what can we learn from “fuel oil” spills for understanding...
TRANSCRIPT
What can we learn from “fuel oil” spills for understanding the fate of Dilbit?
Christopher M. Reddy Woods Hole Oceanographic Institution
Woods Hole, MA
National Academy of Sciences, ““Effects of Diluted Bitumen on the Environment: A Comparative Study.”, presented March 9, 2015
Co-authors
• Robert Swarthout and Robert Nelson (WHOI) • J. Samuel Arey and Jonas Gros (EPFL) • Gregory Wilson and Robyn Conmy (US EPA) • Commander Gregory Hall (US Coast Academy)
No official funding to study Dilbits
Overview
1. Fuel oil vs Dilbit 2. Gas chromatographic analysis of fuel oils
and Dilbits 3. Will Dilbits sink based on past fuel oil spills
(kinetics)? 4. GCxGC analysis of fuel oils and Dilbits 5. Why gas chromatography is not enough. 6. Summary
Fuel oils (first cousins to Dilbits?)
• Fuel oils are used to power marine vessels and generate power.
• Distinct from distillate fuels (e.g., diesel and gasoline).
• Prepared from a hydrocarbon residue produced at a refinery amended with petroleum distillates, or cutting oils, to decrease viscosity and aid in transport and use.
• Because both crude oils and cutting oils vary, there is no standard fuel oil.
Fuel oils
• -Not much fuel oil transported in pipeline but worth considering.
• The oil spill community has a long and successful history with fuel oil spills. – Response – Clean-up – Damage assessment – Restoration Lessons have been learned. Can we “drop in" our knowledge on fuel oils for
Dilbits?
OIL GC-FID CHROMATOGRAMS
Gas Chromatography (GC)
gas mobile phase (helium or hydrogen)
injector
detector
chromatogram
Retention time
amou
nt
oven
column with liquid polymer (polydimethylsiloxane) stationary
phase
Separates complex mixtures into individual compounds and allows them to be measured.
FID
resp
onse
n-alkane carbon number
GC retention time (min) 5 10 15 20 25 30 35 40 45 50 55
Light sweet crude oil released from the Macondo well after the Deepwater Horizon disaster in the Gulf of Mexico in 2010.
Macondo well
n-alkane carbon number
GC retention time (min) 5 10 15 20 25 30 35 40 45 50 55
Falmouth diesel
FID
resp
onse
Diesel fuel purchased from a local gas station in Falmouth, MA
Bouchard 120
FID
resp
onse
n-alkane carbon number
GC retention time (min) 5 10 15 20 25 30 35 40 45 50 55
Fuel oil that was released into Buzzards Bay, MA in 2003 from the Bouchard 120 vessel.
Cosco Busan tank 4
FID
resp
onse
n-alkane carbon number
GC retention time (min) 5 10 15 20 25 30 35 40 45 50 55
Fuel oil that was released from the Cosco Busan vessel that hit the Bay Bridge In San Francisco Bay in 2007
Cosco Busan tank 3
FID
resp
onse
n-alkane carbon number
GC retention time (min) 5 10 15 20 25 30 35 40 45 50 55
Fuel oil that was NOT released from the Cosco Busan vessel that hit the Bay Bridge in San Francisco Bay in 2007
Prestige
FID
resp
onse
n-alkane carbon number
GC retention time (min) 5 10 15 20 25 30 35 40 45 50 55
Fuel oil that leaked in 2002 from the Prestige vessel near the coastlines of Spain and Portugal.
Kirby barge
FID
resp
onse
n-alkane carbon number
GC retention time (min) 5 10 15 20 25 30 35 40 45 50 55
Fuel oil that was released from the Kirby 27706 vessel In Galveston Bay, TX in March 2014
n-alkane carbon number
GC retention time (min) 5 10 15 20 25 30 35 40 45 50 55
Sunderbans furnace oil
FID
resp
onse
2014 spill in Bangladesh
12 17 20 25 30 35 40
n-alkane carbon number
GC retention time (min) 5 10 15 20 25 30 35 40 45 50 55
Dilbit 1A Cold Lake
FID
resp
onse
Composite one month
12 17 20 25 30 35 40
n-alkane carbon number
GC retention time (min) 5 10 15 20 25 30 35 40 45 50 55
Dilbit 1B Coldlake
FID
resp
onse
Composite one month later.
