Organic petrology and RockEval analysis of the Lower Carboniferous Emma Fiord Formation in Sverdrup Basin, Canadian Arctic Archipelago

Organic petrology and RockEval analysis of the Lower Carboniferous Emma Fiord Formation in Sverdrup Basin, Canadian Arctic Archipelago* F. Goodarzi, W. W. Nassichuk and L. R. Snowdon Institute of Sedimentary and Petroleum Alberta, T2L 2A7, Canada

Geology, 3303-33rd Street NW, Calgary,

and G. R. Davies AGAT Technologies Inc., 3650 21st Street NE, Calgary, Alberta, T2E 6V6, Canada

Received 3 October 1986; revised 19 January 1987 Samples of the Lower Carboniferous Emma Fiord Formation from two localities in the Sverdrup Basin of Arctic Canada were examined using reflected white and fluorescent light. The samples from Kleybolte Peninsula on Ellesmere Island show a relatively high level of thermal maturity. In contrast, those from Grinnell Peninsula on Devon Island are immature to marginally mature and include subbituminous coals and oil shales. Two types of oil shales are distinguished on the basis of liptinite content, mineral matrix, RockEval pyrolysis analysis, and concentration of boron. One is characterized by a liptinite-rich, clay-carbonate matrix with a relatively high hydrogen index and boron content, and the other by a liptinite-poor carbonate matrix with a relatively low hydrogen index and boron content. Hydrogen-rich components of these shales consist of alginite, matrix bituminite and minor amounts of exsudatinite and sporinite. Kerogen Types Ill and IV comprise only minor components of the organic matter. Thermal maturity of the Grinnell Peninsula oil shales increases with depth. Matrix bituminite in these oil shales has seeped into cavities and microfractures in the kerogen Types Ill and IV, forming exsudatinite. The distribution and character of the organic constituents and also the concentration of boron in these samples indicate a fresh to brackish water environment. Keywords: Reflectance; Fluorescence; RockEval; Lower Carboniferous

Introduction Samples from the Lower Carboniferous (Vis6an) Emma Fiord Formation in the Canadian Arctic Archipelago have been analysed for the types of organic material present, their maturity, and their environment of deposition. The samples are from two sections of the Emma Fiord Formation in two geographically and tectonically diverse parts of Sverdrup Basin (Figure 1). The general geological setting and detailed lithofacies and sedimentology of the Emma Fiord Formation at these two localities is the subject of another paper (Davies and Nassichuk, in press). One of the major exposures of the Emma Fiord Formation is on Grinnell Peninsula, Devon Island, near the southeastern margin of the Sverdrup Basin (Figure lb). At this location, the formation has a maximum measured thickness of 145 m, and is composed mainly of recessive-weathering, black marlstone and shale with interbedded thin coal seams, and algal and oolitic limestones (Figure 2). The other major exposure of the Emma Fiord Formation is at the type locality on Kleybolte Peninsula, northwestern Ellesmere Island (Figure lc and 3). The Kleybolte Peninsula setting is on the northwestern margin of the Sverdrup Basin, a structural element that was intermittently active *Geological Surveyof Canada Contribution No 41786 0264-8172/87/020132-a4 plus three colour plates $03.00 ©1987 Butterworth & Co. (Publishers) ktd 132

Marine and Petroleum Geology, 1987, Vol 4, May

tectonically from late Paleozoic through to Tertiary time. The Emma Fiord Formation at this location is about 400 m thick, and is composed mainly of recessiveweathering, black, carbonaceous shale and siltstone with rhythmically-interbedded silica-cemented, lithic quartz sandstones and coarse siltstones capped by syntectonic conglomerates. It is overlain by volcanic rocks of the Carboniferous Audhild Formation and is extensively intruded by dykes. Biotic evidence, lithotogical characteristics and the overall tectonic setting, relative to younger upper Paleozoic strata in the Sverdrup Basin, place the Emma Fiord Formation in a lacustrine depositional environment. Because of the lacustrine setting, the organic petrology of the Emma Fiord Formation is of particular significance in terms of the types of organic components and their maturity.

