The attached paper was submitted by Environment to the 34th Arctic and Marine Oilspill Program (AMOP) Technical Seminar on Environmental Contamination and Response, held on October 4- 6, 2011, in Calgary, .

The Behaviour of Heavy Oil in Fresh Water Lakes

B.P. Hollebone*, B. Fieldhouse, G. Sergey, P. Lambert, Z. Wang, C. Yang, M. Landirault Emergencies Science and Technology Division, Environment Canada Environmental Technology Centre Ottawa, Canada [email protected]

Abstract Heavier oils spilled in fresh water have some behavioural similarities to spills in salt water, but their environmental fates strongly reflect the differences between freshwater and marine locations. Some of the environmental factors that can differ in freshwater lakes compared with marine shores include: low water salinity, mixing energies, currents, differing sediment type and size distributions, plant species, benthic types and ecosystems. Many different freshwater spill oil fates have been observed in a recent spill of a heavy residual oil destined for use as an asphalt stock into Wabamun Lake, Alberta. Floating, sinking, submerged, sedimented and refloating oil states have all been reported in the year following the spill. The mechanisms by which the oil reached many of the observed states are unclear and the eventual fate of the oil remaining in the lake remains in question. This paper presents a summary of the analysis of samples gathered over several visits to Wabamun Lake in the first year following the spill. We summarize field reports cataloguing the states of the asphalt stock as the oil aged and the seasons changed. We also present laboratory measurements characterizing samples of oil, water and sediment taken during the site visits over the entire year for oil physical properties; “tarball”/oil particle composition, including sediment, water and hydrocarbon concentrations observed in various oil states. The weathered condition of the oil in the lake is discussed in the context of the physical property and chemical composition data. The sediment and water uptake of the oil in several states has also been measured. Some of the possible mechanisms for the fresh oil evolving into its observed environmental fates are discussed in the context of the field observations and laboratory data. The roles of chemical weathering of the oil, and sediment and water uptake are examined.

1 Introduction On Wednesday, August 3rd, 2005, 43 National Railway Company (CN) rail cars went off the tracks near the summer village of Whitewood Sands, located approximately 65 km west of Alberta, Canada (Alberta Environment, 2005). The lake is in the transition zone between the parkland and boreal forest natural regions and is relatively large (area = 82 km2) and shallow (mean depth = 6.3 m; maximum depth = 11 m). It is generally well mixed, usually with well oxygenated conditions in the entire water column during the open-water period (Mitchell and Prepas, 1990). The lake is moderately- to highly-enriched with nutrients. There is no commercial fishery on the lake, but it is actively fished recreationally for northern pike, yellow perch, and whitefish. The Lake Wabamun basin has a large number of land uses and human activities: mining; coal-fired power generation; farming; major road and rail corridors; residential and recreational activities. A mild drought and increased industrial usage have combined to cause gradual decline in lake level since the early 1990s. Lake Wabamun is unique in being one of the most studied aquatic ecosystems in Alberta. Since at least 1942, scientists have been conducting studies on the lake (Schindler et al., 2004). Taken together, these reports provide a great deal of detailed information about the lake ecosystem (Schindler et al., 2004). Of the train cars involved in the derailment, 11 cars containing heavy fuel oil—HFO 7102—ruptured, spilling 712,000 L of warm, highly viscous oil (Golder, 2006). A single car carrying Pole Treating Oil (PTO) also ruptured, spilling an estimated volume of 88,000 L onto the ground at the derailment site (Golder, 2006). The oil was discharged onto the lawns of residences approximately 100 metres north of the lakeshore, on a moderate slope. The heavy fuel oil flowed down the slope, entering the waters of the north shore of Lake Wabamun near Whitewood Sands shortly after the derailment. The oil spilled into the lake through many paths along a broad front of about a 1/2 kilometer. The flow was aided by the fact that the HFO 7102 had been loaded a few hours before and was still warm and relatively less viscous than it would be at ambient temperature.

2 Disposition of the Oil in the Lake following the Spill In the first few days following the spill, the majority of the oil appeared to be floating on the surface of lake. The spilled fuel oil formed a thick, black slick on the lake surface. Silvery sheens (0.05 μm) rapidly covered the lake. By the end of the first day, thin silver sheens of oil covered most of the east end of the lake. Thick (>1 cm) black slicks of oil lined the north shore, east of the spill site (see Figure 2). Tarballs were reported (discrete ‘balls’ of oil from < 1 cm to 10 cm in diameter) submerged in the affected near-shore regions on the first day of the spill (3 August 2005). Within hours, some of the tarballs were showing neutrally-buoyant behaviour, and were seen riding up and down in the water column. Some would rise to the surface, others would be seen sinking to the bottom. No dispersions of oil in water were observed in the lake. Light crude oils are often observed to form a light-brown to red ‘plume’ of oil in water, especially in high wave (surf) conditions. There were no observations during the Wabamun incident. In addition, solid masses of red-brown “chocolate mousse”, a typical form of stable (crude) oil emulsion, have never been reported over the 3 year history of observation at the spill site to date. Systematic field observations were conducted starting on August 11, 2005 using the shoreline clean-up assessment technique (SCAT). The initial SCAT survey indicated the presence of submerged (in the water column, but not touching bottom) and sunken (in contact with the lake bottom) tarballs along the shorelines and in the near shore, shallower areas of the lake. In addition to the smaller tar-ball shapes, sunken oil also formed cylindrical ‘log’-shapes or large patties (> 10 cm diameter, but less than 5 cm thick) of several meters in length and width. During the SCAT survey, the majority of tarballs or patties were observed near the shores, in water depths ranging between 0.1 and 1.5 m with their frequency diminishing with increasing depth. To establish the extent, character and location of submerged and sunken oil, a variety of techniques were employed from the end of August through October, 2005. These included visual surveys along the shoreline (SCAT) and by SCUBA divers in deeper areas, weighted-‘snare’ sampling (weighted oleophilic sorbent), towed bottom trawls (with oleophilic sorbent), and underwater video surveys (black and white, and colour). Observations of presence and character of submerged and sunken oil were collected during the initial SCAT survey, reed bed delineation, shoreline treatment, and post-treatment SCAT survey. In general, observations were made while travelling on foot in water depths ranging from 0.1 to 1.5 m. General observations of the oil conditions include: 1. Submerged and sunken tarballs were frequent in the near shore area adjacent to oiled shorelines and reed beds. After shoreline treatment a high proportion of oil remained. The coverage of oil varied but was highest in treated reed beds (i.e., delineated and cut). Cut reed beds that intercepted wave energy in the near shore areas contained relatively high densities of tarballs. Typically, the tarballs varied in size from 2 to 10 cm. After high winds, the near shore area could have many of these in the area. A sample of one of the larger of these is shown in Figure 5. The tarballs in this area showed a range of densities (specific gravity). Some of them were neutrally buoyant, and moved around in the area, especially when disturbed by water movement. 2. During the initial assessment (August 2005), the tarballs ranged from ‘fresh’ (thick ‘syrup’) to ‘weathered’ (relatively hard with skins of sediment or organic debris). On relatively warm days, some submerged tarballs would float to the lake’s surface and lose their cohesiveness (‘burst’), resulting in an oil slick and associated sheen. See Figure 7. Broken ‘skins’ can be seen in Figures 11 and 12. 3. During post-treatment assessment (October, 2005), the character of the submerged and/or sunken tarballs varied from ‘fresh’ (south- shore) to ‘intermediate’/’tacky’ (north-shore) to highly ‘weathered’ (east-shore). 4. In the reed bed areas tarballs were observed on the bottom, however during the daytime some of these would rise and create a sheen. Often the tarball shed oil from several points around its circumference. An illustration of one of these is shown in Figure 7. A view of tarballs sunk in an oiled reed bed is shown in Figure 8. A ‘deflated’ tarball ‘skin’ is shown in Figure 11. The oil adhered to the reeds also released oil. Tarballs were also seen re-surfacing in areas not in or near reed beds. 5. A ‘slurry’, composed of finely divided organic matter and small oil particles (<1 cm) was observed on the north shore. This is shown in Figure 4. 6. Conglomerations (‘logs’ and large patties) of organic debris and oil observed on the south shore. Most of the organic debris was reed material. A photo of one of these ‘tar logs’ is shown in Figure 3. A tar mat illustrated in Figure 6. 7. Beach re-oiling occurred until freeze-up. In October, 2005, transects across the lake were surveyed by SCUBA divers, weighted oleophilic snares, dredge and video camera. The transects intersected the known path followed by the surface oil slick. No residual oil was observed away from the shorelines by ant technique. The results of the different survey techniques indicated that the majority of submerged and/or sunken oil is in the form of tarballs observed in the near shore zone (< 5 m water depth). In February 2006, a survey was conducted by Environment Canada and Alberta Environment staff to assess the character of the oil post-freezeup. This consisted of visiting areas known to be heavily-oiled in the fall to assess the character of the submerged and sunken oil. Tarballs were found in several of the areas surveyed; all were in treated (cut) reed beds. The tarballs were small (1 mm to 5 cm in diameter) and consisted of a durable skin covering a centre of relatively fluid oil. Almost all tarballs were collected from the bottom of the lake. A few small particles (<5mm) of highly weathered oil were observed to be frozen into the ice cover. For the spring season of 2006, during the breakup of the ice two surveys of the shorelines have been reported: Nichols, 2006, and Watmough, 2006. In both surveys, tarballs were found the water column and floating on the surface. Oil sheens on the water surface in and amongst the broken ice, particularly in the reed beds most heavily affected by the spill. In some cases only free-floating sheen was observed, in other cases, sheen was observed in association with brown and black oil escaping from a tarball. Heavily weathered oil (black, semi-solid) was found on the bottom of the lake along several shores, particularly associated with the reed beds. In February 2007, a second winter survey was completed by Alberta Environment and Environment Canada, with similar results to the 2006 survey. As before, small tarballs (1 mm to 2 cm in diameter) were found with ‘skins’ covering relatively fresh oil. In addition, several ‘skins’ with cracks and holes were found which had lost their central containment. Such a ‘skin’ can be seen in Figure 12. Highly weathered fragments of oil were also collected from conglomerations firmly attached to plant matter (reed roots) on the bottom of the lake. In several areas, these conglomerations appeared to cover a large area (larger than the holes cut in the ice, 1- 2 m2).

Figure 1 One of the several paths taken by the oil to the lake. This may have resulted in uptake of sediment and organic material (3 August 2005, D. Cymbaluk, EC Enf. AB).

