themodynamically favoured Foundation of PAH Ratios AGAT Science and Technology Talks 2016
  35. 35. © 2015 Chemistry Ma2ers Inc. Double RaKo Plots to DisKnguish Source 35 0.0# 0.2# 0.4# 0.6# 0.8# 1.0# 1.2# 1.4# 0.0# 0.2# 0.4# 0.6# 0.8# 1.0# 1.2# 1.4# 1.6# IcdP#/#BghiP# FLRN#/#PYR# Field&Data& MGP&Source&1& MGP&Source&2& Petroleum&Source&3& Petroleum) Liquid)Fuel) Coal)pyrolysis/combus7on) Pyrolysis/Combus7on) AGAT Science and Technology Talks 2016
  36. 36. © 2015 Chemistry Ma2ers Inc. Principle Components Analysis A double ratio plot is good for 4 compounds. But, we can do better… we can develop analysis to consider variability within all chemicals – Principle Components Analysis (PCA) AGAT Science and Technology Talks 2016 36
  37. 37. © 2015 Chemistry Ma2ers 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# Principle Components Analysis Spill Oil Non-impacted Area Other Areasx AGAT Science and Technology Talks 2016 37
  38. 38. © 2015 Chemistry Ma2ers 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# PAHs from Spill Oil PAHs not from Spill Oil Principle Components Analysis Spill Oil Non-impacted Area Other Areasx 38 AGAT Science and Technology Talks 2016
  39. 39. © 2015 Chemistry Ma2ers Inc. •  PAH fingerprints and marker compounds can identify multiple sources •  Use of patterns, marker compounds, double ratio plots, and statistics can help determine when multiple sources are mixed together Case Study #3 - Conclusions 39 AGAT Science and Technology Talks 2016
  40. 40. © 2015 Chemistry Ma2ers Inc. 12C-2378- TCDD in Serum Using cryo-focusing and HRMS, can achieve 540 ag 2378- TCDD, assuming 70 % recovery; S/N 474 (4 Sigma) m/z 319.8965 [M] Dr. Donald G. Patterson, Jr and Wayman Turner at CDC Zoex - loop modulator 40 AGAT Science and Technology Talks 2016 Where is Science Going?
  41. 41. © 2015 Chemistry Ma2ers Inc. Where is Science Going? 41 Genomic Testing AGAT Science and Technology Talks 2016 Microarray Analysis http://www.mdpi.com/1422-0067/11/9/3397?trendmd-shared=0 http://csmbio.csm.jmu.edu/bioweb/Bio480/Fall07/ microarray/group9/understanding_oxidative_pathways.htm Big Data!!!
  42. 42. © 2015 Chemistry Ma2ers Inc. Conventional GC Analysis Unresolved Complex Matter Nelson et al. Environmental Forensics, 7:33–44, 2006 Straight chained alkanes PAHs Biomarkers The rest AGAT Science and Technology Talks 2016 42
  43. 43. © 2015 Chemistry Ma2ers Inc. Two-Dimensional Gas Chromatography Nelson et al. Environmental Forensics, 7:33–44, 2006 AGAT Science and Technology Talks 2016 43
  44. 44. © 2015 Chemistry Ma2ers Inc. 40 60 80 100 120 140 160 180 200 220 240 500 1000 93 77 39 12167 10750 136 Peak True - sample "L1019714-37 straight:1", peak 435, at 2486 , 1.350 sec , sec 40 60 80 100 120 140 160 180 200 220 240 500 1000 93 77 41 12110553 67 136 Library Hit - similarity 836, "à-Pinene" 4D 1D 2D 3D AGAT Science and Technology Talks 2016 44 Four Dimensions?
  45. 45. © 2015 Chemistry Ma2ers Inc. Local Supply of Shell Diesel AGAT Science and Technology Talks 2016 45
  46. 46. © 2015 Chemistry Ma2ers Inc. Middle East Crude Oil Investigation Alkyl Phenanthrenes/Anthracenes Alkyl Naphthalenes Alkyl Benzenes Alkanes AGAT Science and Technology Talks 2016 46
  47. 47. © 2015 Chemistry Ma2ers Inc. 2D-GC Chromatogram Gasoline sample Soil sample Arson InvesKgaKon AGAT Science and Technology Talks 2016 47 © 2015 Chemistry Ma2ers Inc.
  48. 48. © 2015 Chemistry Ma2ers Inc. Comparison of Gasolines Esso Shell 48© 2015 Chemistry Matters Inc. © 2015 Chemistry Ma2ers Inc. AGAT Science and Technology Talks 2016 48
  49. 49. © 2015 Chemistry Ma2ers Inc. 49 Conclusions •  Environmental Forensics can be used to help determine the source of most contaminaSon •  Some techniques are just good, solid science •  New techniques use latest instrumentaSon and new methods of analysis AGAT Science and Technology Talks 2016
  50. 50. © 2015 Chemistry Ma2ers Inc. Thank you for your attention Contact Info: Chemistry Matters Inc. Court Sandau Cell: 403.669.8566 URL: chemistry-matters.com Visit my website and sign up for email for automatic receipt of my blogs! Twitter: @Chem_Matters LinkedIn: ca.linkedin.com/in/courtsandau Slideshare: www.slideshare.net/csandau 50 AGAT Science and Technology Talks 2016

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