Chapter 4 Fraction bias in the stratigraphic signals of different organic geochemical fractions of the Jet Rock 4.

1 Introduction to molecular stratigraphy using bound biomarkers

Molecular stratigraphy is concerned with characterising sedimentary strata by the use of the organic molecules that they contain (Brassell et al., 1986). These organic molecules provide information that can be used to infer or measure climatic conditions, the nature and type of biological productivity and distinguish the sources that have contributed to the organic matter in sediments and sedimentary rocks. Molecular stratigraphy can also be applied in a sequence stratigraphic framework (Robinson and Engel, 1993), which requires interpreting changes in biomarker compositions and concentrations in the context of changes in relative sea level. Bound biomarkers are biomarkers that are covalently bound into geomacromolecules, but unlike the routinely analysed biomarkers in the free hydrocarbon fraction they cant be analysed by chromatography alone. A degradation or pyrolysis method is required to break apart the large kerogen, asphaltene and resin molecules and convert the biomarkers into hydrocarbons that are amenable to analysis by gas chromatography and gas chromatography-mass spectrometry (Rullktter and Michaelis, 1989). Hydropyrolysis is unique amongst the pyrolysis and degradation methods available because it yields large quantities of biomarkers from resin, asphaltene and kerogen feedstocks, whilst still preserving the thermally-sensitive structural configurations of biomarkers (Love et al., 1995). This study has applied hydropyrolysis to all four fractions of the sedimentary organic matter of the Jet Rock, in effect creating four biomarker records for the same 8m section of the Jet Rock; one free biomarker record corresponding to the free hydrocarbon fraction recovered after solvent extraction, and three bound biomarker records corresponding to the hydrocarbon fractions of the hydropyrolysis products of the resin, asphaltene and kerogen fractions. One important facet of the bound biomarker data obtained by treating different fractions with a variety of pyrolysis and degradation methods is that it has often been reported as better representing stratigraphy (Schaefer et al., 1998) or biogenicity (Love et al., 1998) 1

than biomarker data obtained by analysis of the solvent-extracted free hydrocarbon fraction. This could be because bound biomarker data is obtained from the fractions that better resist contamination by other fluids (e.g. kerogen is immobile and hence easily cleaned from contamination by solvent extraction), because bound biomarkers have more resistance to biodegradation (Rubinstein et al., 1979), or because macromolecular material constitutes a greater part of sedimentary organic matter and is therefore more representative quantitatively. In certain instances bound biomarker data will be the only molecular stratigraphic tool available. However, even when this isnt the case the question is; do the bound biomarkers of one fraction offer a better stratigraphic description than those in another, and are bound biomarkers better than free biomarkers at describing stratigraphy? Another important facet of bound biomarker data is the extent to which the biomarker signals are interchangeable or different from one another. This can only be addressed by measuring and comparing the signals in each fraction. Whatever the reason for bound biomarker data better representing stratigraphy or biogenicity, some measure of a good or correct stratigraphy or biogenicity is needed in the first instance to which the different biomarker records can be compared. For example the Goynuk oil shale bound biomarker data obtained by various degradation methods were compared to optical data, and the 13C isotope ratios of n-alkanes released by hydropyrolysis were found to match the optical the data best (Love et al., 1998). In this study biomarker data has been compared to two quantitative measurements of stratigraphy; TOC and bulk sulphur.

4.2 Bulk geochemical parameters (% TOC and % Sulphur) as environmental proxies

Bulk proxies of palaeoenvironment are well understood, widely accepted and routinely applied (Myers, 1997). For this reason they make a cheap to acquire but good quantitative measure of stratigraphy, to which biomarker data can be compared. One bulk proxy based model, applicable to ancient mudstones and source rocks, is the High TOC Based model (HTB model) (Creaney and Passey, 1993). Many source rocks possess TOC values that rise and fall many times across a given interval creating a

series of nested TOC cycles (Creaney and Passey, 1993). TOC is controlled by productivity, preservation potential and the degree of dilution by inorganic sediment. Such a model is graphically illustrated in Figure 4.1.

terrestrial input to UMSF large part of shelf and UMSF at or above wave base

sea level

terrestrial input to UMSF large part of shelf and UMSF at or beneath wave base

sea level

terrestrial sediments are transported to distal regions of basin

little, if any transportation and deposition of terrestrial sediments in distal region of basin

Figure 4.1. During periods when sea level is low shelf sediment is at wave base and mobile in basin, rates of organic matter dilution are high hence TOC values are low. When sea level is high, shelf sediment is beneath wave base and little dilution occurs, TOC levels will be high. The terms maximum flooding surface, and sequence boundary have not been used, as in this study this model has been applied at the parasequence and not sequence scale.

During periods of high sea level most sediment (terrestrial in origin) is locked up in the upper shore face and shelf areas. Here it is submerged beneath the most frequent storm base and not transported to the most distal regions of a basin, where organic matter will be deposited without dilution from inorganic sediments, hence the TOC values of mudstones deposited during this time are high (see right hand side of Figure 4.1). Conversely, when sea levels are low there is a larger input of inorganic sediment to the distal regions of basins, and TOC values of mudstones deposited during these periods of time will be lower (Pasley et al., 1993). These high TOC based cycles need not only be considered as being present at a sequence scale alone and, could in theory at least, be used as relative measures of sea level within a smaller scale or interval, for example the sub-sequence sampling interval used in this study. Sulphur vs TOC models, which have been well understood for some time, can also be used to infer euxinic conditions in the sedimentary record (Raiswell and Berner, 1985). In general, mudstone intervals with high bulk sulphur are most likely to indicate anoxic sulphide-rich depositional environments with high preservation potential and high TOC. Euxinic episodes such as this are most likely to occur during the decoupling of surface from bottom waters during periods of high sea level when the water column is at its most stratified (Saelen et al., 2000). The two models, based on TOC and bulk

sulphur outlined above, will be used to form a stratigraphic description of the Jet Rock to which biomarker data will be compared.

4.3. Jet Rock stratigraphy

A simple lithological stratigraphic division of the Jet Rock is shown on the left hand side of Figure 4.2 (based on Howarth, 1969). This divides the Jet Rock into a number of beds based on lithology and varying concretion styles. Fourteen samples were collected across the interval shown in Figure 4.2, and their TOC and bulk sulphur measured. Odd numbered samples and sample 6 were selected for further study by hydropyrolysis of their macromolecular fractions (kerogen, asphaltene and resin fractions) see Chapter 3. 4.3.1 Sequence stratigraphic significance and Maximum Flooding Surface (MFS) position Nested TOC cycles are clearly visible in Figure 4.2, and are approximately 2 to 3 m in thickness. These HTB cycles are often outside the boundaries of the beds of Howarth (1969), this is because the bed boundaries of Howarth are based on physical features and compositional changes that can be identified in the field, where as the term bed in sequence stratigraphy refers to discrete units of rock or depositional events (van Wagoner, 1990). In mudstones depositional units are single laminae, typically a mm thick (Macquaker and Taylor, 1996; Macquaker and Howell, 1999); in Figure 4.2 it can be observed that the depositional events that correspond to variation in the composition of the organic matter cut cross the traditional or lithostratigraphic beds of Howarth. At 3 m the cycle length is more suggestive of a parasequence set than a single parasequence (individual parasequences would be expected to be between a quarter to a half of this length) and so the possibility exists of further cyclical variation below the sampling frequency of this study. Two maximum flooding surface (MFS) positions are proposed in current literature. One is concurrent with bed 40 and represents a regionally extensive limestone horizon that underlies bed 41 (Wignall, 1993). The other position, based on more recent bulk chemical, isotopic and microscope data has revised the MFS to bed 35, a condensed section with very high TOC levels (Saelen et al., 2000). This chapter doesnt aim to

address the placement of a MFS but in order to be internally consistent to the High TOC Based model will assume that there is an average fall in sea level across the section from sample 12, which has the highest TOC, to sample 1 which has the lowest.

