What can we learn from “fuel oil” spills for understanding...

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



Falmouth diesel

FID

resp

onse

Diesel fuel purchased from a local gas station in Falmouth, MA

Bouchard 120

FID

resp

onse



Fuel oil that was released into Buzzards Bay, MA in 2003 from the Bouchard 120 vessel.

Cosco Busan tank 4

FID

resp

onse



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



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



Fuel oil that leaked in 2002 from the Prestige vessel near the coastlines of Spain and Portugal.

Kirby barge

FID

resp

onse



Fuel oil that was released from the Kirby 27706 vessel In Galveston Bay, TX in March 2014



Sunderbans furnace oil

FID

resp

onse

2014 spill in Bangladesh

12 17 20 25 30 35 40



Dilbit 1A Cold Lake

FID

resp

onse

Composite one month

12 17 20 25 30 35 40



Dilbit 1B Coldlake

FID

resp

onse

Composite one month later.

12 17 20 25 30 35 40



Cold Lake dilbit - RC

FID

resp

onse

From DFO

12 17 20 25 30 35 40



Dilbit 2A WSC

FID

resp

onse

Composite one month

12 17 20 25 30 35 40



Dilbit 2B WSC

FID

resp

onse

Composite one month later.

12 17 20 25 30 35 40



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

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


FID

resp

onse

Kirby cargo


FID

resp

onse

Seawolf Park – day 9

Mustang Island – day 10


FID

resp

onse



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


Kirby 20mg/mL 1µL injection


Bangladesh – Sandarbans “Furnace Oil” 10mg/mL 2µL injection


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


RC DilBit 1A Cold Lake (composite one month) *27% GC amenable


RC DilBit 1B Cold Lake (composite one month later) *24% GC amenable


NJ DilBit (Cold Lake) *36% GC amenable


RC DilBit 2A WSC (composite one) *33% GC amenable


RC DilBit 2B WSC (composite one month later) *30% GC amenable


RS SCO *86% GC amenable




biomarkers (steranes & hopanes)

saturated hydrocarbons

alkylbenzenes

naphthalenes & benzothiophenes

fluorenes

phenanthrenes & dibenzothiophenes

pyrenes

chrysenes

RC DilBit 2B WSC (composite one month later) *30% GC amenable


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

Saturated Hydrocarbons in the interval between n-C18 and n-C20

n-C18 n-C19 n-C20 phytane

alkylcyclopentane alkylcyclohexane




NJ DilBit *36% GC amenable

Saturated Hydrocarbons in the interval between n-C13 and n-C14


n-C13 3-methyltridecane n-C14

isoprenoid alkane


2-methyltridecane

4-methyltridecane

5-methyltridecane

6 & 7-methyltridecane

cyclic isoprenoid



isoprenoid alkane


2-methyltridecane

4-methyltridecane

5-methyltridecane


cyclic isoprenoid

DilBit Biomarker region


triaromatic steranes benzohopanes

hopanes *Ts/Tm ratio indicates

thermally immature petroleum

Tm

Ts

monoaromatic steranes

diasteranes & steranes





Tm

Ts



archean core ether lipids





Tm

Ts




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?

What can we learn from “fuel oil” spills for understanding...

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