Spill Related Properties of ANS 2010 Crude Oil

for Alaska Tanker Company

Valdez, AK

by

SL Ross Environmental Research Ltd.

March 2010 —————————————————————————————————-

Table of Contents 1. Introduction..................................................................................................................................1 2. Physical Property Tests: Methods and Results ............................................................................1

2.1 Results................................................................................................................................... 2 2.1.1 Evaporation ....................................................................................................................... 2 2.1.2 Density............................................................................................................................... 6 2.1.3 Viscosity............................................................................................................................ 6 2.1.4 Interfacial Tension............................................................................................................. 6 2.1.4 Pour Point .......................................................................................................................... 6 2.1.5 Flash Point ......................................................................................................................... 6 2.1.6 Emulsification Tendency and Stability ............................................................................. 6

3. References....................................................................................................................................7 Appendix A. Oil Property Test Methodology and Relationship to Spill Behavior .........................8

A.1 Evaporation ..................................................................................................................... 9 A.2 Physical properties .......................................................................................................... 9 A.2.1 Density ...................................................................................................................... 10 A.2.2 Viscosity ................................................................................................................... 10 A.2.3 Interfacial Tension .................................................................................................... 10 A.2.4 Pour Point.................................................................................................................. 11 A.2.5 Flash Point ................................................................................................................ 11 A.2.6 Emulsification Tendency and Stability..................................................................... 11

Appendix B. Oil Property Analysis Results for ANS 2010 Crude Oil ..........................................13 ———————————————————————————

4-5 Attachment B

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1. INTRODUCTION When oil is spilled in the marine environment its physical and chemical properties will change over time through the processes of evaporation and emulsification. These changes will affect both the fate and behavior of the spill and the opportunities for using countermeasures effectively. For example, an oil may be relatively fluid and non-viscous when initially spilled, but may become viscous within a short time. It is important to know whether this will happen and how long it will take, defining the so-called Window of Opportunity for countermeasures. The objective of this study was to conduct simulated oil spill weathering experiments on a sample of ANS crude oil collected in Valdez, AK in winter 2010. The quantitative results of the tests (involving both fresh and weathered oil) can be used as input to most oil spill models that are used internationally to predict the fate and behavior of spills of specific oils. 2. PHYSICAL PROPERTY TESTS: METHODS AND RESULTS The laboratory testing described here involved 2.7 L of the crude oil. The oil was subjected to the analyses outlined in Table 2-1. Test temperatures were chosen to cover the typical range of seasonal variation for the open water season in the target region. For a winter temperature of 0°C was chosen and for summer, 15°C. A discussion of the methodology of each of these tests is presented in Appendix A, along with an explanation of the effect that each oil property has on spill behavior. The results of the weathering and analyses of the crude oil are presented separately in the following section. Complete test results can be found in Appendix B. Table 2-1 Test Procedures for Spill-Related Analysis of ANS 2010 Crude Oil Property Test

Temperature(s)Equipment Procedure

Evaporation Ambient (avg. 15.5°C)

Wind Tunnel & ASTM Distillation Apparatus

ASTM D86

Density 0 and 15° Anton Paar Densitometer ASTM D4052

Viscosity 0 and 15° Brookfield DV III+ Digital Rheometer c/w Cone and Plate

Brookfield M/98-211

Interfacial Tension Room Temperature

CSC DuNouy Ring Tensiometer

ASTM D971

Pour Point N/A ASTM Test Jars and Thermometers

ASTM D97

Flash Point N/A Pensky-Martens Closed Cup Flash Tester

ASTM D93

Emulsification Tendency/Stability

0 and 15°C Rotating Flask Apparatus (Hokstad and Daling 1993)

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2.1 RESULTS The results of the property analysis of ANS 2010 are summarized in Table 2-2. The complete test results can be found in Appendix B. The two levels of evaporation noted in the table represent the amounts evaporated from a 2 cm-thick slick in the wind tunnel after two days and two weeks, respectively. 2.1.1 Evaporation ANS 2010 crude oil is a black crude oil. Approximately 28.5% of the oil evaporated after two days in the wind tunnel, and about 34.3% evaporated after two weeks of exposure. Figure 2-1 is a predicted evaporation curve for a spill involving a 10-mm thick slick in a 10-knot wind at 0°C. Please note that the curve only applies at a water temperature of 0°C. If other temperatures (or slick thicknesses and wind speeds) are of interest, these curves can be generated using the equations in Appendix A and data in Appendix B1. Computerized oil spill models automatically do these calculations. Figures 2-2, 2-3 and 2-4 show the effect of evaporation on the properties of oil viscosity, density and pour point.

1 The evaporation curve of the oil in the wind tunnel is shown in Appendix B, plotting the volume fraction of oil evaporated, Fv, on the y-axis versus evaporative exposure, 2, on the x-axis, where 2 is the unit of time expressed in dimensionless form. Equations described in Appendix A and data in Table 2-2 of Appendix B can be used to convert this curve into a more usable form for estimating oil evaporation under various spill conditions of temperature, elapsed time and wind speed.

