Organic Geochemistry 35 (2004) 425441 www.elsevier.

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Evidence for Gloeocapsomorpha prisca in Late Devonian source rocks from Southern Alberta, Canada
Martin G. Fowlera,*, Lavern D. Stasiuka, Mark Hearnb, Mark Obermajera
a

Geological Survey of Canada Calgary, Natural Resources Canada, 3303-33rd Street NW, Calgary, Alberta, Canada T2L 2A7 b Shell Canada Ltd., 400-4 Avenue S.W., Calgary, Alberta, Canada T2P 2H5

Abstract Organic-rich intervals within the Late Devonian Camrose Member of southern Alberta, Canada show optical and chemical characteristics very similar to those of Ordovician samples whose organic matter is dominated by Gloeocapsomorpha prisca-derived alginite. This includes saturate fraction gas chromatograms dominated by n-alkanes with a pronounced odd carbon number up to C19, and much lower abundances of C19+ n-alkanes, acyclic isoprenoids and biomarkers. Microscopy reveals these samples contain G. prisca-like alginite with a morphology that previously has been suggested for the growth of this organism under higher salinity conditions which is in agreement with the depositional environment of the Camrose Member. One unusual feature of the G. prisca-rich samples is the very high concentration of C21 and C23 n-alkylnaphthalenes and n-alkylbenzenes in the aromatic fractions of their extracts. The origin of these compounds is not known but their occurrence could be related to the high concentrations of C21 and C23 n-alkyl phenols that have been noted in pyrolysates of Estonian kukersites by previous workers. Other Camrose Member extracts show very dierent distributions that are more typical for carbonates deposited under anoxic, higher salinity conditions. Many oils that occur in Nisku Formation reservoirs in the Enchant-Hays eld in southern Alberta show saturate fraction gas chromatograms and other evidence that indicate an important contribution to these oils from the G. prisca-rich intervals. These are thought to have a contribution from Camrose Member source rocks. Hence, caution should be used in only attributing G. prisca geochemical characteristics to Cambro-Ordovician oils as, on rare occasions, they can also occur in younger source rocks and their derived oils. Crown Copyright # 2004 Published by Elsevier Ltd. All rights reserved.

1. Introduction Gloeocapsomorpha prisca is the main contributing organism to many Cambro-Ordovician hydrocarbon source rocks where it can make up to greater than 90% of the organic matter (e.g. Reed et al., 1986; Homan et al., 1987; Fowler, 1992). Such source rocks are often called kukersites (Hutton, 1987) after the Ordovician Estonian kukersites in which Zalessky (1917) rst recognized G. prisca. Kukersite-type deposits often make excellent source rocks with high TOC (total organic carbon) contents and HI (Hydrogen Index)

* Corresponding author. Tel.: +1-403-292-7038; fax: +1403-292-7159. E-mail address: mfowler@nrcan.gc.ca (M.G. Fowler).

values indicating Type I organic matter. In other Cambro-Ordovician sediments, the contribution from G. prisca is diluted by input from other organisms and these have been termed diluted kukersites (Fowler, 1992). There has been considerable dispute over what type of organism G. prisca was (e.g. Reed et al., 1986; Homan et al., 1987; Foster et al., 1989; Fowler, 1992; Stasiuk and Osadetz, 1990; Derenne et al., 1992; Wicander et al., 1996; Blokker et al., 2001). Most authors now favour that it was a probable photosynthetic coccoidal cyanophyte, possibly related to the extant Entophysalis major, that had both planktonic and benthic life habits although some still believe it is related to the extant green algae, Botryococcus braunii (e.g. Derenne et al., 1992). G. prisca-rich rocks and their derived oils show a number of distinctive geochemical characteristics. This

0146-6380/$ - see front matter Crown Copyright # 2004 Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.orggeochem.2004.01.017

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is best displayed by their saturate fraction gas chromatograms which are dominated by n-alkanes up to C19 with a pronounced odd carbon number predominance. C20 and higher molecular weight n-alkanes are in much lower concentrations and tend to show no or a very slight odd over even carbon number preference. While immature samples have low to moderate concentrations of acyclic isoprenoids, higher maturity source rock extracts and oils show extremely low concentrations of acyclic isoprenoids. Polycyclic biomarker compounds are also present in very low concentrations. However, monocyclic alkanes are present in higher abundance than in most other oils, with n-alkylcyclohexanes often the second most abundant group of compounds after the n-alkanes. Diluted kukersites dier from these by showing a less pronounced odd carbon number preference of the C13C19 n-alkanes and greater amounts of C19+ n-alkanes and acyclic isoprenoids (e.g. Fowler, 1992). Pyrolysates of G. prisca rich sediments also show

distinctive characteristics. Some are heavily dominated by n-alkyl species, often showing an odd carbon number preference with a low abundance of C19+ compounds (Douglas et al., 1990; Derenne et al., 1992; Blokker et al., 2001), while Estonian kukersite pyrolysates appear to contain a higher abundance of phenols which by analogy with extant Botryococcus braunii could be G. prisca adapting to more saline conditions (Derenne et al., 1992). G. prisca was widespread in tropical epi-continental seas during Cambro-Ordovican time with kukersites or diluted kukersites known to occur on ve present day continents (Fowler, 1992). There are very few reports of G. prisca occurring in post-Ordovician sediments (e.g. Cramer and Diez de Cramer, 1972) with most older reports that suggested a range in age up to Tertiary appearing to be erroneous (Fowler, 1992; Wicander et al., 1996). This led Fowler (1992) to suggest that G. prisca was part of the Ordovician-Silurian extinction

Fig. 1. Map showing location of Camrose Member/Nisku Formation source rocks in southern Alberta and the location of the Enchant-Hays oil eld. Note each township is 66 miles square so the same rocks occur roughly over a 12070 mile (200120 km) area.