12 17 20 25 30 35 40
n-alkane carbon number
GC retention time (min) 5 10 15 20 25 30 35 40 45 50 55
Cold Lake dilbit - RC
FID
resp
onse
From DFO
12 17 20 25 30 35 40
n-alkane carbon number
GC retention time (min) 5 10 15 20 25 30 35 40 45 50 55
Dilbit 2A WSC
FID
resp
onse
Composite one month
12 17 20 25 30 35 40
n-alkane carbon number
GC retention time (min) 5 10 15 20 25 30 35 40 45 50 55
Dilbit 2B WSC
FID
resp
onse
Composite one month later.
12 17 20 25 30 35 40
n-alkane carbon number
GC retention time (min) 5 10 15 20 25 30 35 40 45 50 55
Synthetic Crude Oil
FID
resp
onse
12 17 20 25 30 35 40
Looks easier to “see” the cutting oil (diluent) in a fuel oil compared to the “dil” in the dilbit.
Will Dilbit sink?
• Previous lab studies on Dilbit have shown that evaporative weathering can increase the density (enough to sink in natural waters).
What can we learn from ”historical” fuel oil spills to determine if enough “evaporation” could occur in a real Dilbit spill?
Kinetics?
Loss of the front end versus density
Three past fuel oil spills; “DIRTY BATHTUBS”
• Bouchard 120 (2003; Buzzards Bay, MA) • Cosco Busan (2007; SF Bay, CA) • Kirby (2014; Galveston Bay, TX) -Most samples collected on beaches (no longer on water) -All in “close quarters” -”Dirty Bath Tub” spills
Bouchard 120 spill Buzzards Bay 2003
unresolved complex mixture (UCM)
naphthalene
17 18
17 18
17 18
17 18
Cosco Busan spill San Fransisco Bay 2007
Tank 4
Cutting oil Residue
Shorebird Nov 15
Shorebird Nov 28
Shorebird Dec 11
Shorebird Jan 1
Shorebird Jan 26
Kirby (Texas City) spill Galveston Bay 2014
n-alkane carbon number
FID
resp
onse
Kirby cargo
n-alkane carbon number
FID
resp
onse
Seawolf Park – day 9
Mustang Island – day 10
n-alkane carbon number
FID
resp
onse
Seawolf Park – day 39
n-alkane carbon number
FID
resp
onse
Seawolf Park – day 90
n-alkane carbon number
FID
resp
onse
Loss of the front end versus density
GCxGC DUATHLON
TWO DIMENSIONAL GC: W
HO
I gra
phic
s Bouchard 120 20mg/mL 1µL injection
18 16 14 12 10 8 20 22 24 26 28 30 32 34 36 n-alkane carbon number
biomarkers (steranes & hopanes)
saturated hydrocarbons
alkylbenzenes
naphthalenes & benzothiophenes
fluorenes
phenanthrenes & dibenzothiophenes
pyrenes
chrysenes
Cosco Busan Port Tank #4 20mg/mL 1µL injection
18 16 14 12 10 8 20 22 24 26 28 30 32 34 36 n-alkane carbon number
Kirby 20mg/mL 1µL injection
18 16 14 12 10 8 20 22 24 26 28 30 32 34 36 n-alkane carbon number
Bangladesh – Sandarbans “Furnace Oil” 10mg/mL 2µL injection
18 16 14 12 10 8 20 22 24 26 28 30 32 34 36 n-alkane carbon number
Bouchard 120 20mg/mL 1µL injection
Kirby 20mg/mL 1µL injection
Cosco Busan Port Tank #4 20mg/mL 1µL injection
RC Cold Lake DilBit (from DFO) *28% GC amenable
18 16 14 12 10 8 20 22 24 26 28 30 32 34 36 n-alkane carbon number
RC DilBit 1A Cold Lake (composite one month) *27% GC amenable
18 16 14 12 10 8 20 22 24 26 28 30 32 34 36 n-alkane carbon number
RC DilBit 1B Cold Lake (composite one month later) *24% GC amenable
18 16 14 12 10 8 20 22 24 26 28 30 32 34 36 n-alkane carbon number
NJ DilBit (Cold Lake) *36% GC amenable
18 16 14 12 10 8 20 22 24 26 28 30 32 34 36 n-alkane carbon number
RC DilBit 2A WSC (composite one) *33% GC amenable
18 16 14 12 10 8 20 22 24 26 28 30 32 34 36 n-alkane carbon number
RC DilBit 2B WSC (composite one month later) *30% GC amenable
18 16 14 12 10 8 20 22 24 26 28 30 32 34 36 n-alkane carbon number
RS SCO *86% GC amenable
18 16 14 12 10 8 20 22 24 26 28 30 32 34 36 n-alkane carbon number
RS SCO *86% GC amenable
18 16 14 12 10 8 20 22 24 26 28 30 32 34 36 n-alkane carbon number
biomarkers (steranes & hopanes)
saturated hydrocarbons
alkylbenzenes
naphthalenes & benzothiophenes
fluorenes
phenanthrenes & dibenzothiophenes
pyrenes
chrysenes
RC DilBit 2B WSC (composite one month later) *30% GC amenable
18 16 14 12 10 8 20 22 24 26 28 30 32 34 36 n-alkane carbon number
Using gas chromatography, we could not see something very different from a heavy crude oil !