Figure 2 Another of the paths taken by the oil to the lake. The oil flowed directly over granular material, which may have become incorporated into the oil. The area with suppressed waves is black oil from the shore to past the boats; the darker colour towards the horizon is open water. (3 August 2005, D. Cymbaluk, EC Enf. AB).

Figure 3 One of several ‘tar logs’ seen along the shoreline on the downwind side. This particular one is about 4 m long and 8 cm in diameter (20 August 2005, D. Noseworthy, EC Env. Emerg. AB).

Figure 4 The near shore zone on the north side of the lake. “Slurries” of organic matter mixed with oil formed along most of the effected northern shores of the Lake (20 August 2005, D. Noseworthy, EC AB).

Figure 5 A sample of one of the tarballs taken from the same area as shown in Figure 4 (2 September 2005, M. Fingas, EC ESTD).

Figure 6 A near shore zone. The black areas are tar conglomerations forming on the bottom (7 August 2005, P. Lambert, EC ESTD).

Figure 7 A tarball rising to the surface and releasing sheen (20 August 2005, D. Noseworthy, EC Emerg. AB).

Figure 8 A near shore zone with reeds. The round black areas are all tarballs on the bottom (30 August 2005, S. Krishnaraj, EC Emerg. ON).

Figure 9 Sheening occurred in this area east of the original spill site. The origin of the sheens may have been re-surfacing oil; tarballs were found in this area (2 September 2005, M. Fingas, EC ESTD).

Figure 10 A tarball in a dredge sample taken in the same area as Figure 9 (4 September 2005, M. Fingas, EC ESTD).

Figure 11 Tarball ‘skin’, the weathered outer layer of a tarball. The inner, less weathered, liquid oil has escaped (30 August 2005, S. Krishnaraj, EC Emerg. ON).

Figure 12 Tarball ‘skin’ showing fissures and cracks through which oil has escaped. The skin is composed of highly weathered oil (black, solid) and is less than 1mm thick (22 February, 2007, B. Hollebone, EC ESTD). 3 Physical Fate of Spilled Oil 3.1 Mechanisms for Oil Density Changes Following the release of oil into the environment, the oil changes significantly as it ages. These changes, their rate and severity, determine the eventual fate of oil in the environment. One of the most important changes is the alteration in density, especially important in comparison to that of water. Almost all crude oils and refined products are less dense—“lighter”—than water. Most oils float on water. There are many processes, however, which can cause an oil to become more dense— “heavier”—than water, and so, sink. Some of these natural processes include: 1. Evaporation. As an oil evaporates, the lighter chemicals are removed first, followed by the heavier, leaving the heaviest behind. As the light components of the oil are removed, by evaporation, or by other natural weathering processes, such as dissolution, the remainder of the oil becomes denser. In most cases, even heavily- weathered oil will not sink in water, but it will be denser than the starting oil. 2. Temperature change. The density of oil can change more rapidly than that of water with decreasing temperature. A drop in temperature can cause oil to be more likely to sink; a raise in temperature can cause oil to become more buoyant. 3. Solid matter uptake. Solid matter, meaning sand and other granular material, adhering to oil will increase the density of oil. Many spill experiences have shown that only about 2 to 3% sand is necessary to cause oil to sink (NRC, 1999). Oil may also pick up material that is lighter than water. It should be noted that some of the light material in oil could decrease the density of the oil until such material became wetted. This includes dry grass and insects, which would have initially entrained air into the composite of oil and foreign material. Wetting of this less dense material and subsequent loss of air becomes another process of density increase leading to submergence. 4. Photooxidation and extreme weathering. Oil is susceptible to photooxidation which creates a dense crust on the surface of exposed oil. The resulting material is often more dense than water. 5. Water Uptake. As most oils are less dense than water, water becoming incorporated into the oil can increase the oil density.

As well as increasing in density, there are several processes which decrease the density of oil or an oil conglomeration: 1. Precipitation of particles from the oil. If the oil is fluid enough, larger particles such as sand will move to the bottom and ultimately out of the heavy oil mass. At some point the mass becomes less buoyant and starts moving around in the water column and may rise to the surface. 2. Break-through of oil through cracks, fissures in a sedimented or weathered layer. Less viscous and buoyant oil can flow (slowly) through any cracks or breaks in outer crusts of tarballs. This occurs in water and even on shorelines. Evidence of this process can be seen in Figures 11 and 12. 3. Uptake of matter lighter than oil. Organic matter, such as plant and animal debris, such as insect casings, is much less dense than water and floats readily. Introduction of plant and other organic materials into the oil conglomerations can reduce their density. This can be seen in Figure 4, an oil-organic material ‘slurry’ which was near to being neutrally-buoyant.

3.2 Densities in Wabamun Lake Samples The submergence and sinking of oil on the lake was primarily driven by one process: the taking up of sediments into the oil masses. Densities of the spilled products and several spill samples are shown in Table 1 and plotted on Figure 13 (see Fingas et al., 2006 for methods and details of measurement). Note that on Figure 13 lower densities are shown at the top of the graph, the higher densities towards the bottom. The horizontal black line denotes the density of fresh water at 10°C. Thus, those points plotted below the horizontal line in Figure 13 represent less buoyant, sinking oils, while those plotted above the line float. While both spilled products are buoyant in water, the HFO 7102 product is close to neutral buoyancy (~1% difference). Immediately after the spill however, the oil collected sediment as it travelled down to the lake. This uptake of sediment increased the density of some of the oil. Submerged oil conglomerations (#344) were collected 5 days following the spill approximately 8 to 10 m off shore at a depth of 30 to 40 cm. As can be seen from Table 1, the submerged oil had a sediment load of only 1.3%, but this was still sufficient to cause sinking. The sediment from this sample appeared to be composed of sand and coal. Note that this sample contained only oil and sediment, no significant water content was observed. Samples collected 40 days after the spill showed some interesting differences. From Table 1, it can be observed that all the samples had collected significant sediment, ranging from 3.0% to greater than 11% by weight. In addition, all samples measured had significant water contents; on average, all samples were approximately 25% water by weight with no large deviations. While both of these factors would be expected to increase the density of the oil, free-floating oil “tarballs” were observed, sample #369 being one example. While this tarball was found to be relatively unweathered oil compared with the other samples of similar age (#360, 361, and 376), more importantly, it had a much lower sediment load (3%) than all the other samples. In addition, the sediment density was lower for #369 (1.14 g/mL) than for other samples. The average sediment density observed for all samples was 1.3 g/mL. In contrast, the submerged oil sample of the same age (#376) had a much higher load (11%) of much denser sediment (2.1 g/mL). These lighter solids found in many of the free-floating tarballs (including samples #369, 762, and 763) had high contents of organic matter, including pieces of duff, tree bark and insect casings. Being less dense in water themselves, it is reasonable to think that these materials contributed to the continuing buoyancy of the tarballs. Beyond their own intrinsic buoyancy, it is quite possible that these materials also entrained significant amounts of air into the oil because of incomplete wetting. Free-floating tarballs, #762 and 763 collected 80 days after the spill showed similar characteristics to those collected earlier (#369). The water contents appeared to reach an equilibrium near 25%, while a broad range of sediment loadings, 5% to 18%, was observed.

3.3 Effects of Density on Oil Behaviours Many of the behaviours of oil tarballs and conglomerations reported are controlled primarily by density (see Section 2 above). The density and density changes of the various configurations of oil continue to play a dominant effect on the continuing reports of releases of oil sheens in the lake. The most important of these are the continuing existence of free-floating tarballs, which have been found in every collection trip to the Lake to date. The change in density of HFO 7102 with temperature is shown in Figure 14. An examination of Figure 14 reveals the following: 1. At the ambient temperatures at the time of the spill (10 to 25°C), fresh HFO 7102 would not sink. 2. The density change from 0 to 25°C for oil and oil/sediment conglomerations is much greater than that of water over the same range of temperatures. This indicates that for neutrally buoyant oil, changes in temperature alone are sufficient to cause rising and sinking of tarballs in a freshwater environment. Figure 15 shows that the uptake of material was sufficient to cause sinking of oil masses in freshwater. Uptake of as little as about 1% sand would be sufficient to sink HFO 7102 in fresh water. Note, however, that not all sediment uptakes cause oil to become denser. As shown in Figure 15, less-dense matter decreased the density of the oil. Such light matter, upon further examination, was found to be primarily composed of plant debris and animal remains (mostly insect larvae and casings). As can be seen from Figure 15, some tarballs with a mixture of light and heavy sediments, e.g. samples #360 and #763, were found to have moderate sediment loads, 8% and 5% respectively, but remained neutrally buoyant. Beyond the density effects, the uptake of sediment and water also greatly increase the apparent viscosity of the oil. The HFO 7102 product had a viscosity in the 100 to 1000 cP range, but the apparent viscosities of the tarballs ranged from 500,000 to 5,000,000 cP. This increase gives the tarball formation (and other oil-sediment- vegetable matter conglomerations) considerable cohesion, greatly reducing the probability of the oil breaking into small configurations. Table 1 Densities, Sediment Concentrations and Water Contents of Selected Spill Samples Density % Water %Sediment Sample # Description Collection Location 20 °C (w/w) (w/w) (g/mL) 343 Pole Treating Oil Whitewood Sands 0.943 0 0 341 HFO 7102 Product Whitewood Sands 0.990 0 0 344 Submerged Oil Whitewood Sands 1.031 1.3 0.5 360 Oiled Vegetation West of Sundance 1.00 8.5 32 361 Oiled Vegetation West of Sundance 1.01 13.2 27 369 Tarball Tamarac's Retreat (SG-13) 0.98 3.0 26 376 Oiled Sediment SE-13 1.03 11.4 23 762 Floating Tarball SC-13/SC-14 1.04 18.4 24 763 Floating Tarball SE-04 1.00 5.0 21 764 Floating Tarball SA-11 1.03 7.8 52

0.92

Spilled Pole TreatingOil 0.94

0.96

Spilled 0.98 "Bunker C" Tarball Weathered Floating Tarballs 1.00

Density (g/mL) Density Sinking Oiled 1.02 Weathered Vegetation Oil in Reeds

Submerged Oiled 1.04 Oil Sediment Tarballs

1.06 2-3 Days after Spill 40 Days after Spill 80 Days after Spill

Figure 13 Densities of selected spill samples 0.02

Spilled HFO 7102 0.01 Oil Floats

0.00 Water

Oil Submerges -0.01 Spilled HFO 7102 Fresh water -0.02 Submerged Sample

Submerged Sample -0.03 Density Difference from g.mL 1.000 Density

-0.04 0 5 10 15 20 25

Temperature (Celcius)

Figure 14 Graph of the density changes of the spilled HFO 7102, freshwater and the submerged HFO 7102 product with temperature changes.

