Chapter 5 Bound biomarker information in heavily biodegraded and weathered samples of the Athabasca Tar Sand 5.

1 Introduction
The Athabasca Tar Sand, which contains 1.7 trillion barrels of crude equivalent and is the largest deposit in the SW Canadian tar sand Triangle, is situated in north western Alberta where open cast mines (supplemented by steam assisted gravity drainage SAGD) are set to provide 70 % of Canadas oil production by 2025 (Fowler et al., 2001). The formation of this super giant tar sand has been the subject of study by many authors and only a brief summary is provided here. The first petroleum charges flowed from the west of the WCSB some 80 million years ago (80 Ma), and these were trapped in the unconsolidated McMurray upper marine shoreface sands. The trapping mechanism is thought to have involved the biodegradation of the earliest emplaced oil to produce a heavy immobile bitumen.

Heavy oils in WCSB

Tar Sand Mature Source Migration Pathway
0 100 200 300 kilometers 200 miles

Alberta

Athabasca Tar Sand

100

Figure 5.1. Map showing Western Canadian sedimentary basin, and location of the Athabasca Tar Sand (Creaney et al., 1994).

The migration pathways have been supported by basin simulation studies e.g. Graven (1989), and the trapping mechanism confirmed by the lack of structural or stratigraphic control seen in the Athabasca Tar Sand (Vigrass, 1968). A common source has been

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proposed for the Athabasca, Cold lake and Peace River tar sand deposits (Brooks et al., 1988; Fowler et al., 2001), however it is unclear what this source is as a number of source rocks have sourced many oil deposits in the WCSB (Allan and Creaney, 1991). Based on quantitative grounds the Exshaw formation is thought to have made a significant contribution to the tar sand deposits (Fowler et al., 2001). However in the WCSB there are many other conventional and heavy oil deposits that have been sourced by other formations, e.g. those in mid- to late-Devonian reservoirs sourced by the Duverney Formation, and it is unclear in what quantities these could have contributed to the tar sand deposits (Allan and Creaney, 1992; Creaney et al., 1994). One of the main problems in accurately establishing a source for the tar sand is the heavy biodegradation that the tar sand deposits have undergone, Peters and Moldowan level 7 for the Athabasca deposit and between levels 3 6 for other major tar sand deposits (Creaney et al., 1994). This has radically altered the free sterane molecular components and completely removed the n-alkanes, isoprenoids and many aromatic compounds that could have been used to conclusively relate other less degraded heavy oil and bitumen deposits to the Exshaw formation. For this reason the bound biomarker content of the Athabasca Tar Sand has been extensively studied in the past by a wide variety of methods. This includes chemical degradation (Ekweozar, 1984; Peng et al., 1997; Strausz et al., 1999) as well as hydrous pyrolysis (Fowler & Brooks, 1987; Jones et al., 1988) and pyrolysis (Ekweozar & Strausz, 1983). These studies have mostly not involved the detailed quantification of reaction products (e.g. bound biomarkers) and have mainly focused on the degradation products of the asphaltene fractions, although the resin fraction and whole rock and whole maltene fraction have been considered in certain cases. Thus there is a limited published dataset that allows for a rudimentary consideration of the composition if not the quantities of biomarkers present in each fraction. By using hydropyrolysis, this study has quantified the absolute amounts and composition of steranes, hopanes and tricyclic terpanes present in the macromolecular component of the Athabasca Tar Sand bitumen. Previous bound biomarker studies (Fowler and Brooks, 1987; Richnow et al., 1991; Chapter 3 and 4) noted that bound biomarker profiles generally look distinctly different from their free counterparts in terms of their carbon number composition and isomeric distribution. This obviously presents a problem when applying bound biomarkers to correlation studies. These problems can potentially be overcome by comparing with a bound biomarker database compiled from previous hydropyrolysis studies, and using this to predict free biomarker 138

parameters prior to any biodegradation, this approach is tested in this study. A number of free fraction biomarker parameters for the Athabasca Tar Sand where predicted by this method and have been integrated into the vast body of literature that describes the geochemical characteristics of the major source rocks in the Western Canadian Sedimentary Basin (Leenheer, 1984; Brooks et al., 1988; Allan and Creaney, 1991). This study has focussed on the Athabasca Tar Sand hosted in Lower Cretaceous sediments from north western Alberta. In addition to determining the composition and quantities of biomarkers in each organic fraction (free, resin and asphaltene), the effects of physical weathering (abiotic oxidation and water-washing) on the already biodegraded tar sand composition were also investigated. To this end the samples analysed in this study have been collected from outcrops and mine faces which have been exposed and weathered to different extents. This chapter divides into 3 main areas of discussion. 1) Bulk chemical composition and evidence for the different effects of biodegradation and physical weathering (water washing and abiotic oxidation) processes on organic matter composition. 2) Use of catalytic hydropyrolysis for regeneration of pristine bound biomarker signals from heavily biodegraded bitumen. 3) New insights from bound biomarker data generated by hydropyrolysis for facilitating accurate source rock oil correlations and investigating the origins and thermal maturity of the parent source rock of the Athabasca Tar Sand. 5.1.2 Approaches to oil correlation using free and bound biomarkers The free aliphatic biomarker profiles that are commonly applied for thermal maturity and source assessment, can be altered or destroyed in oils that have been biodegraded (Seifert and Moldowan, 1979; Volkman et al., 1983; Peters and Moldowan, 1993). In the case of the Athabasca Tar Sand, where even the steranes have been heavily degraded and the hopanes mildly altered (Brooks et al., 1988), this makes it extremely difficult to apply biomarkers to petroleum exploration. As noted in Chapter 1, many authors have used a variety of chemical degradation and pyrolysis techniques to obtain bound biomarker signals for correlation purposes (Rubinstein et al., 1979; Cassani and Eglinton, 1986; Fowler and Brooks, 1987; Jones 139

et al., 1988). Bound biomarker data is used in this way because compounds that are covalently-bound into asphaltene and resin matrices are protected relative to their free counterparts from the effects of biodegradation, and retain useful structural and steriochemical information, even when it has been altered or destroyed in the free fraction. Of the aforementioned studies, two of the most comparable and relevant to this investigation were hydrous pyrolysis studies that also focused on the Athabasca Tar Sand (Fowler and Brooks, 1987; Jones et al., 1988). Chemical degradation studies, like pyrolysis and hydrous pyrolysis, have also yielded bound biomarkers from Athabasca Tar Sand asphaltene and resin fractions (Ekweozor, 1984; Peng et al., 1997; Strausz et al., 1999), although these studies were more concerned with elucidating the structural detail of macromolecular components than source information for correlation purposes. While all Athabasca Tar Sand bound biomarker studies show that biomarkers bound into the macromolecular organic fractions of bitumen have been protected from biodegradation, and that the asphaltene fraction represents a source of unaltered biomarker information, none has been able to add more specificity to identifying a parent source rock facies for the Athabasca Tar Sand deposit than any free biomarker study (Fowler and Brooks, 1987; Allen and Creaney, 1991). One reason for this may be that bound biomarker fingerprints can not be directly compared with free biomarker signals for the purposes of oil correlation studies. This is because, as described in Chapter 1, bound biomarkers have distinct inherent differences in composition to their free counterparts (Fowler and Brooks, 1987; Richnow et al., 1991). This bound biomarker study is important because it represents the application of hydropyrolysis, an important new technique, to what is both an old exploration geochemistry problem i.e. establishing a source for the Athabasca Tar Sand, and yet at the same time a valuable reference material that has been extensively studied by a variety of pyrolysis and degradation methods. Hydropyrolysis is unique in its ability to produce high yields of biomarker hydrocarbons with minimal structural and stereochemical alterations (Love et al., 1995), and this will make the comparisons between the results of this study and those of other studies that used chemical degradation methods (Ekweozar, 1984; Peng et al., 1997; Strausz et al., 1999) all the more interesting in investigating the biomarkers present in resins and asphaltenes. By comparing bound biomarker data in this way it should be possible to investigate the 140

degree to which data collected using different analytical methods can be used interchangeably. 5.1.3 Weathering and biodegradation of the Athabasca Tar Sand There are two conceptual frameworks in which the differences in the bulk chemical composition, and bound and free biomarker compositions of the samples of tar sand can be considered. One is as a rock, weathered by the usual physical and chemical geological processes. The other is a reservoired oil altered by biodegradation and waterwashing in possibly two distinct events; an initial subsurface phase and a later phase of exposure at the earths surface.
5.1.3.1 Weathering of the McMurray Sandstone Formation (e.g. the Athabasca Tar Sand)