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event that is often linked with a major glaciation. However, in recent years there have been credible reports of G. prisca in post-Ordovician sediments. Abrams et al. (1999) found Silurian and Lower Devonian intervals showing geochemical characteristics similar to those of Ordovician kukersites in the northeastern Timan Pechora Basin of Russia, although the presence of G. prisca was not visually conrmed. In addition, oils found in Lower Devonian-Carboniferous reservoirs in part of this basin have characteristics similar to kukersite derived oils and were thought to be possibly sourced from these units. Abrams et al. (1999) also report J.M. Moldowan (personal communication, 1996) nding G. prisca characteristics in rock extracts as young as Middle Devonian. G. prisca has been recognized microscopically in Middle Devonian Elk Point Group and Upper Devonian Woodbend Group rocks in eastern Alberta, generally as a minor component of organic-rich intervals (Nowlan et al. 1998a,b; Chow et al., 1995; Stasiuk, 1999a). During the course of our study of Devonian Petroleum Systems of the WCSB (Western Canada Sedimentary Basin), units enriched in G. prisca were also noted in Late Devonian units, especially in the Camrose Member of the Winterburn Group, southern Alberta (Figs. 1 and 2), some of which gave extracts with characteristics similar to those of Ordovician kukersites (Fowler and Stasiuk, 1999). It is these samples and their derived oils that are the subject of this paper.

Concentrator. The gasoline fractions were then passed onto the Gas Chromatograph equipped with a 50 m HP-1 column, with siloxane gum used as a xed phase. The initial temperature was held at 30  C for 10 min and then programmed to 45  C at a rate of 1  C/min. The nal temperature was held for 25 min. The eluting hydrocarbons were detected using a ame ionization detector. Saturate fractions were analyzed using gas chromatography (GC). A Varian 3700 FID gas chromatograph was used with a 30 m DB-1 column. The temperature was programmed from 60 to 300  C at a rate of 6  C/min and then held for 30 min at 300  C. The eluting compounds were detected and quantitatively determined using a hydrogen ame ionization detector. Gas chromatographymass spectrometry (GCMS) was performed on a VG 7070 mass spectrometer with a gas chromatograph attached directly to the ion source. The

2. Methodology Aliquots of possible source rocks were dried and powdered for Rock-Eval/TOC analysis. The instrument used was a Delsi Rock-Eval II pyrolysis unit equipped with a total organic carbon (TOC) analysis module. Duplicate or muliple analyses of the core samples were made. Rock samples selected for extraction were powdered and extracted using azeotropic chloroform: methanol (87:13) mixture for 24 h. Rock extracts and oils were treated with approximately 40 volumes of n-pentane to precipitate the asphaltenes. The deasphalted extracts and oils were fractionated using open column chromatography (3/4 activated alumina and 1/4 activated silica gel with an adsorbent:sample mass ratio of 100:1). Saturates were recovered by eluting with 3.5 ml of pentane/g of adsorbent. Aromatics were recovered by eluting with 4 ml of 50:50 pentane-dichloromethane/g adsorbent and the resins were recovered with 4 ml of methanol/g adsorbent. The gasoline range hydrocarbons (iC5nC8) in the oils were analyzed on a HP5890 gas chromatograph connected to an OI Analytical 4460 Sample Concentrator. A small amount of the whole crude oil was mixed with deactivated alumina and transferred to the Sample

Fig. 2. Stratigraphic nomenclature for Late Devonian units in southern Alberta.

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instrument was controlled by an Alpha Workstation using Opus software. A 30 m fused silica column (DB-5, J&W Scientic) was used for GC separation. The temperature was initially held at 100  C for 2 min and then programmed at 40  C/min to 180  C and at 4  C/min to 320  C. After reaching 320  C the temperature was held for 15 min. The mass spectrometer was operated with a 70 eV ionization voltage, 100 mA lament emission current and interface temperature of 280  C. Mass fragment ions monitored during single ion monitoring experiments included m/z 177.1638, 191.1794, 217.1950, 218.2028, 231.2106 and 259.2262. GC-MS analyses of aromatic hydrocarbons were performed with a HP 6890 Series GC coupled to a HP 5973 Series Mass Selective Detector operated in selective ion monitoring (SIM) mode. The GC was tted with a 30 m0.25 mm i.d. DB-5 column. The temperature was initially held at 100  C for 2 min and then programmed at 3  C/min to 300  C and held for 10 min. The mass spectrometer was operated with a 70 eV ionization voltage, 100 mA lament emission current and an interface temperature of 280  C. Identication of peaks was aided by full scan GCMS analyses of selected samples using a Micromass Autospec-TOF instrument in normal GCMS mode. Pyrolysis-gas chromatography (py-GC) was achieved using a Horizon Instrument Curie Point Pyrolyzer with a wire with a Curie temperature of 610  C on the injector of a HP5890 gas chromatograph. The products were separated on a 30 m DB-1 column using a temperature program of 0300  C at 6  C/min. Organic-rich core samples were prepared for incident light microscopy of dispersed organic matter by mounting rock fragments in epoxy resin. Prior to mounting, small saw-cut core fragments (  1 cm cubes) were initially hand polished while drill cuttings were crushed to 15 mm particulates. Prepared as such, samples were then put into 1 inch diameter circular plastic molds ensuring, where required, perpendicular to bedding, parallel to bedding or random orientation of the particulates. The moulds were lled with epoxy (cold setting epoxy consisting of 2:1 resin and hardener) and left to cure for 2448 h. The pellets were ground and polished on a Buehler Ecomet IV polishing machine. Dispersed organic matter (macerals) was analyzed and classied using white and uorescence incident light microscopy. Three reected light microscope systems were used for organic petrologic analysis: a Leitz MPV II system, a Zeiss UMP system, and a Zeiss Axioplan II system. Fluoresence microscopy was done using water immersion objectives with total magnication up to 1200. A Zeiss Invert 410 confocal laser scanning microscope equipped with 488, 543, and 633 nm lasers are also used, particularly for studying detailed maceral morphology (2D and 3D perspectives) of liptinite and amorphinite macerals under magnication up to 8000 (see Stasiuk, 1999b).