TOC % 0 1 2 3 depth m 4 5 6 7 8
Group I lowest sea level

S%
15 0 2 4 6 8

10

41

HTB cycle

38 37

35
shading key
Group II falling sea level Group III highest sea level

Figure 4.2. Stratigraphy and bulk parameters. The beds are numbered after Howrath (1969) and sample location are denoted by squares. Arrows represent high TOC based (HTB) cycles, and dashed arrows are inferred HTB cycles only measured in part. The shading refers to the facies groups referred to in the text. TOC% = % Total Organic Carbon; S% = Bulk sulphur %

4.3.2 Distinguishing facies groups using High TOC Based (HTB) cycles Each HTB cycle represents a rise and fall in sea level, and based on this interpretation the samples of this study can be classified as one of three facies. Three out the eight samples that were selected for biomarker analysis are found at the base of a cycles have the highest TOCs these are high, or maximum sea level facies. Four out of the eight samples selected for biomarker analysis belong to a facies deposited in periods of falling sea level and are found in the middle of cycles, these are the intermediate sea level facies. Sample 1 is placed in a facies group that represents the lowest sea level 5

position of the section studied. This is for a number of reasons including its much lighter colour, distinctive bitumen composition with a high aromatic yield and low hydrogen index. All references to sea level in this study are relative and it should be noted that these facies groupings are only valid for this study and the length and frequency of sampling used. These same facies groups are also partially delineated by bulk sulphur levels (Figure 4.2). This would be expected given that sulphur is well known to correlate to TOC in the Jet Rock (Raiswell and Berner, 1985). It is important to note that sulphur and TOC maxima are at different depths, the top of beds 37 and 35 respectively, and this perhaps suggests that minimum dilution by inorganic sediment, and the most persistent sulphide deposition and dysoxic conditions did not occur at the same time. The mudstones of the Jet Rock have been proposed to have been deposited in an anoxic water column (Morris, 1974; Raiswell and Berner, 1985; Farrimond et al., 1989; Saelen et al., 2000). However, biomarker confirmation in the form of isorenieratane, or its diagenetic products have never previously been conclusively reported. This study has found alkyl tetramethyl-benzene compounds ranging in carbon number up to the C23 homologue in all fractions of all the samples, and isorenieratane was found in many of the samples (see Chapter 3, Figure 3.11-3.13). This suggests that much of the Jet Rock must have experienced euxinic conditions extending into the photic-zone, whether or not these were episodic or persisted thoughout the entire section is discussed in Chapter 3, although it would seem most likely that they were persistent in the upper beds, and that the extent of euxinic conditions varied most during a short interval during the deposition of the lower beds. 4.3.3 Summary of Jet Rock stratigraphy The Jet Rock member of the Whitby Mudstone Formation must contain many parasequence sets, some of which have been sampled during this study. Parasequence sets are reflected in TOC data that mirrors the associated rise and fall in relative sea level (Figure 4.1). As the TOC values of samples from similar positions in different cycles have similar values, it is assumed that they were deposited under similar conditions (e.g. sea level, and euxinic conditions) and so form a facies group in each instance. The biomarker data of the bound and free fractions will be analysed to see if it 6

falls into these groups by correlating and comparing it to the TOC and bulk sulphur data.

4.4 Aliphatic biomarker data

4.4.1 Different methods of data analysis To reflect the different ways of viewing and interpreting geochemical data, the biomarker data in this thesis has been presented in tables of data, cross-plot matrices and stratigraphic plots. Each method has its own assumptions, benefits and drawbacks as noted in the following sections.
4.4.1.1 Statistical approach

A purely statistical interpretation looks for a significant correlation coefficient between the bulk data and a biomarker parameter, and where present this suggests that the biomarker concerned is a good measure of stratigraphy. Although this method of interpretation is non-arbitrary, it is over simplistic. Furthermore, as the sample size is so small (typically n < 8), the removal of any outlying samples could greatly alter whether a fractions biomarker data appears to represent stratigraphy or not. As removing outlying data is an arbitrary decision, doing so negates the initial advantage of this method. A trend and hence correlation would only result where a smooth continuous transition in a biomarker parameter occurred from the base of a cycle to its top (e.g. smooth change in sea level or mixing of two end member components), or where discrete clusters of data approximated a straight line. Where this isnt the case, a nonlinear trend might be missed and a good stratigraphic indicator missed.
4.4.1.2 Geochemical approach

Cross plot matrices, as well as providing a quick method for screening data when looking for correlations, can also combine facies group information and be used to look for clusters of data rather than for a continuous trend. This is a common method often used in geochemistry, including petroleum geochemistry correlation studies, sediment provenance studies and melt source studies in igneous petrology. The existence of these clusters can be further supported by T-tests, ANOVA or a suitable non-parametric method. However, the low number of samples in this study would complicate such testing, e.g. there is only one sample of facies group 1.

4.4.1.3 Geological approach

Stratigraphic plots are a geological tool often used for the lateral correlation of geological horizons (as opposed to the X-Y statistical correlation mentioned above), which is normally done visually by the identification of crests and troughs and/or minima and maxima. In this study the various biomarker parameters of each fraction could be correlated to the bulk parameters, each other and the simple lithological cross section in Figure 4.2. Hence, although the visual comparison of stratigraphic plots is common in geochemistry, it is the most arbitrary method but the most flexible and sensitive to geological factors.

C29 S dia & C27 R +S

C27 S dia

C27 R dia

C29 R dia

C27 R

C27 S

C28 R C29 S C29

C29 R

1
C30 R C30

0 1 2 3
depth m

RS

RS

3 5 6

41

4 5 6 7 8

38 37 35

7 9 11 13
time

C28 R C29 S C29 +

C27 R

Figure 4.3a. GC-MS m/z 217 traces of the free aliphatic fractions showing sterane distribution and the stratigraphic position of samples. It is difficult to distinguish the facies groups identified in Figure 4.2. 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
C27 S C29 R C30 R

1 5

0 1 2 3
depth m

41

4 5 6 7 8

38 37 35
time

7 9 11

Figure 4.3b. GC-MS m/z 217 traces of the resin hydropyrolysate aliphatic fractions showing sterane distribution and the stratigraphic position of samples. Little stratigraphic information can be gained from the traces, diasteranes probably represent occluded free compounds. For key see Figure 4.3a.

C27 R

C28 R C29 S C29

C27 S

C29 R

C30 R

0 1 2 3
depth m

41

5 6

4 5 6 7 8

38 37 35

7 9 11 13
time

Figure 4.3c. GC-MS m/z 217 traces of the asphaltene hydropyrolysate aliphatic fractions showing sterane distribution and the stratigraphic position of samples. Visual inspection of the asphaltene fraction GC-MS traces allow some visual distinctions to be made between samples at the top of section with higher inputs of terrestrially derived C29 sterane, and samples from lower down that are more marine influenced. For key see Figure 4.3a.
C27 R C29 S C29 C29 R C27 S

C28 R

C30 R

0 1 2 3
depth m

1 3 5

41

4 5 6 7 8

38 37

6 7 9

35

11 13
time

Figure 4.3d. GC-MS m/z 217 traces of the kerogen hydropyrolysate aliphatic fractions showing sterane distribution and the stratigraphic position of samples. Little stratigraphic information can be gained from the traces, although C30 steranes are clearly resolved in every sample. For key see Figure 4.3a.