The Athabasca Tar Sand can be considered an unusual shoreface sandstone cemented by a heavy bitumen (Vigrass, 1969). Cementation occurred when a petroleum-rich pore fluid migrated into the Lower Cretaceous McMurray formation (Graven, 1989) and, due to a chemical change brought about by biodegradation, formed a viscous tarry organic residue that prevented further consolidation, and bound the sand together by its cohesive properties (Fowler et al., 2001). When the Athabasca Tar Sand is exposed at the surface it will weather like any other rock. Minerals and materials present in the rock that are chemically unstable will be attacked by one of four processes. 1) Leaching, which is the continued removal by water of soluble matter from the bedrock. 2) Oxidation, the oxidation of rock components by oxygen rich surface conditions. 3) Hydrolysis, in which water reacts with various rock components as either H+ or OH-, depending on pH conditions 4) Dissolution, in which soluble rock components enter into solution. Biological activity is not normally treated as major weathering process by most geological texts (e.g. Skinner and Porter, 1995) and is normally confined to the action of plant roots etc, but biological activity (biodegradation is considered a major process in the alteration of petroleum in sedimentary basins, Tissot and Welte, 1984). Petroleum forms the cementing matrix of the McMurray sandstone and therefore oil biodegradation ought to be considered an important factor, that can act in addition to the more traditional weathering processes. Biodegradation acts to weaken cohesion by destroying the

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bitumen cement that acts as a rock matrix and could therefore play an important role in weathering large tar sand deposits. In this context the sample set of this study can be seen to comprise weathered and unweathered samples. The weathered samples are characterized by a weathering rind or crust which lends the rock a speckled or white appearance, caused by the leaching and removal of dark bitumen from the surface and the protrusion of white sand grains. Not all the samples are equally weathered as they were collected from different locations, different ages of mine face and from different depths into outcrops.
5.1.3.2 Alteration of reservoired oils

The study of the alteration of reservoired oils concerns the change in composition of the bitumen phase present. Two process of great concern, that make an oil accumulation less economically valuable by removing lower molecular weight compounds and leaving a viscous bitumen enriched in polar compounds, are water washing and biodegradation (Tissot and Welte, 1984). Although the two processes are normally thought to act together, they have been studied separately and seen to have different effects on molecular markers (Kuo, 1994; Taylor et al., 2001). In general, water washing greatly decreases the aromatic and saturate contents, and slightly reduces the NSO (resin) content of bitumens by removing low molecular weight and water soluble polar compounds (e.g. acids, phenols and alcohols). In conceptual terms, this makes water washing very similar to the leaching weathering process described above, in which soluble components are removed from a rock in solution. Few studies concerning the effects of water washing on biomarker parameters have been performed, but both laboratory studies (Kuo, 1994) and field studies (Hwang and Ortiz, 1998) suggest that biomarker distributions and parameters are little effected by water washing. Early stages of biodegradation see the removal of saturates and then aromatic compounds and a rise in the proportion of NSOs (resins) and asphaltenes (Connan, 1984). In contrast to waterwashing, biodegradation has relatively well constrained effects on the biomarker composition of crude oils (Peters and Moldowan, 1993), where biomarkers are removed in distinct but overlapping stages.

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The samples of this study can be divided into two types; one which has undergone a single period of subsurface anaerobic biodegradation associated with the formation of the Athabasca Tar Sand (Brooks et al, 1988; Graven, 1989). The other sample type has undergone a second period of alteration at the surface following exposure, associated with weathering under predominantly abiotic processes such as water washing and abiotic oxidation (although it is likely aerobic biodegradation could have occurred). This sample suite effectively constitutes samples which have been exposed to two periods of alteration. The first period of alteration was severe anaerobic biodegradation intimately associated with the deposits formation, the second period of alteration represents more recent surface alteration. The more recent period of alteration at surface conditions is likely to have been dominated by waterwashing or leaching (the removal of soluble components by water at the surface) and abiotic oxidation, as well as possible aerobic biodegradation. The following section describes the evidence for these processes that can be found in the tar sand bitumen composition, free aliphatic biomarkers as related to the Peters and Moldowan biodegradation scale and hydropyrolysis products of the resin and asphaltene fractions. 5.1.4 Method
Measured quantities of 8 samples of the Athabasca Tar Sand were soxhlet extracted as described in Chapter 2. The extracted bitumen was separated into aliphatic, aromatic, resin and asphaltene fractions using thin layer chromatography and the asphaltene precipitation method described in Chapter 2. Resin and asphaltene fractions were then subjected to hydropyrolysis and the products separated into aliphatic, aromatic and polar fractions following the procedures and methods described in Chapter 2. Hydrocarbon products were analyzed by GC and GC-MS as described in Chapter 2, compound identification being based on retention times and mass spectra.

5.2 Sample and bulk chemical description

5.2.1 Sampling and sample description Five samples of a marine shore face sandstone and two samples of a sideritic horizon were collected from differing locations in the Athabasca Tar Sand deposit. Each sample has to a varying degree, been exposed to biodegradation and abiotic physical weathering processes. Sample information is tabulated in Table 5.1, and it shows that some of the samples (Can 7 to 9) were exposed at the surface and developed a

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weathering rind, other samples were collected from beneath any weathering surface (Can 1 to 6). Table 5.1 Sample description showing lithology and outcrop type
Sample Description Lithology Weathered rind Can 1 Recent mine face McMurray MSF sst N Can 3 Siderite concretion horizon Siderite horizon N Can 4 Fresh new mine face McMurray MSF sst N Can 6 Fractured siderite concretion horizon Siderite horizon N Can 7u* Unweathered inner McMurray MSF sst Y Can 7w* Weathered outer McMurray MSF sst Y Can 8 Abandoned mine face McMurray MSF sst Y Can 9 Oil deficient hanging rock McMurray MSF sst Y Description, where sample was collected from, not age of mine face abandoned>recent>new Lithology, sample lithology note to siderite horizons Weathered rind, presence of leached surface on sample *sample 7 represents a weathering profile and comprises an inner and outer sub-sample MSF sst, Marine shoreface sandstone

5.2.2 Bulk composition of tar sand In Table 5.2 all of the samples can be seen to have high proportions of polar and asphaltene components, this was caused by heavy biodegradation that removed many aliphatic and aromatic compounds (Deroo et al., 1974). It can also be observed that weathering has further altered the bulk organic matter composition of many of the samples collected during this study. Samples 7 to 9, which possess weathering rinds, have much greater proportions of resins and asphaltenes than those that dont. This can be interpreted to be due to water washing, which would be expected to selectively remove aliphatic and aromatic compounds (Kuo, 1994) as well as acids, phenols and alcohols (Taylor et al., 2001). Another observation is the generally lower EOM yields in sample 8 and 9, which could also be attributed to leaching. Sample 6 most probably has a very low EOM yield because it contains a large proportion of non-porous siderite cement, not because of bitumen loss due to weathering or leeching. In Figure 5.2 it can be clearly seen that the proportion of aromatic and aliphatic material decreases between the weathered and unweathered samples, this can be interpreted to represent the effects of a latter stage of physical weathering, analogous to water washing (Kuo, 1994). By ordering the samples as seen in Figure 5.2, it is possible to asses which samples have been most effected by water washing and leaching. In general it would appear that samples 6, 3, 4 and 1 have greatest proportion of aromatics,

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sample 8 then 7u & 7w the next greatest and sample 9 the least. Based on the work of Kuo (1994), which demonstrated that samples that have been water washed have become depleted in aromatics, it can be inferred that sample 6, 3, 4, and 1 are the least water washed and sample 7 to 9 the most.