Table 2-2 Spill-Related Properties of ANS 2010 Crude Oil

Spill-related properties ANS 2010 API° gravity = 36.0

Evaporation (Volume %) 0 28.46 34.32Density (g/cm3)

0 °C 0.867 0.922 0.93415 °C 0.845 0.903 0.923

Dynamic Viscosity (mPa.s) at approx 115 s-1

0 °C 28 896 3,03015 °C 6 121 323

Kinematic Viscosity (mm2/s)0 °C 32 972 3,243

15 °C 8 134 350

Interfacial Tension (dyne/cm)Oil/ Air 25.6 30.3 31.1Oil/ Seawater 12.9 13.8 18.2

Pour Point (°C)-24 -3 3

Flash Point (°C)-5 48 130

Emulsion Formation-Tendency and Stability @ 0 °C Tendency Unlikely Likely Likely Stability Unstable Unstable/Entrained Unstable/Entrained Water Content 0% 38% 35%Emulsion Formation-Tendency and Stability @ 15 °C Tendency Unlikely Unlikely Unlikely Stability Unstable Unstable Unstable Water Content 0% 0% 0%ASTM Modified Distillation Liquid Vapour

Evaporation Temperature Temperature(% volume) (°C) (°C)

IBP 56.1 29.55 108.3 57.9

10 131.1 84.415 152.6 95.420 180.1 118.325 209 149.230 237 17640 362 21850 283 235

Weathering ModelFv =

where: Fv is volume fraction of oil evaporatedθ is evaporative exposureTk is environmental temperature (K)

C1 = 7556C2 = 12.70C3 = 5374

ln[1 + (C1/Tk)θexp(C2-C3/Tk)](C1/Tk)

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Figure 2-1 Evaporation of ANS Crude

0.000

0.050

0.100

0.150

0.200

0.250

0.300

0.350

0.400

0 24 48 72 96 120 144 168 192 216

Elapsed Time (hr)

Fv (V

olum

e Fr

actio

n Ev

apor

ated

)

Water Temp (°C ): 0 Wind Speed (knots): 10 Thickness (mm): 10

Figure 2-2 Effect of Evaporation on Oil Viscosity

1

10

100

1,000

10,000

0 10 20 30 40Percent Loss to Evaporation (volume)

Dyn

amic

Vis

cosi

ty

(at a

ppro

xim

atel

y 60

s-1

)

Viscosity @ 0°CViscosity @ 15°C

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Figure 2-3 Effect of Evaporation on Oil Density

0.8400.8500.8600.8700.8800.8900.9000.9100.9200.9300.940

0 10 20 30 40Percent Loss to Evaporation (volume)

Den

sity

(g/c

m3)

Density @ 0°CDensity @ 15°C

Figure 2-4 Effect of Evaporation on Pour Point

-25

-20

-15

-10

-5

0

5

0 20

Percent Loss to Evaporation (volume)

Pour

Poi

nt (°

C)

40

-5-

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2.1.2 Density ANS 2010 is a medium-gravity crude, with a density of 0.844 g/cm3 at 15.5°C (API gravity of 36°). 2.1.3 Viscosity The oil has relatively low viscosity that is typical of medium-gravity oils. At 0°C the viscosity of the fresh oil is about 28 cP (mPa.s). The viscosity increases to 896 cP after 28.5% evaporation and to 3030 cP after 34.3% evaporation. 2.1.4 Interfacial Tension The oil/water interfacial tension of ANS 2010 oil was measured using standard laboratory water with 35 ppt of salt. The value measured was 12.9 dynes/cm, which is lower than the typical range of most crude oils. This indicates that the crude may contain surfactants that have been added to modify its flow properties. 2.1.4 Pour Point ANS 2010 crude is non-waxy oil, having a pour point of below -24°C when fresh. This increases to -3°C at 28.46 percent evaporation and 3°C at 34.32 percent evaporation. This means that spills of the oil that occur at approximately 0°C will initially be fluid but will begin to gel once evaporative losses approach 34%. 2.1.5 Flash Point ANS 2010 has a very low flash point (-5°C) when fresh. This rises after 34.3% evaporation to 130°C. 2.1.6 Emulsification Tendency and Stability From the viewpoint of spill countermeasures and slick persistence, emulsification is a very negative process because strongly emulsified oils are highly viscous — they can have ten to 100 times the viscosity of the parent oil. It is general believed that oils that have relatively high concentrations of asphaltenes are the most likely to form stable water-in-oil emulsions. Some oil spills do not form emulsion immediately, but once evaporation occurs and the asphaltene concentration increases, the emulsification process begins and usually proceeds quickly thereafter. One characteristic of ANS 2010 crude oil is that it has no tendency to form stable water-in oil emulsions when mixed with seawater at 15°C. At 0°C, once evaporation losses reach 28.5% the oil begins to form entrained water emulsions in the test apparatus. These are noted as unstable/entrained in Table 2.2 because although the water content of the emulsion after 24 hours settling was in the range indicative of entrained water emulsions (see Appendix A), there were no visible large water droplets in the fluid. This behavior may be associated with the weathered oil having a pour point near the test temperature.

