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Oil Sands Products Spill Response Studies
at Environment Canada Emergencies Science and Technology Section
Environment Canada Ottawa, ON
National Academy of Sciences Washington D.C.
9 March 2015
NAS, Wash. D.C., 9 March 2015 page 2
Oil Sands Products Spill Response Studies
Goal: Supply the knowledge responders need to prepare for, and respond to marine
spills
Four pillars: 1. Identify Spill Hazards 2. Assess Environmental Vulnerabilities 3. Develop Risk Assessment tools 4. Test Response Tools
NAS, Wash. D.C., 9 March 2015 page 3
Joint Federal Project
• Environment Canada • Fisheries and Oceans Canada • Natural Resources Canada
NAS, Wash. D.C., 9 March 2015 page 4
Identify Spill Hazards
• Oil sands product composition and properties – Physical bulk properties: density, viscosity, flashpoint, vapour pressure – Chemical Composition: Groups (“SARA”, CCME), Analytes (n-Alkanes,
PAH, aPAH, “biomarkers”) – Develop forensic markers/toolbox for identification of oil sands products – Lead: B. Hollebone, WS&T
• Fate and Behaviour studies – Weathering/Buoyancy (lab simulations, meso-scale, shoreline microcosm) – Evaporation, Dissolution and Emulsification – Photo-oxidation and oil breakdown – Sedimentation and oil-aggregate formation – Leads: B. Hollebone, A. Khelifa WS&T
• Health and safety information for responders – Development of guidebook for Responder H&S for oil sands product spills. – Leads: P. Lambert, WS&T
NAS, Wash. D.C., 9 March 2015 page 5
Hazards: Oil Sands Products Composition and Properties Develop database of oil sands products composition and properties to support operational modelling and response
Degree of Evaporation (Mass Loss w/w%) Fresh (0%)
W1 (8.5%)
W2 (16.9%)
W3 (25.3%)
W4 (26.5%)
Sulphur Content (% w/w) 3.0 4.1 4.5 4.9 4.8 Water Content (% w/w) 1.5 0.9 0.2 0.0 0.0 Flash Point (°C) < -5 < -5 29 159 173 Pour Point (°C) < -25 < -25 -6 24 33 Density (g/mL) 0°C 0.9399 0.9646 0.9949 1.0214 1.0211
15°C 0.9253 0.9531 0.9846 1.0127 1.0140 20°C 0.9148 0.9547*
API Gravity 20.9 16.6 12.0 8.2 8.0 Dynamic Viscosity 0°C 1.30E+03 9.82E+03 2.04E+05 9.35E+07 >1.00E+08 (mPa•s) 15°C 347 1.72E+03 2.97E+04 2.52E+05 7.91E+06
40°C 59.8 348* Emulsion Formation Stability Class Entrained Entrained Entrained Entrained DNF Tendency and Stability Complex Modulus (Pa) 44.6 89.7 467 1.26E+04 N/A
Water Content (%w/w) 40 35 33 6 N/A Surface Tension 0°C 31.2 31.9 NM NM NM (Air/Oil, mN/m) 15°C 30.2 31.1 31.2 NM NM
20°C 27.5 Interfacial Tension 0°C 24.8 NM NM NM NM (Oil/Water, mN/m) 15°C 24.2 28.0 NM NM NM Interfacial Tension 0°C 25.0 NM NM NM NM (Oil/33‰ Brine, mN/m) 15°C 23.8 26.0 NM NM NM
Access Western Blend (winter) Physical Properties AWB (winter)
aPAH compostion
NAS, Wash. D.C., 9 March 2015 page 6
Hazards: Environmental Forensics
• Develop protocols for forensic identification of oil and weathered oil – Essential tool for response and planning, to judge spill extent and
endpoints, to verify identity and quantity of spilled oil. – Essential tool to enable other research: fate and behaviour, toxicology
• Relies on unique chemical compositions of oil sands products – Evaluation of n-Alkanes, PAH/APAH and saturate “biomarkers”
• Used in real spills – Enbridge Line 6b, Kalamazoo River, MI – Exxon-Mobil Pegasus, Mayflower AK
Requires survey of products moved by ship and through pipelines
NAS, Wash. D.C., 9 March 2015 page 7
Top – Spilled product, Mayflower 2013 Bottom – Source Oil, Pegasus pipeline
NAS, Wash. D.C., 9 March 2015 page 8
NAS, Wash. D.C., 9 March 2015 page 9
Hazards: Fate and Behaviour • Evaluate changes to product properties and composition
induced by environmental weathering: Evaporation, Dissolution, Photo-degradation
• Examine behaviours of products in the environment as it weathers: Sinking/buoyancy, Emulsification, Dispersion, Sedimentation and oil-aggregate formation
• Interactions with shorelines in microcosms, adhesion to surfaces, penetration and flushing from simulated beaches
• Longer-term studies of weathering and behaviour in meso-scale simulators and wave tanks to better quantify longer-term spill fates in more realistic conditions
Work to date indicates that diluted bitumen products have unique behaviours and weathering characteristics
NAS, Wash. D.C., 9 March 2015 page 10
Hazards: Initial dilbit buoyancy studies Conditions Fate Behaviour
• No sediment • All weatherings of dilbit