Sideritic Horizon 100 80 60

Mc Murray Formation

Weathering Profile

Hanging Rock

Sat

% of EOM

Aro

40 20

Res

Asph 0 6 3 4 1 8 sample 7u 7w 9

Figure 5.2. Bitumen composition. The size of the aromatic fractions decreases noticeably with degree of water washing or physical weathering. The error bars correspond to the weighing accuracy, this is noticeably lower for the asphaltenes for which it is particularly hard to obtain weights due to DCM. Sat = saturated hydrocarbons; Aro = aromatic hydrocarbons; Res = resins; Asph = asphaltenes

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Table 5.2. Yield data for solvent extraction, fractionation and hydropyrolysis (mg/g EOM) Bitumen
EOM

Asphaltene Hydropyrolysis yield tot 31 83 32 6 269 150

dup dup

Resin Hydropyrolysis yield tot 183 118 121 ali 94 70 61 aro 22 27 30 pol 66 22 30

Solvent yield asph 220 189 314 115 370 411 248 580 nd nd nd nd nd nd nd nd 253 50 117 93 75 94 437 157 159 63 321 134 134 375 119 136 102
dup

% 19 15 15 7 17 15 10 9 nd nd 285 429 171 4 1 216 266 205 7 14 11 1 18

dup

res 268 333 304 174 29 17 37 312 201 16 5 10

aro

ali

ali

aro

pol

Can1

Can3

Can4

Can6

129 392 628

86 266 234

10 67 109

33 59 284

Can7w

Can7u

Can8

38 52 23 35

21 35 40 46

4 6 12 12

488 129 nd nd

111 89 nd nd

92 22 nd nd

285 18 nd nd

Can9

Can7u1

Can7u2

EOM = (extractable organic matter / sediment) X 100

tot = total yield of solubles after hydropyrolysis

ali = aliphatic; aro = aromatic; pol = polar

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5.2.3 Biodegradation assessment from free biomarker hydrocarbons All the samples possess free biomarker traces which show heavy signs of biodegradation, e.g. the complete removal of all n-alkanes and isoprenoids (Peters and Moldowan, 1993). In addition, biodegradation has proceeded to such a stage that many of the cyclic alkane biomarkers have also been altered. In general there is a degree of correspondence between the proportion of polar material (resin and asphaltene) in a sample, and the level to which its free cyclic biomarkers have been degraded. The one exception to this is sample 1, for which the free biomarker traces are the most altered, but whose bitumen composition is not particularly enriched in polar (resin and asphaltene) material relative to the other fractions. Hence samples 3 and 4 appear to be the least biodegraded (Peters and Moldowan 7), samples 7u, 7w, 8 and 9 of similar levels of biodegradation and sample 1 the most biodegraded (approaching Peters and Moldowan level 9).

C27 Ts C27 Tm + TT C30 S&R C28 Bis C29 C29 C30 C30

TT C23 TT C24

TT C25 S&R

TT C26 S&R

TT C28 S&R

TT C29 S&R

Can 3

C31
SR

G + TT C 33 +C 32

SR

SR

Can 4

C29
SR

most altered

G C29 C30
SR

SR

S R

Can 9

G C29 Can 1 C30

SR

SR

S R

SR

S R

elution time
Figure 5.3. Free fraction m/z 191 fragmentograms. Changes with increasing degrees of biodegradation include a rise in the proportion of tricyclic terpanes, gammacerane and Tm hopane. Compare sample 1 and sample 3. TT C 23 = C23 13(H), 14(H) tricyclic terpane (note various tricyclic terpane isomers are not individually labeled); C 27Ts = C27 18a(H)-22, 29, 30 trisnorneohopane; C27 Tm = 17a(H)-22, 29, 30 trisnorhopane; C29 =C29 17(H), 21(H) hopane; C29 =C29 17(H), 21(H) hopane; C31 S = C31 17(H), 21(H) (22S) hopane; C31 R = C31 17(H), 21(H) (22R) hopane. G gammacerane.

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The key differences between the different free fraction hopane m/z 191 traces (Figure 5.3) are the greater relative amounts tricyclic terpanes relative to hopanes and the larger proportions of gammacerane and C27 to C29 hopanes (including C28 28,30 bisnorhopane) relative to higher carbon number hopanes in the most biodegraded samples. Tricyclic terpanes are commonly known to be more resistant to biodegradation than hopanes (Palacas et al., 1986), and both gammacerane and tricyclic terpanes have been previously reported to become enriched in other WCSB tar sands with biodegradation (Brooks et al., 1988). Previous work also suggests that 28,30 bisnorhopanes become enriched in tar sands with biodegradation (Brooks et al., 1988).

C27 S dia

C29 S dia

C27 R dia

C29 R dia

regular C29 steranes

S R

Can 3

most altered

Can 4

Can 9
R S

Can 1

elution time
Figure 5.4. Free fraction m/z 217 fragmentograms. The ratios of S/R diasteranes and regular steranes, in addition to the sterane carbon number distributions, reflect differing levels of biodegradation. In general the most biodegraded samples have greater proportions of the higher carbon number homologues with the R isomer. C27 S dia = C27 13(H), 17(H) (20S) diasterane; C27 R dia = C27 13(H), 17(H) (20R) diasterane; C29 S dia = C29 13(H), 17(H) (20S) diasterane; C29 R dia = C29 13(H), 17(H) (20R) diasterane; C27 S = C27 5(H), 14(H), 17(H) (20S) sterane; C27 R = C27 5(H), 14(H), 17(H) (20R) sterane; C27 R+S = C27 5(H), 14(H), 17(H) (20S) + (20R) steranes; C27 = C27 5(H), 14(H), 17(H) sterane.

Key differences observed in the m/z 217 sterane traces (fig. 3) are a drop in the amount of 13(H),17(H)C27 (20S) diasterane relative to 13(H), 17(H)C27 (20R) diasterane consistent with stereoselective degradation of the C27 13(H), 17(H) 20 S isomer

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(Seifert and Moldowan, 1979), and an increase in the proportion of the C29 diasterane homologues consistent with the selective destruction of lower sterane homologues (Seifert and Moldowan, 1979; Brooks et al., 1988). Assigning the samples a single position on the Peters and Moldowan (1993) biodegradation scale is not straight forwards. The freshest and most unaltered samples (e.g. sample 3 and 4 in Figure 5.2 and 5.3) show little or no hopane alteration and the diasteranes are only slightly altered this would be about level 7 on the Peters and Moldowan biodegradation scale. Sample 9 and 1 have greater tricyclic terpane/hopane ratios but their hopanes are still present; however, considering that their diasteranes have begun to be heavily degraded this puts them some where between level 8 and 9. This could be explained by an early phase of anaerobic biodegradation in which hopanes were not effected, and a latter more aggressive weathering period of what is likely to have been aerobic biodegradation at the surface, in which diasteranes have been significantly biodegraded and the hopane phase of degradation begun. 5.2.4 Assessment of oxidation using hydropyrolysis products As noted in the sample description, some of the samples have undergone a phase of weathering at the surface, a component of this would be expected to involve the removal of soluble components by water, a process analogous to water washing in reservoirs (Kuo, 1994; Taylor et al., 2001). Evidence for this physical process is presented in Figure 5.2 (e.g. decreases in proportion of aromatics), but many samples also appear to have been oxidised at surface conditions, by either a biologically mediated (oxic-biodegradation) or an abiotic route.

149

0.0 0.5 1.0 1.5 2.0 2.5

C1C & MB[c]P

B[ghi]Pe

Pyrene area / UCM area

C1C & MB[c]P

DMBP P

MBP

Fa Py

Can 3

DMBP P

Can 4
MBP

Fa

Py

Can 3
C1C & MB[c]P

B[ghi]Pe

Can 8
Py

Can 8

MBP

Fa

Can 6

B[ghi]Pe

DMBP P

Can 1

Co C1C & MB[c]P B[ghi]Pe MBP DMBP P Fa Py Co C1C & MB[c]P Py B[ghi]Pe DMBP P MBP Fa Co

Can 1

Can 7u 1&2

Can 7u 1

Can 7w

Can 7w

elution time

Figure 5.5. GC-FID traces of the aromatic fraction of the asphaltene hydropyrolysate showing the differing degrees of surface oxidation expressed by the proportion of PAH to aromatic UCM. For fuller description of aromatic compounds see Figure 5.10. MBP = methylbiphenyls; DMBP & EBP = dimethylbiphenyls & ethylbiphenyls; P = phenanthrene; Fa = fluranthene; Py = pyrene; MPy = methylpyrenes; C1C & MB[c]P = methylchrysene & methyl-benzo[c]phenanthrene; B[ghi]Pe = benzo[g,h,i]perylene; Co = Coronene