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3. REFERENCES Fingas, M., B. Fieldhouse and J. Mullin. 1998. Studies of Water-in-Oil Emulsions: Stability and

Oil Properties. Proceedings of the 21st Arctic and Marine Oilspill Technical Seminar. Environment Canada, Ottawa. pp 1-26

Hokstad, J. and P. Daling. 1993. Methodology for Testing Water-in-Oil Emulsions and

Demulsifiers. Description of Laboratory Procedures. In Formation and Breaking of Water-in-Oil Emulsions: Workshop Proceedings Marine Spill Response Corporation, Washington DC, MSRC Technical Report Series 93-108, pp 239-254

Mackay, D., W. Stiver and P.A. Tebeau. 1983. Testing of crude oils and petroleum products for

environmental purposes. In Proceedings of the 1983 Oil Spill Conference, American Petroleum Institute, Washington, D.C., pp 331-337.

Zagorski, W. and D. Mackay. 1982. Water in oil emulsions: a stability hypothesis, in

Proceedings of the 5th Arctic and Marine Oilspill Program Technical Seminar, Environment Canada, Ottawa, ON, pp 61-74.

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APPENDIX A. OIL PROPERTY TEST METHODOLOGY AND

RELATIONSHIP TO SPILL BEHAVIOR

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A.1 EVAPORATION The oil was divided into three aliquots. Two aliquots were weathered in a wind tunnel: one for two days and one for two weeks. Depending on the conditions at a spill site, this is typically equivalent to a few hours and a few days at sea. In addition, the fresh oil was subjected to a modified ASTM distillation (ASTM D86-90, modified in that both liquid and vapor temperature are measured) in order to obtain two oil-specific constants for evaporation prediction purposes. Evaporation is correlated using Evaporative Exposure (θ), a dimensionless time unit calculated by:

θ = kt/x

where: k = a mass transfer coefficient [m/s] (determined experimentally in the laboratory wind tunnel or by an equation related to wind speed for spills at sea)

t = elapsed time [s] x = oil thickness [m]

The distillation information is used in conjunction with the wind tunnel data to predict evaporation rates for oil spills at sea. A.2 PHYSICAL PROPERTIES The oils were subjected to the analyses outlined in Table 1. Test temperatures are chosen to represent typical values for the region for those tests that are temperature-sensitive, such as density and viscosity. Table 1: Test procedures for oil analysis

Property Test Temperature(s) Equipment

Procedure

Evaporation Ambient Wind Tunnel ASTM Distillation Apparatus

ASTM D86

Density 1° and 15 °C Anton Paar Densitometer ASTM D4052

Viscosity 1° and 15 °C Brookfield DV III+ Digital Rheometer c/w Cone and Plate

Brookfield M/98-211

Interfacial Tension Room Temperature CSC DuNouy Ring Tensiometer ASTM D971

Pour Point N/A ASTM Test Jars and Thermometers ASTM D97

Flash Point N/A Pensky-Martens Closed Cup Flash Tester ASTM D93

Emulsification Tendency/Stability 1° and 15 °C Rotating Flask Apparatus (Hokstad and

Daling 1993)

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A.2.1 Density Density, the mass per unit volume of the oil (or emulsion), determines how buoyant the oil is in water. The common unit of density is grams per millilitre or cubic centimetre (g/mL or g/cm3); the SI unit is kg/m3, which is numerically 1000 times the value in g/mL. The density of spilled crude oil increases with weathering and decreases with increasing temperature. Density affects the following spill processes:

• Sinking - if the density of the oil exceeds that of the water it will sink; • Spreading - in the early stages of a spill, more dense oils spread faster; • Natural dispersion - more dense oils stay dispersed more easily; and, • Emulsification stability - dense oils form more stable emulsions.

A.2.2 Viscosity Viscosity is a measure of the resistance of oil to flowing, once it is in motion. The common unit of dynamic viscosity is the centi-Poise (cP); the SI unit is the milli-Pascal second (mPas), which is numerically equivalent to the centi-Poise. The common unit of kinematic viscosity (calculated by multiplying the dynamic viscosity by the density) is the centi-Stoke (cSt) the SI unit is the square millimetre/second (mm2/s), which is numerically equivalent to the centi-Stoke. The viscosity of spilled crude oil increases as weathering progresses and decreases with increasing temperature. Viscosity is one of the most important properties from the perspective of spill behavior and affects the following processes:

• Spreading - viscous oils spread more slowly; • Natural and chemical dispersion - highly viscous oils are difficult to disperse; • Emulsification tendency and stability - viscous oils form more stable emulsions; and, • Recovery and transfer operations - more viscous oils are generally harder to skim and

more difficult to pump.