10

C30 C30

C29 Ts C29 C27 Ts C27 Tm

C31

C32

C33

C34 SR

C29

SR

SR

SR

SR

TT C25 S&R

TT C28 S&R

TT C29 S&R

1 2 3
depth m

41

4 5 6 7 8

38 37 35

TT C26 S&R

TT C23

0
TT C21 TT C22

time

Figure 4.4a. GC-MS m/z 191 traces of the free aliphatic fractions showing hopane and tricyclic terpane distributions and the stratigraphic position of samples. As with the steranes it is difficult to distinguish the facies groups identified in Figure 4.2 by visual inspection of traces alone. TT C 23 = C23 13(H), 14(H) tricyclic terpane (note various tricyclic terpane isomers are not individually labeled); C27Ts = C27 18(H)-22, 29, 30-trisnorneohopane; C27 Tm = 17(H)-22, 29, 30trisnorhopane; 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.
C30 C30 C31 C32 C33 C29 C34 SR C27 Tm C35 SR

TT C29 S&R

TT C24

SR

SR

SR

TT C31 S&R

TT C30 S&R

TT C33 S&R

TT C34 S&R

TT C25 S&R

TT C26 S&R

1 2 3
depth m

41

4 5 6 7 8

38 37 35

Figure 4.4b. GC-MS m/z 191 traces of the resin hydropyrolysate aliphatic fractions showing hopane and tricyclic terpane distribution and the stratigraphic position of samples. The proportions of extended tricyclic terpanes discriminate the samples from the base and top of the HTB cycles identified in Figure4.2.

TT C29 S&R

TT C35 S&R

TT C22

TT C24

TT C28 S&R

TT C23

C35

11

C27 Tm

C29 C29 C30 C30

C31

C33

C34 SR

C32

SR

SR

SR

0
TT C25 S&R TT C26 S&R TT C28 S&R TT C29 S&R TT C21 TT C22 TT C24

41

2 3
depth m

4 5 6 7 8

38 37 35

TT C23

time

Figure 4.4c. GC-MS m/z 191 traces of the asphaltene hydropyrolysate aliphatic fractions showing hopane and tricyclic terpane distribution and the stratigraphic position of samples. Little stratigraphic variation can be visually identified on the traces.
TT C25 S&R TT C26 S&R TT C28 S&R TT C23 C31 S&R C29 C29 C30 C30 C32 C31 C34 SR C27 Tm C33 C35 SR TT C21 TT C22 TT C24

TT C29 S&R

SR SR

SR

0 1 2 3
depth m

41

4 5 6 7 8

38 37 35

time

Figure 4.4d. GC-MS m/z 191 traces of the kerogen hydropyrolysate aliphatic fractions showing hopane and tricyclic terpane distribution and the stratigraphic position of samples. Little stratigraphic variation can be visually identified on the traces, aside from the more prominent C 31 and C32 moretanes (17(H), 21(H) hopanes) in sample 1.

C35 SR

12

4.4.2 Biomarker ratios and proxies In general, no obvious changes in facies can be picked out by visual inspection of the GC-MS traces alone, although a few exceptions to this need to be noted. There is a larger proportion of C29 sterane in sample 1s free and asphaltene fractions than in the samples underneath, similarly a distinction might be drawn between sample 5 and 6 based on the greater proportion of C29 sterane in sample 5s kerogen hydropyrolysate (Figure 4.3a-d). These observations can be explained by greater inputs of terrestriallyderived C29 sterane (Grantham and Wakefield, 1988; Peters and Moldowan, 1993) to facies group I, than to group II in the case of sample 1 and 3, and greater inputs of terrestrially-derived C29 sterane to facies group II than to group III in the case of samples 5 and 6. In each instance these differences correspond to the tops of HTB cycles identified in Figure 4.2, e.g. the periods of lowest sea level within each HTB cycle. C31 and C32 moretanes (hopanes with the 17(H), 21 (H) structural configuration), which have also been associated with terrestrially-derived organic matter (Hoffman et al., 1984), are more abundant in sample 1s kerogen fraction hydropyrolysate than in any other fraction. This along with sample 1s vastly greater proportions of PAH in its kerogen pyrolysis products would support increased terrestrial input to this sample, perhaps representing the products of forest canopy fires or oxidation of sedimentary organic matter during transport. These observations, along with the low Hydrogen Index (HI) and distinctive aromatic-rich bitumen composition (see Table 3.3 and 3.3 in Chapter 3), also further justify the singling out of this sample as a separate facies group. Extended tricyclic terpanes have an uncertain origin, but have been associated with C40 polyprenol precursors present in Tasmanities algae (McCaffery et al., 1994). The m/z 191 traces of the resin hydropyrolysates show an inverse distribution to that of the C29 steranes, e.g. low amounts in sample 1, and greater amounts in sample 5 than 6, suggesting a proportionally lesser input from algae to samples collected from the top of parasequences/ HTB cycles; i.e. the periods of lowest sea level. However as discussed in Section 3.3.7 (Chapter 3), it is also possible that some of the hopanes in the resin fraction may represent hopanes from the free hydrocarbon fraction that co-precipitated with the resin fraction during sample preparation.

13

However, because trends were generally difficult to discern from the GC-MS traces alone, peak areas were used to calculate a number of biomarker parameters. Many of the parameters showed a similarity to the results obtained by Principal Component Analysis (PCA). Their meaning and interpretation is discussed along with that of the principal components in Section 4.4.2. Ternary plots of sterane carbon number composition, a frequently used method for discriminating different facies in oils and source rocks (Peters and Moldowan, 1993), appears to discriminate the three facies in some of the fractions. The free fraction data cluster close together but separate out into the three facies (Figure 4.5a), whilst resin and kerogen sterane compositions (Figure 4.5b and 4.5d) do not distinguish the three facies clearly.

50
e t er an

6a) free

50
ne C 29 R

50

6b) resin

50
C 29 R

Rs

25

Rs

ter a

ste ran

ste

75

25

28

0 75

50
C27 R sterane

25

100 0

0 75

28

75

ran

50
C27 R sterane

25

100 0

6c) asphaltene
50
e t er an

6d) kerogen
50
ne C 29 R

50

50
C 29 R

Rs

25

Rs

ter a

ste ran

ste

75

25

28

0 75

50
C27 R sterane

25

100 0

0 75

28

75

ran

50
C27 R sterane

25

100 0

shading key

Group I lowest sea level

Group II falling sea level Group III highest sea level

Figure 4.5a-4.5d. Sterane ternary diagrams constructed from C27 C29 5(H), 14(H), 17(H) 20R steranes. Only the free and asphaltene sterane ternary diagrams discriminate facies clearly. The asphaltene-bound biomarkers seem the most sensitive and disperse well along the C27 axis. For facies codes see Figure 4.2