Evidence for this is present in the GC-FID traces of the aromatic fractions of asphaltene hydropyrolysis products. Various PAH and hetro-atom containing compounds have been known to be major constituents of Athabasca Tar Sand asphaltenes for some time, and have been found in the products of a number of chemical degradation methods (Frakman et al., 1990; Payzant et al., 1991; Mojelsky et al., 1992; Peng et al., 1997; Strausz et al., 1999). The PAH tend to be of much lower abundance in chemical degradation products than either bridging methylene chains or n-alkyl chains attached to aromatic units, although it should be noted that these products themselves typically represent only about 30 % of the asphaltene molecule (Mojelsky et al., 1992). The partially condensed aromatic, napthenic nuclei which represents 57 % of asphaltene

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molecule is little effected by chemical degradation (Strausz et al., 1999), and perhaps for the this reason large ring number PAH, such as benzo [g,h,i] perylene and coronene, have not been reported in chemical degradation studies. The PAH that are recovered by ruthenium ion catalysed oxidation (RICO) are in the form of benzocarboxylic acids, however the diagnostic benzohexacarboxylic acids that are the reaction products of large pericondensed PAH are hard to identify due to the preferential creation of other benzocarboxylic acids with lesser numbers of acid groups (Strausz et al., 1999). This makes the presence of relatively condensed PAH (5 rings or greater) in the pyrolysis products of this study of note in and of it self, proving the presence large ring number PAH as relatively significant structural units of the Athabasca asphaltene. Also of interest is the relative proportion of these PAH to the aromatic UCM, which appears to vary between the various fractions as shown in Figure 5.5. A numerical measure in the form of a pyrene/aromatic UCM ratio has been plotted alongside the GC-FID traces. The ordered plot of this data shown on the left hand side of Figure 5.5, shows a good correspondence to visual observations of the GC-FID traces. This variation shows only the slightest association to the Peters and Moldowan biodegradation levels of the various samples, e.g. sample 1 and 3 show a great degree of variation between their PAH/aromatic UCM ratios, but generally this is not observed for the majority of the other samples. Sample 7u and 7w had been equally biodegraded, and water washed (denoted by Peters and Moldowan levels and % aromatics), however their Py/aromatic UCM ratios are very different; 7w is more oxidised and has a significantly higher Py/aromatic UCM ratio than 7u. This would suggest that surface oxidation and water washing processes act separately. Further evidence for the decoupling of the surface oxidation process from water washing is provided by sample 9, which possesses the second highest level of biodegradation and is most water washed (as denoted by its very low proportion of aromatic material), but does not have very prominent PAH and possesses a large aromatic UCM suggesting that it has undergone little surface oxidation. (Figure 5.7)

151

CAN 4

CAN 1

131 R R R

127 R

Figure 5.6. Showing the changes in UCM composition between sample 1 and 4 as expressed by the m/z 131 and 127 traces. This suggests that the aromatic fraction UCM of the asphaltene hydropyrolysis products of sample 4, the freshest sample, is less oxidised than that of sample 1.

The evidence for the observed changes being linked to surface exposure and oxidation is two-fold. First is the aromatic UCM composition. Figure 5.6 shows m/z 131 and 127 traces for sample Can 4 (which was collected from a fresh mine face), and sample Can 1 (collected from a slightly older mine face that has been exposed to the surface for a longer period of time). For the purpose of monitoring changes in the aromatic UCM composition two ions have been assumed to be diagnostic for tetralin (m/z 131) and napthalene (m/z 127) fragments. These fragments are not assumed to have been derived from any one specific compound or series of compounds, but are proposed to originate from a very wide range of tetralin and napthalene based compounds originally bound into the aromatic nucleus of the asphaltene molecule. Although these fragmentations will not be the primary mass spectrometer fragmentations for most of these compounds, they will be generic for a wide range of compounds whose primary cleavage patterns are too wide ranging and diverse to monitor individually. What is evident from Figure 5.6 is that sample 4, which is the least exposed and freshest sample, contains a greater 152

proportion of tetralin containing compounds to napthalene compounds than sample 1, which appears to contain greater proportion of PAH. Further proof of the link between weathering and aromatic UCM reduction can be supplied by samples which were collected from fresh mine faces, which always possess low ratios of pyrene to aromatic UCM in their asphaltene hydropyrolysis products e.g. samples 3 & 4 and sample 7u which was collected from beneath a weathering surface. The large contrast between the inner and outer of sub-samples of sample 7 (Can 7u inner, and Can 7w outer) also collaborates this. Thus there is a link between the duration of surface exposure, Py/aromatic UCM ratio and the proportion of napthalene and tetralin based compounds present in the asphaltene hydropyrolysates. It can be concluded that as the duration of surface exposure increases the ratio of PAH/aromatic UCM rises and the proportion of tetralin based compounds present in hydropyrolysis products decreases. The second piece of evidence for surface oxidation and not water washing being responsible for the Py/aromatic UCM ratios observed in the asphaltene hydropyrolysis products, is the theoretical position of the large condensed PAH sheets at the centre of asphaltene macromolecules, and the lack of correlation between indicators of water washing, such as the proportion of free hydrocarbon fraction aromatics and the Py/aromatic UCM parameter (e.g. sample 7u and 7w have identical bitumen compositions but different Py/aromatic UCM ratios in their asphaltene hydropyrolysates Figure 5.7). This suggests that the PAH were not occluded by or chelated in asphaltene aggregates and simply removed in solution or leached away by surface waters.

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5.2.5 Summary of biodegradation, waterwashing and weathering

0.9 Free hydrocarbon fraction C27 dia sterane S/S+R 0.8 0.7 0.6 0.5 Most Biodegraded 0.4 3 4 8 6 9 1 7w 7u Sample b) Measure of water washing, physical weathering. 400 Bitumen composition aromatics mg/g 300 200 100 0 6 1 3 4 8 Sample 2.50 Asphaltene hydropyrolysate Py / aromatic UCM 2.00 1.50 1.00 0.50 0.00 9 4 3 8 Least Degree of Oxidation 6 1 7u1 7u2 7w c) Measure of surface oxidation, weathering Highest Degree of Oxidation 9 7w 7u Heavily water washed Least water washed a) Measure of Biodegradation

Least Biodegraded

Sample Figure 5.7. Plots showing the different sample orders obtained by plotting measures of a) biodegradation, and weathering processes b) water washing and c) surface oxidation. The sample orders are different for each parameter, suggesting that the processes have different effects and have mostly acted independently of each other. C27 diasterane S/S+R = C27 13(H), 17(H) (20S) / C27 13(H), 17(H) (20S) + C27 13(H), 17(H) (20R) diasterane; aromatics mg/g = concentration of aromatics mg / g EOM; Py/UCM = area of pyrene / area of aromatic UCM measured on GC-FID trace.

It is important to highlight that the effects of biodegradation, oxidation and waterwashing are not the same, and although they may operate simultaneously it 154

appears that they proceed independently of each other. This is best illustrated by ranking the samples using appropriate measures for the different alteration processes; anaerobic biodegradation and physical weathering which further separates into water washing and surface oxidation/ aerobic degradation (biotic or abiotic) processes. In Figure 5.7, a diasterane parameter 13(H), 17(H) C27 (20S)/ [13(H), 17(H) C27 (20S+20R)] has been used to represent the extent of biodegradation, the concentration of aromatics (mg/g EOM) in the bitumen has been used to monitor the degree of water washing, and the ratio of pyrene to aromatic UCM in the asphaltene hydropyrolysate to asses the degree of surface oxidation. In general, if the samples are ordered by the various parameters than different orders and groupings are arrived at each time. For example the most biodegraded sample (sample Can1) is not the most water washed. Similarly, although sample 7u and 7w have equivalent Peters and Moldowan biodegradation levels and bitumen fraction compositions, they have experienced much different levels of surface oxidation. Latter weathering stages may well have included aerobic biodegradation for some of the samples, particularly sample 1 which has a high proportion of PAH, and whose biomarker profiles suggest significant latter stages of biodegradation in comparison to other samples. Sample 4s biomarker traces are amongst the least altered relative to other fractions, and it contains a relatively low proportion of PAH in its asphaltene hydropyrolysis products.

