comprehensive two-dimensional gas ... - gulf coast … · date 21 steranes/diasteranes: molecular...
TRANSCRIPT
COMPREHENSIVE TWO-DIMENSIONAL GAS
CHROMATOGRAPHIC (GC×GC) PETROLEUM FINGERPRINTING
UTILIZING TRADITIONAL & NON-TRADITIONAL BIOMARKERS
AND HIGH RESOLUTION TIME OF FLIGHT MASS
SPECTROMETRY PETROLEOMICS SPECTRAL ANALYSIS TOOLS
Gulf Coast Conference – Galveston, Texas October 16, 2018
Robert K. Nelson,† Jagoš R. Radović, ∫∫ & Christopher M. Reddy†
†Department of Marine Chemistry & Geochemistry,Woods Hole Oceanographic Institution, Woods Hole, MA, USA
∫∫Department of Geoscience, University of Calgary, Calgary, Alberta, Canada
DATE
2
Abstract
In order to perform detailed studies on the source, transport, and ultimate fate of acute and chronic releases of petroleum hydrocarbons, high-resolution separations of target and non-target compounds and compound classes from complex mixtures such as petroleum frequently require techniques with high resolving power. Comprehensive two-dimensional gas chromatography (GC×GC) coupled with flame ionization detection (FID), time of flight mass spectrometry (TOF-MS), and high resolution time of flight mass spectrometry (HRT-MS) are three of the high resolution tools employed in our laboratory for high fidelity chromatographic separations of useful biomarker compounds (molecular fossils) for petroleum forensics. Here we present a number of examples of crude oil fingerprinting examples utilizing traditional and un-traditional oil spill forensic compounds in order to gain a more complete understanding of (a) which compounds persist in the environment and (b) how we can use high resolution techniques to forensically identify specific petroleum sources.
October 16, 2018
DATE
3
Goals – To Forensically Identify Crude Oil and Refined
Petroleum Products Released Into The Environment
Study the ultimate fate of spilled petroleum products – can we predict how spilled products will
weather?
Can we provide useful an timely information to spill response and damage assessment
professionals?
By comparing results from spills that have occurred over the past 40 years can we forecast and
hind-cast complex petroleum weathering effects such as biodegradation, photooxidation,
evaporation, and dissolution.
Utilize traditional and non-traditional biomarker compounds to identify release sources.
*Adding new forensic compounds to our arsenal.
To do this, we seek to compare and contrast the composition of spilled products in order to
identify molecular insights that expand our traditional approaches to studying spills.
October 16, 2018
DATE
4
We Study Crude Oil and
Refined Petroleum Product Spills
Florida; Buzzards Bay, MA (1969) Bouchard 65; Buzzards Bay, MA (1974)
Bouchard 120; Buzzards Bay, MA (2003) Hebei Spirit; South Korea (2007) Prestige; Portugal (2002)
Exxon Valdez (1989)
October 16, 2018
DATE
5
We Study
Known & Unknown Samples
Natural oil seeps; Gulf of Mexico (everyday)
DDT/oil residues; CA coast (1950s/1960s) Unknown samples; Gulf of Mexico (2014)
Natural oil seeps; Santa Barbara, CA (everyday)
Texas City (Kirby); Galveston, TX (2014)
Sundarbans; Bangladesh (2014)
October 16, 2018
DATE
6
We Study Pipeline Spills and Other Accidents
Kalamazoo River; Michigan (2010) Yellowstone River; Montana (2015) Sanchi Tanker; Condensate, East China Sea (2018)
Refugio pipeline; Highway 101, CA (2015)
October 16, 2018
DATE
7
USS Arizona – Pearl Harbor, Hawaii
October 16, 2018
DATE
8
GC×GC Facility at WHOI
https://www2.whoi.edu/site/gcxgcfacility/
October 16, 2018
DATE
9
What happens to petroleum in the environment?
October 16, 2018
DATE
10
Forensically Useful Petroleum Biomarkers
Environmentally recalcitrant molecules are the most useful
compounds for fingerprinting petroleum products.