3. Results 3.1. Geology The regional geology of the Winterburn Group in southern Alberta is summarized in Kissling (1996). In the area that extends from Townships 1 to 15 and Ranges 1 to 25W4 (Fig. 1), over which we sampled 22 cores, the Frasnian-aged Camrose Member/Nisku Formation strata (Fig. 2) are represented by a  30 m thick sequence that displays a shallowing-upward prole, with dolomitized marine shelf facies to peritidal, lagoon and tidal at facies. Three mappable, potential source rock units have been identied within the Camrose Member/ Nisku Formation section in this area, two in the Camrose Member and one in the Nisku Formation (Fowler et al., 2001). Here we concentrate on the evidence for G. prisca within the Camrose Member potential source rock intervals as there was little or no evidence for G. prisca within the Nisku Formation potential source interval in this area. 3.2. Optical evidence for the occurrence of G. prisca Macerals within potential source rocks of the Camrose Member/Nisku Formation in southern Alberta are derived from both marine and terrestrial sources and suggest variable and uctuating paleodepositional conditions (Fowler et al., 2001). Coccoidal alginite macerals and shallow water organic facies are an important component of some Camrose Member potential source rocks (Fig. 3). Several varieties of coccoidal alginite macerals appear to be present in these rocks (e.g. G. prisca, Botryococcus, Pediastrum-like?), but the majority have morphological features consistent with G. prisca (Fig. 3) and are hereafter referred to as G. prisca. G. prisca alginites are very abundant and dominant in the Camrose Member at 10-4-1-9W4 (1185.75 and 1185.95 m), at 15-35-7-22W4 (1942.5 m) and at 13-32-7-20W4 (especially at 1665.9 m) (Fig. 3). Similar G. priscadominated organic facies also occur in the Camrose Member at 16-31-10-4W4 (1379.37 and 1379.58 m) and 6-22-6-23W4 (2324.9 and 2325.8 m), although the alginites at these locations, and particularly the latter, are softened and largely altered due to thermal alteration and probable S-enrichment (Fig. 3). Petrographic evidence for in situ oil generation from G. prisca alginite is particularly clear at the 7-22W4 location where solid bitumen and crude oil inclusions are abundant (Fig. 3). Stasiuk et al. (1993) described three G. prisca microfacies in Late Ordovician rocks of the Saskatchewan portion of the Williston Basin, two disseminated (A and B) and a stromatolitic facies. Disseminated A microfacies consists of small (generally < 5 to 20 mm), thinwalled G. prisca alginite colonies typically consisting of no more than 12 individual cells. Disseminated B

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Fig. 3. Photomicrographs of dispersed organic matter within Ordovician kukersites, Williston Basin (ac) and Nisku Formation/ Camrose Member source units (dl), Alberta. Incident, conventional uorescent light (a, dk), and laser scanning uorescence microscopy (LSM; b,c); water immersion. Scale on photo a is for all photos except b and c (scale on photo b). (a). G. prisca showing mainly open cell morphology (o) but also some closed (c) morphology. (b, c). LSM image of open and closed cellular morphology in G. prisca. (d). Solid bitumen (b) associated with G. prisca enriched organic facies. (eh). Abundant small to medium colonies of coccoidal G. prisca alginite (Gp) associated with intense yellow-uorescing Prasinophyte alginite (p) in photo e. (il). Thermally mature G. prisca alginite (Gp) associated with abundant bitumen. Low (k) and high (l) magnication images showing thermally mature G. prisca associated with abundant bitumen (b) and crude oil inclusions (hc) in late calcite cements from 7-20W4 location. Note the softening of G. prisca with closed cellular structure resulting from thermal maturity eects.

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microfacies is similar although it consists of larger G. prisca colonies (up to 100 mm) with much thicker cell walls and development of the colony by a thickened sheath. Disseminated A is thought to represent the earlier growth stage of G. prisca, while disseminated B is a more advanced growth stage under more stressful conditions, probably related to the development of algal blooms (Stasiuk and Osadetz, 1990; Stasiuk, 1999a). The stromatolitic G. prisca microfacies are characterized by algal mats with upper surface microtextures, such as domes, pinnacles, pustules or phototactic structures (Stasiuk, 1999a). This could form via the disseminated B stage or directly at the sedimentwater interface. The disseminated B and stromatolitic microfacies are the most volumetrically important in the Ordovician of the Williston Basin (Stasiuk and Osadetz, 1990). The cell size, cellular organization and shape of the G. prisca colonies observed in the Camrose Member are similar to those previously described for the Ordovician (e.g. Stasiuk and Osadetz, 1990) (Fig. 3). However, there are some notable dierences. Only the disseminated A and B G. prisca microfacies were observed while the stromatolitic microfacies rarely occurs in the Camrose Member/Nisku Formation samples or any other Devonian samples where we have noted G. prisca. A closed and open morphology characterizes disseminated B G. prisca alginites in Ordovician sediments of the Williston Basin but almost all the disseminated B alginite noted in the Upper Devonian rocks is characterized by a closed morphology (Fig. 3). Closed and open cellular morphology can easily be distinguished using both conventional uorescence microscopy and confocal laser scanning uorescence microscopy (Fig. 3ac), the latter is within the same range of magnication as used by Derenne et al. (1992) to demonstrate the two morphotypes of G. prisca alginite. The alginite colonies in the Upper Devonian samples also tend to be considerably smaller than those found in Ordovician sediments, ranging from  5 to 50 mm in diameter (Fig. 3). 3.3. Extract characteristics Camrose Member extracts show variable saturate fraction gas chromatogram (SFGC) characteristics. These range from a sample (Fig. 4a) that gave a SFGC closely resembling those from Ordovician G. prisca rich samples to those that show no odd or even carbon number preference with high abundances of acyclic isoprenoids and biomarkers (Fig. 4c) and those that show intermediate characteristics (Fig. 4b). The samples with higher concentrations of higher molecular weight nalkanes and biomarkers in their SFGCs have biomarker distributions characterized by low pristane/phytane ratios, a relatively high abundance of C20+ acyclic isoprenoids and a m/z 191 mass chromatogram (Fig. 5c) that shows a pronounced C34 homohopane prominence,

a relatively high abundance of gammacerane and low amounts of tricyclic and tetracyclic terpanes. These are characteristics that are generally associated with carbonate and elevated salinity depositional environments (e.g. Peters and Moldowan, 1993, pp. 141142, 209) which is in agreement with those interpreted for the Camrose Member (Fowler et al., 2001). Sterane carbon number distributions vary from a slight C27 predominance to a pronounced C29 predominance. Microscopic examination of these samples indicates little to no contribution from G. prisca to their organic matter. As noted earlier, some samples have organic matter dominated by G. prisca and hence resemble Ordovician kukersite deposits. The location that showed the best combined optical and chemical evidence of a G. prisca contribution in this study was the lower potential source interval of the Camrose Member at 13-32-7-20W4.

Fig. 4. Saturate fraction gas chromatograms of Camrose Member extracts from southern Alberta. C15, C20 and C25 are the C15, C20 and C25 n-alkanes, respectively; Pr and Ph are pristane and phytane; H is 17a(H)-hopane, and peak indicated with an asterisk is C17 n-alkylcyclohexane.