155

C29 hopane SR SR

C23 TT

C30 hopane C32 hopane

Diasterane and sterane hump

C34 hopane SR SR n36

n18

free
n16 n20 n22

SR

n24

Ph n28

n18

resin
n16 n20 n22

Elution time

Figure, 5.8 GC-FID traces of the aliphatic fractions of sample Can 4s free DCM extract, and resin and asphaltene hydrpyrolysates. n18 = C18 n-alkanes; Pr = pristane; Ph = phytane; TT = tricyclic terpane

n32

asphaltene

n28

Pr

Ph

n24

n32

C35 hopane

156

5.3 Bound biomarkers analysis

5.3.1 Regeneration of pristine biomarker signals by hydropyrolysis
5.3.1.1 Free fraction

Figure 5.8, 5..9 and 5.10 show the GC-FID and GC-MS m/z 217 traces of the free hydrocarbon fractions and resin and asphaltene hydropyrolysate hydrocarbon fractions of sample 4 (Can 4 is the least biodegraded tar sand sample). The GC-FID traces of the free fraction show that n-alkanes, methylphenanthrenes and most PAH compounds are absent due to biodegradation, and the GC-MS m/z217 traces in Figure 5.9 show that most of the regular sterane content has been removed. Hopanes and tricyclic terpanes are the dominant aliphatic constituents that are visible in the free fraction traces in Figure 5.8, whilst mono- and triaromatic steroids are the principal resolvable aromatic compounds still visible on the GC-FID traces in Figure 5.6, consistent with the other studies on the effects of biodegradation on the aromatic fractions of oils (Connan, 1984) . Chrysenes and phenanthrene, whilst still present, are of low abundance in the free aromatic fraction. Benzo[d]hopanes were also present in the free aromatic fraction but were not observed in either of the aromatic fractions of the resin and asphaltene hydropyrolysis products. These observations are in accord with previous studies of the effects of biodegradation on the Athabasca Tar Sand (Mackenzie et al., 1983; Wardroper et al., 1984; Brooks et al., 1988), and more generally Figures 5.8, 5.9 and 5.10 would suggest that the Athabasca Tar Sand had been subjected to shallow subsurface biodegradation. This is because the pattern of biomarker alteration, degradation of steranes and not hopanes, absence of demethylated hopanes and tricyclic terpanes, matches that seen in many other large heavy tar sand deposits that have been biodegraded in shallow surface or close to shallow surface conditions (Cassani and Eglinton, 1991).
5.3.1.2 Resin and asphaltene fractions

Hydropyrolysis of the resin fraction has generated partially biodegraded biomarker signals and n-alkane GC envelopes (Figure 5.4). The resin aliphatic GC trace shows a series of n-alkanes and small isoprenoid peaks typical of a non-biodegraded oil, however a considerable aliphatic UCM is also present and the resin sterane trace in Figure 5.9 is noisy, attesting to the relatively low quantities of regular steranes generated from the resin fraction. Methylphenanthrenes are present in the aromatic fraction of resin hydropyrolysate, and the chrysenes are far more prominent constituents 157

than in the free aromatic fraction. However, compared to the aromatic compounds of the asphaltene hydropyrolysate, the earlier eluting PAH with 3 or fewer rings seem to have been altered by biodegradation. Higher ring PAH bound into the resin fraction appear to have been better persevered, perhaps representing the survival of highly condensed aromatic macromolecular nuclei at the centre of the macromolecule. Thus it seems that the resin fraction has been partly effected by biodegradation (Peters & Moldowan 1 minor alteration of n-alkanes). The asphaltene hydropyrolysate has a GC envelope typical of that from a nonbiodegraded oil, and in comparison to the resin fraction it has only a small aliphatic UCM (Figure 5.8). Its sterane trace is less noisy and useful for source discrimination and facies evaluation, this is described latter in the discussion of the Athabasca Tar Sand biomarkers. A full range of PAH compounds are also present, and significantly a number of large 5 ring or greater methylated and unmethylated PAH structures are present; benzopyrenes, benzoperylenes and coronene. These compounds have not been reported in previous chemical degradation studies of the structure of the Athabasca Tar Sand asphaltenes (Mojelsky et al., 1992; Strausz et al., 1999). The aromatic UCM is only seen in some samples as already discussed, and based on Figure 5.6 contains both napthalene and tetralin compounds. Other work has shown that a range of other aromatic compounds with a variety of complex alkylation patterns are structural constituents of the Athabasca asphaltene (Payzant et al., 1991; Mojelsky et al., 1992), and that these may also constitute some of the aromatic UCM. The resin and asphaltene fractions hydropyrolysis products have a distribution of aromatic compounds that requires further attention. First the biphenyls, which form a series of peaks that elute early on, could represent desulphurisation products created by the action of the ammonium dioxydithiomolybdate catalyst on dibenzothiophenes and other related compounds that contain intramolecular sulphur and are known to be present in chemical degradation products of the Athabasca Tar Sand asphaltene (Frakman et al., 1990; Peng et al., 1997). Secondly; naphthalene compounds are present in low abundance in the resin and asphaltene hydropyrolysates. In part this is due to the greater dominance of higher ring number PAHs, but preferential loss of the lighter end volatile naphthalene compounds cant be ruled out (either due to trapping inefficiency during hydropyrolysis a liquid nitrogen cooled trap might over come this, or during 158

evaporation of solvent to concentrate products). Thirdly; benzo[d]hopanes are a relatively prominent constituents of the free aromatic fraction but are not present in the resin and asphaltene hydropyrolysates.

C29 S C29 R + S

C27 S

C29 S

C27 R

C29 R

C29 R

C27 R

free
C29 S C29 R + S C29 R C29 R C30 R + S C30 R

C27 S C27 R + S C27 R

C28 R + S C28 R C29 S C29 R + S

resin

asphaltene

time Figure 5.9. Sample Can 4 sterane m/z 217 traces of the free, resin and asphaltene fractions showing 13(H), 17(H) diasteranes, and 5(H), 14(H), 17(H) and 5(H), 14(H), 17(H) regular steranes. (See Figure 5.4 for key).

It can be concluded that even in heavily biodegraded bitumens, such as the Athabasca Tar Sand, hydropyrolysis can regenerate pristine biomarkers, n-alkanes and aromatic hydrocarbons from the asphaltene fraction. The resin fraction also contains useful biomarker information, but this is less protected from biodegradation than the asphaltene fraction. Hydropyrolysis of resins may still be a worthwhile exercise to retrieve biomarker information, especially for samples whose asphaltene contents are low.

159

mono- and triaromatic steroids

C1C & MB[c]P

B[e]Py

Can 1 free ?M B[?] y P B[ghi]Pe

benzohopanes

Fa

Py

Can 1 resin P

Can 4 asphaltene
Unressolved complex alkylation paterns are seen in the less biodegraded samples

Py

DMBP & EBP

MP

M BP

Fa

M Py

C1C & M B[c]P

DMP

B[e]Py

B[ghi]Pe

?MB[???]Pe

elution time

Figure 5.10. GC-FID traces of the aromatic hydrocarbons in the free DCM extract, and resin and asphaltene hydropyrolysates for sample Can 1. Can 4s asphaltene aromatic hydrocarbon hydropyrolysates are also shown for comparison. MBP = methylbiphenyls ; DMBP & EBP = dimethyl -biphenyls & ethylbiphenyls ; P = phenantharene ; MP = methylphenantharene ; DMP = dimethylphenantharene ; Py = pyrene; Fa = fluranthene ; MPy = methylpyrene ; C 1 C & MB[c]P = methylchryesene & methyl-benzo[c] phenantharene ; B[e] Py = benzo[e]pyrene; ?MB[?] Py = benzopyrene with unspecified methyl substitutions; B[ghi]Pe = bezo [g,h,i]perylene; ?MB[???]Pe = bezoperylene with unspecified methyl substitutions; Co = Coronene; MCo = methylcoronene