14

The best stratigraphic description is offered by the asphaltene fraction, whose data plot along the C27 sterane axis clearly discriminating the three facies observed in the TOC data (Figure 4.5c). Free and asphaltene-bound C27 and C29 sterane data correlate well with each other and to bulk sulphur levels (but not TOC) (Table 4.1), and their cross plots also discriminate different facies in a similar manner (Figure 4.6) e.g. the most marine sample has the least C29 steranes which are predominantly derived from higher plants, and the most C27 steranes which are derived from algae. Stratigraphic peaks appear in the same places as those of the TOC data (Figure 4.7), although the crests do not and are not always of the expected magnitude (which may represent the limit of analytical precision).
1.30 1.20 1.10 1.00 0.90 0.80 0.70 0.60 0.50 0.40 0.0 I free II free III free I kerogen II kerogen III kerogen 1.30

Hopane / Sterane

Hopane / Sterane

1.20 1.10 1.00 0.90 0.80 0.70 0.60 0.50 0.40 0.0 I free II free III free I kerogen II kerogen III kerogen

2.0

4.0

6.0

8.0

5.0

10.0

15.0

% bulk sulphur
50 45 40 35 30 25 20 15 10 5 0 0.0 18 16 14 12 10 8 6 4 2 0 0.0

% TOC

% C27 R sterane

I free II free III free I asphaltene II asphaltene III asphaltene

Hopane C29-30/ C23 tri

I asphaltene II asphaltene III asphaltene

2.0

4.0

6.0

8.0

5.0

10.0

15.0

% bulk sulphur

% TOC

Figure 4.6. Cross plots of various biomarker parameters measured in different fractions. Different biomarker parameters differentiate facies best in different fractions. TOC= % Total organic carbon; Sulphur = sample % Sulphur; %C 27 R sterane = % of C27 5(H), 14 (H) 17(H) 20 R sterane/ sum C27 to C29 5(H), 14 (H) 17(H) 20 R sterane; Hopane C29-30/C23 tri = sum C29 to C30 17(H), 21 (H) + 17(H), 21(H) hopane / C23 13(H), 14(H) tricyclic terpane; Hopane/Sterane = C29 to C30 17(H), 21 (H) + 17(H), 21(H) hopane / sum C27 to C29 5(H), 14 (H) 17(H) 20 R sterane. For facies codes see Figure 4.2

Hopane/sterane ratios have previously been reported as corresponding well to sequence stratigraphic interpretations (Robinson and Engel, 1993). Here the free hopane/sterane parameter correlates well with TOC, and this can be observed in both stratigraphic 15

section and in a cross plot (Figure 4.6, 4.7 and Table 4.1). The kerogen hopane/sterane ratio has some degree of similarity to the TOC trend stratigraphically (Figure 4.7), but this is not great and isnt confirmed by a statistically significant correlation coefficient (Table 4.1). Only in the asphaltene fraction do bound hopane/tricyclic ratios reflect the different facies clearly, as well as showing a significant statistical correlation coefficient to the TOC data (Table 4.1, Figure 4.6, Figure 4.7). In summary, the biomarker ratios presented in this study appear to reflect stratigraphy best in the free and asphaltene fractions where they most closely correlate, and correspond to the TOC data and the three facies groups.

16

Hopane/Sterane %C27 R sterane %C29 R sterane

%C28 R sterane Hopane C 29-30/ C23 tri

TOC %

Sulphur %

0 2 4 6 8 asphaltene 0 2 4 6 8 kerogen 8 6 4 2

free 0

resin

depth m 0 2 4 6 8

depth m

17

Figure 4.7. Stratigraphic plots of biomarker parameters, note that TOC & sulphur data are available for more samples than are biomarker data. TOC= % Total organic carbon; Sulphur = sample % Sulphur; %C 27 R sterane = % of C 27 5(H), 14 (H) 17(H) 20 R sterane/ sum C 27 to C 29 5(H), 14 (H) 17(H) 20 R sterane; Hopane C 29-30 /C23 tri = sum C 29 to C30 17(H), 21(H) + 17(H), 21(H) hopane / C23 13(H), 14(H) tricyclic terpane; Hopane/Sterane = C 29 to C30 17(H), 21(H) + 17(H), 21(H) hopane / sum C 27 to C29 5(H), 14 (H) 17(H) 20 R sterane.

Table 4.1 Biomarker parameters and their correlation coefficients

Facies Hopane / Sterane 1 3 5 6 7 9 11 13 I low II med III high II med IImed III high III high II med Free 0.48 0.51 0.48 0.55 0.72 0.67 0.63 0.74 0.6 Resin 0.43 0.18 0.3 0.32 0.51 0.32 0.2 0.3 Asphaltene 0.51 0.6 0.86 0.65 0.4 0.47 1.21 0.96 0.1 0.1 Kerogen 1.02 0.93 0.92 0.77 0.98 1.19 1.07 1.14 0.6 TOC% 3.6 3.8 6.8 3.9 4.9 5.1 11.2 8.9 0.9 0.5 Sulphur 3.3 4.3 5.8 4.5 4.7 5.1 4.7 4 0.4 0.4

Free* Kerogen* %C27 R sterane 1 3 5 6 7 9 11 13 Free* Asphaltene* %C29 R 1 3 5 6 7 9 11 13 Free* Resin* Asphaltene* 1 3 5 6 7 9 11 13

I low II med III high II med IImed III high III high II med

28 29 34 30 33 35 32 32 0.8

44 nd 41 37 59 42 43 nd 0.2 -0.1 39 nd 35 37 25 39 39 nd 0.6 0.5 3 nd 0.9 2 4 4 2 nd 0

23 33 43 40 39 44 45 36 0.8

43 38 43 37 37 42 35 37 0.1 -0.3 37 36 35 42 36 36 40 41 0.4 0.3 0 12 nd 7 12 11 17 18 21 0.7 0.5 0.4

3.6 3.8 6.8 3.9 4.9 5.1 11.2 8.9 0.4 0.5 3.6 3.8 6.8 3.9 4.9 5.1 11.2 8.9 0 0.2 -0.3

3.3 4.3 5.8 4.5 4.7 5.1 4.7 4 0.8 0.8 3.3 4.3 5.8 4.5 4.7 5.1 4.7 4 -0.8 -0.2 -0.7

I low II med III high II med IImed III high III high II med

51 42 39 44 40 42 46 45 0.6 0.7

56 46 42 40 33 36 37 46 0.7 0.5

Hopane C29-30/ C23 tricyclic terpane 3.6 3.3 3.8 4.3 6.8 5.8 3.9 4.5 4.9 4.7 5.1 5.1 11.2 4.7 8.9 4 Free* 0.3 -0.7 Resin* 0 -0.2 -0.3 Asphaltene* 0.4 -0.1 0.8 0.1 Kerogen* 0.7 0.5 0.4 0.6 -0.3 * Correlation coefficient, significant values are in bold (for = 95 %, n = 7, r is significant at 0.56) for facies codes see Figure 4.2. For biomarker parameter key see Figure 4.6. I low II med III high II med IImed III high III high II med 17 16 8 18 12 13 19 20 1.2 nd 4 5 1.3 6 16 3 0.4 -0.1