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Three samples of interlaminated organic-rich mudstones were taken between 1665.0 and 1665.90 m depth. This interval contains abundant shell fragments (brachiopod and bivalve) and sh fragments (e.g. sh bones). The maceral assemblage for this interval (Fig. 3) is dominated by G. prisca disseminated A and B alginite with very minor amounts of Prasinophyte alginite and acanthomorphic acritarchs. The depositional environment is thought to have had oxygenated surface waters with periodically more restricted anoxic bottom water conditions, possibly related to times of increased G. prisca productivity. These samples have TOC contents ranging from 10.60 to 16.76% and HI values from 797 to 864 mg HC/g TOC. Their Tmax values are 439441  C which are higher than might be expected for the level of maturity at this location (  0.70% vitrinite reectance

equivalent: Stasiuk and Fowler, 2002) but not for Type I organic matter. The SFGC of the sample from 1665.9 m (8842) is very similar to those of Ordovician kukersites (Fig. 4a). It shows a pronounced odd carbon number predominance of the C17 and C19 n-alkanes and low amounts of C20+ n-alkanes, acyclic isoprenoids and biomarkers. It also has relatively high concentrations of n-alkylcyclohexanes with the peaks of these compounds clearly apparent in the SFGC (Fig. 4a). A m/z 82 mass chromatogram (Fig. 6a) shows an odd carbon number predominance of these compounds over the C15-C23 range with an abrupt decrease in concentration after C23. This is a somewhat dierent distribution for these compounds compared with other North American kukersite extracts and derived oils which usually show a

Fig. 5. m/z 191 and m/z 217 mass chromatograms showing the distributions of terpanes and steranes, respectively, for Camrose Member organic-rich samples from southern Alberta. Peaks identied in Table 2.

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distribution similar to that of the n-alkanes (Fowler et al., 1986; Fowler, 1992). An extract of the Late Ordovician Collingwood Member from southern Ontario has been reported with a predominance of C23 and C25 nalkylcyclohexanes but with C14C31 homologues also present in moderate to high abundance (Fowler, 1992). The biomarker distribution of sample # 8842 (Fig. 5, Table 1) is dierent to most of the other Camrose Member/Nisku Formation organic-rich intervals that show no optical or chemical evidence of a major G. prisca contribution. This includes higher abundances of C27 and C29 17a(H)-hopanes relative to C30 17a(H)hopane, lower gammacerane and C34 homohopane prominence, lower Ts/Tm, much higher diasterane/regular ratio and a higher abundance of short-chain steranes (Fig. 5a, Table 1). Steranes are in much lower abundance than hopanes. While these characteristics cannot be attributed to a G. prisca contribution with any certainty, some of these characteristics have been previously noted for Ordovician kukersites and their derived oils, including the predominance of diasteranes over regular steranes (Longman and Palmer, 1987; Fowler, 1992), a relatively higher abundance of C27 and C29 hopanes (Zumberge, 1987) and the large predominance of hopanes over steranes (Fowler, 1992). It is noteworthy that the Family C oils of Abrams et al. (1999), which have SFGCs suggesting that they have a

source rock containing a signicant G. prisca contribution, show many similar biomarker characteristics including a C34 homohopane predominance, a much greater abundance of the C24 tetracyclic terpane than the C23 tricyclic terpane and relatively high abundances of diasteranes compared with the regular steranes. Evidence for a contribution from G. prisca to other Camrose Member samples is less obvious. A sample from 10-4-1-9W4 (sample #8664, Table 1) that optically showed a minor persistent contribution from G. prisca has intermediate geochemical characteristics between the 13-32-7-20W4 kukersite-like sample and samples that show no evidence of a G. prisca contribution. It has a slight odd carbon number preference up to C19 and lower abundance of acyclic isoprenoids and biomarkers (Fig. 4b). This sample also has a higher concentration of monocyclic alkanes than most other samples showing a pronounced odd carbon number preference up to C23 similar to the 13-32-7-20W4 sample (Fig. 6b). n-Alkylcyclohexanes are present in other samples (e.g. Fig. 6c) but in much lower abundance and with a dierent carbon number distribution. The 10-4-1-9W4 sample also shows intermediate biomarker characteristics including only a minor C34 homohopane prominence, a high C29/ hopane ratio, high diasteranes/regular steranes and C21 sterane/C29 sterane and low gammacerane/hopane ratios (Fig. 5b, Table 1). A number of other samples

Table 1 Geochemical data for Camrose Member/Nisku Formation extracted samples and a typical crude oil from the Nisku Formation reservoir (sample #2091) GSC # Location Depth (m) TOC% HI %HC S/A Pr/Ph Pr/17 S/(S+R) dia/reg 21/29 27:28:29 Ts/Ts+Tm 29/hop 23/hop g/hop alkylarom 21/21+23 8664 10-4-1-9W4 1185.75 7.15 895 21.71 0.29 1.20 0.27 0.46 0.61 0.41 47:10:43 0.21 0.75 0.10 0.17 high 0.56 8842 13-32-7-20-W4 1665.90 16.76 856 23.35 0.70 n.d. 0.02 0.45 1.94 0.79 43:13:44 0.13 0.74 0.07 0.11 high 0.74 8686 6-29-12-12W4 1276.55 2.26 765 40.85 0.53 0.69 0.21 0.47 0.75 0.44 33:14:53 0.17 0.72 0.06 0.14 high 0.69 8666 11-27-8-17W4 1418.06 4.19 800 17.87 0.26 0.71 1.14 0.27 0.10 0.08 38:11:51 0.21 0.49 0.29 0.52 low 0.98 8685 6-29-12-12W4 1269.72 3.72 784 25.46 0.28 0.83 0.27 0.46 0.68 0.32 15:15:70 0.27 0.73 n/d 0.35 high 0.98 2091 3-18-13-14W4 1331.5-1386.0 n/a n/a 76.48 0.62 0.58 0.12 0.45 0.86 0.68 37:16:47 0.28 0.76 0.32 0.11 high 0.77

N/anot applicable; TOC% total organic carbon; HIHydrogen Index;%HCweight percent hydrocarbons; S/Asaturated/ aromatic hydrocarbons ratio; Pr/Phpristane/phytane ratio; Pr/17pristane/n-C17 ratio; S/(S+R)5a(H),14a(H),17a(H) 20S/ (20S+20R)C29 sterane; dia/reg- 13b(H),17a(H) 20SC27 diasterane/5a(H),14a(H),17a(H) 20RC27 sterane; 21/29C21 sterrane/ 5a(H),14a(H),17a(H) 20RC29 sterane; 27:28:29normalized relative abundance of C27, C28 and C29 regular steranes based on aaa isomers; Ts/Ts+Tm18a(H)-trisnorhopane/(18a(H)-trisnorhopane+17a(H)-trisnorhopane); 29/hop17a(H)-norhopane/ 17a(H),21b(H)-hopane; 23/hopC23 tricyclic terpane/17a(H),21b(H)-hopane; g/hop- gammacerane/17a(H),21b(H)-hopane; alkylarom-relative abundance of n-alkylaromatics in aromatic fraction; 21/21+23C21/(C21+C23) n-alkylnaphthalenes.