?MB[???]Pe

Co

Can 1 asphaltene

?M B[?] y P

MCo

160

5.3.2 Biomarker yields The biomarker yields (Table 5.3), suggest that in line with other studies of marginal- to oil-window mature source rocks (Murray et al., 1998), the majority of biomarkers are present in the free fraction. In the absence of kerogen, the resin fraction appears to contain a greater proportion of the bound biomarkers than the asphaltene fractions. Note that this is also the case when the asphaltene fraction constitutes more of the organic matter than the resin fraction, as is the case with sample 9. Thus the relative enrichment of organic matter in recalcitrant asphaltene material by extensive degrees of weathering hasnt served to make the asphaltene fraction the dominant bound biomarker pool. However in general the more weathered samples that have been water washed (samples 7w, 8, 9) do contain more total bound biomarkers than their non-water washed counterparts. This is as a result of the removal of free highly polar compounds (such as acids and phenols) that are soluble in water (Taylor et al., 2001) leading to the relative compositional enrichment of the bitumen in resin and asphaltenes macromolecules that contain covalently bound biomarkers, over non-macromolecular components that coelute with the polar fractions. Table 5.3. Biomarker yields (g/g EOM) obtained from the different fractions
Sample Steranes Hopanes Tricyclics free res asph free res Asph Free Res asph Can 1 nq 5 4 963 8 4 765 13 5 Can 3 nq 4 4 1680 9 7 756 15 7 Can 4 nq 3 2 1303 6 3 570 9 4 Can 6 nq 5 1 1627 8 2 783 19 1 Can 7u nq 33 1 1254 75 3 557 113 2 Can 7w nq 27 8 1478 60 15 540 105 16 Can 8 nq 22 4 1518 43 7 715 80 9 Can 9 nq 12 7 1299 27 15 570 57 17 Dup 7u2 nq nq 1 nq nq 2 nq nq 2 free = free hydrocarbon fraction; res = resin fraction; asph = asphaltene fraction biomarker concentrations ppm EOM, g/g EOM

In summary; the asphaltene fraction contains equal quantities of tricyclic and hopane terpanes, whilst the resin fraction contains greater quantities of tricyclic terpanes. The free fraction contains more hopanes than tricyclic terpanes. There are greater quantities of steranes bound into the resin than asphaltene fraction in line with nature and position of sterane (Kohnen et al., 1991) binding in the geomacromolecule. Diasteranes are only present at significant concentrations in the free fraction (see also Fowler & Brooks, 1987; Chapter 3 and 4).

161

Table 5.4. Sterane biomarker parameters

Composition Composition Maturity Asphaltene Resin asphaltene resin C27 C28 C29 C27 C28 C29 C29 S/S+R Can 1 0.81 0.08 0.12 0.47 0.19 0.34 0.34 0.49 Can 3 0.41 0.20 0.39 0.58 0.08 0.34 0.29 0.50 Can 4 0.40 0.21 0.40 0.56 0.16 0.28 0.30 0.46 Can 6 0.42 0.19 0.39 0.53 0.17 0.30 0.32 0.47 Can 7u 0.35 0.21 0.44 0.51 0.19 0.30 0.33 0.47 Can 7w 0.39 0.20 0.41 0.52 0.21 0.27 0.34 0.48 Can 8 0.38 0.22 0.40 0.38 0.23 0.39 0.34 0.47 Can 9 0.38 0.20 0.42 0.50 0.19 0.31 0.34 0.45 dup 7u2 0.36 0.19 0.45 nd nd nd 0.32 nd Composition; ternary sterane composition using (22R) regular steranes Maturity; maturity parameter using = C29 (20S)/ C29 (20S) + C29 (20R) sterane nd = not determined; dup = duplicate Sample

Table 5.5. Hopane biomarker parameters

C35/C34+C35 C32S/S+R C35S/S+R C30 /+ Free Resin asph free Resin asph Free resin Asph free resin asph Can 1 0.56 0.56 0.56 0.18 0.10 0.24 0.60 0.52 0.51 0.66 0.53 0.56 Can 3 0.54 0.65 0.57 0.07 0.09 0.18 0.59 0.54 0.51 0.60 0.49 0.51 Can 4 0.55 0.63 0.56 0.06 0.09 0.18 0.59 0.56 0.51 0.61 0.54 0.53 Can 6 0.55 0.53 0.51 0.07 0.08 0.17 0.59 0.56 0.52 0.63 0.57 Can 7u 0.54 0.76 0.57 0.07 0.10 0.14 0.60 0.53 0.52 0.60 0.50 0.52 Can 7w 0.53 0.78 0.56 0.07 0.12 0.22 0.59 0.54 0.54 0.62 0.48 0.52 Can 8 0.51 0.75 0.58 0.06 0.09 0.16 0.60 0.55 0.52 0.63 0.50 0.55 Can 9 0.52 0.81 0.54 0.06 0.11 0.16 0.59 0.53 0.54 0.64 0.48 0.55 dup 7u2 nd nd 0.57 nd nd 0.14 nd nd 0.55 nd nd 0.51 C35/C34+C35; proportion of C25 (20S)+(20R) / C25 (20S)+(20R) + C25 (20S)+(20R) hopane C30 /+; maturity parameter = C30 17(H), 21(H)/ C30 17(H), 21(H) + C30 17(H), 21(H) hopanes C32 S/S+R & C35 S/S+R; maturity parameters =17(H), 21(H) (22S)/ 17(H), 21(H) (22S) +17(H), 21(H) (22R) hopane; measured in C35 and C32 hopanes respectively, which are less sensitive to coelution from extended tricyclic terpanes nd = not determined; dup = duplicate; asph = asphaltene Sample

Table 5.6. Tricyclic terpane parameters

Sample C23/C28+C29 C23tri/C30hop Free Resin asph Free resin Asph Can 1 0.49 0.57 0.63 1.60 3.30 2.76 Can 3 0.52 0.59 0.44 0.52 4.73 1.41 Can 4 0.51 0.53 0.50 0.63 3.94 1.85 Can 6 0.51 0.77 0.41 0.71 8.06 0.83 Can 7u 0.51 0.58 0.45 0.55 4.43 1.25 Can 7w 0.43 0.62 0.46 0.45 5.27 1.71 Can 8 0.48 0.61 0.42 0.71 5.59 1.76 Can 9 0.50 0.65 0.44 0.72 7.79 1.66 dup 7u2 nd nd 0.46 nd nd 1.58 C23/C28+C29 = C23 13(H), 14(H) tricyclic terpane/ C28 13(H), 14(H) (S+R) + C29 13(H), 14(H) (S+R) tricyclic terpanes C23tri/C30hop = C23 13(H), 14(H) tricyclic terpane/ C30 17(H), 21(H) hopane nd = not determined; dup = duplicate; asph = asphaltene

162

50

50 asphaltene Sample 3&6 resin

ne

C 29

Rs ter a

Sample 1&4 Sample 7-9

ane ter Rs

25

Sample 1 asphaltene

75

28

100 100 75

C27 R sterane

50

25

Figure 5.11. Ternary plot showing sterane compositions by fraction. The asphaltene and resin fraction contain steranes with different compositions.

5.3.3 Variation in the biomarker composition of the three fractions

5.3.3.1 Steranes

A comparison between the free and bound steranes would be misleading as the free steranes, as noted earlier, have been severely altered by biodegradation. However it is important to highlight that both the resin and asphaltene hydropyrolysis products contain proportions of C21 and C22 pregnanes, as well as C27 to C30 regular steranes with S/R, and structural configurations that are close to that which would have been expected in a non-biodegraded oil that had not had its proportion of steranes relatively enhanced by the selective degradation of isomers (Figure 5.9). The asphaltene fraction contains a lesser proportion of isomers than the resin fraction and also has a C29 (20 S)/(20S)+(20R) parameter value lower than that of the resin fraction; asphaltene values range from 0.29 to 0.34 and resin values between 0.45 and 0.50 (Table 5.4). This suggests that the biomarkers bound into the asphaltene fraction have been sterically protected (Siefert, 1978; Rubinstein et al., 1979) than those bound into the resin fraction, which generally accords with the chemical degradation data reported by other studies of the Athabasca asphaltenes (Peng et al., 1999). Distinct differences also exist in the sterane carbon number distribution of the Athabasca resin and asphaltene fractions. Differences between asphaltene bound and free fraction sterane compositions have previously been reported (Fowler and Brooks,

163

1987). Figure 5.11, a ternary plot of the sterane compositions of the asphaltene and resin fractions, clearly displays these differences as well as the distinctive sterane composition of the samples collected from the sideritic horizons that generally plot close together. These values have a very similar distribution to those from chemical degradation studies (Peng et al., 1999), as opposed to those from hydrous pyrolysis studies which tend to show greater proportions of C27 and C28 (20R) regular steranes (Fowler and Brooks, 1987). This has important significance for correlation studies as discussed latter, and suggests that hydropyrolysis has not cracked or altered sterane carbon number distributions to any great degree.