A.2.3 Interfacial Tension Interfacial tension is a measure of the surface forces that exist between the interfaces of the oil and water, and the oil and air. The common unit of interfacial tension is the dyne/cm; the SI unit is the milli-Newton/metre (mN/m), which is numerically equivalent to the dyne/cm. Chemical dispersants work by reducing the oil/water interfacial tension to allow a given mixing energy (i.e., sea state) to produce smaller oil droplets. Emulsion breakers also work by lowering the oil/water interfacial tension; this weakens the continuous layer of oil surrounding the suspended water droplets and allows them to coalesce and drop out of the emulsion. Interfacial tensions (oil/air and oil/water) are fairly insensitive to temperature, but are affected by evaporation. Interfacial tension affects the following processes:

• Spreading - interfacial tensions determine how fast an oil will spread and whether the oil will form a sheen;

• Natural and chemical dispersion - oils with high interfacial tensions are more difficult to disperse naturally, chemical dispersant work by temporarily reducing the oil/water interfacial tension;

• Emulsification rates and stability; and,

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• Mechanical recovery - oleophilic skimmers (e.g., rope-mop and belt skimmers) work best on oils with moderate to high interfacial tensions.

A.2.4 Pour Point The pour point is the lowest temperature (to the nearest multiple of 3 °C) at which crude oil will still flow in a small test jar tipped on its side. Near, and below this temperature, the oil develops a yield stress and, in essence, gels. The pour point of an oil increases with weathering. Pour point affects the following processes:

• Spreading - oils at temperatures below their pour points will not spread on water; • Viscosity - an oil’s viscosity at low shear rates increases dramatically at temperatures

below its pour point; • Dispersion - an oil at a temperature below its pour point may be difficult to disperse; and, • Recovery - crude oil below its pour point may not flow towards skimmers or down

inclined surfaces in skimmers A.2.5 Flash Point The flash point of crude oil is the temperature at which the oil produces sufficient vapors to ignite when exposed to an open flame or other ignition source. Flash point increases with increasing evaporation. It is an important safety-related spill property. A.2.6 Emulsification Tendency and Stability The tendency of crude oil to form water-in-oil emulsions (or “mousse”) and the stability of the emulsion formed are measured by two numbers: the Emulsification Tendency Index (Zagorski and Mackay 1982, Hokstad and Daling 1993) and the Emulsion Stability (adapted from Fingas et al. 1998). The Emulsification Tendency Index is a measure of the oil’s propensity to form an emulsion, quantified by extrapolating back to time = 0 the fraction of the parent oil that remains (i.e., does not cream out) in the emulsion formed in a rotating flask apparatus over several hours. If a crude oil has an Emulsification Tendency Index between 0 and 0.25 it is unlikely to form an emulsion; if it has a Tendency Index between 0.25 and 0.75 it has a moderate tendency to form emulsions. A value of 0.75 to 1.0 indicates a high tendency to form emulsions. Recently the Emulsion Stability assessment has been changed to reflect the four categories suggested by Fingas et al. 1998. Emulsion types are selected based on water content, emulsion rheology and the visual appearance of the emulsion after 24 hours settling. The four categories, and their defining characteristics, are:

1. Unstable – looks like original oil; water contents after 24 hours of 1% to 23% averaging 5%; viscosity same as oil on average

2. Entrained Water – looks black, with large water droplets; water contents after 24 hours of 26% to 62% averaging 42%; emulsion viscosity 13 times greater than oil on average

3. Meso-stable – brown viscous liquid; water contents after 24 hours of 35% to 83% averaging 62%; emulsion viscosity 45 times greater than oil on average

4. Stable – the classic “mousse”, a brown gel/solid; water contents after 24 hours of 65% to 93% averaging 80%; emulsion viscosity 1100 times greater than oil on average

Under the old emulsion stability assessment scheme, the stability was determined by the fraction of the original oil that remained in the emulsion after 24-hours settling (0 to 0.25 = unstable, 0.25 to 0.75 = fairly stable, 0.75 to 1 = very stable).

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Both the Tendency Index and Stability generally increase with increased degree of evaporation. Colder temperatures generally increase both the Tendency Index and Stability (i.e., promote emulsification) unless the oil gels as the temperature drops below its pour point and it becomes too viscous to form an emulsion. Emulsion formation results in large increases in the spill's volume, enormous viscosity increases (which can reduce dispersant effectiveness), and increased water content (which can prevent ignition of the slicks and in situ burning).