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have characteristics intermediate between those of the kukersite-like sample (sample #8842) and samples interpreted to have no or very little G. prisca contribution (e.g. sample #8666). These were interpreted to have a signicant G. prisca contribution which is also supported by their aromatic hydrocarbon distributions and pyrolysis-gas chromatography data discussed below. The major compounds in the aromatic fractions of many of the rock extracts are C21 and C23 alkylated aromatic hydrocarbons. This is shown for a lower potential source rock sample from 6-29-12-12W4 (sample #8686) in Fig. 7. The mass spectra of the major compounds are very simple with the two major peaks being the base fragment ion (m/z 92, 141, 155) and a M+ ion. The C21 and C23 n-alkylbenzenes and n-alkylnaphthalenes are the major compounds with lower amounts of C21 and C23 alkylmethylnaphthalenes. The carbon number distributions of the n-alkylnaphthalenes and n-alkylbenzenes show a strong tendency to mirror each other for this sample set (Fig. 8), suggesting these compounds have a similar origin. The relative amounts of C21 and C23 compounds varies. All samples show a predominance of the C21 compounds except one which

Fig. 6. Representative m/z 82 mass chromatograms of Camrose Member organic-rich samples.

shows a slight predominance of C23. Extracts of the potential source rock at the base of the Camrose Member have lower values for the C21/(C21+C23)parameter than other source rock intervals (Table 1). Thus there could be a palaeoevironmental control on this parameter. This could be related to the dierent, deeper water organic facies previously noted for this interval compared with other Camrose/Nisku organic-rich units which were deposited under more restricted shallower conditions (Fowler et al., 2001). The m/z 92 and 141 mass chromatograms show that lower homologues are in very low abundance with a slight odd carbon number predominance over the C15C19 range. Sample #8842, which is one of the higher maturity source rock samples examined here, shows greater amounts of C20 and lower alkyl aromatic compounds than the other samples with an odd carbon number preference (Fig. 8). These may be derived from cracking of the C21 and C23 compounds or their precursors. There is possible evidence in these mass chromatograms of extremely low abundances of C23+ homologues, up to C30 for the alkylbenzenes and up to C25 for the alkylnaphthalenes. The m/z 155 mass chromatogram shows the presence of multiple isomers for the alkylmethylnaphthalenes. Aryl isoprenoids (i.e. 1-alkyl-2,3,6-trimethylbenzenes) which are thought to be derived from photosynthetic green sulphur bacteria (Summons and Powell, 1987; Hartgers et al., 1994) can only be detected in low abundance in samples with lower concentrations of the C21 and C23 alkylbenzenes because these latter compounds usually dominate the m/z 133 and 134 mass chromatograms due to their considerably higher abundance. This is in contrast to most of the other Devonian source rocks the Western Canada Sedimentary Basin, such the Duvernay Formation, which have much higher concentrations of aryl isoprenoids (e.g. Requejo et al. 1992). The aromatic fraction of the Collingwood Member sample from southern Ontario mentioned earlier that had a predominance of C23 and C25 n-alkylcyclohexanes was also analyzed for comparison with the Camrose Member extracts. C21 and C23 n-alkylnaphthalenes and n-alkylmethylnaphthalenes were not detected. There was a relatively high abundance of n-alkylbenzenes up to C30 with the C23C25 members in highest concentrations. Thus the distributions of the n-alkylcyclohexanes and n-alkylaromatics in the Ordovician Collingwood sample are very dierent to the Upper Devonian Camrose Member samples. The concentration of the C21 and C23 benzenes and alkylnapthalenes varies in the Camrose Member/Nisku Formation extracts. There does not seem to be any obvious correlation with the source rock interval or proximity to anhydrite intervals. However, there does seem to be some correlation with the presence of G. prisca alginite. A subjective assessment of the relative abundance of these compounds is provided in Table 2.

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Fig. 7. Aromatic hydrocarbon data for an organic-rich Camrose Member sample from 6-29-12-12W4 (1276.55 m); (a) Total Ion Chromatogram (TIC), (b) m/z 92 mass chromatogram, (c) m/z 141 mass chromatogram, (d) m/z 155 mass chromatogram.

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High abundance indicates that these are among the most abundant aromatic compounds in the extracts. Generally, these compounds are in either very high or very low abundance. It is noticeable that the C21 and C23 alkylaromatic species are more abundant in samples where other geochemical characteristics suggested a signicant G. prisca contribution based on SFGC characteristics (n-alkane distributions, concentration of acyclic isoprenoids and biomarkers) and biomarker features (e.g. minor C34 homohopane prominence, lower gammercerane/hopane ratio). For example, these compounds are in high abundance in the kukersite-like sample #8842, but in much lower concentrations in a sample such as #8666 which is believed to have little G. prisca contribution (Fig. 10).

High abundances of alkylated benzenes and naphthalenes have been noted previously in sediments thought to be deposited under elevated salinity conditions or their derived oils (Connan et al., 1986; Williams et al., 1993). They have et al., 1988; Sinninghe Damste been attributed a probable bacterial precursor. C21 compounds were found by Connan et al. (1986) and Williams et al. (1988) to be in highest abundance in their et al. (1993) noted a variety samples. Sinninghe Damste of alkylbenzene distributions in Mulhouse Basin samples including some that showed a large predominance of C23 with the C25 also in much higher concentrations than other homologues. They did not observe the C21 and C23 predominance displayed by the Camrose Member samples.

Fig. 8. Aromatic hydrocarbon data for an organic-rich Camrose Member samples from 13-32-7-20W4 (1665.9 m) and 11-27-8-17W4 (1418.0 m).