1.08

1.06 Sand

1.04

Mixed heavy 1.02 Mixed Sinks 1.00 floats Resulting Density g/mL Resulting Density Light 0.98

0.96 0246

Percent Material Added

Figure 15 Graph of the density changes by uptake of the various materials found in the tarball samples. 4 Chemical Fate of Spilled Oil

4.1 Summer and Fall of 2005 In the days and months following the incident, Environment Canada staff collected samples for chemical analyses. Samples were collected immediately following the event from the immediate area of the spill (Whitewood Sands) from pooled product near the overturned railcars. Samples were collected over the following months as part of the shoreline assessment process. These included oiled vegetation, oiled sediments, and free-floating and submerged/beached tarballs. Finally, samples were collected in the winters of 2006 and 2007 from locations that were known to have remained contaminated with oil. Detailed chemical analyses have been carried out on representative samples of all the observed forms of oil in the lake. All samples have been analyzed by the Oil Research Laboratory of the Emergencies Science Division of Environment Canada using the procedure described in Wang et al., 1994. Some of these results are shown in Figure 16, which presents the gas chromatograms by flame ionization detection (GC-FID) of the spilled products and some of the samples collected from the shorelines. Information on the samples and their collection locations can be found in Table 2. Concentrations of total PAHs, selected families of PAH alkylated series and petroleum biomarkers are shown in Table 3. Detailed information including individual chemical distributions and instrumental chromatograms of selected samples can be found in Appendix 1 on Tables 5 through 8 and on Figures 16 through 22. The top two chromatograms on Figure 16 show the GC traces of the products spilled taken from pools near the crash site (Wang 2005). The top trace is that of the pole treating oil (#342). More detailed analyses revealed that it largely composed of aromatic hydrocarbons, approximately 60% by weight, and has relatively few saturate or paraffinic components. In addition, the concentrations of both the oil-characteristic alkylated PAH homologous series and the EPA-priority PAHs are extremely high (total PAH 134,424 μg/g oil). This was also the only sample found to contain significant amounts of BTEX and alkyl benzenes mono-aromatics. The HFO 7102 product (#341) is primarily composed of saturated hydrocarbons (Wang 2005). The heavy fuel oil (#341) also contains a high content of aromatic hydrocarbons (48%) and has high concentrations of PAHs (60383 μg/g oil). In comparison a typical Bunker-C fuel has a total aromatic content of 29% and a total PAH content of 29000 μg/g oil. The spilled product is has 2-2.5 times more aromatic content than a typical Bunker-C/Fuel Oil No. 6 product. The PAHs of the HFO 7102 are predominantly 2-ring alkylated naphthalenes, with smaller amounts of the alkylated 3-ring phenanthrene and fluorene homologous series. The oil contains comparatively little high-molecular-weight alkylated chrysenes (4-rings). The 2-ring biphenyl was the highest concentration of the EPA priority PAHs; the larger 4- and 5-ring PAH compounds were in comparatively low concentration or non-detectible. No BTEX compounds were detected in any samples, except for those of the pole-treating oil (#342). The heavy fuel oil (#341) also had low concentrations of oil-characteristic biomarkers (terpanes and steranes) in comparison with most crude oils. Only 97 μg/g oil total was found. The heavy oil collected from a pool near the ruptured rails cars (#341) has been compared in detail with a sample of oil provided by the Imperial Oil Strathcona refinery in Edmonton, Alberta (Wang, 2008). These two samples are identical in all ways within the expected measurement uncertainty of the measurements. All samples of oil collected from the lake to date have chemical fingerprints which match, within the expected changes caused by prolonged environmental exposure, with sample #341, and therefore with the product loaded onto the train at the Strathcona Refinery. It is unlikely that any of the oil samples collected in the lake came from a source other than the derailment of 3 August 2005. In contrast, the two spilled products, the PTO (#342) and the heavy fuel oil 7102 (#341) are readily distinguishable by distinct signatures of both the alkylated polycyclic aromatic hydrocarbons (PAHs) and hopane and sterane biomarkers. No samples of sunken or stranded oil collected from the lake appear to have contained the PTO product. Figure 16 also shows chromatograms of oiled residue on lake reeds (#368, middle graph) and for two tarballs (#369 and #762, bottom two plots). Comparing these traces to that of the HFO 7102 product, it is apparent that while on the lake, the oil weathered considerably, as evidenced by the loss of most of the lighter components. The oil on the reeds, which formed a very thin layer is heavily weathered approximately 40 days after the incident. The tarball collected from SG-13 on the same day (#368, second from bottom) is also significantly weathered, though not as much as the oil on the reed cuttings. It is clear from the bottom graph of Figure 16, however, that not all of the tarballs weathered at an equal rate. The last tarball sample (#762), collected approximately 80 days after release, is only moderately weathered. Clearly, some free-floating oil was able to survive until near freeze-up in a largely fresh, lightly- weathered state. Finally, both the PAH and biomarker analyses (Wang et al., 2006) found that all of the oil samples taken from the lake and the shorelines showed strong evidence of being from the bunker-like product, and were unlikely to contain much of the pole treating oil product. Detailed chemical information on the selected samples discussed above can be found in the tables and figures of Appendix 1. From this data, the following observations can be made concerning the chemical make-up of the collected oil samples over the timeline of the spill:

4.2 Winter of 2005/2006 The TPH values were determined to be in the range of 180-270 mg/g of sample for the oil-vegetation and tarball samples. These are typical values for the HFO 7102. This is because many heavy the bunker fuels contain high percentage of asphaltenes and polars which are readily retained on the cleanup column, resulting in lower TPH (the sum of total saturates and aromatics) value. Sample 366 (clean sediment collected from Seba Beech) and the WAB-Blank sediment sample demonstrate very lower TPH values (0.09 and 0.5 mg/g of sample respectively). In addition, no n-alkanes were detected in these two samples, clearly demonstrating that the background sample sample 366 from the west end of the lake away from the spill was not contaminated by the spilled oil. The parent PAHs and alkyl derivatives are very abundant in all samples (save the clean background samples). The total PAHs including 5 the alkylated PAH homologous series and other EPA priority PAHs were determined to be in a range of 30,000-52,000 μg/ g of sample, significantly higher than in most crude oils. Note that only trace amounts of PAHs were detected in the sediment sample 366 and WAB- blank sample: 0.4 and 54 μg/g of sample for sample 366 and WAB-blank, respectively, indicating these two samples were not contaminated by the spilled oil. The alkylated naphthalenes are most abundant PAH family, followed by alkylated phenanthrene and fluorene homologous series among the 5 alkylated PAH series. In comparison with other 4 alkylated PAH series, the concentrations of the high-molecular-weigh alkylated chrysenes (4-rings) were found very low: only around 100-150 μg/g of sample. From Table 3, however, it can be seen that in some samples there has been a relative loss of total naphthalenes compared with sample #341. In addition, there has been a comparative enrichment of the higher-mass phenanthrenes and fluorine compounds. This is consistent with evaporative weathering of the samples, but little biodegradation. Of the EPA priority PAHs, the 2- and 3-ring PAHs including biphenyl, acenaphthylene, acenaphthene, and anthracene are most abundant (Table 7). Concentrations of both n-alkanes and biomarkers are low in the spill samples in comparison with most crude oils (Table 6). The trace PAH concentrations in the blank sediment are suggestive of pyrogenic PAHs. These PAHs are mostly likely generated from anthropogenic activities on the Lake, including power generation, the near-by transportation corridors and recreational vehicles on the lake (Table 7).

4.1 Winter of 2006/2007 In comparison to the fresh spill sample, almost all n-alkanes were degraded in samples taken during the second winter in the lake. Biodegredation of the alkanes is evident in all of the samples. The carbon preference index (CPI) is close to 1 in all oil samples measured, indicating the petroleum character of the samples. However, CPI values were determined to be as high as 10.5, 10.3, 3.2 and 6.3 for four water/sediment samples, indicating biogenic hydrocarbons becoming dominant components (Table 7). Tarball and oil conglomeration samples demonstrate residual n-alkane distribution patterns characteristic of the spilled Wabamun HFO 7102 oil. That is, n- alkanes distribute in a relatively narrow carbon range (C10-C28) with relatively lower abundances (Table 6). Perylene in the sediment samples shows unusually high concentration in comparison with oil samples. High concentrations of perylene have been reported in anoxic aquatic sediments with high biological productivity and have been associated with terrestrial input from rivers and estruaries. Concentrations of perylene > 10% of the total 5-ring PAH isomers often indicate a diagenetic input. Clearly, perylene concentrations in the total 5-ring PAH isomers are much greater than 10% in these 4 water/sediment samples, indicating perylene may originate mainly from terrestrial biogenic precursors. The total PAHs were determined to be 12291, 7986, 6339, 6391, 3734, 9166, and 18746 μg/g of sample (ppm) for the weathered tarball/patch samples 1029, 1040, 1043 (Reeds), 1049, 1052, 1055, and 1060, respectively (see also Table 3). In comparison with the fresh HFO 7102, 6% to 30% of the original PAHs remain in these oil samples. The dominance of alkylated naphthalenes, followed by alkylated phenanthrene and fluorene homologous series among the 5 alkylated PAH series, is apparent. By contrast, concentrations of high-molecular-weigh alkylated chrysenes (4-rings) are quite low (Table 7). In comparison with the “fresh” spilled HFO 7102 oil (#341), the weathering of naphthalene and its alkylated homologues is very pronounced. The naphthalene family abundances were ranked as C0N < C1N