• Floats as oil-water mixture • Floats and spreads like thick oil, e.g., Burnaby, BC
• Suspended fine and medium sediment
• Fresh to moderate weathering of dilbit
• Large part of oil sinks as fine oil particles
• Suspended in water column, sinks, and disperses, e.g., Kalamazoo MI
• Suspended fine and medium sediment
• Highly weathered dilbit
• Floating oil “balls” • Floats and “balls” can disperse
• Suspended coarse sediment
• All weatherings of dilbit
• Large part of oil floats as water-oil mixture
• Some sunken oil/sand agglomerations
• Most oil floats and spreads like thick oil
• Few oil/sand agglomerations sink
NAS, Wash. D.C., 9 March 2015 page 11
Submerged and Sunken Dilbit
Fresh Light evaporation Moderate evaporation
Dilbit mixed with high concentration of fine sediment for 8 hours, allowed to settle for 24 hours
(15 °C, sea water---3.3% salt, Access Western Blend oil)
NAS, Wash. D.C., 9 March 2015 page 12
Evaluation of Density and particle size
Density evaluation using mixtures of water: ethylene glycol for settled layer of CLB Winter Fresh in saltwater: kaolin mixture. The 60:40 water: ethylene glycol is considered as transition point
Oil Oil 15 ºC (g/cm3)
Density of oil-kaolin (1-2 µm)
Oil-DC benthic sediment (2-60 µm)
Cold Lake (winter), Fresh 0.925 (Emulsion-Meso)
1.059 (Disperse-Sink)
1.070 (Disperse-Sink)
Cold Lake (winter), W2, 15.75% weathered
0.982 (Emulsion Entrained)
1.140 (Disperse-Sink)
1.180 (Disperse-Sink)
Cold Lake (winter), W4, 25.2% weathered
1.009 (Emulsion Entrained)
0.999 (Tarballs-Float)
0.999 (Tarballs-Float)
0
2
4
6
8
10
12
0.01 0.1 1 10 100 1000 10000
Volu
me
(%)
Particle size (µm)
Comparison of Particle Size Distribution
natural sediment KA04 CLB fresh ‒ KA04
CLB W2 15.75% ‒ KA04
NAS, Wash. D.C., 9 March 2015 page 13
Floating Oil “Balls”
Highly evaporated dilbit mixed with saltwater and fine sediment
Oil has very high viscosity, similar to native bitumen
Discrete oil “balls” form after mixing (fingernail size)
Floats in seawater
Photos: Access Western Blend, 25% evaporated, 8 hours at 15 °C)
NAS, Wash. D.C., 9 March 2015 page 14
Vulnerability Assessment
• Identify vulnerable locations near possible shipping routes, including:
– Human infrastructure, – Ecologically significant communities, sensitive species, and
habitats, and sensitive shorelines. – Response requirements: access, and pre-selection of
appropriate response options
• Initial phases have focussed on the Canadian west coast, future work will expand to cover four designated response areas
NAS, Wash. D.C., 9 March 2015 page 15
Initial Shoreline Studies
• Objectives – study the fate and behaviour and cleanup of diluted bitumen on
marine shorelines under various conditions – deliver operational guidance and scientific information that is
legally defensible and credible to spill responders for shoreline treatment option decisions
• Literature review of the impacts of bitumen and fuels on marine shorelines
• Initial aerial shoreline survey of the Douglas and Grenville Channels, BC in 2013 and 2014
• Lead: P. Lambert, B. Hollebone, WS&T
NAS, Wash. D.C., 9 March 2015 page 16
Shoreline Assessments
• Shoreline survey of the Douglas and Grenville Channels, BC in 2013 and 2014, by air and boat
• Additional surveys panned in 2015
• Shoreline segmentation and classification
• Shoreline material collection for laboratory studies
• Collaboration with WCMRC and DFO
NAS, Wash. D.C., 9 March 2015 page 17
Risk Assessment
• Provide responders with accurate, situation-specific forecasts of spill evolution
– Predictive numerical modeling capacity to forecast spill evolution and impacts on identified vulnerabilities
• Work to date: Spill modelling – Incorporate new databases for oil sands product – Incorporate new wind and hydrodynamic data – Simulation of hypothetical spills – Lead: A Khelifa, WS&T
• Work to date: Weather and Atmospheric Modelling – Incorporate improved high resolution wind modeling, including high resolution
atmospheric modeling window centered over Northern BC towards the provision of detailed surface winds and other parameters near the surface.
– Develop hydrological modeling to support DFO's FVCOM. – Coupling atmospheric and ocean models. – Lead: R. Hogue, MSC
NAS, Wash. D.C., 9 March 2015 page 18
Response Tools
• Evaluate technologies and techniques for Physical and chemical mechanisms that serve to detect, contain, destroy or mitigate spilled petroleum products.