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The C21 and C23 alkylaromatic compounds in the G. prisca-rich Camrose Member samples may have a similar origin to the high concentrations of n-alkyl phenols, especially C21 and C23, that have been noted in some Ordovician kukersite pyrolysates from Estonia (Derenne et al., 1990; Blokker et al., 2001). These alkyl phenols occur in much lower concentrations in pyrolysates from another Ordovician kukersite deposit, the Guttenberg Member (Derenne et al., 1990; Blokker et al., 2001). This was attributed to G. prisca growing under conditions of higher salinity during deposition of the Estonian kukersite by Derenne et al. (1990, 1992) and/or due to the higher maturity of the Guttenberg Member (Blokker et al., 2001). The Camrose Member samples that have signicant G. prisca contribution were likely deposited under conditions of elevated salinity, considering their close association with evaporites, and thus may be the source of the C21 and C23 alkylaromatics. The results of pyrolysis-gas chromatography also appear to show the inuence of a G. prisca contribution to some samples. As indicated in Fig. 9, both the #8842 and #8664 samples show similar pyrograms to an Ordovician Yeoman Formation kukersite pyrolysate from the Williston Basin, Canada. The Ordovician sample shows a decrease in abundance after C17 for alkenealkane doublets which is also shown by the two Camrose Member samples, suggesting that a large proportion of the organic matter of these samples is likely
Table 2 Biomarker compounds identied in saturate fraction mass fragmentograms shown in Figs. 5 and 10 Peak Compound 1 2 3 4 5 6 7 8 9 10 11 12 13 Fig. 9. Whole-rock pyrograms of (a) Upper Ordovician Yeoman Formation kukersite interval from southeast Saskatchewan portion of Williston Basin and (bd) Late Devonian Camrose Member organic-rich interval samples from southern Alberta, (b) G. prisca-rich sample from 13-32-7-20W4 (1665.9 m), (c) Moderately-rich G. prisca sample from 10-4-1-9W4 (1185.75 m) and (d) G. prisca-poor sample from 11-27-8-17W4 (1418.06 m). 12 and 17 are the C12 and C17 alkenealkane doublets, TMB is tetramethylbenzene. a b c d e f g h C23 tricyclic terpane C24 tetracyclic terpane 18a(H),22,29,30-trisnorhopane(Ts) 17a(H),22,29,30-trisnorhopane (Tm) 17a(H),21b(H)-30-norhopane 17a(H),21b(H)-hopane moretane 17a(H),21b(H)-homohopanes (S & R) gammacerane 17a(H),21b(H)-bishomohopanes 17a(H),21b(H)-trishomohopanes 17a(H),21b(H)-tetrakishomohopanes 17a(H),21b(H)-pentakishomohopanes pregnane diacholestane 20S 5a(H),14a(H),17a(H)-cholestane (20S) 24-methyl-5a(H),14a(H),17a(H)-cholestane 24-ethyl-5a(H),14a(H),17a(H)-cholestane (20S) 24-ethyl-5a(H),14b(H),17b(H)-cholestane (20S & 20R) 24-ethyl-5a(H),14a(H),17a(H)-cholestane (20R) 24-propyl-5a(H),14a(H),17a(H)-cholestane (20S & 20R)

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derived from G. prisca. Other Camrose Member/Nisku Formation samples that were thought not to have a signicant G. prisca contribution show very dierent pyrograms (Fig. 9d) with much higher amounts of higher molecular weight compounds. They all show a relatively large tetramethylbenzene (TMB) peak. This compound is thought to be mostly derived from aryl isoprenoids and their precursors found in Chlorobiacae (Hartgers et al., 1994). The #8664 sample shows a small TMB peak that is not evident in the #8842 sample, once again suggesting it was deposited in an intermediate environment between those of the G. prisca-rich and -poor intervals. 3.4. Southern Alberta oils The Nisku reservoired oils at Enchant-Hays in southern Alberta (Fig. 1) are thus far the only major eld discovered in the Nisku Formation in this region. In total, 21 oils from Nisku Formation reservoirs from the Enchant-Hays area were analyzed for this study. Most of these oils show features that allow them to be dierentiated from all other Devonian oils of the WCSB. This is most apparent in their SFGCs which commonly show a high abundance of n-alkanes up to C17, often with a distinct odd carbon number predominance over the C15C19 range, followed by a rapid

decrease in concentration to C18 and then a more gradual decrease in abundance with no odd or even carbon number preference (Fig. 10). The samples tend to show a low abundance of acyclic isoprenoids and biomarkers relative to n-alkanes. Most oils share other characteristics in common including, low saturate/aromatic ( < 0.76) and pristane/phytane ratios ( < 0.82), low amounts of rearranged steranes and hopanes compared to their unrearranged counterparts, a predominance of the C24 tetracyclic terpane over the C26 tricyclic terpanes and a signicant gammacerane peak (Fig. 10c). Some also show a C34 homohopane prominence. Aryl isoprenoids are present in these oils as relatively minor components. The C21 and C23 n-alkybenzenes and nalkylnaphthalenes are among the most abundant aromatic hydrocarbons in these oils. The C21 compounds are in much higher concentrations than their C23 homologues, often by a factor of two or more (Fig. 10b). Enchant-Hays oils also have gasoline range hydrocarbon distributions that dier from almost all the other Devonian oils analyzed from Western Canada. They show a very high abundance of n-alkanes relative to other compounds, with aromatics such as toluene present in very low concentrations. This leads to some unusual values for gasoline range parameters such as the very high heptane values which are more typical of supermature oils (i.e. heptane values > 30) (Thompson,

Fig. 10. Geochemical data for a Nisku Formation oil from southern Alberta (Hays 3-18-13-14W4, 1331.5-1386.0 m). (a) Saturate fraction gas chromatogram (annotation of peaks as in Fig. 4), (b) partial aromatic hydrocarbon TIC; MNmethylnaphthalenes, MPmethylphenanthrene, 21B and 23Bn-alkylbenzenes, 21N and 23Nn-alkylnaphthalenes (c) m/z 191 mass chromatogram, (d) m/z 217 mass chromatogram; peaks identied in Table 2.

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1983). While low concentrations of aromatics can be attributed to water-washing, in the case of these Nisku oils it is thought to relate to their source organic matter as these gasoline range characteristics are also similar to those shown by Ordovician kukersite derived oils from the Williston Basin (Fowler et al., 1998).