Table 2 Description of representative samples ESTD Collection Sample type Collection location sample No. date 342 Pole Treating Oil, Car PROX 43307, Wab. AB; N53o, 34.063’- Aug. 06, 2005 pooled oil W114o, 35.185’ 341 Heavy Fuel Oil, Midway between rail and lake by public Aug. 06, 2005 pooled oil access road, Wab. AB; N53o, 34.051’-W114o, 35.234’ 340 Oil, dip sample Pool B by overturned Car PROX 43307, Aug. 06, 2005 Wab. AB; N53o, 34.063’-W114o, 35.185’ 345 Water, surface sheen “Green Dock”, midway between Access Road Aug. 08, 2005 and Site #7, Wab. AB; N53o, 34.045’-W114o, 35.201’ 339 Water, dip sample Pool A by overturned Car PROX 43307, Aug. 06, 2005 Wab. AB; N53o, 34.063’-W114o, 35.185’ 344 Water, submerged oil “Green Dock”, midway between Access Road Aug. 08, 2005 and Site #7, Wab. AB; N53o, 34.045’-W114o, 35.201’ 360 Oiled vegetation West of Sundance Sep. 09, 2005 matrix 361 Oiled vegetation West of Sundance Sep. 09, 2005 matrix 368 Oiled vegetation Trans-Alta Pumphous (SG04), Wab., AB; Sep. 11, 2005 matrix N53o, 51.702’-W114o, 56.219’ 369 Tarball Tamarac’s Retreet (SG 13), Wab., AB; N53o, Sep. 11, 2005 53.090’-W114o, 59.283’ 762 Intermediate tarball 5-50 cm water depth, 1-5 m offshore of SC- Oct. 20, 2005 13 and SC-14, Wab. AB 763-top Weathered tarball, 5-50 cm water depth, 1-5 m offshore of SE- Oct. 20, 2005 Skin layer 04, Wab. AB 763-bottom Weathered tarball, 5-50 cm water depth, 1-5 m offshore of SE- Oct. 20, 2005 Interior 04, Wab. AB 764 Weathered oil on 5-50 cm water depth, 1-5 m offshore of SA- Oct. 20, 2005 reeds 04, Wab. AB 1029 Tarball SA-13 Ascot Reed Bed, S2 Feb 21, 2007 1040 Composite tarball SB-11 Razzi's Point S1A Feb 21, 2007 1049 Individual tarball SE-13(i) Blueberry Point S1 Feb 22, 2007 1052 Oil Particle SE-13(i) Blueberry Point S1 Feb 22, 2007 1055 Individual tarball SG-15 Tamarak Beach S2 Feb 22, 2007 1060 Oil closely associated SC-07 Grebe Marsh near S1 Feb 21, 2007 with root mass 366 Clean Sediment (S144), Wab. AB; N53o, 55.764- Sep. 11, 2005 W114o, 73.397’ WAB-blank Sediment Wab. AB Table 3 Relative PAH and Biomarker Concentrations In Selected Samples ESTD Age ∑ PAH ∑ N ∑ P ∑ F ∑ biomarker Sample type sample # (days) 341 HFO 7102, pooled 3 100% 100% 100% 100% 100% 360 Oiled Vegetation 37 47% 31% 97% 80% 135% 361 Oiled Vegetation 37 64% 48% 112% 98% 157% 368 Oiled Vegetation 39 55% 33% 120% 101% 205% 369 Tarball 39 67% 47% 126% 116% 174% 376 Oiled sediment 40 62% 43% 118% 104% 169% 762 Weathered tarball 78 85% 74% 115% 108% 155% 763-top Skin of weathered 78 59% 36% 125% 104% 215% tarball 763- Interior of weathered 78 57% 36% 118% 100% 194% bottom tarball 764 Weathered oil on reeds 78 37% 21% 85% 67% 146% 1029 Tarball 567 20% 12% 42% 39% 47% 1040 Composite oil 567 13% 7% 28% 27% 39% 1049 Individual tarball 567 10% 5% 24% 21% 35% 1052 Oil Particle 568 6% 2% 14% 14% 42% 1055 Individual tarball 568 15% 9% 33% 29% 31% 1060 Oil closely associated 568 31% 23% 59% 29% 56% with root mass

Notes: Age: The number of days after 3 August 2005. ∑ PAH: The concentration of all PAHs (alkylated PAHs + EPA priority) relative to sample #341. ∑ N, ∑ P, ∑ F: The total concentration parent and alkylated derivatives of naphthalene, phenanthrene and fluorine, respectively, relative to the total concentrations of sample #341. ∑ biomarker: The total concentrations of petroleum-specific biomarkers relative to sample #341 Pole Treating Oil (#342) Whitewood Sands 6 Aug., 2005

"Bunker C" Product (#341) Whitewood Sands 6 Aug., 2005

Oil residue on reeds (#368) Tamarac's Retreat SG 13 Sept. 11, 2005

Tarball (#369) Tamarac's Retreat SG-13 Sept. 11, 2005

Tarball (#762) SC-13/SC-14 Oct. 20, 2005

Figure 16 Gas Chromatograms (by Flame-ionization detection) of selected samples 5 Biodegredation Potential of Spilled Oil Observations of submerged and/or sunken oil in the near shore area of Lake Wabamun raised the issue of long-term persistence of residual oil in this freshwater ecosystem. The indigenous Lake Wabamun sediment microorganisms were tested on some of the residual oil taken from lake Wabamun under ideal laboratory conditions. This determines the upper limit of the biodegradation rate of the oil, with the understanding that in less-than-ideal in situ conditions will likely result in lower levels of biodegradation over an equivalent time span. The biodegradation potential of the oil in Lake Wabamun was assessed by laboratory tests using microbes naturally present in oil-contaminated Lake Wabamun sediment (Zrum and Sergey, 2006). The HFO was recovered from the lake and incubated at 22°C for 4 weeks and at 4°C for 8 weeks. The indigenous Lake Wabamun sediment microbes were found to readily degrade a proportion of the HFO, with small amounts being degraded under both incubation conditions, compared with a typical Alberta crude oil. At 22°C, biodegradation accounted for a loss of only 12% by weight of the HFO added to the cultures. This reflects the small proportion of low-molecular weight hydrocarbons considered to be biodegradable and the high proportion of components that either are not readily biodegradable or are not detectable in the spilled HFO 7102 oil. Competent hydrocarbon-degrading microbes exist in Lake Wabamun sediment. However, the mass of HFO 7102 oil that they are likely to be able to degrade is small due to the recalcitrant nature of the oil. This is likely exacerbated by the formation of “tarballs” which limit microbial access to the biodegradable components of the spilled oil. These laboratory tests indicate that a large proportion of the spilled oil will persist even under optimum conditions for biodegradation.

Table 4. Biodegradation losses from Bunker C oil calculated by combining data from test cultures regardless of inoculum source (n=6). Biodegradation is expressed both as mass loss (mean ± 1 standard deviation) due to biological processes and as a percentage of the original Bunker C oil added to the cultures (from Zrum and Sergey, 2006). Biodegradation, mg/g sample a % initial of oil biodegraded (mean ± 1 stdev) (mean ± 1 stdev) Analyte 22°C, 4 wks 4°C, 8 weeks 22°C, 4 wks 4°C, 8 weeks Class TPH 117 ± 19.9 67.5 ± 13.3 12 6.8 TSH 53.1 ± 11.0 19.2 ± 9.6 5.3 1.9 TAH 63.6 ± 13.2 49.0 ± 5.7 6.4 4.9 Total 7.8 ± 0.1 7.2 ± 1.2 0.8 0.7 n-alkanes Total 28.4 ± 2.5 19.6 ± 3.1 2.8 2.0 PAHs 6 Summary

The spilled product, HFO 7102, is very abundant in PAHs and has a very high aromatic content compared to similar Bunker C or HFO fuels. The spilled HFO has 2 to 2.5 times more aromatic content than similar fuels. All of the oil samples analyzed have chemical compositions consistent with the HFO 7102 sample loaded onto the train at the Strathcona refinery in Endmonton, Alberta. As late as February 2007, 568 days following the spill, oil was found in the lake in primarily two forms: • Large (>5 cm), flat conglomerations on the lake bottom. These are high density, high viscosity mats and patties, often tangled into vegetation. They are not highly mobile. See Figures 5, 6, and 10 for examples of this type of conglomeration. • Small (<5 cm), spherical balls of soft, fluid oil surrounded by a tough, weathered layer of oil. These are easily stirred up from the bottom and seem to readily move with currents and wind. See Figures 7 and 8 for examples. The oil that remained in the lake as of that date was all higher density than the fresh HFO 7102 released during the derailment. This density increase has been caused by i) evaporative weathering of the oil; ii) sediment uptake; and iii) water uptake. The large conglomerations tested have all been found to be highly weathered, have high sediment loadings and high water contents. All of these factors combine to make them negatively buoyant. Further, the high viscosities of these patties and mats allow them to become bound into the root structures of the lake vegetation, effectively cementing them to the lake floor. The tarballs found, by contrast, are much less chemically weathered, are lower viscosity and have moderate sediment loads. Densities range from negatively buoyant to neutrally buoyant. Tarball densities are close enough to that of water that temperature changes can cause them to rise in warm water and sink in cooler water. Tarballs appear to be mobile in the lake. One cause of random sheens appears to be release of relatively unweathered oil from the centers of free-floating tarballs. An example of this can be found in Figure 9. The weathered casings can crack and tear, see Figure 12, causing the fluid oil inside to be released, see Figure 7. As long as this tarball form persists in the lake, relatively fresh sheens of oil can be expected to occur. The oil has been found to degrade significantly, especially in the large conglomerate form. The primary mechanism of removal appears to be biodegradation. Oils in the tarball form have been found to contain up to 30% of the PAHs of the fresh oil, 19 months following the spill. A laboratory study of the biodegradation potential indicates that even under ideal laboratory conditions, significant aromatic and PAH content may persist for up to 5- 10 years. 7 References

Alberta Environment, Wabamun Lake Spill 2005: General Information on the Spill, http://www3.gov.ab.ca/env/water/WabamunLake.html, 2005.

Fingas, M.F., B.P. Hollebone, B. Fieldhouse, “The Density Behaviour of Heavy Oils in Water”, in the Proceedings of the Twenty-Ninth Arctic and Marine Oil Spill Program Technical Seminar, Environment Canada, Ottawa, Ontario, pp. 57-77, 2006.

Golder Associates Ltd., Final Detailed Remediation Plan Wabamun Derailment Site Canadian National Railway Company PIN 2401257, Project No. 05-1324-102, Calgary, AB, 126 pp., 2006.

Mitchell, P. and E. Prepas, Atlas of Alberta Lakes, University of Alberta Press, Edmonton, AB, http://alberta-lakes.sunsite.ualberta.ca/, 1990.

Nichols Environmental (Canada) Ltd., Field Obervations Of Oiling Conditions, Lake Wabamun On April 8, 2006, Nichols File: M5087 – Bac, Edmonton, Ab, 2006

Schindler, D.W., A.-M. Anderson, J. Brzustowski, W.F. Donahue, G. Goss, J. Nelson, V. St. Louis, M. Sullivan, S. Swanson, Lake Wabamun:A Review of Scientific Studies and Environmental Impacts, Submitted to the Minister of Alberta Environment, Edmonton, AB, http://www3.gov.ab.ca/env/water/reports/wabamun/Wabamun_Report_Dec04.pdf, 44 p., 2004.

