What can we learn from fuel oil spills for understanding the fate of Dilbit? Christopher M. Reddy Woods Hole Oceanographic Institution Woods Hole, MA

Transcription

1 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

2 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)

3 No official funding to study Dilbits

4 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

5 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.

6 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?

7 OIL GC-FID CHROMATOGRAMS

8 Gas Chromatography (GC) chromatogram injector amount gas mobile phase (helium or hydrogen) detector Retention time oven column with liquid polymer (polydimethylsiloxane) stationary phase Separates complex mixtures into individual compounds and allows them to be measured.

9 Macondo well FID response Light sweet crude oil released from the Macondo well after the Deepwater Horizon disaster in the Gulf of Mexico in GC retention time (min) n-alkane carbon number

10 Falmouth diesel Diesel fuel purchased from a local gas station in Falmouth, MA FID response GC retention time (min) n-alkane carbon number

11 Bouchard 120 FID response Fuel oil that was released into Buzzards Bay, MA in 2003 from the Bouchard 120 vessel GC retention time (min) n-alkane carbon number

12 Cosco Busan tank 4 FID response Fuel oil that was released from the Cosco Busan vessel that hit the Bay Bridge In San Francisco Bay in GC retention time (min) n-alkane carbon number

13 Cosco Busan tank 3 FID response Fuel oil that was NOT released from the Cosco Busan vessel that hit the Bay Bridge in San Francisco Bay in GC retention time (min) n-alkane carbon number

14 Prestige FID response Fuel oil that leaked in 2002 from the Prestige vessel near the coastlines of Spain and Portugal GC retention time (min) n-alkane carbon number

15 Kirby barge FID response Fuel oil that was released from the Kirby vessel In Galveston Bay, TX in March GC retention time (min) n-alkane carbon number

16 Sunderbans furnace oil 2014 spill in Bangladesh FID response GC retention time (min) n-alkane carbon number

17 Dilbit 1A Cold Lake Composite one month FID response GC retention time (min) n-alkane carbon number

18 Dilbit 1B Coldlake Composite one month later. FID response GC retention time (min) n-alkane carbon number

19 Cold Lake dilbit - RC From DFO FID response GC retention time (min) n-alkane carbon number

20 Dilbit 2A WSC Composite one month FID response GC retention time (min) n-alkane carbon number

21 Dilbit 2B WSC Composite one month later. FID response GC retention time (min) n-alkane carbon number

22 Synthetic Crude Oil FID response GC retention time (min) n-alkane carbon number

23 Looks easier to see the cutting oil (diluent) in a fuel oil compared to the dil in the dilbit.

24 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?

25 Loss of the front end versus density

26 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

27 Bouchard 120 spill Buzzards Bay 2003

28 naphthalene unresolved complex mixture (UCM)

29 18 17

30 18 17

31 18 17

32 18 17

33 Cosco Busan spill San Fransisco Bay 2007

34 Tank 4 Cutting oil Residue

35 Shorebird Nov 15

36 Shorebird Nov 28

37 Shorebird Dec 11

38 Shorebird Jan 1

39 Shorebird Jan 26

40 Kirby (Texas City) spill Galveston Bay 2014

41 FID response Kirby cargo n-alkane carbon number

42 FID response Seawolf Park day 9 n-alkane carbon number

43 FID response Mustang Island day 10 n-alkane carbon number

44 FID response Seawolf Park day 39 n-alkane carbon number

45 Seawolf Park day 90 FID response n-alkane carbon number

46 Loss of the front end versus density

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48 Bouchard 120 TWO DIMENSIONAL GCxGC GC: 20mg/mL 1µL injection DUATHLON chrysenes pyrenes phenanthrenes & dibenzothiophenes fluorenes naphthalenes & benzothiophenes alkylbenzenes biomarkers (steranes & hopanes) WHOI graphics saturated hydrocarbons n-alkane carbon number