These molecules should not susceptible to:
Evaporation
Photooxidation
Dissolution (water-washing)
Biodegradation
October 16, 2018
DATE
11
Why Are Biomarkers Useful? Deepwater Horizon - Sterane, Diasterane, & Hopanoid Biomarkers
1st Dimension Retention Time (seconds)
2n
d D
imen
sion
Ret
enti
on
Tim
e (s
econ
ds)
Deepwater Horizon
Cocodrie, LA May 31, 2010
Deepwater Horizon
Cocodrie, LA
October 16, 2018
DATE
12
Biomarker Comparison – Louisiana Crudes
Deepwater Horizon
Cocodrie, LA
EPA WP-681 Southern Louisiana Light Sweet Crude
Eugene Island Block 330
October 16, 2018
DATE
13
(a) Ixtoc I Crude
(b) Deepwater Horizon – Macondo Well Crude
(c) Exxon Valdez Cargo
0
2
4
0
2
4
0
2
4
18 16 14 12 10 8 20 22 24 26 28 30 32 34 36
Biomarker Comparison
Ixtoc I, Deepwater Horizon, and Exxon Valdez
October 16, 2018
DATE
14
Biomarker Comparison
Ixtoc I, Deepwater Horizon, and Exxon Valdez
Biomarker Ratio Ixtoc I Deepwater Horizon Exxon Valdez
Ts/Tm 0.66 1.30 0.78
Ts/H 0.24 0.23 0.20
Tm/H 0.37 0.18 0.26
Dia C27Ba-20S/H 0.65 1.18 0.36
Dia C27Ba-20R/H 0.50 0.90 0.31
C28aBB-20R/H 0.32 0.37 0.27
C28aBB-20S/H 0.21 0.21 0.18
C29aBB-20R/H 0.53 0.64 0.35
C29aBB-20S/H 0.36 0.32 0.25
NH/H 1.19 0.52 0.67
C29-Ts/H 0.27 0.24 0.22
HH(S)/H 0.85 0.50 0.57
HH(R)/H 0.63 0.36 0.41
norbiphytane/H 0.80 1.72 0.80
biphytane/H 1.23 1.42 0.66
norbiphytane/biphytane 0.65 1.22 1.21
norbiphytane/n-C34 0.20 0.32 0.67
biphytane/n-C35 0.43 0.33 0.71
October 16, 2018
DATE
15
Biomarker Comparison
NIST SRM-1582 Replicate Analysis
October 16, 2018
DATE
16
Hopanoids:
Molecular Fossils derived from Prokaryotes
Ts
Tm
BNH NH H
Thermal Maturation
Indicator Ratio
18α(H)-22,29,30-trinorneohopane
C27H46 Mass: 370
17α(H)-22,29,30-trinorhopane
C27H46 Mass: 370
17α(H),21β(H)-28,30-bisnorhopane
C28H48 Mass: 384
17α(H),21β(H)-30-norhopane C29H50 Mass: 398
17α(H),21β(H)-hopane
C30H52 Mass: 412
October 16, 2018
DATE
17
Seep Oil Hopanoids (Coal Oil Point, CA)
Ts Tm
BNH NH
H
HH
SORCOP
(S) (R)
October 16, 2018
DATE
18
17α(H),21β(H)-hopane HRT Mass Spectrum
October 16, 2018
DATE
19
October 16, 2018
Hopanoid Biodegradation Indicator Molecules
17α(H),21β(H)-hopane Formula: C30H52 Mass: 412
Unique Ion m/z 191
17α(H),21β(H)-25-norhopane Formula: C29H50 Mass: 398
Unique Ion m/z 177
8,14-secohopane Formula: C30H54 Mass: 414
Unique Ion m/z 123
sesquiterpanes
(drimanes)
Formula: C16H30 Mass: 222
Unique Ion m/z 123
Formula: C15H28 Mass: 208
Unique Ion m/z 123
DATE
20
Steranes/Diasteranes:
Molecular Fossils derived from Eukaryotes
October 16, 2018
Exxon Valdez Cargo
DATE
21
Steranes/Diasteranes:
Molecular Fossils derived from Eukaryotes
October 16, 2018
Exxon Valdez Cargo
DiaC27βα-20S
DiaC27βα-20R
DiaC28βα-20S,24R
DiaC28βα-20S,24S DiaC29βα-20S,24S&R
DiaC28βα-20R,24S&R
DiaC29βα-20R,24S&R
C27ααα-20S
C27ααα-20R C27αββ-20R
C27αββ-20S C29αββ-20R
C29αββ-20S C29ααα-20S
C29ααα-20R C28αββ-20R
C28αββ-20S
DATE
22
Steranes:
Molecular Fossils derived from Eukaryotes