Wang, Z., M. Fingas, and K. Li, "Fractionation of ASMB Oil, Identification and Quantitation of Aliphatic Aromatic and Biomarker Compounds by GC/FID and GC/MSD (Parts I&II)", Journal of Chromatographic Science, Vol. 2, pp. 361-382, 1994.

Wang, Z., Characterization and Identification of Spill Oil Samples from Alberta Derailed Train Oil Spill Incident, Oil Research Section, ESTD Memorandum report 2005-07, Environment Canada, 2005.

Wang, Z., Characterization and Identification of Spill Oil Samples (2nd set of samples) from Alberta Derailed Train Oil Spill Incident, Oil Research Section, ESTD Memorandum report 2006-03, Environment Canada, 2006.

Wang, Z., Characterization and Identification of Spill Oil Samples from Alberta Derailed Train Oil Spill Incident, Oil Research Section, ESTD Memorandum report 2007-05, Environment Canada, 2007.

Wang, Z., Forensic Fingerprinting and Comparison of the Oil Sample from Imperial Oil Strathcona Refinery and the Wabamun Spill Oil Sample, Oil Research Section, ESTD Memorandum report 2008-06, Environment Canada, 2008. Watmough, M., Wabamun Lake Reedbed Reconnaissance Report, Internal Memo, Canadian Wildlife Service, Environment Canada, April 12, 2006.

Zrum, L, G. Sergy, Potential for Biodegradation of Sub-Littoral Residual Oil by Naturally Occurring Microorganisms following the Lake Wabamun Train Derailment, Alberta Environment, July 14, 2006. Appendix 1 Chemical Data and Chromatograms of Selected Samples

Table 5 Hydrocarbon group analysis results TSH/TPH TAH/TPH Resolved peaks/TPH Sample No. TPH (%) (%) (%) 342 749 mg/g oil 36.1 63.9 50.6 341 273 mg/g oil 48.0 52.0 34.3 340 500 mg/g oil 34.2 65.8 44.4 345 0.62 mg/L water 51.3 48.7 17.0 339 957 mg/L water 39.5 60.5 46.3 344 5.13 mg/L water 40.4 59.6 39.1 360 181 mg/g oil 53.9 46.1 26.1 361 216 mg/g oil 368 235 mg/g oil 58.7 41.3 18.2 369 233 mg/g oil 54.8 45.2 23.7 762 266 mg/g oil 55.6 44.4 27.5 763-top 230 mg/g oil 57.9 42.1 23.1 763-bottom 216 mg/g oil 56.0 44.0 22.9 764 160 mg/g oil 57.6 42.4 26.0 1029 107 mg/g oil 52.3 47.7 22.8 1040 77 mg/g oil 51.7 48.3 19.1 1048 27 mg/g oil 62.9 37.1 23.0 1049 63 mg/g oil 54.9 45.1 19.6 1052 68 mg/g oil 53.8 46.2 9.3 1054 20 mg/g oil 59.4 40.6 21.5 1055 73 mg/g oil 51.1 48.9 21.1 1060 140 mg/g oil 53.1 46.9 27.3 366 0.09 mg/g sediment - - - WAB-blank 0.54 mg/g sediment - - -

Table 6 n-Alkane quantitation results 342 341 340 345 339 344 360 361 368 369 762 763- 763- 764 1029 1040 1048 1049 1052 1054 1055 1060 366 WAB- Compounds top bottom blank (mg/g) (mg/g) (mg/g) (mg/L) (mg/L) (mg/L) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/L) (mg/L) (mg/L) (mg/g) (mg/g) (mg/g) (mg/g) n-C8 0.00 0.05 0.03 0.000 0.00 0.000 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA n-C9 0.00 0.08 0.04 0.000 0.00 0.000 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA n-C10 0.00 0.07 0.06 0.000 0.01 0.000 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA n-C11 0.25 0.09 0.12 0.000 0.07 0.000 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA n-C12 1.46 0.18 0.30 0.000 0.28 0.001 0.00 0.00 0.00 0.00 0.04 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA n-C13 2.92 0.50 1.04 0.000 1.46 0.005 0.04 0.09 0.02 0.04 0.28 0.04 0.04 0.02 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.05 NA NA n-C14 3.67 0.82 1.73 0.000 2.75 0.010 0.23 0.40 0.13 0.26 0.85 0.20 0.23 0.15 0.07 0.03 0.02 0.03 0.00 0.01 0.07 0.24 NA NA n-C15 3.17 1.07 1.90 0.000 3.34 0.014 0.48 0.74 0.38 0.73 1.21 0.56 0.60 0.42 0.19 0.08 0.05 0.10 0.00 0.02 0.19 0.53 NA NA n-C16 2.75 1.09 1.82 0.001 2.72 0.016 0.63 0.90 0.52 0.95 1.22 0.79 0.83 0.63 0.30 0.14 0.05 0.18 0.00 0.03 0.29 0.72 NA NA n-C17 2.65 1.03 1.50 0.001 2.63 0.018 0.86 1.05 0.68 1.00 1.23 1.00 1.00 0.86 0.27 0.13 0.20 0.20 0.00 0.27 0.31 0.76 NA NA Pristane 2.11 0.35 0.76 0.001 1.43 0.007 0.36 0.43 0.50 0.46 0.48 0.45 0.45 0.33 0.26 0.19 0.04 0.15 0.13 0.02 0.17 0.30 NA NA n-C18 1.25 0.99 1.15 0.001 2.04 0.016 0.88 1.03 0.66 1.00 1.11 1.02 1.05 0.95 0.22 0.11 0.05 0.20 0.00 0.03 0.30 0.68 NA NA Phytane 1.33 0.35 0.54 0.001 1.28 0.005 0.36 0.41 0.51 0.48 0.44 0.47 0.46 0.35 0.21 0.16 0.05 0.14 0.14 0.03 0.13 0.24 NA NA n-C19 0.94 0.93 0.90 0.001 1.44 0.017 1.01 1.10 0.73 1.08 1.18 1.21 1.12 1.10 0.24 0.12 0.06 0.22 0.00 0.04 0.31 0.72 NA NA n-C20 0.86 1.00 0.77 0.001 1.05 0.018 1.03 1.15 0.74 1.10 1.23 1.24 1.22 1.20 0.22 0.10 0.05 0.23 0.00 0.03 0.32 0.76 NA NA n-C21 0.61 0.81 0.59 0.000 0.65 0.014 0.79 0.87 0.51 0.80 0.95 0.93 0.91 0.94 0.15 0.07 0.05 0.17 0.00 0.05 0.23 0.59 NA NA n-C22 0.32 0.49 0.33 0.000 0.35 0.009 0.52 0.54 0.34 0.50 0.61 0.60 0.59 0.58 0.09 0.04 0.03 0.10 0.00 0.02 0.14 0.35 NA NA n-C23 0.17 0.31 0.16 0.000 0.12 0.005 0.30 0.31 0.19 0.27 0.34 0.35 0.33 0.34 0.05 0.02 0.12 0.06 0.00 0.11 0.07 0.19 NA NA n-C24 0.07 0.14 0.08 0.000 0.05 0.003 0.15 0.15 0.10 0.14 0.16 0.17 0.17 0.17 0.04 0.01 0.03 0.03 0.00 0.02 0.04 0.10 NA NA n-C25 0.02 0.06 0.03 0.000 0.05 0.002 0.14 0.24 0.20 0.18 0.19 0.20 0.23 0.26 0.02 0.00 0.18 0.02 0.00 0.15 0.02 0.05 NA NA n-C26 0.01 0.02 0.01 0.000 0.04 0.001 0.03 0.04 0.03 0.03 0.04 0.04 0.04 0.04 0.01 0.00 0.02 0.00 0.00 0.02 0.01 0.01 NA NA n-C27 0.01 0.02 0.01 0.000 0.04 0.002 0.03 0.04 0.02 0.02 0.02 0.02 0.04 0.03 0.01 0.00 0.24 0.00 0.00 0.28 0.00 0.01 NA NA n-C28 0.02 0.02 0.01 0.000 0.01 0.001 0.03 0.03 0.02 0.02 0.02 0.02 0.03 0.03 0.01 0.00 0.01 0.00 0.00 0.02 0.00 0.00 NA NA n-C31 0.05 0.02 0.01 0.000 0.00 0.001 0.02 0.03 0.02 0.02 0.02 0.02 0.03 0.02 0.00 0.00 0.10 0.00 0.00 0.15 0.00 0.00 NA NA n-C32 0.04 0.02 0.01 0.000 0.00 0.001 0.02 0.03 0.01 0.02 0.02 0.01 0.03 0.02 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 NA NA n-C33 0.04 0.01 0.01 0.000 0.00 0.000 0.01 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 NA NA n-C34 0.02 0.02 0.01 0.000 0.00 0.000 0.01 0.00 0.01 0.02 0.01 0.01 0.02 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA n-C35 0.03 0.01 0.01 0.000 0.00 0.000 0.01 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA n-C36 0.02 0.01 0.01 0.000 0.00 0.000 0.01 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA n-C37 0.03 0.01 0.00 0.000 0.00 0.000 0.01 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA n-C38 0.01 0.01 0.01 0.000 0.00 0.000 0.01 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA n-C39 0.02 0.00 0.00 0.000 0.00 0.000 0.01 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA n-C40 0.01 0.00 0.00 0.000 0.00 0.000 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA n-C41 0.01 0.00 0.00 0.000 0.00 0.000 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA n-C42 0.00 0.00 0.00 0.000 0.00 0.000 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA n-C43 0.00 0.00 0.00 0.000 0.00 0.000 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA n-C44 0.00 0.00 0.00 0.000 0.00 0.000 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 NA NA Sum 24.9 10.6 14.0 0.009 21.8 0.168 8.02 9.67 6.37 9.25 11.7 9.39 9.55 8.54 2.38 1.21 1.46 1.84 0.27 1.37 2.58 6.30 NA NA Diagnostic Ratios n-C17/Pri 1.25 2.97 1.98 0.83 1.84 2.70 2.41 2.46 1.37 2.17 2.54 2.21 2.24 2.61 1.01 0.69 4.72 1.35 0.00 12.0 1.83 2.53 NA NA n-C18/Phy 0.94 2.83 2.11 0.72 1.59 2.96 2.41 2.50 1.28 2.08 2.55 2.18 2.29 2.73 1.10 0.65 0.93 1.44 0.00 0.88 2.23 2.81 NA NA Pri/Phy 1.59 0.99 1.39 0.94 1.11 1.20 0.98 1.04 0.96 0.95 1.11 0.97 0.97 0.95 1.28 1.16 0.77 1.10 0.91 0.76 1.26 1.24 NA NA Odd alkanes 10.9 4.96 6.33 0.003 9.8 0.008 3.74 4.52 2.77 4.21 5.47 4.36 4.37 4.03 0.95 0.42 1.04 0.78 0.00 1.14 1.13 2.90 NA NA Even alkanes 10.6 4.95 6.33 0.003 9.31 0.008 3.56 4.31 2.59 4.10 5.35 4.11 4.27 3.83 0.97 0.43 0.33 0.77 0.00 0.18 1.16 2.87 NA NA CPI 1.04 1.00 1.00 0.87 1.05 1.01 1.05 1.05 1.07 1.03 1.02 1.06 1.02 1.05 0.98 0.98 3.20 1.01 NA 6.33 0.97 1.01 NA NA Table 7 PAH Quantitation Results