RC DilBit 1A (cold) *27% GC amenable
RC DilBit 1B *24% GC amenable
NJ DilBit (Cold Lake) *36% GC amenable
RC Cold Lake DilBit *28% GC amenable
RC DilBit 2A *33% GC amenable
RC DilBit 2B *30% GC amenable
RS SCO *86% GC amenable
Saturated Hydrocarbons in the interval between n-C18 and n-C20
n-C18 n-C19 n-C20 phytane
alkylcyclopentane alkylcyclohexane
RS SCO *86% GC amenable
n-C18 n-C19 n-C20 phytane
alkylcyclopentane alkylcyclohexane
RC DilBit 1A *27% GC amenable
RC DilBit 1B *24% GC amenable
n-C18 n-C19 n-C20 phytane
alkylcyclopentane alkylcyclohexane
n-C18 n-C19 n-C20 phytane
alkylcyclopentane alkylcyclohexane
RC DilBit 2A *33% GC amenable
RC DilBit 2B *30% GC amenable
n-C18 n-C19 n-C20 phytane
alkylcyclopentane alkylcyclohexane
n-C18 n-C19 n-C20 phytane
alkylcyclopentane alkylcyclohexane
NJ DilBit *36% GC amenable
RC Cold Lake DilBit *28% GC amenable
n-C18 n-C19 n-C20 phytane
alkylcyclopentane alkylcyclohexane
Saturated Hydrocarbons in the interval between n-C13 and n-C14
RS SCO *86% GC amenable
n-C13 3-methyltridecane n-C14
isoprenoid alkane
alkylcyclopentane alkylcyclohexane
2-methyltridecane
4-methyltridecane
5-methyltridecane
6 & 7-methyltridecane
cyclic isoprenoid
RC DilBit 1A *27% GC amenable
n-C13 3-methyltridecane n-C14
isoprenoid alkane
alkylcyclopentane alkylcyclohexane
2-methyltridecane
4-methyltridecane
5-methyltridecane
6 & 7-methyltridecane
cyclic isoprenoid
RC DilBit 1B *24% GC amenable
n-C13 3-methyltridecane n-C14
isoprenoid alkane
alkylcyclopentane alkylcyclohexane
2-methyltridecane
4-methyltridecane
5-methyltridecane
6 & 7-methyltridecane
cyclic isoprenoid
RC DilBit 2A *33% GC amenable
n-C13 3-methyltridecane n-C14
isoprenoid alkane
alkylcyclopentane alkylcyclohexane
2-methyltridecane
4-methyltridecane
5-methyltridecane
6 & 7-methyltridecane
cyclic isoprenoid
RC DilBit 2B *30% GC amenable
n-C13 3-methyltridecane n-C14
isoprenoid alkane
alkylcyclopentane alkylcyclohexane
2-methyltridecane
4-methyltridecane
5-methyltridecane
6 & 7-methyltridecane
cyclic isoprenoid
NJ DilBit *36% GC amenable
n-C13 3-methyltridecane n-C14
isoprenoid alkane
alkylcyclopentane alkylcyclohexane
2-methyltridecane
4-methyltridecane
5-methyltridecane
6 & 7-methyltridecane
cyclic isoprenoid
RC Cold Lake DilBit *28% GC amenable
n-C13 3-methyltridecane n-C14
isoprenoid alkane
alkylcyclopentane alkylcyclohexane
2-methyltridecane
4-methyltridecane
5-methyltridecane
6 & 7-methyltridecane
cyclic isoprenoid
DilBit Biomarker region
RS SCO *86% GC amenable
triaromatic steranes benzohopanes
hopanes *Ts/Tm ratio indicates
thermally immature petroleum
Tm
Ts
monoaromatic steranes
diasteranes & steranes
RC DilBit 1A *27% GC amenable
triaromatic steranes benzohopanes
hopanes *Ts/Tm ratio indicates
thermally immature petroleum
Tm
Ts
monoaromatic steranes
diasteranes & steranes
archean core ether lipids
RC DilBit 2A *33% GC amenable
triaromatic steranes benzohopanes