Types of organic matter in oil shales Oil shale 'is a fine grained sedimentary rock containing indigenous organic matter, mostly insoluble in ordinary petroleum solvents, from which significant amounts of shale oil can be extracted by pyrolysis (i.e. heating in a retort)' (Macauley, 1984, p. 3). The use of the term 'significant' leaves the definition somewhat open ended, but in general, oil shales are rich in hydrogen derived from plant lipids. Sapropelic coals (boghead and cannel coals) are formed by physical and biological degradation of

Lower Carboniferous Emma Fiord Formation." F. Goodarzi et al. r,,

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formed by alteration of hydrogen-rich macerals (e.g. alginite, cutinite, resinite and sporinite) during coalification (Teichmtiller and Wolf, 1977; Durand et al., 1983). Chemical or bacterial decomposition of animal, planktonic or bacterial lipids also may result in the formation of bituminite (Teichmfiller, 1982; Snowdon el al., 1986). Bituminite is broadly classified into three types. Bituminite I is formed as a result of decomposition of algae (Teichm~ller and Ottenjann , 1977; Teichmfiller and Wolf, 1977; Gormly and Mukhopadhyay, 1983). Bituminite II is regarded as bacterially-altered plant lipids and decomposition products of phyto- and zoo-plankton (Teichmtiller and Wolf, 1977; Gormly and Mukhopadhyay, 1983: Snowdon et al., 1986).

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existing coal-peat and selective removal of humic components of coals. Bogheads include algae, which were either introduced by transportation or which were living at the point of accumulation of degraded materials, and water- or wind-borne plant spores (Moore, 1968). Sapropelic coals are formed under shallow water conditions and have limited spatial extent, both laterally and vertically (Moore, 1968). Boghead shale is a boghead coal that is extensively contaminated by clay minerals and quartz, and represents the sapropelic facies of a carbonaceous shale (Stach, 1982). Low-rank sapropelic coals are marked by high hydrogen content in the form of fat and protein (Teichmtiller, 1982). Alginite is the main liptinitic maceral in boghead coal and torbanite (alginite-rich oil shale), and is the oil-rich maceral that forms kerogen Type I (Brooks, 1981). It has the lowest aromaticity of all macerals in bituminous coal (Millaid and Murchison, 1969). Alginites in the Carboniferous bogheads resemble two forms of multicellular algae, Pila and Reinschia: these two algae are comparable with the recent green alga Botryococcus braunii (Blackburn and Temperley, 1936). Pila and Reinschia have both been found in the Carboniferous in the Northern Hemisphere; for example, at Torbane Hill in Scotland (Moore, 1968; Teichmiiller, 1982). Thermal decomposition (catagenesis) of alginite results in the formation of bituminite (Teichmtiller, 1982). Bituminite is a secondary maceral which is

[ • ' ] M a r l s t and o n eshale Plant d e t r i t u s 90

,,o} Ooids 1 Sample l o c a t i o n s

,$ E

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30 ¸

0

=essive, p r o b a b l y m a r l s t o n e c a r b o n a c e o u s shale

)rmed Franklinian r o c k s : v,,u,'ian or older

Figure 2 Grinnell Peninsula section of E m m a Fiord F o r m a t i o n Devon Island (Figure I, P a r t B)

Marine and Petroleum Geology, 1987, Vol 4, May

133

Lower Carboniferous Emma Fiord Formation: F. Goodarzi et al.

K L E Y B O L T E P E N I N S U L A SECTION, E L L E S M E R E IS.

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300

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ROCKS:

Figure 3 Kleybolte Peninsula section of Emma Fiord Formation Ellesmere Island (Figure 1. Part C)

134

M a r i n e and P e t r o l e u m G e o l o g y , 1987, Vol 4, M a y

Lower Carboniferous Emma Fiord Formation." F. Goodarzi et Figures 4 and 5 Morphology of organic components of oil shale samples from Grinnell section, Emma Fiord Formal plane-polarized, reflected white and fluorescent light (blue-violet, exciter filter 450 nm, barrier filter, 520 nm), oil immersion: the I axis of each photograph is 240 microns

OO Figure 4a Shale in reflected white bight. Vitrinite (V), semi-fusinite (SF), fusinite (F), inertodetrinite (ID), pyrite (P), carbonate (C) are present

O

Figure 4ai Same view under fluorescent light. Alginite sporinite (S), liptodetrinite (LD), cell-filling exsudatinite granular bituminite Type I (B) and bitumen (BI) are present

0 O

0 0

Figure 4b Shale in reflected white light containing resinite (R), sporinite (S), bituminite (B), inertodetrinite (ID) and pyrite (P)

Figure 4bi Same view under fluorescent light. Alginite resinite (R), sporinite (S), and string of granular bituminit~ are present

Figure 4c Botryococcus algae (A) and sporinite (S)

Figure 4d Botryococcus algae (A), oxidized algae (OA) shov oxidation rim (O), and sporinite (S) in shale

Marine and Petroleum

G e o l o g y , 1987, V o l 4, M a y

Lower Carboniferous Emma Fiord Formation: F. Goodarzi et al.