• Detection – Portable instruments evaluation and protocol development for in-
sediment shoreline oil and dispersed oil at sea – Lead: P. Lambert, WS&T
• Countermeasures – Dispersant testing fresh/weathered dilbit samples – Continuing evaluation of dispersant, shoreline-treating agent and
other products – New protocol development – Lead: B. Fieldhouse, P. Lambert, WS&T
NAS, Wash. D.C., 9 March 2015 page 19
Response Tools: Detection
• Oil profiling using portable instruments – Identification and differentiation of oil (including dilbit) from
background materials in-situ – Infrared (FTIR) and fluorescence
• Detection and monitoring of oil (including dilbit) in the water column
– Towed fluorometers – C-3 Turner
NAS, Wash. D.C., 9 March 2015 page 20
Response tools: Dispersant Effectiveness • Two products tested so far: Access Western Blend (AWB)
and Cold Lake Blend (CLB) • Dispersant effectiveness (Corexit EC9500A) determined by
the low-energy Swirling Flask Test & the high-energy Baffled Flask Test at temperatures from 5 to 25 °C
• Dispersants were ineffective at all temperatures in the SFT, while the BFT had a positive response for most conditions
• Estimated “Window of Opportunity” for dispersant effectiveness limited to <12 hrs at temperatures below 15 °C
“Dilbit” products have very short windows for application of oil spill dispersants.
NAS, Wash. D.C., 9 March 2015 page 21
Dispersants: Time Window-of-Opportunity
Time window-of-opportunity for Access Western Blend using Corexit EC9500A
NAS, Wash. D.C., 9 March 2015 page 22
Outputs to date
• Publications – Yang, C., Wang, Z., Yang, Z., Hollebone, B., Brown, C.E., Landriault, M., Fieldhouse, B.,
Chemical fingerprints of Alberta oil sands and related Products., (2011) Environmental Forensics, 12 (2), pp. 173-188
• 36th AMOP Technical Seminar on Environmental Contamination and Response, June 2013 :
– Wang, Z., Yang, C., Yang, Z., Hollebone, B., Brown, C.E., Landriault, M., Fieldhouse, B., Liu, Y., Zhang, G., Hewitt, M., Parrott, J., Frank, R.A., Forensic source differentiation of petrogenic, pyrogenic, and biogenic hydrocarbons in Canadian oil sands environmental samples, (2013)
• Federal Government Technical Report, 2014 – Environment Canada, Fisheries and Oceans Canada, Natural Resources Canada,
“Properties, Composition and Marine Spill Behaviour, Fate and Transport of Two Diluted Bitumen Products from the Canadian Oil Sands”.
– http://www.ec.gc.ca/scitech/6A2D63E5-4137-440B-8BB3-E38ECED9B02F/1633_Dilbit%20Technical%20Report_e_v2%20FINAL-s.pdf
• EC Oil Properties Database
NAS, Wash. D.C., 9 March 2015 page 23
Outputs to date, continued
• International Oil Spill Conference - Poster – M. Goldthorp, P. Lambert and C. Brown, “Survey of Portable Oil Detection Methods”.
• 37th AMOP Technical Seminar on Environmental Contamination and Response, Canmore, AB June 2014
– B. Fieldhouse, A. Mihailov, and V. Moruz, “Weathering of Diluted Bitumen and the Implications to the Effectiveness of Dispersants ”, pp. 388-352.
– M. Goldthorp, B. Fieldhouse, P.G. Lambert, C. Yang, and C.E. Brown, “Oil Profiling Using Portable Instruments”, pp. 401-414.
– S. Laforest, P.G. Lambert, J. Duffe, L. Gamble, B. Chaudhary, and C.E. Brown, “Studies on the Fate and Behaviour of Diluted Bitumen on Marine Shorelines”, pp. 415-427.
Future: • Interspill 2015
– B. Hollebone et al, Simulated Environmental Weathering Behaviours of Diluted Bitumen – S. Laforest, P.G. Lambert and M. Goldthorp, The development of a shoreline oil spill R&D program for
diluted bitumen on marine shorelines • 38th AMOP Technical Seminar on on Environmental Contamination
and Response, BC
NAS, Wash. D.C., 9 March 2015 page 24
Ongoing work
• Preparedness to support response to potential spills: – Adding new oils to the oil properties and composition database
▪ Input to Spill models ▪ Oil forensics for spill monitoring
– Pre-mapping continues in northern BC – Testing of spill treating agents – Spill modelling data (meteorology, hydrology, oil properties)
• Research and development to support improved response – New research on dilbit behaviours: weathering, dispersion,
sedimentation, shoreline “stickiness” and penetration – Persistence to long-term breakdown – Better response technologies and detection – New physics for spill models.
NAS, Wash. D.C., 9 March 2015 page 25
NAS, Wash. D.C., 9 March 2015 page 26
Contact Information
Dr. Bruce Hollebone Emergencies Science and Technology Section
Environment Canada Email: bruce.hollebone@ec.gc.ca
Tel: (613) 998-9622
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