Compounds 342 341 340 345 339 344 360 361 368 369 762 763-top 763-bottom 764 (µg/g) (µg/g) (µg/g) (µg/L) (µg/L) (µg/L) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) Alkylated PAHs Naphthalene C0-N 419 390 283 0.02 116 17.7 7.36 3.38 4.31 18.9 4.62 4.44 4.23 0.03 C1-N 13045 9488 8260 0.03 2604 279 616 201 324 2398 335 393 187 0.01 C2-N 28270 14698 16940 0.56 6736 275 3017 2340 4123 9851 3051 3118 1571 0.01 C3-N 27216 12628 16635 3.17 7817 203 5585 6474 9434 12957 6975 6852 4116 0.01 C4-N 16007 6279 9462 8.62 2894 93.0 4108 5177 6369 7040 5325 5242 3339 0.01 Sum 84958 43483 51580 12.4 20167 867 13333 14196 20255 32264 15690 1560 9217 0.06 Phenanthrene C0-P 3579 1798 1744 0.56 1730 42.2 1229 1376 1571 1741 1424 1384 1010 0.01 C1-P 8508 3739 5891 4.20 5303 75.6 3466 4270 4561 4177 4484 4289 3042 0.01 C2-P 8854 1881 4552 6.32 5445 42.5 2382 3036 3073 2583 3173 2904 2117 0.02 C3-P 2762 538 1498 2.64 1590 11.0 633 808 812 675 841 777 559 0.00 C4-P 510 146 265 0.69 261 2.82 160 202 202 171 208 195 144 0.01 Sum 24214 8102 13951 14.4 14328 174 7871 9691 10218 9347 10130 9550 6872 0.04 Dibenzothiophene C0-D 19.8 461 191 0.13 35.0 11.2 275 312 379 425 339 327 223 0.00 C1-D 44.7 1142 525 1.10 32.1 22.6 963 1183 1270 1205 1300 1227 838 0.00 C2-D 420 1136 759 3.24 231 21.3 1217 1530 1550 1355 1718 1581 1081 0.00 C3-D 292 481 376 2.17 165 9.62 528 664 650 572 717 662 470 0.00 Sum 776 3220 1851 6.65 463 64.7 2983 3689 3848 3558 4074 3796 2612 0.00 Fluorene C0-F 1274 426 717 0.04 945 12.0 181 186 277 376 205 201 128 0.00 C1-F 4713 1257 2424 0.78 3030 28.6 889 1071 1362 1364 1125 1098 711 0.00 C2-F 11245 2240 4679 4.47 5315 39.9 1851 2401 2615 2408 2438 2320 1554 0.00 C3-F 7238 1591 4203 5.90 4437 30.0 1493 1922 2131 1822 1979 1891 1307 0.00 Sum 24470 5513 12023 11.2 13727 110 4413 5580 6385 5969 5747 5509 3701 0.01 Chrysene C0-C 0.44 7.96 3.01 0.03 0.91 0.09 9.50 11.66 11.43 9.65 12.8 11.54 8.58 0.02 C1-C 3.06 23.7 13.6 0.10 1.89 0.44 29.8 38.2 38.0 34.5 41.0 38.9 27.2 0.01 C2-C 2.06 39.9 15.1 0.15 2.61 0.57 50.7 59.9 62.1 54.4 66.0 60.3 46.2 0.01 C3-C 0.87 25.0 14.4 0.10 2.01 0.44 35.3 42.3 43.9 39.8 45.6 42.5 30.9 0.01 Sum 6.43 96.5 46.1 0.39 7.43 1.53 125 152 155 138 165 153 113 0.05 Total alkylated PAHs 134424 60415 79450 45.0 48693 1218 28726 38739 33309 40862 51277 35806 34619 22515 Other EPA priority PAHs Biphenyl 1709 219 938 0.002 1175 7.01 24.2 47.7 13.3 24.4 78.6 17.8 18.7 8.63 Acenaphthylene 66.1 79.5 88.1 0.001 26.4 1.53 17.6 30.0 14.0 22.2 50.0 17.0 16.5 8.70 Acenaphthene 161 311 119 0.005 335 9.12 68.6 123 58.6 102 188 71.4 68.6 38.6 Anthracene 27.8 137 96.0 0.082 21.9 3.22 79.6 108 95.5 118 136 96.4 90.0 55.0 Fluoranthracene 22.9 15.5 22.6 0.034 22.3 0.27 12.9 16.0 15.7 15.6 13.9 16.1 14.7 11.1 Pyrene 102 19.7 60.2 0.118 82.7 0.45 29.9 33.6 38.3 38.5 32.5 41.6 36.0 26.4 Benz(a)anthracene 0.28 2.05 1.33 0.007 0.22 0.04 2.62 2.47 3.11 2.97 2.79 3.23 2.94 2.10 Benzo(b)fluoranthene 0.21 1.24 0.86 0.006 0.28 0.03 1.76 1.77 1.91 1.93 1.64 2.14 1.86 1.56 Benzo(k)fluoranthene 0.06 0.28 0.21 0.002 0.06 0.01 0.53 0.43 0.37 0.39 0.36 0.45 0.32 0.28 Benzo(e)pyrene 0.08 2.96 1.88 0.012 0.22 0.06 3.69 4.09 4.84 4.56 3.92 5.10 4.49 3.32 Benzo(a)pyrene 0.16 2.61 1.53 0.011 0.18 0.05 2.80 3.04 3.67 3.67 3.17 3.84 3.37 2.36 Perylene 0.18 1.03 0.73 0.004 0.08 0.02 0.99 1.15 1.35 3.18 1.38 1.33 1.13 0.77 Indeno(1,2,3-cd)pyrene 0.00 0.21 0.30 0.002 0.14 0.01 0.92 0.51 0.52 0.50 0.42 0.56 0.46 0.35 Dibenz(ah)anthracene 0.00 0.79 0.47 0.003 0.03 0.01 1.34 0.98 1.11 1.06 0.91 1.08 0.96 0.72 Dibenzo(ghi)perylene 0.00 1.42 0.68 0.005 0.10 0.03 2.07 1.99 2.33 2.29 1.77 2.25 2.02 1.52 Total EPA priority PAHs 2089 794 1331 0.29 1664 21.8 250 375 255 341 515 280 262 161 Total PAHs 136513 61208 80781 45.3 50357 1240 28975 39114 33563 41203 51792 36087 34881 22676 Diagnostic ratios 2-m-N:1-m-N 1.80 2.01 1.76 1.65 1.48 1.59 1.47 1.49 1.22 1.30 1.54 1.36 1.40 1.38 4-:2-/3-:1-DBT 1.00:0.33:0.07 1.00:1.01:0.21 1.00:1.02:0.22 1.00:0.84:0.19 1.00:0.52:0.10 1.00:1.03:0.19 1.00:1.01:0.21 1.00:1.03:0.22 1.00:1.01:0.21 1.00:1.01:0.21 1.00:1.02:0.21 1.00:1.02:0.21 1.00:1.01:0.22 1.00:1.01:0.22 (3-+2-)/(4-/9-+1-m-phen) 2.60 2.18 2.52 1.79 2.27 2.32 2.20 2.22 2.19 2.17 2.25 2.16 2.18 2.21 (C2D/C2P):(C3D/C3P) 0.05:0.11 0.69:0.89 0.17:0.25 0.51:0.82 0.04:0.10 0.50:0.88 0.51:0.83 0.51:0.84 0.50:0.82 0.50:0.80 0.52:0.85 0.54:0.85 0.54:0.85 0.51:0.84 Naphs:Phens:DBTs: 3.51:1.00:0.03: 5.37:1.00:0.40: 3.70:1.00:0.13: 0.86:1.00:0.46: 1.41:1.00:0.03: 4.98:1.00:0.37: 1.69:1.00:0.38: 2.30:1.00:0.38: 1.46:1.00:0.38: 1.98:1.00:0.38: 3.45:1.00:0.38: 1.55:1.00:0.40: 1.63:1.00:0.40: 1.34:1.00:0.38: Fluors:Chrys 1.01:0.00 0.68:0.01 0.86:0.003 0.78:0.03 0.96:0.001 0.63:0.01 0.56:0.02 0.60:0.02 0.58:0.02 0.62:0.02 0.64:0.01 0.57:0.02 0.58:0.02 0.54:0.22 Pyrogenic index 0.02 0.01 0.02 0.01 0.03 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Table 7 PAH Quatitation Results (continued) Compounds 1029 1040 1048 1049 1052 1054 1055 1060 366 WAB-blank (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) Alkylated PAHs Naphthalene C0-N 0.15 0.00 0.74 0.00 0.00 0.12 0.00 0.93 0.01 14.9 C1-N 11.7 2.29 6.33 6.83 0.76 1.10 20.8 269 0.03 1145 C2-N 517 212 80.3 243 38.2 17.5 573 2242 0.23 5586 C3-N 2371 1398 247 1058 347 76.5 1776 4517 0.56 8552 C4-N 2122 1496 235 1000 678 101 1402 3105 0.71 5456 Sum 5022 3108 570 2308 1064 196 3771 10133 1.55 20754 Phenanthrene C0-P 245 129 33.5 113 29.9 19.3 388 718 3.85 1496 C1-P 1541 955 154 831 285 78.2 1207 2188 1.74 4026 C2-P 1189 856 143 739 537 89.4 815 1409 1.27 2647 C3-P 343 254 51.5 208 233 33.4 220 369 0.73 697 C4-P 68.7 39.6 16.2 45.9 50.1 6.68 45.1 66.9 0.92 177 Sum 3387 2233 399 1936 1135 227 2675 4750 8.51 9042 Dibenzothiophene C0-D 79.2 36.7 8.82 39.0 9.9 3.56 86.8 184 0.12 349 C1-D 494 308 48.5 277 106 24.1 332 675 0.06 1125 C2-D 702 494 83.0 425 337 52.4 415 801 0.11 1359 C3-D 296 226 46.5 182 199 32.3 188 345 0.09 584 Sum 1572 1064 187 923 651 112 1021 2006 0.38 3416 Fluorene C0-F 33.7 14.6 4.48 18.1 3.28 1.88 48.9 48.9 0.24 271 C1-F 388 224 37.7 195 77.2 15.0 317 317 0.15 1128 C2-F 910 648 106 489 317 48.7 668 668 0.17 2243 C3-F 809 585 108 433 401 53.9 556 556 0.18 1747 Sum 2141 1471 256 1135 799 119.4 1590 1590 0.74 5389 Chrysene C0-C 4.29 3.04 1.70 1.8 3.23 4.90 2.59 4.74 3.65 10.0 C1-C 14.7 11.3 4.03 8.5 10.7 5.15 8.95 17.4 1.98 34.6 C2-C 20.6 15.8 5.12 15.9 21.3 4.18 10.6 25.7 1.24 55.4 C3-C 11.7 10.2 3.95 7.56 11.2 1.10 6.23 12.5 0.60 38.4 Sum 51.3 40.3 14.8 33.8 46.4 15.3 28.4 60.4 7.47 138 Total alkylated PAHs 12173 7916 1426 6336 3696 670 9086 18540 0.16 Other EPA priority PAHs Biphenyl 0.92 0.23 0.61 0.68 0.08 0.12 2.36 13.8 N/A 0.00 Acenaphthylene 2.85 1.40 0.48 1.39 0.44 0.13 3.68 12.1 N/A 0.00 Acenaphthene 10.7 5.97 1.71 7.66 1.17 0.76 14.4 52.6 N/A 0.00 Anthracene 48.7 34.2 5.11 24.0 11.3 4.22 37.9 83.5 N/A 0.00 Fluoranthracene 8.02 5.78 4.37 5.11 4.32 9.24 5.04 9.92 N/A 0.03 Pyrene 20.4 17.3 5.28 13.2 15.1 8.97 14.0 26.5 N/A 0.02 Benz(a)anthracene 20.4 0.95 0.88 0.60 0.78 4.42 0.78 1.25 N/A 0.01 Benzo(b)fluoranthene 0.91 0.65 1.03 0.51 0.68 5.16 0.55 0.80 N/A 0.03 Benzo(k)fluoranthene 0.00 0.00 0.21 0.00 0.00 1.89 0.00 0.00 N/A 0.01 Benzo(e)pyrene 1.64 1.48 1.10 1.19 1.80 2.58 1.31 2.07 N/A 0.01 Benzo(a)pyrene 1.71 1.32 0.83 1.01 1.32 4.06 0.97 1.98 N/A 0.01 Perylene 0.62 0.43 0.79 0.00 0.48 8.18 0.00 0.62 N/A 0.01 Indeno(1,2,3-cd)pyrene 0.00 0.00 0.00 0.00 0.00 2.16 0.00 0.00 N/A 0.01 Dibenz(ah)anthracene 0.00 0.00 0.00 0.00 0.00 0.62 0.00 0.00 N/A 0.00 Dibenzo(ghi)perylene 0.88 0.69 0.68 0.00 0.83 2.06 0.00 0.80 N/A 0.01 Total EPA priority PAHs 118 70.3 23.1 55.4 38.3 54.6 80.9 206 N/A 0.15 Total PAHs 12291 7986 1449 6391 3734 725 9166 18746 N/A 0.31 Diagnostic ratios 2-m-N:1-m-N 1.08 0.90 2.11 0.86 0.68 1.39 1.18 1.41 N/A N/A 4-:2-/3-:1-DBT 1.00:0.90:0.20 1.00:0.85:0.20 1.00:0.89:0.19 1.00:0.86:0.19 1.00:0.61:0.21 1.00:0.85:0.19 1.00:0.94:0.17 1.00:0.93:0.19 N/A N/A (3-+2-)/(4-/9-+1-m-phen) 1.93 1.75 1.90 1.68 1.10 1.77 2.24 2.11 N/A N/A (C2D/C2P):(C3D/C3P) 0.59:0.86 0.58:0.89 0.58:0.90 0.58:0.88 0.63:0.85 0.592:0.97 0.51:0.85 0.57:0.94 N/A N/A Naphs:Phens:DBTs: 0.00:0.01:0.24: 0.00:0.00:0.14: 0.00:0.00:0.34: 0.00:0.01:0.24: 0.00:0.00:0.06: 0.00:0.01:0.17: 0.00:0.02:0.41: 0.00:0.09:0.72: N/A N/A Fluors:Chrys 1.12:1.00 0.93:1.00 1.05:1.00 1.06:1.00 0.51:1.00 0.76:1.00 1.27:1.00 1.45:1.00 Pyrogenic index N/A N/A Table 8 Quantitation results and diagnostic ratios of target biomarkers