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APPENDIX B. OIL PROPERTY ANALYSIS RESULTS FOR ANS 2010

CRUDE OIL

Oil Weathering ANS 2010 Volume Weathered(ml) 970

Volume for 2cm thick 969.50Tray 7 Tray 8 Average Air Temp Tray thickness (m) 0.02001031

Tray Mass (g) 241.0 240.9 15.5 °CFv vs. Theta Modeling

Date/Time Fm Oil Fv Evaporative ModelTray 7 Tray 8 Tray 7 Tray 8 Tray 7 Tray 8 Density Tray 7 Tray 8 Exposure Evaporate

(g) (g) (g) (g) (g/cm3) (Corrected) (Fv)26/01/2010 13:03 1066.9 1054.2 825.9 813.3 0.000 0.000 0.844 0.000 0.000 0.0 0.00026/01/2010 13:30 1047.5 1036.1 806.5 795.2 0.023 0.022 0.850 0.030 0.029 236.0 0.11026/01/2010 14:05 1034.4 1023.3 793.4 782.4 0.039 0.038 0.854 0.051 0.049 541.9 0.14026/01/2010 14:40 1023.6 1012.5 782.6 771.6 0.052 0.051 0.858 0.067 0.066 847.8 0.15726/01/2010 15:12 1015.2 1004.3 774.2 763.4 0.063 0.061 0.861 0.080 0.079 1127.5 0.16826/01/2010 15:45 1005.3 994.4 764.3 753.5 0.075 0.074 0.864 0.096 0.094 1415.9 0.17626/01/2010 16:50 991.3 980.9 750.3 740.0 0.092 0.090 0.868 0.117 0.115 1984.1 0.18927/01/2010 9:15 908.5 898.5 667.5 657.6 0.192 0.191 0.895 0.238 0.237 10593.3 0.253

27/01/2010 16:24 894.7 884.9 653.7 644.0 0.208 0.208 0.899 0.257 0.257 14342.9 0.26428/01/2010 9:10 875.0 865.5 634.0 624.6 0.232 0.232 0.906 0.285 0.284 23135.7 0.282

28/01/2010 13:00 872.3 862.6 621.7 0.236 0.907 0.288 25146.0 0.28628/01/2010 17:20 859.2 618.3 0.240 0.908 0.293 27418.5 0.28929/01/2010 9:15 850.4 609.5 0.251 0.911 0.305 35765.5 0.299

29/01/2010 16:30 847.0 606.1 0.255 0.912 0.310 39567.5 0.30301/02/2010 10:30 833.3 592.4 0.272 0.916 0.329 74179.3 0.32702/02/2010 9:10 830.1 589.2 0.276 0.917 0.333 86066.2 0.333

03/02/2010 10:00 830.0 589.1 0.276 0.917 0.333 99089.3 0.33804/02/2010 9:20 822.9 582.0 0.284 0.920 0.343 111325.8 0.342

820.2

2-day 2-week 2-day 2-week

Mass of Oil + Tray Mass of Oil

-14-Fm 0.232 0.284 Fv 0.285 0.343

Density ANS 2010Measurements Density Constants for SL Ross Model API Gravity

Mass Density Temperature Density Constant 1 (slope, kg/m3) 207.054 Standard Density Temperature, To (K) 288.72Evaporated (g/cm3) (°C) Density Constant 2 (kg/K.m3) 1.152 Standard Density (kg/m3) 844.629

(Fm) API Gravity @ 15.5°C 36.030 0.871 -2.9 Calculations0 0.845 15.3 Temperature Density Density Volume T-To

0.23 0.926 -3.2 (°C) (g/cm3) (kg/m3) Evaporated (K)0.23 0.903 15.4 (Fv)0.28 0.936 -2.0 0 0.867 867 0 -15.560.28 0.922 15.7 0 0.922 922 0.285 -15.56

0 0.845 15.46 0 0.934 934 0.343 -15.560.23 0.903 15.46 15 0.845 845 0 -0.560.28 0.922 15.46 15 0.903 903 0.285 -0.56

15 0.923 923 0.343 -0.56slope 0.266 15.5 0.922 922 0.000

intercept 0.844r2 0.995

840850860870880890900910920930940

0.00 0.10 0.20 0.30 0.40Fv

Den

sity

(kg/

m^3

)

840850860870880890900910920930940

-20 -15 -10 -5 0T-To

Den

sity

(kg/

m^3

)

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Wind Tunnel Calibration Toluene

Tray Mass (g)

Elapsed Mass TolueneTime Tray5 Tray 9(s) (g) (g)

0 826.6 824.11620 791.2 804.73720 752.3 791.65820 716.7 780.87740 684.5 772.4

Tray5 Tray 9 Averageslope -0.01819524 -0.006423 -0.012309

E (kg/s) -1.2309E-05Wind Tunnel Temperature, T (K) 288.6242 15.46 °CToluene Vapor Pressure, P (kPa) 2.269