18

4.4.3 Principal Components Analysis (PCA) Principal components analysis (PCA) provides a method of summarising quantitative multivariate data by combining biomarker variables into single principal components that best describe variation in the data set as a whole (Davis, 1984). PCA has a number of advantages; it objectively produces ratios and parameters that would not have other wise been thought of, and it can reduce many biomarker ratios to a cross plot or a single principal component that can be plotted stratigraphically (Farrimond et al., 1990). Principal components analysis was undertaken using normalised compositions of the sterane, hopane and tricyclic terpane biomarkers, which were entered into SPSS, a commercially available software package. The individual compounds used are listed in Table 4.2, and these were chosen with the aim of best representing stratigraphy, after taking into account possible causes of biomarker variation that include: 1) Variation due to non-equivalence of bound biomarkers from different fractions. As highlighted in the previous chapter, different fractions have different biomarker compositions. 2) Variation due to/with stratigraphy. This is the main cause of variation that this study aims to observe and investigate by PCA. 3) Variation due to maturity. The biomarker data of different fractions in the same sample appear to have different maturities on account of the different levels of steric protection, this could be considered under the heading 1) above. The stratigraphic section is very short and the same fractions of different samples ought to appear isomature. 4) Different levels of analytical imprecision for the four fractions. Small errors in sample preparation and data processing could cause variation that overwrites or obscure stratigraphic signals. Variation due to differences in maturity on account of steric protection (no. 3 above) was reduced by summing the various isomers prior to data normalisation, e.g. the sum of (22S) and (22R) hopanes and only the 17(H), 21 (H) hopane isomers were used. Variation due to the non-equivalence of the biomarker content of different fractions (no. 1 above) was reduced by leaving out compounds only found in one fraction such as

19

diasteranes and 18-trisnorneohopanes (Ts-type hopanes). These measures have served to enhance stratigraphic signals in the biomarker data, however it is difficult to counteract low levels of precision in the resin fraction data and it is possible that where stratigraphic signals arent observed (as in the case of the resin fraction) that this is the cause. Table 4.2. Biomarker variables used in PCA
Tricyclic Terpanes TTC20 TTC21 TTC22 TTC23 TTC24 TTC25 S+R TTC26 S+R TTC28 S+R TTC29 S+R TTC30 S+R C24 Tetracyclic For key to biomarker compounds see Figures 4.3 and 4.4. Hopanes C27 Tm C29 + C30 + C31 S+R C32 S+R C33 S+R C34 S+R C35 S+R Steranes C27 S+R C28 S+R C29 S+R C30 S+R

The results obtained by principal components analysis are often interpreted after factor rotation (axis rotation) has been performed on the principal components extracted from the first analysis. Factor rotation redistributes the variance from a number of principal components between a lesser number of principal components. Although a range of factor rotation methods were available on the software package that was used, ultimately rotated factors were not used for two reasons. Firstly, factor rotation appeared to enhance the differences between the different fractions over any stratigraphic variation. Secondly, a fairly clear interpretation of the unrotated factor scores was possible, and this was not much improved by factor rotation (although the treatment of data prior to the PCA, e.g. summing the different hopane isomers, did significantly improve the results). Table 4.3. Variance explained by the four significant principal components
Principal Component 1 2 3 4 By component % 54 17 12 7 cumulative variance % 54 71 83 90

20

4.4.3.1 Principal components analysis (PCA) results

PCA produced four significant principal components (PC) that described 89 % of the variance of bound and free sterane, hopane and tricyclic terpane biomarkers. By use of factor scores (correlation coefficients between PC and variable), the four principal components are interpreted in the following sections. Table 4.4, Principal Component loadings 1
0.96 0.95 0.95 0.95 0.93 0.86 -0.86 -0.86 0.84 0.83 -0.82 -0.78 0.77 0.77 -0.76 -0.74

Principal Component 2 3
0.15 0.05

4
-0.13

TT C26 S+R 0.18 -0.03 -0.03 TT C24 0.06 -0.19 0.01 TT C21 0.12 0.16 -0.13 TT C23 0.19 0.16 -0.19 TT C28 S+R -0.16 -0.36 0.04 TT C20 0.40 -0.04 0.05 C31 S+R 0.40 -0.13 -0.7 C33 S+R 0.46 0.06 0.15 TT C25 S+R 0.45 0.15 0.15 TT C29 S+R 0.31 0.11 -0.38 C32 S+R 0.12 -0.07 0.51 C34 S+R 0.50 0.28 0.06 TT C30 S+R -0.05 -0.25 0.31 Tetra24 0.01 -0.03 0.52 C35 S+R 0.40 -0.20 0.43 C30 -0.29 0.01 -0.74 -0.53 C29 0.02 -0.06 C27 Tm -0.70 -0.59 -0.07 -0.48 0.21 0.75 C28 S+R -0.01 0.14 -0.56 0.62 C29 S+R -0.42 -0.29 0.42 0.66 C30 S+R -0.07 -0.49 0.57 -0.58 C27 S+R Data are ordered by significance For key to the biomarker parameters see Table 4.2, Significant loadings (significant at = 0.05, 95 % confidence interval) are in a larger size font 4.4.3.2 Principal component 1

Principal component 1 (PC 1) explained 54.4 % of the selected data variance and has large positive tricyclic and tatracyclic loadings and negative C30+ hopane loadings and in effect is a hopane/tricyclic terpane ratio. Hopane and tricyclic terpane biomarkers are generally good correlation tools, but are fairly ubiquitous and indicative of a rather broad range of biological inputs (Peters and Moldowan, 1993). Hopanes are derived from prokaryotes, whereas tricyclic terpanes are associated with various algal and bacterial lipids (Aquino Neto et al., 1983). It is interesting to note that the PC scores suggest that the prokaryote-derived asphaltene C30 to C35 hopane proportions are highest

21

in samples associated with periods of high sea level (high TOC), whereas the proportion of the (commonly thought to be algal-associated) tricyclic terpanes are lesser in these samples (Table 4.5). This is supported by the significant correlation between asphaltene PC 1 scores and TOC (Table 4.5), stratigraphic plots (Figure 4.5c) and cross plots (Figure 4.9). The association of higher carbon number asphaltene-bound hopane homologues, and not tricyclic terpanes, with periods of highest sea level can be explained by high bacterial activity or better preservation of hopanes in the depositional environment. The latter is evidenced by the fact that it is higher carbon number hopanes and not their lower number homologues that show this association (Peters and Moldowan, 1991). Why the hopane/tricyclic terpane parameters reflect stratigraphy in the asphaltene fraction alone is difficult to explain, as none of the other fractions PC 1 scores describe stratigraphy. With the exception of the asphaltene fraction, the other fractions have similar PC 1 values, and thus a large proportion of the 54.4 % variance, in the biomarker data of the total sedimentary organic matter, is stratigraphic variation in the asphaltene fraction. This in turn could be used to argue that asphaltene-bound hopane and tricyclic terpane biomarkers have best described stratigraphy, as they vary the most and give the greatest response to subtle changes in sea level.
4.4.3.3 Principal component 2