O Figure 4e Shale consists of alginite (A), sporinite (S),

Figure 4f Sporinite (S) showing internal structure

liptodetrinite (LD), and matrix bituminite (MB). Exsudatinite (E) displaying high fluorescence intensities and filling the cell lumens of inertinite (I)

O

O Figure 4g Exsudatinite (E) filling the cavity of inertinite (I)

Figure 4h Oil shale containing non-fluorescing fusinite (F), and fluorescing alginite (A), sporinite (S), matrix bituminite (MB), and cell-filling exsudatinite (E)

O

O

O Figure 5a Shale containing vitrinite

(V), fusinite inertodetrinite (ID), and sporinite (S); white light

O

(F),

O

Figure 5ai Same view under fluorescent light, vitrinite (V) and fusinite (F) are not fluorescing, alginite (A), sporinite (S), liptodetrinite (LD), matrix bituminite (MB), and cavities and microfractures filled with exsudatinite are present. The granular sporinite ($1) consists of lycopod spores (fern)

Marine and Petroleum Geology, 1987, Vol 4, May

C3

L o w e r Carboniferous E m m a F i o r d F o r m a t i o n : F. Goodarzi et

Figure 5b Shale contains vitrinite Type IIIB showing granularity

Figure 5bi Same view under fluorescent light. Alginite (,

(VB), and non-granular Type IIIC (VC), semifusinite (SF) and fusinite in clay marlstone; reflected white light

sporinite (S) and cell-filling exsudatinite (E) are present

O Figure 5c Shale containing vitrinite Type Ilia (VA), Type IIIb (VB),

Figure 5¢i Same view under fluorescent light. Sporinite ('.

inertodetrinite (ID), micrinite (M), alginite (A) and sporinite (S)

shows the two-layered structure. Alginite (A) is present

OG Figure 5d Alginite in Boghead (sample 8, Table 1) perpendicular to bedding

Figure 5e Shale containing alginite (A), sporinite (S), matr bituminite (MB) and non-fluorescent kerogen Types III and P Note the presence of exsudatinite (E) in internal cavity sporinite (S)

Marine and Petroleum

Geology,

1987, V o l 4, M a y

C

Lower Carboniferous Emma Fiord Formation: F. Goodarzi et al.

Figure 6 Morphology of organic components of sediments from Kleybolte section, reflected light, oil immersion, magnification as in

Figure 4

Bituminite III is a product of liptinite of higher terrestrial plants and humic materials (Teichmtiller and Ottenjann, 1977; Gormiy and Mukhopadhyay, 1983; Snowdon et al., 1986). Williams (1983) and Macauley et al. (1985) have summarized the classification and properties of oil shales. Macauley et al. (1985) have divided oil shales into non-marine (continental) and marine types, based on their kerogen composition and occurrence of organic and inorganic fossils. Oil shales are formed under anoxic conditions, where high algal input due to prolific planktonic growth in surface water results in an abundance of sapropelic organic material in sediment, which becomes preserved under anaerobic conditions. Torbanite is a continental oil shale deposited under lagoonal conditions, commonly in association with peat-forming swamps. Torbanite forms in basins with restricted water inflow in areas free from ulmic materials, for example: (1) in small shallow basins with water supply from rainfall or by seepage through layers of peat, or (2) in the centres of larger basins, where the waters are well aerated and the input of humic organic material is restricted (Moore, 1968). Torbanite contains mainly alginite, with some input of other liptinite macerals (bituminite and sporinite) and vitrinite and inertinite. Cook et al. (1981) stated that torbanite may contain up to 90 vol% alginite. The Canadian Arctic is a promising area for exploration for coals, petroleum and gas. However, with the exception of coal, relatively few studies of organic material have been carried out. Ricketts and Embry (1984, 1986) and Bustin (1985) reported on the coal deposits of the Arctic, while Goodarzi et al. (in press) examined Cretaceous coals of Melville Island. The organic petrology and geochemistry of sediments in the central Arctic have been studied by Brooks et al. (1986 in press).