Ideal Gas Constant (R, kPa.m^3/kg.mol.K) 8.314Molecular Weight of Toluene (W, kg/kg.mol) 92.13

Tray Area (A, m^2) 0.048475

K = ERT/APW (m/s) -0.002914951

Mackay Constants ANS 2010(automated)

Point Fv Tb/T H ln(H)

1 0.015 1.267 1.231E-04 -9.0022 0.039 1.310 6.637E-05 -9.6203 0.058 1.342 5.549E-05 -9.7994 0.073 1.368 4.575E-05 -9.9925 0.087 1.393 5.320E-05 -9.8416 0.105 1.424 3.650E-05 -10.2187 0.176 1.549 1.419E-05 -11.1638 0.247 1.673 5.190E-06 -12.1699 0.271 1.713 3.119E-06 -12.678

10 0.286 1.741 2.023E-06 -13.11111 0.291 1.749 2.094E-06 -13.07712 0.299 1.763 1.469E-06 -13.43113 0.308 1.778 1.240E-06 -13.60014 0.320 1.799 5.457E-07 -14.42115 0.331 1.819 3.689E-07 -14.81316 0.333 1.823 1.051E-08 -18.37117 0.338 1.832 7.922E-07 -14.049

calculated adjustedFv vs. Theta B (-slope) 10.56338 15

Fv vs. Theta A (intercept) 4.675242 12.7

Wind Tunnel Calibration

300.0400.0500.0600.0700.0800.0900.0

0 2000 4000 6000 8000 10000Elapsed Time (s)

Tolu

ene

Rem

aini

ng

(g)

ASTM Distillation ANS 2010

200 ml Fresh oil

Volume Fraction TemperatureDistilled Distilled Liquid Vapor

(mL) (Fv) (°C) (°C)IBP 0.00 56.1 29.510 0.05 108.3 57.920 0.10 131.1 84.430 0.15 152.6 95.440 0.20 180.1 118.350 0.25 209 149.260 0.30 237 17680 0.40 362 218

100 0.50 283 235

slope 503.8intercept 85.1

Distillation Constant A (slope, K) 503.8Distillation Constant B (intercept, K) 358.3

ASTM Distillation

y = 503.76x + 85.0950

50

100

150

200

250

300

350

400

0.00 0.10 0.20 0.30 0.40 0.50

Volume Fraction Evaporated (Fv)

Liqu

id T

empe

ratu

re (°

C)

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ANS Crude - Fv vs Theta

0.000

0.050

0.100

0.150

0.200

0.250

0.300

0.350

0.400

0 30,000 60,000 90,000 120,000Evaporative Exposure

Fv

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Viscosity ANS 2010Viscosity Constants for SL Ross Model

Mass Shear Standard Viscosity Temperature (K) 273.16Evaporated Viscosity Temperature rpm Spindle # Rate ln(Viscosity) Standard Viscosity (cP) 27.70

(Fm) (cP) (°C) (s-1) Viscosity Constant 1 12.150 27.7 0.0 30.0 CP-42 115.0 3.321 Viscosity Constant 2 (K-1) 9989.010 6.4 15.0 30.0 CP-42 115.0 1.856

0.23 896.3 0.0 60.0 CP-52 120.0 6.7980.23 121.2 15.0 30.0 CP-42 115.0 4.7970.28 3030.0 0.0 60.0 CP-52 120.0 8.0160.28 322.6 15.0 30.0 CP-42 115.0 5.776

VolumeEvaporated Viscosity Temperature ln(Viscosity) 1/T-1/To

(Fv) (cP) (°C) (K-1)0 27.7 0.0 3.321 00 6.4 15.0 1.856 -0.000190443

0.28 896.3 0.0 6.798 1.34024E-070.28 121.2 15.0 4.797 -0.0001904430.34 3030.0 0.0 8.016 1.34024E-070.34 322.6 15.0 5.776 -0.000190443

Volume Viscosity ViscosityEvaporated 1°C 15°C

(Fv) (cP) (cP)0 27.7 6.4

0.28 896.3 121.20.34 3030.0 322.6

0.000

2.000

4.000

6.000

8.000

10.000

-0.0002 -0.00015 -0.0001 -0.00005 0 0.00005

1/T-1/To

ln(V

isco

sity

)

0.000

2.000

4.000

6.000

8.000

10.000

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4

Fv

ln(V

isco

sity

)

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Pour Point ANS 2010

Test Results Pour Point Constants for SLR Spill Model

Fv Initial Pour Point (K) 249.0118Measured Reported Pour Point Constant 0.309734

(°C) (°C)0.000 -25 -240.285 -5 -30.343 1 3

slope 77.12737intercept -24.13821

Pour Point

-25-20-15-10-505

0.000 0.100 0.200 0.300 0.400

Fv

Pour

Poi

nt (°

C)Interfacial Tension ANS 2010

Interfacial Tension Constants for SL Ross ModelFv Interfacial Tension Dial Reading Correction Factor (F) Oil/Water Interfacial Tension (dyne/cm) 12.594