Principal component 2 explained 17.2 % of the variance. Part of this variation is caused by the different degrees to which C29 R sterane and C27 Tm and C29 hopanes and C34 and C35 extended hopanes are proportionally bound into the various fractions (e.g. more sterane in the smaller macromolecules). This can be seen in Figure 4.8 but also in the average PC 2 scores of the free, resin, asphaltene and kerogen fraction which array in order of fraction size (0.8, 0.4, -0.2 and -1 respectively; Table 4.5). However, PC 2 also distinguishes stratigraphy in the free and kerogen fractions, this can be seen in the way that data group into facies in the cross plots (Figure 4.9). The free data correlate with TOC (Table 4.5 and Figure 4.5a) and both the kerogen and free data correlate well with sulphur (Table 4.5 and Figure 4.5a and b). This principal component is mainly influenced by C29 sterane which is normally a terrestrial (higher plant) biomarker in Mesozoic samples (Grantham and Wakefield, 1988; Peters and Moldowan, 1993), and C27 Tm and C29 hopane derived from the alteration of diploptene, diplopterol and bacteriohopanetetrol precursors, which could have been at least partly derived from outside of the environment of deposition. Higher number C34 and C35 hopane 22

homologues, which have factor scores of a ve sign (i.e. opposite sign of correlation to that of the C29 R sterane and C27Tm and C29 hopane PC values), can only be derived from C35 bacteriohopanetetrol and are more likely to originate from bacterial activity in the depositional environment (as they represent well-preserved hopane structures). Free fraction PC 2 scores correlate well with TOC and bulk sulphur, and the kerogen fraction PC 2 scores only correlate with bulk sulphur (Table 4.5) suggesting links to both the preservation potential of the depositional environment (e.g. correlation to bulk sulphur) and varying inputs of terrestrial derived organic matter (e.g. correlation to TOC). Consequently, principal component 2 can be interpreted in three ways. Firstly, that euxinic events associated with high sea level and a stratified water column (Saelen et al., 2000) led to the enhanced preservation of C35 (and C34) hopane precursors via sulphur incorporation (Sinninghe Damste et al., 1989; Peters and Moldowan, 1991) at the same time as large-scale sulphur deposition (and preservation of biomarker structures) during euxinic conditions, hence the correlation of PC 2 to bulk sulphur. During other periods of time this preservation route for C35 hopanes does not exist and C35 hopanes are altered to lower carbon number homologues. Secondly, that C29 R steranes and C27Tm and C29 hopanes are terrestrially derived from outside of the basin of deposition (indirectly via transport from the shore face; see Figure 4.1), whereas the C34 and C35 hopanes are indigenous to the area of deposition. During periods of low sea level, terrestrial-derived sediments (organic and inorganic) are more mobile and reach the deeper parts of the basin in larger proportions (see Figure 4.1, and Pasley et al., 1993), swamping contributions from autochthonous organic matter. When sea level is high terrestrial-derived sediments are submerged beneath the storm base on the upper shore face and immobilised (Figure 4.1), this would increase the relative contribution of indigenous organic matter to the total sedimentary organic matter. If this were the dominant process than PC 2 would be expected to correlate better with TOC than bulk sulphur. Thirdly, both the prior mechanisms could work together but with various degrees of influence in the different fractions, and it may even be that the parameter represents different things in different fractions, e.g. sulphur incorporation and redox conditions in

23

TOC resin
0 2 depth m 4 6 8

1 2 4

sulphur

free fraction.

free

depth m

asphaltene
0 2 depth m 4 6 8

kerogen

depth m

vs. allochthonous organic matter inputs which are controlled by relative sea level in the

the depositional environment in the kerogen fraction, and the balance of autochthonous

Figure4. 8. Stratigraphic traces of the principal component scores of the four fractions. In general it can be seen that not all principal components, in all fractions represent stratigraphy. For discussion see text.

24

2.50

principal component 2

3.00 I free 0.50 -0.50 -1.50 -2.50 0 5 10 15 II free III free I kerogen II kerogen III kerogen

principal component 1

1.50

2.00 I asphaltene 1.00 0.00 -1.00 -2.00 0 5 II asphaltene III asphaltene

% TOC

% TOC

10

15

2.50 I free II free 0.50 -0.50 -1.50 -2.50 0 2 III free I kerogen II kerogen III kerogen

2.50 I free

principal component 2

principal component 4

1.50

1.50 0.50 -0.50 -1.50 -2.50

II free III free I asphaltene II asphaltene III asphaltene I kerogen II kerogen III kerogen

% bulk sulphur

% bulk sulphur

Figure 4.9. Principal component scores vs TOC or sulphur. Different principal components discriminate facies best in different fractions. PC 1 = principal component 1; PC 2 = principal component 2 etc. For facies codes see Figure 4.2 4.4.3.4 Principal components 3 and 4

Principal component 3 explains 11.5 % of the scaled data variance. The PC 3 scores of the kerogen, asphaltene and resin fraction increase in magnitude roughly with macromolecule size (e.g. 0.61, -0.53 and 1.1). Principal component 3 appears to describe and distinguish stratigraphy well in the free fraction (Table 4.5, Figure 4.5a ), but only very generally in the kerogen fraction (Table 4.5, Figure 4.5d). From the loadings in Table 4.4 it can be interpreted as a hopane/sterane ratio. In chapter 3 the hopane/sterane ratio was observed to vary between fractions, thus it appears that at least 11.5 % of variation in the biomarker data of the total sedimentary organic is due to the inherent biomarker bias of the different fractions. Principal component 4 explains 6.4 % of the variance. The free, asphaltene and kerogen PC 4 scores generally describe stratigraphy well (Figure 4.5a,c and d), correlate well with TOC (Table 4.5) and discriminate different facies well in cross plots (Figure 4.9). The loadings shown in Table 4.4 show that it can be interpreted as a C27/C30 sterane ratio, which is extremely sensitive to marine organic matter input (Peters and Moldowan, 1993). C30 Steranes are derived from 24-n-propylcholestanes synthesised by 25

chrysophyte algae and presumably their increased proportions could correspond to an increased autochthonous marine contribution to sedimentary organic matter during periods of higher regional sea level.

3.5

2.5 2 PC1 54% var 1.5 1 0.5 0 -0.5 -1 -1.5 -2 -3 -2

lte ne

facies group

as p

I low II med III high

fraction

gen kero

ha

free asphaltene kerogen

free
-1 0 PC2 17% var 1 2

Figure 4.10. Plot of kerogen, asphaltene and free PC 1 and PC 2 scores. Kerogen and free samples from the most marine facies plot on the right of the graph. This corresponds to greater preservation and input of bacterially-derived C35 and C34 hopanes relative to C29 steranes, C27 Tm hopane and C29 hopanes, compounds that are terrestrially derived and more likely to have had long transportation times and to have been derived from outside of the region of deposition. Asphaltene biogenicity is expressed by a tricyclic terpane ratio that has an opposite sense to that of the kerogen and free fractions. 4.4.3.5 Summary of aliphatic biomarker molecular stratigraphy

Figure 4.10 summarises the principal components analysis results of the Jet Rock sterane, hopane and tricyclic terpane biomarker data. It highlights that the biomarker compositions differs between the various fractions, but also that they reflect stratigraphy in different ways (i.e. note the various vectors of data trends in PC space in Figure 4.10). Some of this variation, such as the cluster of data by fraction along PC 2 (and also to an extent along PC 3; not shown), can be explained by the inherent biomarker characteristics and biases of each fraction. A significant proportion of the variation, such as the asphaltene PC 1 data and the kerogen and free hydrocarbon

26

fraction PC 2 and PC 4 data, is stratigraphic. It can be concluded that different biomarkers reflect stratigraphy differently in the various facies. Initially it might have been expected that kerogen-bound biomarkers would have best represented stratigraphy; actually it appears that this is not the case. The biomarker content of all fractions apart from the resin fraction can represent stratigraphy fairly well. But based on the data in this study comprising steranes, hopanes and tricyclic terpanes, if any one fraction could be declared the best biomarker stratigraphic tool this would be the asphaltene fraction. Source rock asphaltene-bound steranes appear to be a very sensitive stratigraphic tool (Figure 4.5c) and its asphaltene PC 1 scores, which are analogous to a hopane/tricyclic terpane ratio, discriminate the different facies suggested by TOC data most clearly of all the fractions. Despite the complex differences between the distributions of biomarkers in the different fractions, if a biomarker pool in one fraction is considered on its own, its distribution of biomarkers can be accounted for by a very simple model. Figure 4.6, 4.8 and 4.10 all show that the distribution of biomarkers in the Jet Rock can be described by a very simple mixing model that underpins the high TOC based model (HTB model). In the model there are two sources of biomarkers, an allochthonous terrestrial source that contains terrestrial biomarkers (e.g. C29 R steranes) and biomarkers that are degraded and oxidised (e.g. alteration of hopane side chain), and an autochthonous marine source which comprises marine biomarkers (e.g. C30 R steranes) and biomarkers that are well preserved (e.g. preservation of hopanes with extended side chains). The mobility of the allochthonous pool of terrestrial organic matter within the basin is controlled by sea level, and during periods of low sea level greater mobilisation of this pool occurs and samples deposited in periods of low sea level bear a greater terrestrial influence and received greater inputs of allochthonous sedimentary organic matter. Such a simple model consisting of only two main sources is partially backed up by the tendency of the biomarker ratios and principal components of in some samples to plot along predominantly linear mixing lines (e.g. most of the data in Figure 4.6, 4.8 and 4.10 almost approximate to straight lines).