October 16, 2018
DATE
23
Steranes to Diasterane Molecular Rearrangments
*Thermal Maturation Indicator Molecules
13β(H),17α(H)-20S-diacholestane (C27H48)
13β(H),17α(H)-20R-diacholestane (C27H48)
13α(H),17β(H)-20S-diacholestane (C27H48)
13α(H),17β(H)-20R-diacholestane (C27H48)
October 16, 2018
5α(H),14α(H),17α(H)-20S-cholestane (C27H48)
5α(H),14β(H),17β(H)-20R-cholestane (C27H48)
5α(H),14β(H),17β(H)-20S-cholestane (C27H48)
5α(H),14α(H),17α(H)-20R-cholestane (C27H48)
DATE
24
October 16, 2018
13β(H),17α(H)-20S-diacholestane HRT Mass Spectrum
DATE
25
October 16, 2018
SORCOP
Monoaromatic Steroids
“C-Ring”
Monoaromatic
Steroids
DATE
26
Monoaromatic Steroids
October 16, 2018
DATE
27
October 16, 2018
“C-ring” Monoaromatic Steroids
(1) (2) (3)
(4)
(5)(6)
(7)
(8) (9) (10)
DATE
28
C27 5B(S) MAS - HRT Mass Spectrum
DATE
29
Side Track: Non-traditional Biomarkers
for Environmental Forensics
Archeal Core
Ether Lipids
October 16, 2018
DATE
30
Non-traditional Biomarkers
2α-methyl-17α(H),21β(H)-hopane
(cyanobacterial origin)
17α(H),21β(H)-22S-pentakishomohopane
Ts
Tm
Prokaryotic
Diasterane
C27βα-20R
Eukaryotic
24-ethyl-5α(H),14α(H),
17α(H)-20R-cholestane
C ring monoaromatic steroid
C295β-20S
triaromatic steroid
C28-20R
Archeal biphytane
October 16, 2018
DATE
31
Archeal Core Ether Lipids PNAS 2007
October 16, 2018
DATE
32
GC×GC-FID chromatograms
(mountain plots) of the solvent
extract from sample OC-114m of
the Hoyle Formation.
(Upper) Enlargement of region
with archaeal core lipids. Multiple
peaks joined to a single molecular
structure are diastereomers.
(Lower) Complete chromatograph.
Archeal Core Ether Lipids PNAS 2007
October 16, 2018
DATE
33
Figure 8.21 GC × GC–FID biomarker regions of (A)
fresh oil collected 150 m from the ruptured pipeline on
May 20, 2015; (B) fresh oil collected on May 19, 2015,
on the beach and ~450 m down current from the location
where the oil first entered the ocean; and (C) naturally
seeped oil collected in 2005 directly at Coal Oil Point,
Santa Barbara, CA.
2015 Refugio Oil Spill
October 16, 2018
DATE
34
norbiphytane
Archeal Core Ether Lipid Biomarkers
October 16, 2018
DATE
35
October 16, 2018
DATE
36
October 16, 2018
DATE
37
October 16, 2018
DATE
38
October 16, 2018
DATE
39
October 16, 2018
DATE
40
Back on Track
October 16, 2018
DATE
41
Confidence - The Power of High Resolution TOF Coupled with
GC×GC: m/z 234 compounds
231 232 233 234 235 236 237 238
1e4
2e4
3e4
M/Z
234.1402
235.1439
231 232 233 234 235 236 237 238
1e4
2e4
3e4
4e4
5e4
6e4
M/Z
234.0498
235.0533
232.0342
Benzonaphthothiophene C16H10S
Theoretical mass: 234.0498
Observed mass: 234.0498
Mass error: 0 ppm
C4-Phenanthrene C18H18
Theoretical mass: 234.1403
Observed mass: 234.1402
Mass error: -0.43 ppm
The difference between
C4-Phenanthrene and
Benzonaphthothiophene
is 386.5 ppm
October 16, 2018
DATE
42
GC×GC - High Resolution - TOF How Dou You Rapidly Find and Identify
Compounds of Forensic Interest? You Need a Map!