Oil/Water Oil/Air Oil/Water Oil/Air Oil/Water Oil/Air Oil/Water Interfacial Tension Constant 0.905(dyne/cm) (dyne/cm) (dyne/cm) (dyne/cm) Oil/Air Interfacial Tension (dyne/cm) 25.618

0.000 12.9 25.6 13.8 28.6 0.941 0.896 Oil/Air Interfacial Tension Constant 0.6300.285 13.8 30.3 14.2 33.7 0.977 0.9000.343 18.2 31.1 17.8 34.5 1.021 0.900

slope 11.403 16.132intercept 12.594 25.618

0.05.0

10.015.020.025.030.035.0

0.000 0.050 0.100 0.150 0.200 0.250 0.300 0.350 0.400

Fv

Inte

rfac

ial T

ensi

on

(dyn

e/cm

) Oil/WaterOil/AirLinear (Oil/Water)Linear (Oil/Air)

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SL Ross Model ANS 2010Modeling Constants

Standard Density 844.629 kg/m3Standard Density Temperature 288.720 K

Density Constant 1 207.054 kg/m3Density Constant 2 1.15203 kg/K.m3Standard Viscosity 27.70000 cP

Standard Viscosity Temperature 273.160 KViscosity Constant 1 12.1468Viscosity Constant 2 9989.01 K-1

Oil/Water Interfacial Tension 12.5939 dyne/cmAir/Oil Interfacial Tension 25.6184 dyne/cm

Oil/Water Interfacial Tension Constant 0.90540Air/Oil Interfacial Tension Constant 0.62972

Initial Pour Point 249.012 KPour Point Constant 0.30973

ASTM Distillation Constant A (slope) 503.765 KASTM Distillation Constant B (intercept) 358.255 K

Emulsification Delay 9999999999Initial Flash Point 262.287 K

Flash Point Constant 1.24869Fv vs. Theta A 12.70000Fv vs. Theta B 15.00000

B.Tg 7556.47B.To 5373.82

Flash Point ANS 2010

Test Results Flash Point Constants for SLR Spill ModelInitial Flash Point (K) 262.287

Fv Flash Point Flash Point Constant 1.249(°C)

0.000 -50.285 480.343 130

slope 327.515532intercept 262.286967

-10

40

90

140

0.000 0.100 0.200 0.300 0.400Fv

Flas

h Po

int (

°C)

-22-

-23-

Emulsification Tendency and Stability - 0°CTest Results 300ml H2O 0.0 °C

oil @ 15.0 °Cmixing don 0.0 °Csettling don 15.0 °C

Final 24 hr 0.0 °Ctwo replicates of each oil

Fresh Oil Weathered Two Days Weathered Two WeeksAll measurements in mm Emulsion Free Oil Emulsion Free Oil Emulsion Free Oil Emulsion Free Oil Emulsion Free Oil Emulsion Free Oil

Start 0 0 0 10 0 10 0 10 0 10 0 10After first hour mixing 0 9 0 9 13 0 14 0 12 0 7 0

plus 10 minutes 0 9 0 9 13 0 13 0 13 0 9 0plus 20 minutes 0 9 0 9 13 0 13 0 13 0 10 0plus 30 minutes 0 9 0 9 13 0 13 0 13 0 11 0

After second hour mixing 0 10 0 9 14 0 15 0 13 0 12 0plus 10 minutes 0 9 0 8 15 0 14 0 13 0 12 0plus 20 minutes 0 9 0 9 14 0 14 0 15 0 15 0plus 30 minutes 0 9 0 9 13 0 15 0 14 0 14 0

After third hour mixing 0 10 0 9 13 0 15 0 12 0 10 0plus 10 minutes 0 9 0 9 13 0 15 0 15 0 15 0plus 20 minutes 0 9 0 9 13 0 14 0 15 0 14 0plus 30 minutes 0 9 0 9 13 0 13 0 13 0 13 0

After fourth hour mixing 0 9 0 8 15 0 16 0 12 0 8 0plus 10 minutes 0 9 0 9 15 0 16 0 16 0 13 0plus 20 minutes 0 9 0 9 15 0 16 0 17 0 14 0plus 30 minutes 0 9 0 9 15 0 16 0 17 0 14 0

Appearance Brown solid 0 0 0 0 0 0

Brown viscousliquid 0 0 0 0 0 0

Black withlarge droplets 0 0 0 0 0 0

Looks like oil X X X X X Xplus 24 hour 0 9 0 9 16 0 16 0 15 0 16 0

note: Bottle #6 was smeared with oil after each hour. This tied up a lot of oil until the half hour measureConclusions: Fresh Oil Weathered Two Days Weathered Two Weeks Tendency Unlikely Likely Likely Stability Unstable Unstable/Entrained Unstable/Entrained Water Content 0% 38% 35% (after 24 hr)