27

Table 4.5. PC scores and their correlation to TOC and bulk sulphur
Fraction Free Facies I low II med II med II med II med III high III high III high Sample 1 3 6 7 13 5 9 11

PC1
-0.71 -0.84 -0.94 -0.60 -1.12 -0.27 -0.74 -1.14

PC2
-0.28 0.08 0.28 0.98 1.40 1.43 1.37 1.44

PC3
0.42 0.91 0.56 0.47 -0.59 0.04 -0.20 -0.80

PC4
1.54 1.69 1.07 1.16 0.30 0.85 0.70 -0.24

Cor TOC cor sulphur Resin

-0.44 0.50 I low II med II med II med II med III high III high III high 1 3 6 7 13 5 9 11
0.15 nd 0.58 -0.59 nd 1.57 0.00 0.08

0.74 0.68
0.17 nd -0.74 0.02 nd 0.97 1.11 1.06

-0.90 -0.19
0.56 nd 3.22 1.34 nd 1.03 0.43 0.61

-0.93 -0.30
-0.35 nd 0.26 -2.54 nd -0.89 -0.30 -1.67

Cor TOC Cor sulphur Asphaltene

0.09 0.48 I low II med II med II med II med III high III high III high 1 3 6 7 13 5 9 11
2.83 nd 0.79 2.42 0.81 0.51 0.27 -1.37

0.63 0.49
0.32 nd -0.27 0.75 -0.86 -1.10 0.23 -0.33

-0.36 -0.01
-1.03 nd -1.04 -0.70 0.87 0.41 -1.42 -0.85

-0.44 -0.17
1.51 nd -0.47 -0.01 -0.49 -0.57 -0.67 -1.48

Cor TOC Cor sulphur Kerogen

-0.76 -0.50 I low II med II med II med II med III high III high III high 1 3 6 7 13 5 9 11
-0.32 nd -0.06 -0.12 -0.47 0.22 -0.45 -0.50

-0.53 -0.33
-2.03 nd -0.87 -1.65 -1.15 -0.22 -1.06 -1.05

0.45 0.13
-0.18 nd -0.54 0.27 -0.84 -1.09 -0.84 -1.02

-0.70 -0.65
0.77 nd 0.53 0.68 -0.33 -0.54 -0.11 -0.40

Cor TOC Cor sulphur Figure 4.2.

-0.40 0.50

0.34 0.82

-0.62 -0.46

PC 1 = principal component 1; PC 2 = principal component 2 etc.

-0.78 -0.58 F or facies codes see

cor TOC r value of PC to TOC; cor sulphur r value of PC to bulk sulphur; values significant at = 0.05 (95 % confidence interval) are in bold nd = not determined

28

4.5. Aromatic hydrocarbon data

A clear stratigraphic trend can be seen in the GC-FID traces of the aromatic hydrocarbon fraction of the kerogen hydropyrolysates (Figure 4.11); PAH compounds that elute after phenanthrene are a far lesser constituent of the kerogens from the samples in the lowest part of the section than in the samples at the top of the section. In fact the larger ring number PAH are hardly visible in the GC traces of sample 11 at all. Using this distribution of PAH and the relative abundance of resolvable compounds, clear distinctions can be drawn between the three samples from bed 41, but also more generally between bed 41 and the beds and samples beneath which do not have particularly prominent PAH visible in their GC-FID traces (Figure 4.11). This trend is not visible in the free aromatic hydrocarbon fraction traces which are more uniform through the section (Figure 4.12).

Py Mpy MFa

MBp

P MP

MC

B[ghi]Pe

1 2
depth m

41

3 4 5 6 7 8 35
time

38 37

DMN

DMP

DMBp

Co

X2

Figure 4.11. GC-FID traces of the aromatic hydrocarbon fraction of the kerogen hydropyrolysis tars. DMN = dimethylnapthalene; MBp = methylbiphenyl; P = phenanthrene; MP = methylphenanthrene; dimethylphenanthrene; Py = pyrene; MPy = methylpyrene; Fl = fluoranthene; MC = methylchrysene; B[ghi]Pe = benzo[g,h,i] perylene; Co = coronene. Note that all samples where on-column injected at the same concentration . Trace heights are scaled by abundance or FID response, but sample 3-13 are at twice the scale of sample 1.

29

MP DMP

1 2
depth m

41

3 4 5 6 7 8 35
time

38 37

Figure 4.12. GC-FID traces of the aromatic fraction of the free DCM extract. MN = methylnapthalene; DMN = dimethyl napthalene; EN = ethylnapthalene; P = phenanthrene; MP = methylphenanthrenes; DMP = dimethylphenanthrene; TAS = triaromatic steroids.

4.5.1 Limit of detection of PAH To investigate whether or not large ring PAH were absent or simply present in lower abundance in the beds and samples beneath bed 41, GC-MS was used to search for ions that were diagnostic for pyrene, methylpyrene, methylchrysene, benzo[g,h,i]perylene and coronene. Appropriate mass chromatograms that indicate the presence of these compounds are shown in Figure 4.13. Figure 4.14 shows that these compounds and these show that these compounds are present but in much lower proportions relative to the UCM. Pyrene and coronene, that have a more condensed aromatic structure, appear to be relatively more abundant (in comparison to the methylpyrenes and methylfluoranthenes for example) in sample 1, than in sample 5 and 11. This may reflect greater contributions of aromatic compounds derived from combustion or oxidation of organic matter to sample 1 than to other samples.

MN EN DMN

TAS

30

MPy + MFa

B[ghi]Pe

Py

Sample 1

MC

Sample 5 Fa

Sample 11a Fa

elution time

Figure 4.13. Overlay of GC-MS 202, 216, 242, 276 and 300 m/z ion traces that show large ring PAH to be present in the kerogen hydropyrolysates in low abundances throughout the section. For key see Figure 4.11.