49 Cosco Busan Port Tank #4 20mg/mL 1µL injection n-alkane carbon number

50 Kirby 20mg/mL 1µL injection n-alkane carbon number

51 Bangladesh Sandarbans Furnace Oil 10mg/mL 2µL injection n-alkane carbon number

52 Bouchard mg/mL 1µL injection

53 Kirby 20mg/mL 1µL injection

54 Cosco Busan Port Tank #4 20mg/mL 1µL injection

55 RC Cold Lake DilBit (from DFO) *28% GC amenable n-alkane carbon number

56 RC DilBit 1A Cold Lake (composite one month) *27% GC amenable n-alkane carbon number

57 RC DilBit 1B Cold Lake (composite one month later) *24% GC amenable n-alkane carbon number

58 NJ DilBit (Cold Lake) *36% GC amenable n-alkane carbon number

59 RC DilBit 2A WSC (composite one) *33% GC amenable n-alkane carbon number

60 RC DilBit 2B WSC (composite one month later) *30% GC amenable n-alkane carbon number

61 RS SCO *86% GC amenable n-alkane carbon number

62 RS SCO *86% GC amenable chrysenes pyrenes phenanthrenes & dibenzothiophenes fluorenes naphthalenes & benzothiophenes alkylbenzenes biomarkers (steranes & hopanes) saturated hydrocarbons n-alkane carbon number

63 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! n-alkane carbon number

64 RC DilBit 1A (cold) *27% GC amenable

65 RC DilBit 1B *24% GC amenable

66 NJ DilBit (Cold Lake) *36% GC amenable

67 RC Cold Lake DilBit *28% GC amenable

68 RC DilBit 2A *33% GC amenable

69 RC DilBit 2B *30% GC amenable

70 RS SCO *86% GC amenable

71 Saturated Hydrocarbons in the interval between n-c 18 and n-c 20

72 RS SCO *86% GC amenable alkylcyclopentane alkylcyclohexane n-c phytane 18 n-c 19 n-c 20

73 RC DilBit 1A *27% GC amenable alkylcyclopentane alkylcyclohexane n-c phytane 18 n-c 19 n-c 20

74 RC DilBit 1B *24% GC amenable alkylcyclopentane alkylcyclohexane n-c phytane 18 n-c 19 n-c 20

75 RC DilBit 2A *33% GC amenable alkylcyclopentane alkylcyclohexane n-c phytane 18 n-c 19 n-c 20

76 RC DilBit 2B *30% GC amenable alkylcyclopentane alkylcyclohexane n-c phytane 18 n-c 19 n-c 20

77 NJ DilBit *36% GC amenable alkylcyclopentane alkylcyclohexane n-c phytane 18 n-c 19 n-c 20

78 RC Cold Lake DilBit *28% GC amenable alkylcyclopentane alkylcyclohexane n-c phytane 18 n-c 19 n-c 20

79 Saturated Hydrocarbons in the interval between n-c 13 and n-c 14

80 RS SCO *86% GC amenable alkylcyclopentane alkylcyclohexane cyclic isoprenoid 6 & 7-methyltridecane 5-methyltridecane 2-methyltridecane n-c 13 isoprenoid 4-methyltridecane 3-methyltridecane n-c alkane 14

81 RC DilBit 1A *27% GC amenable alkylcyclopentane alkylcyclohexane cyclic isoprenoid 6 & 7-methyltridecane 5-methyltridecane 2-methyltridecane isoprenoid n-c 13 4-methyltridecane 3-methyltridecane alkane n-c 14

82 RC DilBit 1B *24% GC amenable alkylcyclopentane alkylcyclohexane cyclic isoprenoid 6 & 7-methyltridecane 5-methyltridecane 2-methyltridecane isoprenoid n-c 13 4-methyltridecane 3-methyltridecane alkane n-c 14