Emulsification Tendency and Stability - 15°C

Test Results 300ml H2O 15.0 °Coil @ 15.0 °Cmixing don 15.0 °Csettling don 15.0 °CFinal 24 hr 15.0 °Ctwo replicates of each oil

Fresh Oil Weathered Two Days Weathered Two WeeksAll measurements in mm Emulsion Free Oil Emulsion Free Oil Emulsion Free Oil Emulsion Free Oil Emulsion Free Oil Emulsion Free Oil

Start 0 10 0 10 0 10 0 10 0 10 0 10After first hour mixing 0 9 0 9 12 0 10 0 10 0 10 0

plus 10 minutes 0 9 0 9 10 0 10 0 10 0 10 0plus 20 minutes 0 9 0 9 10 0 10 0 10 0 10 0plus 30 minutes 0 9 0 9 10 0 10 0 10 0 10 0

After second hour mixing 0 9 0 9 12 0 12 0 13 0 12 0plus 10 minutes 0 9 0 9 12 0 11 0 12 0 12 0plus 20 minutes 0 9 0 9 11 0 10 0 12 0 12 0plus 30 minutes 0 9 0 9 11 0 10 0 12 0 11 0

After third hour mixing 0 9 0 9 13 0 12 0 13 0 12 0plus 10 minutes 0 9 0 9 11 0 11 0 13 0 13 0plus 20 minutes 0 9 0 9 11 0 11 0 13 0 12 0plus 30 minutes 0 9 0 9 10 0 11 0 12 0 12 0

After fourth hour mixing 0 9 0 9 12 0 12 0 12 0 12 0plus 10 minutes 0 9 0 9 11 0 11 0 12 0 12 0plus 20 minutes 0 9 0 9 10 0 11 0 12 0 12 0plus 30 minutes 0 9 0 9 10 0 11 0 12 0 12 0

Appearance Brown solid 0 0 0 0 0 0

Brown viscousliquid X X X X X X

Black withlarge droplets 0 0 0 0 0 0

Looks like oil X X X X X Xplus 24 hour 0 9 0 9 0 9 0 9 0 9 0 9

Conclusions: Fresh Oil Weathered Two Days Weathered Two Weeks Tendency Unlikely Unlikely Unlikely Stability Unstable Unstable Unstable Water Content 0% 0% 0% (after 24 hr)

-24-

Viscosity Measurements with Brookfield DV-III+ Rheometer

ViscosityNominal Test Temperature 0.0 15.0

Viscosity RPM Spindle Shear Rate Viscosity RPM Spindle Shear RateFresh 27.7 30.0 CP-42 115.0 6.4 30.0 CP-42 115.02 Day Weathered 896.3 60.0 CP-52 120.0 121.2 30.0 CP-42 115.02 Week Weathered 3030.0 60.0 CP-52 120.0 322.6 30.0 CP-42 115.0

Spindle RPM % Torque Viscosity Shear Rate TempcP °C

Fresh CP-42 15 3.3 28.2 57.6 -0.130 6.5 27.7 115.0 -0.1 <===45 9.5 27.0 173.0 -0.160 12.5 26.7 230.0 -0.190 18.4 26.2 346.0 -0.1120 24.3 25.9 461.0 -0.1180 35.7 25.4 691.0 -0.1250 49.3 25.2 960.0 -0.1

2 Day Weathered CP-52 15 10.5 1389.0 30.0 -0.130 16.8 1111.0 60.0 -0.145 22.3 983.4 90.0 -0.160 27.1 896.3 120.0 -0.1 <===90 36.4 802.6 180.0 -0.1120 44.8 740.8 240.0 -0.1180 60.9 671.4 360.0 -0.1250 78.2 620.7 500.0 -0.1

2 Week Weathered CP-52 15 40.2 5318.0 30.0 -0.230 60.5 4002.0 60.0 -0.245 77.1 3400.0 90.0 -0.260 91.6 3030.0 120.0 -0.2 <===90 -over- 180.0 -0.2

Fresh CP-42 15 0.8 6.8 57.6 15.030 1.5 6.4 115.0 15.0 <===45 2.3 6.5 173.0 14.960 3.0 6.4 230.0 14.990 4.4 6.3 346.0 14.9

120 5.8 6.2 461.0 14.9180 8.7 6.2 691.0 14.9250 11.9 6.1 960.0 14.9

2 Day Weathered CP-42 15 14.9 127.1 57.6 14.930 28.4 121.2 115.0 14.9 <===45 41.1 116.9 173.0 14.960 53.2 113.5 230.0 14.990 77.8 110.6 346.0 14.9120 -over- 461.0 14.9

2 Week Weathered CP-42 15 39.1 333.7 57.6 14.930 75.6 322.6 115.0 14.9 <===45 -over- 173.0 14.9

-25-