C30 Hop

C29 Hop

G + TT C33 + C31 S

} C31

C27 Ts C27 Tm

} C32

C31 S

C31 R

SR

C35 R

C35 S

SR

C34 R

C28 Bis

C34 S

free

C32 S & R + C34TT

C29 Hop

C30 Hop

resin

asphaltene
elution time

Figure 5.12. GC-MS m/z 191 traces of sample 4s free, resin and asphaltene fractions. Hopanes are present in all fractions, but different carbon numbers dominate in different fractions. The asphaltene fraction also contains greater proportions of moretanes ( hopanes) than the resin and free fractions. For key see Figure 5.3. 5.3.3.2 Hopanes

Hopanes constitute the main resolvable component of the free fraction, but are only trace constituents of asphaltene and resin hydropyrolysis products. They range from C27 to C35 and include and configurations, although the hopane compound 18,

164

21, - 22,29,30 trisnorhopane (Ts) is not found bound into the asphaltene fraction, suggesting as previously reported (Fowler and Brooks, 1987; Bishop et al., 1998) that it is a diagenetic product that is concentrated in the free fraction. Similarly C 28 28, 30 bisnorhopane, which has not been found in either Athabasca asphaltene chemical degradation or hydrous pyrolysis products (Fowler and Brooks et al., 1987; Peng et al., 1999), is probably not present in asphaltene or resin hydropyrolysis products, although this is harder to prove conclusively due to possible co-elution with C31 extended tricyclic terpanes. Gammacerane is a key indicator compound in the Athabasca Tar Sand and other WCSB oil sand and heavy oil deposits, where its relative prominence on m/z 191 traces has been increased in the free fraction by biodegradation (Brooks et al., 1988). As observed for the hydropyrolysis products of Kimmeridge kerogens (Bishop et al., 1998; Murray et al., 1998) gammacerane is present in resin and asphaltene hydropyrolysates. In the resin fraction hopanes, particularly the C31 to C34 hopane homologues, are very much lesser constituents as compared to the tricyclic terpanes.

17 21 22 S/S+R (H), (H)

free free average 0.70 0.65 0.60 0.55 0.50 0.45 0.40

res res average

asph asph average

31

32

33

34

35

hopane carbon number Figure 5.13. Graph showing increase in 17(H), 21(H) (22S) / 17(H), 21(H) (22S) + 17(H), 21(H) ( 22R) hopane maturity parameter for hopane homologue carbon number and by fraction.

The resin fraction shows considerable enrichment in C35 hopanes (Figure 5.12, Table 5.5), and resin bound C35 hopanes also have an anonymously low (22S)/(22S)+(22R) ratio (Figure 5.13, Table 5.5), this may to some degree represent a more recent less mature and/or biological input, although if this has occurred it is important to note that the biological C35 hopane is not present. Different biomarker pools are dominated by

165

various hopane homologues; the free fraction by C29 and C30 hopanes; the resin fraction by C27Tm and C35 hopanes; the asphaltene fraction by C27Tm, C29 and C32 hopanes. Hopane 17(), 21(H) / 17(), 21(H) + 17(), 21(H) and 17(), 21( H) (22S)/(22S)+(22R) ratios are greatest in the free fraction, lesser in the resin fraction and least in the asphaltene fraction. This suggests that greater steric protection exists for hopanes in the bound fractions but that this steric protection is proportional to the size and cross linking of the macromolecule (e.g. the larger asphaltene molecule offers the most steric protection).

C29 Hop

C30 Hop

TT C28 S&R

TT C25 S&R

TT C26 S&R

Sample 4 free

Sample 4 resin TT C23

TT C29 S&R

TT C24

TT C28 S&R

TT C29 S&R

TT C30 S&R

C27 Tm + TT C30 S&R

TT C23

G + TT C34 +C32 Hop

TT C25 S&R

TT C26 S&R

TT C31 S&R

TT C33 S&R

TT C34 S&R

Sample 7u resin

Sample 4 asphaltene

elution time Figure 5.14. GC-MS m/z 191 tricyclic terpanes. Tricyclic terpanes and, extended tricyclic terpanes in particular are much more abundant in the resin and asphaltene fractions than in the free fraction. For key see Figure 5.3.

5.3.3.3 Tricyclic terpanes

Tricyclic terpanes, like hopanes are a major resolvable component of the free fraction but are only a trace (ppm) component of the resin and asphaltene bound biomarker 166

TT C35 S&R

TT C24

pools.

The

tricyclic

terpanes

of

all

fractions

are

dominated

by

the 13(), 14(H) configuration, but extended tricyclic terpanes up to C36 are only visible in the resin and asphaltene fractions (Figure 5.14). In the case of the later eluting extended tricyclic terpanes, as noted by other workers (Moldowan et al., 1983; McCaffrey et al., 1994), a broadening of the first peak is observed which corresponds to the presence of additional chiral centers on the terpane side chain. C30 tricyclic terpanes are only present in relatively minor concentrations in the free and asphaltene fractions, but appear far more prominent in the resin fraction. In general the resin fraction appears to be greatly enriched in tricyclic terpanes relative to hopanes. 5.3.4 Application of Athabasca Tar Sand bound biomarkers to source correlation There are two views on the origins of the Athabasca Tar Sand (Creaney et al., 1994); one which involves a single Exshaw source for the Athabasca Tar Sand and other associated deposits (Brooks et al., 1988), and another that involves a number of contributions from the many different petroleum systems that are present in the Western Canadian Sedimentary Basin (Allan and Creaney, 1991). Additional factors concerning the tar sands origin are possible contributions from the Wiliston Basin (Leenher, 1984), migration pathways (Graven, 1989), maturation history and timing of biodegradation (Fowler et al., 2001). Quantitative arguments support the Exshaw formation as it is the only WCSB source rock with the areal extent necessary to source the tar sand, heavy oil and bitumen deposits (Fowler et al., 2001). If it wasnt for the heavy biodegradation undergone by many of the tar sand deposits, it would be a simple matter of comparing key biomarker parameters of the Exshaw and Athabasca Tar Sand to prove a correlation. To try and overcome the effects of biodegradation on free biomarkers, asphaltene bound biomarkers have been investigated (Fowler and Brooks, 1987; Jones et al., 1988). These confirm many genetic associations to a certain extent, but can only go so far due to pyrolysis artefact and the inherent differences in biomarker composition between bound and free biomarkers, e.g. sterane composition, dominant hopane carbon number and the level of thermal maturity denoted by biomarker maturity parameters. It is important to bear this in mind when interpreting the bound biomarkers of this study. For example the absence of diasteranes in the resin and asphaltene fraction doesnt imply

167

that the Athabasca Tar Sand (to any significant degree) was sourced by the Nordegg formation, for which the absence of diasteranes is a distinctive biomarker trait in the WCSB (Allen and Creaney, 1991) this is a normal feature of bound steranes (Seifert, 1978). However the absence of key indicator biomarkers, which are normally present in both bound and free fractions, can still be very useful in assigning a geochemical biomarker fingerprint to a biodegraded oil in which free aliphatic biomarker data has been altered or destroyed. Important geochemical fingerprints are, the presence of gammacerane, the particularly low level of C28 sterane (which in Figure 3.4 in Chapter 3 and Figure 5.11 in this chapter is seen to vary little between fractions) and the presence of C30 sterane. The presence of C30 steranes suggest, that even though gammacerane is present, the source rock was deposited in marine conditions although it may have received organic matter inputs from a hypersaline environment. Additionally, the low proportions of C28 steranes constrain the source rock to a Lower Palaeozoic age, as after this period C28 steranes become far more prominent in oils and source rock bitumens (Grantham and Wakefield, 1988). There are a number of Lower Palaeozoic source rocks in the WCSB and their characteristics are listed in Table 5.7. Even if quantitative arguments based on the areal extent of mature source rock subcrops are ignored, the lack of prominent extended tricyclic terpanes in the Duverney, and absence of gammacerane in the Cynthia, makes it unlikely that these formations could have made any quantitatively significant contributions that are large enough to be discerned using a non-quantitative or statistical analysis of fossil lipid and biomarker data.