October 16, 2018
DATE
43
5 10 15 20 25 30
0
2
4
6
8
10
12
14
16
C#
RDBE
Region - sample "Deepwater Horizon (15mg/mL) 122017", Deconvoluted, (180s, 0s) - (11287.2s, 16.0046s)
HC' HC N' N O' O O2' O2 NO' NO NO2' NO2 S' S SO' SO SO2' SO2 SO3' SO3 SO4' SO4
DWH Ring Double Bond Equivalents (RDBE) vs Carbon Number for Molecules
Containing a Sulfur Atom
October 16, 2018
DATE
44
Ixtoc I Ring Double Bond Equivalents (RDBE) vs Carbon Number for
Molecules Containing a Sulfur Atom
5 10 15 20 25 30
0
2
4
6
8
10
12
14
16
C#
RDBE
Region - sample "Ixtoc I (15mg/mL)", Deconvoluted, (180s, 0s) - (11287.2s, 16.0046s)
HC' HC N' N O' O O2' O2 NO' NO NO2' NO2 S' S SO' SO SO2' SO2 SO3' SO3 SO4' SO4
October 16, 2018
DATE
45
Ixtoc I Ring Double Bond Equivalents (RDBE) vs Carbon Number for
Molecules Containing a Sulfur Atom
October 16, 2018
DATE
46
Ixtoc I Ring Double Bond Equivalents (RDBE) vs Carbon Number for
Molecules Containing a Sulfur Atom
October 16, 2018
DATE
47
GC×GC Subtraction Chromatogram
Ixtoc I minus DWH
October 16, 2018
DATE
48
Ixtoc I Ring Double Bond Equivalents (RDBE) vs Carbon Number for
Molecules Containing a Sulfur Atom
October 16, 2018
DATE
49
Ixtoc I – GC×GC-HRT
Benzothiophene Suite
October 16, 2018
DATE
50
Ixtoc I – GC×GC-HRT
Dibenzothiophene Suite
October 16, 2018
DATE
51
Ixtoc I – GC×GC-HRT
Phenanthrothiophene Suite
October 16, 2018
DATE
52
Ixtoc I – GC×GC-HRT
Benzonaphthothiophene Suite
October 16, 2018
DATE
53
Ixtoc I – GC×GC-HRT
Chrysenothiophene Suite
October 16, 2018
DATE
54
Ixtoc I Accurate Mass Measurements
Dibenzothiophene Mass Spectrum
Dibenzothiophene
C12H8S
monoisotopic mass (m/z): 184.0341
RDBE = 9
observed mass: 184.0343
mass error: 1.0868 ppm
October 16, 2018
DATE
55
Literature Search – Sulfur Heterocycles
October 16, 2018
DATE
56
DWH Ring Double Bond Equivalents (RDBE) vs Carbon Number for Molecules
Containing a Nitrogen Atom
October 16, 2018
DATE
57
Ixtoc I Ring Double Bond Equivalents (RDBE) vs Carbon Number for
Molecules Containing a Nitrogen Atom
October 16, 2018
DATE
58
Ixtoc I Accurate Mass Measurements
C1 (methyl) carbazoles
October 16, 2018
DATE
59
Ixtoc I Accurate Mass Measurements
C2, C3, C4, & C5 carbazoles
October 16, 2018
DATE
60
Ixtoc I
Deepwater
Horizon
carbazoles
benzocarbazoles
Comparison of carbazoles and benzocarbazoles in
Ixtoc I and DWH
October 16, 2018
DATE
61
Summary
The combination of GC×GC, high resolution TOF, and petroleomics based mass spectral analysis software tools rapidly provides an extensive inventory of the hydrocarbon compounds found in crude oils.
HRT accurate mass data provides a high degree of confidence to peak assignments.
We are well positioned to include Archean biomarkers into environmental forensics.
GC×GC has matured into a platform that provides superior results capable of delivering a high-level of quality control.
High resolution data will help to predict the long-term fate of persistent petroleum hydrocarbons in the environment.
With GC×GC-HRT-MS, we are paving the way for identifying more “forensically useful chemicals” for studying the fate of petroleum in the environment.
October 16, 2018
DATE
62
Acknowledgements
Thank-you!
October 16, 2018
DATE
63
DOI Wilmington, CA (1972) Biomarker Region
October 16, 2018
DATE
64
DOI Wilmington, CA (1972) Biomarker Region
October 16, 2018
DATE
65
Jackpot Seep, Santa Barbara, CA - Biomarker Region
October 16, 2018
DATE
66
October 16, 2018
Jackpot Seep, Santa Barbara, CA - Biomarker Region
DATE
67
Jackpot Seep, Santa Barbara, CA - Biomarker Region
October 16, 2018