4.5.2 Origin of the PAH in the kerogen hydropyrolysates The large ring PAH can be interpreted to have been likely to have been derived from the combustion or oxidation of organic matter that was probably terrestrial in origin. However, the interpretation of the biphenyl compounds needs to be treated with a degree of caution because they are almost completely absent or present in a much lower abundance in the free aromatic hydrocarbon fractions. It is likely that they are, at least in part, derived from the defunctionalisation of dibenzothiophenes and other intramolecular sulphur-containing compounds. It is still clear however, that they behave in a similar way to the combustion-derived PAH. The combustion-derived PAH can be interpreted in the classic way of representing material produced by natural fires (Killops and Massoud, 1992). Alternatively, they could also be interpreted as deriving from the oxidation of terrestrially-derived organic matter during its long residence in the water column and shoreface areas by a process similar to that which was observed in the weathering of the Athabasca Tar Sand asphaltenes (Chapter 5, Figure 5.5). An additional piece of evidence supporting a non pyrolytic origin for a majority of the PAH in sample 1 is that fluoranthene is not very prominent compared to pyrene. In other studies, of both macromolecular and hydrocarbon PAH, where PAH of a clear pyrolytic or combustion origin are present, compounds containing a five membered ring (such as

Co

31

fluoranthene and fluorene) are more prominent (Killops and Massoud, 1992; Brocks et al., 2003). Variation in the relative abundance of PAH in kerogen hydropyrolysates can be related to changing sea level in two possible ways. The first is that it reflects a greater primary input of allochthonous terrestrial- and combustion- derived PAH when there is a greater land/delta area and more terrestrial primary productivity, and/or when a drier climate persists and forest fires are more common. The second cause of variation may be related to the mobility of terrestrial sedimentary organic matter within the basin of deposition. If this is the case it may be that the overall primary inputs of terrestrial organic matter do not fluctuate greatly over geological time, but that the allochthonous terrestrial organic matter is more easily mobilised from the shoreface region and transported to distal regions of the basin when wave base is lower (for description see Figure 4.1).

B[ghi]Pe

Sample 1

Sample 3

Sample 5 m/z 55 m/z 276

elution time

Figure 4.14. Overlain GC-MS traces of the 276 and 55 m/z ions. The 276 ion was chosen because it corresponds to benzo[ghi]perylene, a PAH compound visible in sample 1s GC-MS trace, the 55 ion was chosen because it best typifies the shape of the aromatic UCM in the kerogen pyrolysates. It is likely to represent a minor GC-MS fragmentation that is common to a range of polycyclic aromatic compounds with complex alkyl substitutions present in the UCM.

32

PAH arent observed in the GC-FID traces because of the large UCM present, this effectively swamps the quantitatively less abundant PAH. The effects of this can be seen in the GC-MS traces in Figure 4.14; a trace of an ion (m/z 55) that characterizes a component of the aromatic UCM is not visible at all above the base line in sample 1, just visible in sample 3 and approaching that of the benzo[ghi]perylene peak in sample 5 (although it should be noted that the entirety of the UCM visible on the TIC or GCFID traces in Figure 4.11 completely swamps the benzo[ghi]perylene and other PAH peaks). Aromatic UCMs have received very little attention, but they are commonly accepted to comprise alicyclic aromatic compounds with complex alkylation patterns (Simoneit and Fetzer, 1996). In the natural environment aromatic UCMs like this are associated with oils and bitumens derived from organic matter that is microbial in origin, the resolvable component of which often contains polymethylated napthalenes and phenanthrenes that have been derived bacterial terpane precursors (Puttmann and Villar, 1987; Killops, 1991). Aromatic UCMs are also found in the natural pyrolysis products of marine organic matter e.g. oils generated from exclusively marine organic matter (organic matter with no higher plant material) by hydrothermal activity at ocean ridges (Simoneit, 1993). Thus a third explanation for the distribution of PAH is that there is an increase in autochthonous marine sedimentary organic matter in form the aromatic UCM and polymethylated napthalenes and phenanthrenes when sea level is high. It is likely that all three process could occur together during periods of high sea level; a decrease in the mobility of terrestrially derived organic matter, a decrease in the primary production of allochthonous terrestrial organic matter and an increase in inputs of marine organic matter due to a rise in marine primary productivity. 4.5.3 Why do kerogen-bound PAH better represent stratigraphy? The role of the isolation of allochthonous inputs of terrestrially-derived higher plant material in controlling PAH distributions in kerogen pyrolysates is further supported by the occurrence of jet or small carbonaceous flakes, the fossil remains of the higher plant material present in the Jet Rock. Although such organic material is not a great constituent of the Jet Rock, it is present. Once jet is incorporated into shelf sediments it will be subject to the same sedimentary processes (OBrien, 1990). Thus from a sequence stratigraphic point of view the relative abundance of jet and its constituent 33

macromolecular PAH will be more closely tied to changes in sea level than the free aromatic hydrocarbons, which can also be derived via a range of diagenetic processes (Puttmann and Villar, 1987; Killops, 1991; Borrego et al., 1997), particularly the polymethylated napthalene and phenanthrene compounds that are the most prominent resolved compounds on the free aromatic hydrocarbon GC-FID traces in Figure 4.12. The distribution of jet in hand specimen is described in Chapter 3, and broadly corresponds to the occurrence of large-ring PAH compounds in the GC-FID traces of the aromatic fraction of kerogen hydropyrolysates, i.e. it is most abundant in bed 41.

4.6 Conclusions
The Jet Rock contains a number of high TOC based (HTB) cycles that can be used for stratigraphic description. In this study, at the sampling scale used, high TOC based cycles represent parasequence scale variation which can be used to identify different facies in the otherwise homogeneous black shale of the Jet Rock. Recognition of this scale of variation is important, for example significantly different stratigraphic interpretations would have been arrived at if only samples 3 and 7 had been analysed. These samples, although collected from different beds four meters apart, display similar geochemical characteristics, and between them do not represent the variability of the Jet Rock. Sterane, hopane and tricyclic terpane biomarker signals of all the fractions have been compared to the high TOC based model of stratigraphy, and the results show that apart from the resin fraction, all fractions contain biomarker data that can be used as stratigraphic tools in the form of various ratios and parameters. However these tools, whilst all being capable of describing stratigraphy, are different in each fraction and a biomarker combination that is good at describing stratigraphy in one fraction might well be useless or function differently in another and represent different processes. This is illustrated by the high proportions of PAH bound into the kerogen fraction which correspond to the transportation and deposition of woody material during periods of low sea level, and the aromatic compounds in the free aromatic fraction that are the result of the diagenetic alteration of various precursors which varies little over geological time. Asphaltene and resin-bound biomarker stratigraphic signals are much more difficult to attribute to any single process than those of the free hydrocarbon and

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kerogen fractions, however their GC-FID and GC-MS traces are still distinctive and different. In the Jet Rock the asphaltene fraction contains a sterane distribution that is very good for distinguishing facies, and the proportions of asphaltene-bound hopanes and tricyclic terpanes also appear to be useful for distinguishing different facies. The resin fraction appeared to be the least useful for identifying changes in facies, although the extended tricyclic terpanes appeared to be able to distinguish different positions in the HTB cycles. If it had been possible to obtain accurate extended tricyclic terpane peak areas that werent effected by co-elution with hopanes, than their inclusion in a PCA may also show the resin fraction to be a useful stratigraphic tool. The organic matter of the Jet Rock received allochthonous inputs from shoreface areas which contained terrestrial organic matter (higher plant and bacterial in nature) that had been oxidised and degraded in shallow waters above wave base, and large inputs of autochthonous marine organic matter that are well persevered (probably by rapid sulphur incorporation) and appear to have been derived predominantly from algae, but also from other bacterial sources (including inputs from green sulphur bacteria). Relative sea level appears to have been the controlling factor in influencing the contributions the two different sources made to the sedimentary organic matter preserved in the Jet Rock. This variation in the proportions of the two sources that comprise the sedimentary organic matter can be conceptualised as a simple mixing model in which variation is on a parasequence set or parasequence scale.

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