168

Table 5.7, WCSB source rock biomarker characteristics (based on published data for source rock extracts and oils)
Duverney Cynthia Exshaw WCSB Bakken Williston Doig Nordeg Colorado group Age Devonian Devonian Devonian " Triassic Jurassic Cretaceous Sterane 27 = 29 27 < 29 27 << 29 27 >= 29 27 = 29 27 >= 29 28 > 29 > 27 hop/tri low tri/hop low tri/hop bisnorhopane nobisnorhopane little 35 hop high hop/tri 35 >>34 hop 29>= 30 hop low tri/hop ETT N C33 + C34 + " C33 + N N Gammacerane Y N Y " Y Y N C30 tri N Y lots Y little Y Y N N small

Athabasca Tar Sand Free

35 = 34 C34 + Y Y little bisnorhopane Resin Na 27 > 29 35 > 34 C34 + Y Y lots tris >> hops Asphaltene Na 27 =< 29 35 =34 C34 + Y Y lots tris = > hop Sterane: sterane characteristics based on R steranes. * For the Athabasca Tar Sand this was calculated using Figure 5.15. hop/tri : general characteristics of the terpane distributions including; tri/hop = amount of C23 tricyclic terpane compared to C30 hopane on m/z 191 trace; absence or presence of C28 17(H), 21(H) bisnorhopane; 35 > 34 = proportion of C35 to C34 17(H), 21(H) 20 S & R hopanes. ETT: extended tricyclic terpanes visible on m/z 191 trace; N = not present; C33 + = tricyclic terpanes upto C33 are present; C34 + = tricyclic terpanes upto C34 are present Gammacerane: Y= present; N= not present C30 tri: C30 tricyclic terpanes; Y = prominent, N = not very prominent Based on source rock extract and oil data in Leenheer, (1984); Allan and Creaney, (1992); Creaney et al., (1994).

Na

27 << 29*

The Wiliston Basin Bakken formation, an Exshaw equivalent situated to the south of the WCSB, had been proposed a potential contributor to the Alberta tar sands (Leenheer, 1984). However, based on the absence of C28 28, 30 bisnorhopane, Brooks et al. (1988) ruled out the Bakken as a contributor instead preferring the WCSB Exshaw formation. However C28 28,30 bisnorhopane while present in many Exshaw sourced oils, is absent or of very low prominence on the m/z 191 trace of a conventionally Exshaw sourced oil in Allan and Creaney (1991). Thus the Bakken might not necessarily be ruled out as an Athabasca source on the strength of this single biomarker characteristic. A reconstructed sterane composition, calculated using data from other hydropyrolysis studies (see Table 5.8), suggests that the Athabasca Tar Sand would have had a sterane composition in which C29 steranes were more prominent than

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C27 steranes. This is a feature consistent with many other less biodegraded Mississippian, Jurassic and Cretaceous reservoired oils sourced by the Exshaw formation (Fowler et al., 2001). The Bakken (Leenheer, 1984; Creaney et al., 1994) and Lodgepole (Creaney et al., 1994) formations are quantitatively of a similar size and are depositional equivalents to the Exshaw formation, but they do not show the same C29 over C27 sterane prominance that the Exshaw formations does, thus they are not a likely sources for the Athabasca Tar Sand or did not make as great a contribution as the Exshaw. The possibility of major contributions from other non-Exshaw sources remains, but it can only be concluded that these have been very slight in the case of the Athabasca Tar Sand and have left no distinctive biomarker finger print.
0.6 0.55 Free C29 20 S/S+R 0.5 0.45 0.4 0.35 0.15 0.25 0.35 0.45 Asphaltene C29 20 S/S+R 0.2 0.2 0.5 y = 0.6053x + 0.291 R2 = 0.9385 r = 0.7 0.4

% sterane in free hydropyrolysate

0.3 r = 0.81

0.3 0.4 0.5 % sterane in asphaltene hydropyrolysate

0.6

Figure 5.15. Jet Rock data used to reconstruct non-biodegraded sterane parameters in Table 5.8.

% C27 R sterane

% C29 R sterane

Calculating a maturity for the Athabasca Tar Sand based on sterane parameters is not straight forward as in this study both diasterane and regular sterane (20S)/(20S+20R) parameters have been altered by biodegradation. Hopane % (22S)/(22S+22R) maturity parameters appear to be at, or very close to equilibrium values showing only that the source rock had passed the threshold of oil generation (Ro% ~ 0.68). The moretane hopane maturity parameters (hopane / + ) would place the Athabasca source further into the oil window, but an exact position is hard to deduce as this parameter can be influenced by facies effects (Hoffman et al., 1984). The steranes in the resin and asphaltene hydropyrolysates are unaffected by biodegradation, but these would be expected to be considerably less mature than their free counter parts. This is a consequence of the steric protection of covalently bound biomarkers in macromolecules (Seifert, 1978; Murray et al., 1998), which preserves thermally sensitive biomarkers 170

further into the oil window, but means that parameters measured in the biomarkers of various fractions can not be directly compared. One way to overcome this is to use another dataset to convert or change bound biomarker parameters to a free equivalent. Based on sterane % (22S)/(22S+22R) parameters measured in the hydropyrolysis products of different fractions (Murray et al., 1998; Jet Rock), the free fraction might be expected to have a value that is closest to that of the resin fraction, but considerably higher, e.g. at least 50 % and definitely more. Using a straight line model based on a regression analysis of Jet Rock data to predict what free sterane C29 % (20S)/(20S+20R) values would have been produces the values shown in Table 5.8. Although these values (average 49 to 50 %) seem rather low equating to a vitrinite reflectance value of Ro% 0.8-0.9, this may be because of facies differences between the Jet Rock and Athabasca Tar Sand, a non-linear relationship between the free and asphaltene % (20S)/(20S+20R) parameter at higher values, or the non-comparability between source rock and reservoired oil data. This still places the Athabasca source a third of the way through the oil window, a position generally in accord with moretane/hopane parameters (C30 /+ hopane). The Athabasca Tar Sand was generated from a mature source approaching the middle of the oil window. Table 5.8. Reconstructed free fraction sterane biomarker parameters
% (20R) sterane composition C29 Sterane C27 C28 C29 SUM % (20S)/(20S+20R) Can 1 nd nd nd nd nd Can 3 32 25 43 100 47 Can 4 32 26 43 100 47 Can 6 33 24 43 99 48 Can 7u 31 26 44 101 50 Can 7w 32 25 43 100 50 Can 8 32 27 43 101 51 Can 9 32 25 44 100 50 dup 7u2 31 24 45 100 48 % (20S)/(20S)+(20R) = 100 X C29 (22S)/ C29 (22S) + C29 (22R) steranes nd = not determined; SUM = the sum of the calculated C27, C28 and C29 steranes. This should equal 100%, the slight deviance from this value is of use in assessing the robustness of the relationships in Figure 5.15.

5.4 Conclusions

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The samples of the Athabasca Tar Sand examined in this study contain organic matter which shows evidence for anaerobic biodegradation, waterwashing and surface oxidation (and aerobic biodegradation). The effects of these processes were identified using biomarker ratios, bitumen composition and ratios based on aromatic compounds present in the hydropyrolysis products. These ratios and parameters were used to rank the samples and then deduce if the sequence was the same for the each process. It was not, and this can be taken as evidence that these processes may operate semiindependently of each other and can proceed to differing extents in the same sample. The aliphatic constituents that are covalently bound into asphaltene macromolecules appear to be resistant to biodegradation and the other weathering processes. Hydropyrolysis can be used to regenerate biomarkers from the asphaltenes of heavily biodegraded tar sands. The biomarkers that are covalently bound into the resin fractions appear to have been slightly altered by biodegradation but to a much smaller degree than those of the free fraction, thus they would be a second choice for biomarker information for correlation purposes. Biodegradation has concentrated hopanes in the free fraction to such a degree that they are now a major GC resolvable component of the bitumen, regular steranes have been removed from the free fraction and thus their concentration relative to the total extractable organic matter has increased in the resin and asphaltene fractions. Biomarker data in the asphaltene hydropyrolysates suggests that the source of the Athabasca Tar Sand was marine, with inputs from a hypersaline environment. The predicted free sterane composition contained low amounts of C28 sterane consistent with a Palaeozoic source, and greater proportions of C29 than C27 sterane consistent with the Exshaw biomarker characteristics described by Creaney et al. (1994). Maturity data suggests that the source was early to mid mature, approximately a third of the way through the oil window.

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