763- 763- WAB- 342 341 340 345 339 344 360 361 368 369 762 764 366 1029 1040 1048 1049 1052 1054 1055 1060 Compounds top bottom blank (µg/g) (µg/g) (µg/g) (µg/L) (µg/L) (µg/L) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g) (µg/g)

17.7 28.1 16.6 0.03 0.00 0.36 29.8 35.2 45.0 39.0 34.1 46.4 42.2 31.4 0.00 12.0 9.96 2.33 9.02 10.7 1.93 8.73 15.0 0.00 C21 5.82 9.63 7.68 0.01 0.00 0.14 11.6 13.7 18.5 14.9 13.2 18.1 16.8 12.5 0.00 3.61 3.37 0.75 3.13 3.62 0.81 2.86 4.94 0.00 C22 11.2 30.3 18.4 0.05 0.01 0.51 46.9 54.2 70.5 60.0 52.4 73.7 66.5 49.7 0.00 19.1 16.0 3.86 13.9 16.6 4.35 11.7 22.0 0.03 C23 1.03 13.4 6.56 0.02 0.11 0.24 18.9 22.1 28.6 24.5 21.4 30.2 26.7 20.6 0.00 8.46 6.66 1.61 5.57 7.69 1.91 5.30 9.02 0.02 C24 0.00 0.72 1.23 0.03 0.32 0.04 2.74 2.92 3.94 3.36 2.99 4.23 3.70 2.76 0.02 1.58 0.79 1.08 0.93 1.08 4.42 0.82 1.49 0.15 C29 0.00 2.17 1.22 0.03 0.34 0.06 3.38 3.81 4.99 4.03 3.84 5.29 4.71 3.69 0.03 1.56 1.06 1.56 1.13 1.44 3.55 1.09 1.80 0.21 C30 0.00 2.50 0.00 0.02 0.12 0.03 1.19 1.05 1.59 1.54 1.54 1.85 1.73 1.35 0.01 0.70 0.54 0.53 0.38 0.45 1.54 0.36 0.56 0.09 C31(S) 0.00 2.27 0.00 0.02 0.10 0.03 0.91 0.85 1.21 1.12 1.13 1.38 1.27 1.07 0.02 0.34 0.24 0.85 0.35 0.32 3.11 0.20 0.41 0.08 C31(R) 0.00 0.67 0.00 0.00 0.00 0.00 0.76 0.69 1.05 0.90 0.87 1.33 1.09 0.84 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.09 C32(S) 0.00 0.00 0.00 0.00 0.00 0.00 0.61 0.57 0.84 0.73 0.68 1.03 0.83 0.64 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.07 C32(R) 0.00 0.00 0.00 0.00 0.00 0.00 0.57 0.60 0.92 0.81 0.77 0.98 0.91 0.66 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.06 C33(S) 0.00 0.00 0.00 0.00 0.00 0.00 0.48 0.52 0.77 0.67 0.69 0.75 0.60 0.43 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.03 C33(R) 0.00 0.00 0.00 0.00 0.00 0.00 0.52 0.50 0.58 0.64 0.66 0.85 0.76 0.58 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.04 C34(S) 0.00 0.00 0.00 0.00 0.00 0.00 0.15 0.30 0.52 0.23 0.41 0.61 0.00 0.29 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.02 C34(R) 0.00 0.00 0.00 0.00 0.00 0.00 0.41 0.49 0.74 0.57 0.84 0.81 0.81 0.44 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.04 C35(S) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.40 0.38 0.48 0.60 0.00 0.27 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.02 C35(R) Ts 0.00 0.13 0.30 0.01 0.12 0.01 0.55 0.61 0.92 0.74 0.72 1.05 0.91 0.59 0.00 0.00 0.00 0.22 0.00 0.00 0.52 0.00 0.00 0.02 Tm 0.00 1.56 0.45 0.01 0.07 0.02 2.01 1.97 2.67 2.26 1.94 3.03 2.68 2.05 0.01 0.00 0.00 0.69 0.00 0.00 1.73 0.00 0.00 0.10 0.00 2.65 1.59 0.06 0.63 0.10 5.08 5.82 7.43 5.95 5.89 7.93 7.47 5.44 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.12 C27 αββ 0.00 1.78 1.70 0.03 0.00 0.05 2.50 3.06 3.75 3.48 2.85 4.28 4.01 2.81 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.12 C28 αββ 0.00 1.68 1.60 0.04 0.00 0.06 3.13 3.91 4.89 4.09 4.07 5.27 5.05 3.74 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.22 C29 αββ Total 35.7 97.5 57.4 0.36 1.83 1.62 132 153 200 170 151 210 189 142 0.22 47.4 38.6 13.5 34.4 41.8 23.9 31.0 55.3 1.53 Diagnostic ratios 10.9 2.27 2.81 2.20 0.12 2.14 2.48 2.45 2.47 2.44 2.45 2.44 2.49 2.41 NA 2.26 2.41 2.39 2.50 2.15 2.27 2.20 2.44 NA C23/C24 NA 14.0 15.0 1.36 0.04 8.73 13.9 14.2 14.1 14.9 13.6 13.9 14.1 13.4 NA 12.2 15.1 2.48 12.3 11.48 1.22 10.7 12.2 NA C23/C30 NA 6.15 5.36 0.62 0.33 4.08 5.61 5.80 5.72 6.09 5.57 5.72 5.68 5.58 NA 5.43 6.29 1.04 4.91 5.34 0.54 4.87 5.00 NA C24/C30 NA 1.58 0.99 1.37 NA 1.53 1.62 1.49 1.52 1.45 1.45 1.50 1.48 1.46 NA NA NA NA NA NA NA NA NA NA C27αββ/C29αββ