83 RC DilBit 2A *33% GC amenable alkylcyclopentane alkylcyclohexane cyclic isoprenoid 6 & 7-methyltridecane 5-methyltridecane 2-methyltridecane isoprenoid n-c 13 4-methyltridecane 3-methyltridecane alkane n-c 14

84 RC DilBit 2B *30% GC amenable alkylcyclopentane alkylcyclohexane cyclic isoprenoid 6 & 7-methyltridecane 5-methyltridecane 2-methyltridecane isoprenoid n-c 13 4-methyltridecane 3-methyltridecane alkane n-c 14

85 NJ DilBit *36% GC amenable alkylcyclopentane alkylcyclohexane cyclic isoprenoid 6 & 7-methyltridecane 5-methyltridecane 2-methyltridecane isoprenoid n-c 13 4-methyltridecane 3-methyltridecane alkane n-c 14

86 RC Cold Lake DilBit *28% GC amenable alkylcyclopentane alkylcyclohexane cyclic isoprenoid 6 & 7-methyltridecane 5-methyltridecane 2-methyltridecane isoprenoid n-c 13 4-methyltridecane 3-methyltridecane alkane n-c 14

87 DilBit Biomarker region

88 RS SCO *86% GC amenable triaromatic steranes benzohopanes monoaromatic steranes Ts Tm hopanes *Ts/Tm ratio indicates thermally immature petroleum diasteranes & steranes

89 RC DilBit 1A *27% GC amenable triaromatic steranes benzohopanes monoaromatic steranes Ts Tm hopanes *Ts/Tm ratio indicates thermally immature petroleum archean core ether lipids diasteranes & steranes

90 RC DilBit 2A *33% GC amenable triaromatic steranes benzohopanes monoaromatic steranes Ts Tm hopanes *Ts/Tm ratio indicates thermally immature petroleum archean core ether lipids diasteranes & steranes

91 RC DilBit 2B *30% GC amenable triaromatic steranes benzohopanes monoaromatic steranes Ts Tm hopanes *Ts/Tm ratio indicates thermally immature petroleum archean core ether lipids diasteranes & steranes

92 RC DilBit 1B *24% GC amenable triaromatic steranes benzohopanes monoaromatic steranes Ts Tm hopanes *Ts/Tm ratio indicates thermally immature petroleum archean core ether lipids diasteranes & steranes

93 NJ DilBit *36% GC amenable triaromatic steranes benzohopanes monoaromatic steranes Ts Tm hopanes *Ts/Tm ratio indicates thermally immature petroleum archean core ether lipids diasteranes & steranes

94 RC Cold Lake DilBit *28% GC amenable triaromatic steranes benzohopanes monoaromatic steranes Ts Tm hopanes *Ts/Tm ratio indicates thermally immature petroleum archean core ether lipids diasteranes & steranes

95 Subtraction Chromatograms

96 Subtraction Chromatograms

97 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 row

98 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 row

99 DilBit 2B minus DilBit 2A red peak = more abundant in DilBit 2B blue peak = more abundant in DilBit 2A row

100 Cold Lake minus DilBit 2A (WSC) red peak = more abundant in Cold Lake blue peak = more abundant in DilBit 2A row

101 What is non GC-amenable? The vast majority of oil spills have been studied only by gas chromatography (GC). We are missing the majority of the GC is an incredibly powerful analytical system, but cannot easily analyze for compounds: - Will not dissolve in appropriate solvent material in a Dilbit and even less once weathered. - Non-volatile - Thermally unstable - Analytically sticky Non-GC amenable properties

102 Living in an iphone society using cordless phone technoloy to study Dilbits

103 Look beyond GC TLC Thin layer chromatography-flame ionization detection

104 1A Cold Lake 1B Cold Cake RC Cold Lake (DFO) 2A WSC 2B WSC NJCL Cold Lake DILBITS SCO distance migrated (cm)

105 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?

106 STOP

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