4. Discussion Both optical and chemical evidence indicate a signicant contribution from G. prisca to the organic matter of Camrose Member potential source rock intervals. Organic petrological observations show that the morphology of G. prisca in these Late Devonian samples is very similar to that observed in many Ordovician kukersite deposits. However, there is a strong predominance of G. prisca with the closed morphology within the Camrose Member samples. The extract characteristics of the samples believed to have a major G. prisca contribution are also similar to those of Ordovician kukersites. For example, SFGCs with a predominance of odd numbered n-alkanes up to C19 and lower abundances of C20 and higher n-alkanes, acyclic isoprenoids and biomarkers. Saturated hydrocarbon biomarker distributions, especially those of the most G. prisca-rich sample (sample #8842), also have similar features to those reported for Ordovician kukersite samples. However, there is a signicant dierence in the aromatic hydrocarbons with the Camrose Member samples having high concentrations of C21 and C23 n-alkylnaphthalenes and n-alkylbenzenes which have not been previously reported for Ordovician samples. The origin of these compounds is still uncertain but their empirical association with G. prisca-rich samples suggest that their precursors are biochemical components of this organism. They may have a similar origin to the C21 and C23 n-alkylphenols that are abundant in the pyrolysates of Estonian kukersite (Derenne et al., 1990, 1992; Blokker et al., 2001). Derenne et al. (1992) showed that increasing salinity from 0 to 10 g/l of NaCl could inuence the morphology of extant Botryococcus braunii and its production of phenols. By analogy, they suggested that variations in salinity could be the cause of similar changes observed for G. prisca in dierent Ordovician rocks. The range of salinity chosen by Derenne et al. (1992) for their experiments with Botryococcus braunii reect those in which this organism mostly thrives (i.e. freshwater to brackish) and did not range up to normal seawater salinity. There is considerable geological evidence that G. prisca lived mostly in normal marine environments during the Ordovician including for example, the Middle Ordovician Guttenberg Member of the Decorah Formation in Iowa (Ludvigson et al., 1996) and Upper Ordovician kukersite intervals in the Williston Basin,

Saskatchewan (Kendall, 1976; Stasiuk and Osadetz, 1990). The Camrose Member intervals enriched in G. prisca are always associated with interbedded evaporites and dolomites suggesting that the organism was living in conditions of higher than normal salinity. Thus, although G. prisca is likely a dierent type of organism to Botryococcus braunii, the adoption of the closed cellular morphology and the high abundance of C21 and C23 alkylaromatic compounds may represent a similar response to growth under higher salinity conditions for this organism. The saturate fraction gas chromatograms, aromatic hydrocarbon distributions and gasoline fraction hydrocarbons all suggest that the organic-rich intervals that are the source of most of the Enchant-Hays oils had a signicant G. prisca contribution. The saturated hydrocarbon biomarkers give more ambiguous evidence for the origin of the oils. This can be explained by the Camrose Member/Nisku Formation potential source rocks containing several dierent organic facies (Fowler et al., 2001). Hence, any oils that are derived from them might reasonably be expected to have contributions from units with dierent geochemical characteristics, some indicative of a signicant G. prisca contribution and others not. The SFGCs of the Enchant-Hays oils from Nisku Formation reservoirs with the predominance of odd number n-alkanes up to C19 (Fig. 10a), and the relatively high abundance of C21 and C23 n-alkylaromatics (Fig. 10b) strongly suggest that G. prisca-rich intervals were a major source of hydrocarbons for these Late Devonian oils. These source rock intervals tend to contain much lower concentrations of biomarkers than intervals where G. prisca made a lesser contribution to their organic matter. Hence, the distribution of biomarkers in the Enchant oils would likely show a greater inuence from the non-G. prisca source intervals than other compound classes which might explain why they have intermediate characteristics. This paper conclusively demonstrates the presence of G. prisca in Late Devonian sediments in southern Alberta using both optical and chemical evidence. In addition, G. prisca-like coccoidal algae have also been optically distinguished as a minor contributor to the organic matter in other Middle and Late Devonian units within the Western Canada Sedimentary Basin (WCSB) that do not show the chemical ngerprint for G. prisca (Stasiuk, unpublished results). These include the Middle Devonian Keg River and Winnipegosis formations and Late Devonian Duvernay Formation in central and northern Alberta, and the Winnipegosis Formation and Late Devonian Birdbear Formation, that is equivalent in age to the Camrose Member/Nisku Formation intervals discussed in this paper, in southern Saskatchewan. However, in all of the other WCSB Devonian units G. prisca is only rarely found as a minor component in organic-lean intervals deposited under

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shallow water oxidizing conditions within carbonate platform settings. This suggests that the precursor of their G. prisca alginite lived in the photic zone of mainly shallow water depositional environments. Despite the oxidative conditions and apparent low algae-biological productivity within the water column during deposition of these sediments, some marine alginite macerals were nonetheless preserved, probably as a result of selective preservation of highly resistant algaenan biomacromolecules found in the outer cell walls derived from the G. prisca precursor (e.g. Tegelaar et al., 1989). Prasinophyte algae such as Tasmanites and Leiosphaeridia are the main primary producers contributing to the organic matter of the most of the Devonian source rocks in the WCSB such as the Duvernay and Keg River formations (Chow et al., 1995). The presence of G. prisca as a signicant contributor to Camrose Member potential source rocks and not to any of the several other Devonian source rocks in the Western Canada Sedimentary Basin (Fowler et al., 2001), allows us to speculate on the post-Ordovician history of this organism. The geological record clearly shows that G. prisca lost its position as a dominant algae in the open marine tropical seas after the Ordovician-Silurian extinction event. This probable cyanophyte (Foster et al., 1989; Stasiuk and Osadetz, 1990; Wicander et al., 1996) was replaced in this environmental niche by Prasinophytes and other green algae. It survived in shallow water, near-shore environments that are not typically considered conducive to source rock development. It may also have had an ability to tolerate higher salinity conditions which are not as favourable to Chlorophytes, and thus could have thrived in some of these environments at least until the Late Devonian where it can be a major contributor to petroleum source rocks, such as those in the Camrose Member. This speculation is obviously based on data from just one basin but it will be interesting to see if other postOrdovician occurrences of G. prisca are also associated with strata deposited under higher than normal salinity. Reports to date such as that of Abrams et al. (1999) do not provide enough data to verify this.