hopanes *Ts/Tm ratio indicates
thermally immature petroleum
Tm
Ts
monoaromatic steranes
diasteranes & steranes
archean core ether lipids
RC DilBit 2B *30% GC amenable
triaromatic steranes benzohopanes
hopanes *Ts/Tm ratio indicates
thermally immature petroleum
Tm
Ts
monoaromatic steranes
diasteranes & steranes
archean core ether lipids
RC DilBit 1B *24% GC amenable
triaromatic steranes benzohopanes
hopanes *Ts/Tm ratio indicates
thermally immature petroleum
Tm
Ts
monoaromatic steranes
diasteranes & steranes
archean core ether lipids
NJ DilBit *36% GC amenable
triaromatic steranes benzohopanes
hopanes *Ts/Tm ratio indicates
thermally immature petroleum
Tm
Ts
monoaromatic steranes
diasteranes & steranes
archean core ether lipids
RC Cold Lake DilBit *28% GC amenable
triaromatic steranes benzohopanes
hopanes *Ts/Tm ratio indicates
thermally immature petroleum
Tm
Ts
monoaromatic steranes
diasteranes & steranes
archean core ether lipids
Subtraction Chromatograms
Subtraction Chromatograms
0 200 400 600 800 1000 1200 1400 1600 1800
550
500
450
400
350
300
250
200
150
100
50
0
row
DilBit 1B minus DilBit 1A (Cold lake one and month later) red peak = more abundant in DilBit 1B blue peak = more abundant in DilBit 1A
0 200 400 600 800 1000 1200 1400 1600 1800
550
500
450
400
350
300
250
200
150
100
50
0
row
DilBit 2B minus DilBit 2A (WSC month and one month later) red peak = more abundant in DilBit 2B blue peak = more abundant in DilBit 2A
0 200 400 600 800 1000 1200 1400 1600 1800
550
500
450
400
350
300
250
200
150
100
50
0
row
DilBit 2B minus DilBit 2A red peak = more abundant in DilBit 2B blue peak = more abundant in DilBit 2A
0 200 400 600 800 1000 1200 1400 1600 1800
550
500
450
400
350
300
250
200
150
100
50
0
row
Cold Lake minus DilBit 2A (WSC) red peak = more abundant in Cold Lake blue peak = more abundant in DilBit 2A
What is non GC-amenable?
The vast majority of oil spills have been studied only by gas chromatography (GC).
• GC is an incredibly powerful analytical system, but
cannot easily analyze for compounds: - Will not dissolve in appropriate solvent - Non-volatile - Thermally unstable - Analytically sticky
Non-GC amenable properties
We are “missing” the majority of the material in a “Dilbit” and even less once weathered.
Living in an iPhone society using “cordless phone” technoloy to study Dilbits
Look beyond GCTLC
Thin layer chromatography-flame ionization detection
1A Cold Lake 1B Cold Cake RC Cold Lake (DFO)
NJCL Cold Lake 2A WSC
SCO
2B WSC
DILBITS
0 2 4 6 8 10 distance migrated (cm)
Summary
• Lessons can be learned from fuel oils although not exactly the same as Dilbits
• Use field studies to confirm lab work • Need to expand past gas chromatography—a powerful
tool—but does not capture most of the material. • Without a more robust inventory on what may spill how
can you make the most well informed decisions or recommendations?
STOP