500000 342 400000

300000

200000 Abundance 100000

0 0 4 8 121620min 500000

400000 341

300000

200000 Abundance 100000

0 0 4 8 121620min 500000 340 400000

300000

200000 Abundance 100000

0 0 4 8 121620min 500000 345 400000

300000

200000 Abundance 100000

0 0 4 8 121620min 500000 344 400000 300000

200000 Abundance 100000

0 0 4 8 121620min

Figure 17A GC-FID chromatogram of representative samples

368

369

762

366

WAB-blank

0 4 8 121620min

Figure 17B GC-FID chromatogram of representative samples

5.0 4.0 342 3.0 2.0

Conc. (mg/g) 1.0 0.0 Pri C8 C9 Phy C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 C41 C42 C43 C44 5.0 4.0 341 3.0 2.0

(mg/g) Conc. 1.0 0.0 Pri C8 C9 Phy C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 C41 C42 C43 C44 5.0 4.0 340 3.0 2.0

Conc. (mg/g) Conc. 1.0 0.0 Pri C8 C9 Phy C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 C41 C42 C43 C44 0.010 0.008 345 0.006 0.004 0.002 Conc. (mg/L water) 0.000 Pri C8 C9 Phy C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 C41 C42 C43 C44 0.10 0.08 344 0.06 0.04 0.02 Conc. (mg/L water) 0.00 Pri C8 C9 Phy C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 C41 C42 C43 C44 5.0 4.0 368 3.0 2.0

Conc. (mg/g) Conc. 1.0 0.0 Pri

C8 C9 Phy C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 C41 C42 C43 C44 5.0 4.0 369 3.0 2.0 Conc. (mg/g) 1.0 0.0 Pri C8 C9 Phy C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 C41 C42 C43 C44 5.0 4.0 762 3.0 2.0

Conc. (mg/g) 1.0 0.0 Pri C8 C9 Phy C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 C41 C42 C43 C44

Figure 18 Distribution of n-alkanes in representative samples

3500000 342 2800000 2100000 1400000 Abundance 700000 0 5 101520253035404550min 3500000

2800000 341

2100000

1400000 Abundance 700000

0 5 101520253035404550min 3500000 340 2800000

2100000

1400000 Abundance 700000

0 5 101520253035404550min 3500000 345 2800000 2100000

1400000

Abundance 700000 0 5 101520253035404550min 3500000 344 2800000

2100000

1400000 Abundance 700000

0 5 101520253035404550min

Figure 19A GC-MS chromatogram of PAHs and BTEX of representative samples

1500000 368 1200000

900000

600000 Abundance 300000

0 5 101520253035404550min 1500000 1200000 369 900000 600000 Abundance 300000 0 5 101520253035404550min 1500000 762 1200000 900000 600000 Abundance 300000 0 5 101520253035404550min 1500000 366 1200000 900000 600000 Abundance 300000 0 5 101520253035404550min 1500000 WAB-blank 1200000 900000 600000 Abundance 300000 0 5 101520253035404550min

Figure 19B GC-MS chromatogram of PAHs and BTEX of representative samples

30000 2000 Other EPA Priority PAHs 25000 342 1500 1000 20000 500 g/g) 0 μ Fl IP Pe Py 15000 An Acl DA Ace Bph BeP BaP BbF BkF DgP BaA 10000 Conc. ( 5000 0 Fluo Chry Phen C1-F C2-F C3-F C1-P C2-P C3-P C4-P Naph C1-C C2-C C3-C C1-D C2-D C3-D C1-N C2-N C3-N C4-N Diben 30000 341 2000 Other EPA Priority PAHs 25000 1500 1000 20000 500 g/g) 0 μ Fl IP Pe Py

15000 An Acl DA Ace Bph BeP BaP BbF BkF DgP BaA 10000 Conc. ( 5000 0 Fluo Phen Chry C1-F C2-F C3-F C1-P C2-P C3-P C4-P Naph C1-C C2-C C3-C C1-D C2-D C3-D C1-N C2-N C3-N C4-N Diben 30000 2000 25000 340 1500 Other EPA Priority PAHs 1000 20000 500 g/g) 0 μ

Fl IP Pe 15000 Py An Acl DA Ace Bph BeP BaP BbF BkF DgP BaA 10000 Conc. ( 5000 0 Fluo Phen Chry C1-F C2-F C3-F C1-P C2-P C3-P C4-P Naph C1-C C2-C C3-C C1-D C2-D C3-D C1-N C2-N C3-N C4-N Diben 50 345 0.20 Other EPA Priority PAHs 40 0.15 0.10 0.05 30 0.00 g/L water) Fl IP Pe Py An Acl DA μ Ace Bph BeP BaP BbF BkF DgP 20 BaA

10 Conc. ( 0 Fluo Phen Chry C1-P C2-P C3-P C4-P C1-F C2-F C3-F Naph C1-C C2-C C3-C C1-N C2-N C3-N C4-N C1-D C2-D C3-D Diben 500 20 344 15 Other EPA Priority PAHs 400 10 5 300 0 Fl IP Pe g/L water) Py An Acl DA Ace Bph BeP BaP BbF BkF DgP BaA μ 200

100 Conc. ( 0 Fluo Phen Chry C1-P C2-P C3-P C4-P C1-F C2-F C3-F Naph C1-C C2-C C3-C C1-N C2-N C3-N C4-N C1-D C2-D C3-D Diben

Figure 20A Distribution of PAHs in representative samples

15000 200 368 150 Other EPA Priority PAHs 12000 100 50 g/g) 9000 0 μ Fl IP Pe Py An Acl DA Ace Bph BeP BaP BbF BkF DgP 6000 BaA Conc. ( 3000

0 Fluo Chry Phen C1-F C2-F C3-F C1-P C2-P C3-P C4-P Naph C1-C C2-C C3-C C1-N C2-N C3-N C4-N C1-D C2-D C3-D

Diben 150000 369 200 Other EPA Priority PAHs 120000 150 100 50 g/g) 90000 0 μ Fl IP Pe Py An Acl DA Ace Bph BeP BaP BbF BkF DgP 60000 BaA

Conc. ( 30000

0 Fluo Phen Chry C1-F C2-F C3-F C1-P C2-P C3-P C4-P Naph C1-C C2-C C3-C C1-D C2-D C3-D C1-N C2-N C3-N C4-N Diben 15000 762 200 Other EPA Priority PAHs 12000 150 100 50 g/g) 9000 0 μ Fl IP Pe Py An Acl DA Ace Bph BeP BaP BbF BkF DgP 6000 BaA

Conc. ( 3000 0 Fluo Phen Chry C1-P C2-P C3-P C4-P C1-F C2-F C3-F Naph C1-C C2-C C3-C C1-N C2-N C3-N C4-N C1-D C2-D C3-D Diben 1.0 366 0.20 Other EPA Priority PAHs 0.8 0.15 0.10 0.05 g/g) 0.6

μ 0.00 Fl IP Pe Py An Acl DA Ace Bph BeP BaP BbF BkF DgP 0.4 BaA Conc. ( 0.2 0.0 Fluo Phen Chry C1-F C2-F C3-F C1-P C2-P C3-P C4-P Naph C1-C C2-C C3-C C1-N C2-N C3-N C4-N C1-D C2-D C3-D Diben 10.0 10.0 WAB-blank 7.5 Other EPA Priority PAHs 8.0 5.0 2.5

g/g) 6.0 0.0 μ Fl IP Pe Py An Acl DA Ace Bph BeP BaP BbF BkF DgP 4.0 BaA Conc. ( 2.0 0.0 Fluo Phen Chry C1-P C2-P C3-P C4-P C1-F C2-F C3-F Naph C1-C C2-C C3-C C1-N C2-N C3-N C4-N C1-D C2-D C3-D Diben

Figure 20B Distribution of PAHs in representative samples

25000 342 20000 (m/z 191) 15000 10000 Abundance 5000 0 25 30 35 40 45 50min 55 25000 20000 341 (m/z 191) 15000 10000 Abundance 5000 0 25 30 35 40 45 50min 55 25000 340 20000 (m/z 191) 15000 10000 Abundance 5000 0 25 30 35 40 45 50min 55 25000 345 20000 (m/z 191) 15000 10000 Abundance 5000 0 25 30 35 40 45 50min 55 25000 344 20000 (m/z 191) 15000 10000 Abundance 5000 0 25 30 35 40 45 50min 55

Figure 21A GC-MS chromatogram of biomarker terpanes (m/z 191) of representative samples

25000 368 20000 (m/z 191) 15000

10000 Abundance 5000

0 25 30 35 40 45 50min 55 25000

20000 369 (m/z 191) 15000

10000 Abundance 5000

0 25 30 35 40 45 50min 55 25000 762 20000 (m/z 191) 15000

10000 Abundance 5000

0 25 30 35 40 45 50min 55 25000 366 20000 (m/z 191) 15000

10000

Abundance 5000

0 25 30 35 40 45 50min 55 25000 WAB-blank 20000 (m/z 191) 15000

10000

Abundance 5000 0 25 30 35 40 45 50min 55

Figure 21B GC-MS chromatogram of biomarker terpanes (m/z 191) of representative samples

1500 342 1200 (m/z 218) 900

600 Abundance 300

0 30 33 36 39 42min 45 1500 341 1200 (m/z 218) 900

600 Abundance 300

0 30 33 36 39 42min 45 1500 340 1200 (m/z 218) 900

600 Abundance 300

0 30 33 36 39 42min 45 1500 345 1200 (m/z 218)

900

600 Abundance 300

0 30 33 36 39 42min 45 1500 344 1200 (m/z 218) 900

600 Abundance 300

0 30 33 36 39 42min 45

Figure 22A GC-MS chromatogram of biomarker steranes (m/z 218) of representative samples

1500 368 1200 (m/z 218) 900

600 αββ

Abundance αββ

αββ 27 29 C 28

300 C C

0 30 33 36 39 42min 45 1500 369 1200 (m/z 218) 900

600 Abundance 300

0 30 33 36 39 42min 45 1500 762 1200 (m/z 218) 900 600 Abundance 300 0 30 33 36 39 42min 45 1500 366 1200 (m/z 218) 900

600 Abundance 300

0 30 33 36 39 42min 45 1500 WAB-blank 1200 (m/z 218) 900

600 Abundance 300

0 30 33 36 39 42min 45

Figure 22B GC-MS chromatogram of biomarker steranes (m/z 218) of representative samples