5. Summary and conclusions Some Late Devonian Camrose Member potential source rock samples show characteristics that suggest a contribution to their organic matter by the organism G. prisca whose presence is very rarely noted in postOrdovician strata. G. prisca characteristics are best demonstrated by a lower Camrose Member sample from 13-32-7-20W4 that shows a saturate fraction gas chromatogram very similar to Ordovician kukersite samples, including an odd/even predominance of n-alkanes up to C19, much lower abundances of C19+ n-alkanes, acyclic

isoprenoids and biomarkers, and relatively high concentrations of n-alkylcyclohexanes. Other samples show a range of characteristics intermediate between the kukersite and those more typical for carbonate environments. Microscopy conrms that G. prisca alginite is the dominant component of the 13-32-7-20W4 sample and major constituent of many other samples that show the G. prisca chemistry. The morphology of the Late Devonian G. prisca is generally similar to that observed in Ordovician samples although the closed cellular morphology is more common which could be related to growth of this organism under elevated salinity conditions. An unusual feature of many of the Camrose Member/Nisku Formation extracts is the very high concentrations of C21 and C23 n-alkylaromatic compounds, especially n-alkylnaphthalenes and n-alkylbenzenes in their aromatic fractions. This distribution does not seem to have been previously reported and the origin of these compounds is still uncertain. However, the C21 and C23 n-alkylaromatics are in higher concentrations in those samples with a high G. prisca contribution to their organic matter and hence their occurrence could be related to the biochemistry of this organism. The n-alkylaromatics may have a similar origin to the C21 and C23 n-alkylphenols that have been noted in high concentrations in some kukersite pyrolysates from Estonia that could be due to G. prisca growing under higher salinity conditions (Derenne et al., 1990, 1992; Blokker et al., 2001). Thermally mature equivalents of the Camrose Member/Nisku Formation potential source rocks are considered the source of the oils that occur in Nisku Formation reservoirs in the Enchant-Hays eld of southern Alberta. Saturate fraction and gasoline range gas chromatograms, and the presence of the n-alkylaromatics in the Enchant-Hays oils in relatively high concentrations indicates an important contribution from G. prisca-rich intervals. We have demonstrated conclusively using both optical and chemical evidence that G. prisca was a contributor to some very organic-rich intervals within the Late Devonian Camrose Member. We have also observed G. prisca optically as an occasional, minor component in organic-lean intervals in other Middle and Late Devonian units of the Western Canada Sedimentary Basin where its presence is not readily chemically evident. Hence, G. prisca did survive the Ordovician-Silurian extinction event but appears to lose much of its ecological niche to prasinophytes and other green alga that dominate most of the organic-rich Devonian intervals within the Western Canada Sedimentary Basin. These data and other reports (e.g. Abrams et al., 1999) indicate that caution should be used in unequivocally attributing a Cambro-Ordovician age to sediments and oils having G. prisca geochemical characteristics, as these can also occur in rocks as young as the Late Devonian.

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M.G. Fowler et al. / Organic Geochemistry 35 (2004) 425441 Late Ordovician Age from Canada. In: Schidlowski, M. et al. (Eds.), Early Organic Evolution: Implications for Mineral and Energy Resources. Springer-Verlag, Berlin, Heidelberg, pp. 336356. Fowler, M.G., Stasiuk, L.D., 1999. Presence of Gloeocapsomorpha prisca in Devonian sediments of the Western Canada Sedimentary Basin. In: 19th International Meeting on Organic Geochemistry, September 1999, Istanbul, Turkey, Abstracts Part 1, pp.163164. Fowler, M.G., Abolins, P., Douglas, A.G., 1986. Monocyclic alkanes in Ordovician organic matter. Organic Geochemistry 10, 815823. Fowler, M.G., Stasiuk, L.D., Li, M., Obermajer, M., Osadetz, K.G., Idiz, E., 1998. Reexamination of the Red River Petroleum System, southeastern Saskatchewan, Canada. In: Christopher, J.E., Gilboy, C.F., Paterson, D.F., Bend, S.L. (Eds.), Eighth International Williston Basin Symposium, Saskatchewan Geological Society Special Publication No. 13, pp. 1113. Fowler, M.G., Stasiuk, L.D., Hearn, M., Obermajer, M., 2001. Devonian hydrocarbon source rocks and their derived oils in the Western Canada Sedimentary Basin. Bulletin of Canadian Petroleum Geology 49, 117148. , J.S., Requejo, A.G., Allan, Hartgers, W.A., Sinninghe Damste J., Hayes, J., Ling, Y., Xie, T.-M., Primack, J., de Leeuw, J.W., 1994. A molecular and carbon isotopic study towards the origin and diagenetic fate of diaromatic carotenoids. Organic Geochemistry 22, 703725. Homann, C.F., Foster, C.B., Powell, T.G., Summons, R.E., 1987. Hydrocarbon biomarkers from Ordovician sediments and fossil alga G. prisca Zalessky 1917. Geochimica et Cosmochimica Acta 51, 26812697. Hutton, A.C., 1987. Petrographic classication of oil shales. International Journal of Coal Geology 8, 203231. Kendall, A.C., 1976. The Ordovician Carbonate Succession (Bighorn Group) of Southern Saskatchewan. Saskatchewan Department of Mineral Resources, Report 180. Kissling, D.L., 1996. The Nisku Formation of south Alberta and northwest Montana: birth to burial of an Upper Devonian barrier-lagoon complex. In: Longman, M.W., Sonneneld, M.D. (Eds.), Paleozoic Systems of the Rocky Mountain Region. Society for Sedimentary Geology, Rocky Mountain Section, pp. 97116. Longman, M.W., Palmer, S.E., 1987. Organic geochemistry of Mid-Continent Middle and Late Ordovician oils. American Association of Petroleum Geologists Bulletin 71, 938950. lez, Ludvigson, G.A., Jacobson, S.R., Witzke, B.J., Gonza L.A., 1996. Carbonate component chemostratigraphy and depositional history of the Ordovician Decorah Formation, Upper Mississippi Valley. In Witzke, B.J., Ludvigson, G.A. and Day, J. (Eds.) Paleozoic Sequence Stratigraphy: Views from the North American Craton. Geological Society of America Special Paper 306. Nowlan, G.S. (Compiler and editor), 1998a. The Lower Paleozoic: A New Frontier in the Western Canada Basin, Part 1, Report to Partners 19931994. Geological Survey of Canada Open File Report #3416. Nowlan, G.S. (Compiler and editor), 1998b. The Lower Paleozoic: A New Frontier in the Western Canada Basin, Part 2, Report to Partners 19941995. Geological Survey of Canada Open File Report #3603.

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