measured in the range of 400-700 nm and fluorescent curves were generated using a Zonax microcomputer equipped with a plotter. The fluorescence spectra were obtained using an ultraviolet (365 nm) excitation filter and a 420 nm barrier filter. This combination allowed the determination of fluorescence spectra of hydrogen-rich components of the samples with ~'max (wavelength of maximum intensity) > 420 nm. The fluorescence properties determined included colour, ~'max and Red to Green Quotient (Table 1). Fluorescence intensities (I) of samples were also determined (Table 1) at 546 nm using a combination of 450 nm excitation and 510 barrier filter, and a Leitz fluorescence standard following the recommendation of Jacob (1976). Photomicrographs were taken under reflected and under fluorescent light. 120.0

90.0 A

E

v e,-

60.0

Experimental Polished specimens were made of samples of the coal and oil shales according to the recommendations of Mackowsky (1982). These samples were examined using reflected white-light and fluorescent light microscopy. Reflectance measurements in oil (n = 1.518 at 24°C) were determined using a Zeiss MPM II reflected light microscope fitted with white (halogen) and fluorescent light (HBO) sources. Spectral intensities were

30.0

I

o

50

lOO

% Kerogen

1

2

3

4

5

Figure 7 Organic-inorganic components data profile in Grinnell

section 1. Alginite (1), other liptinite (2), matrix bituminite (3), kerogen Types III and IV (4) and mineral matter (5) M a r i n e and P e t r o l e u m G e o l o g y , 1987, Vol 4, M a y

135

E

< o

oo

o o ,<

63

3

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Q. "13

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E

Clay-Carb

32916

09

Coal

32891

01

53.0

55.0

57.0

60.0

64.0

67.0

84.0

90.0

95.0

104.0

108.0

Depth (m)

0.50

0.44

0.26

0.32

0.35

0.30

0.27

0.26

0.30

0.31

0.37

%Roil

1.0

2.2

19.2

9.8

3.0

2.6

25.8

38.2

13.0

3.0

2.6

A1

6.2

--

5.4

6.0

0.8

1.0

11.8

4.0

0.2

--

--

EX+Bi 2

TYPE I

- -

--

60.0 0.8 89.0

1.0

2.0

4.0

0.8

2.0

4.0

4.0

2.4

Present

1.8

2.0

Present

-64.4

2.0 Present

1.8

Present

55.4

50.0

2.0

78.4

1.0

0.8

-Present

S4

--

- -

M.Bi 3

III +IV

II

2.6

97.1

11.2

13.8

95.2

92.0

1.0

6.8

1.4

96.0

96.6

Min. MATTER

--

1.15 -1.16

3.10 3.00 3.50

2.80

0.32

--

0.32

0.34

-1.47

--

1.80

- -

0.35

2.00

0.38

0.73

2.46

1.50

0.50

--

--

S

4.46

5.18

2.76

--

2.56 3.00 4.62

EX

A

Fluorescence i n t e n s i t y (/)

32919 32917 32916 32915 32914 32910 32908 32900 32899 32893 32891

11 10 09 08 07 06 05 04 03 02 01

1HI = S2/TOC 2OI = S3ITOC

GSC no.

433 434 431 435 434 431 433 436 433 434 421

Tmax 0.05 0.09 3.96 11.23 3.81 0.26 0.21 0.89 7.62 0.06 1.85

$1 5.58 6.14 243.01 376.08 224.32 15.20 15.47 89.10 258.98 3.70 47.01

$2

2 Rock E v a l / - r o c p y r o l y s i s o f s a m p l e s f r o m Grinnell Section, D e v o n Island

Sample no.

T a b l e

2.45 3.18 18.67 25.15 23.81 4.20 3.75 10.81 33.89 1.88 52.78

$3

1.52 1.87 39.36 47.46 33.26 4.59 4.16 16.44 53.60 1.14 69.59

TOC

367 328 617 792 674 331 371 541 483 324 067

HI 1

1A: A l g i n i t e ; 2Bi: B i t u m i n i t e , EX: E x s u d a t i n i t e ; 3M.Bi.: M a t r i x b i t u m i n i t e ; 4S: S p o r i n i t e ; SB: B r i g h t alginite; 6D: Dull alginite

Carbonate

Clay-Carb

32893

32899

02

03

Clay-Carb

32908

05

32900

Carbonate

32910

06

04

Clay-Carb

Carbonate

32914

07

Clay-Carb

Carbonate

32917

10

32915

Carbonate

32919

11

08

Lithology

GSC no.

Sample no.

%Kerogen

Table 1 Optical p r o p e r t i e s , p e t r o l o g i c a l analysis and b o r o n c o n t e n t o f the s a m p l e s f r o m Grinnell Peninsula on Devon Island

161 170 047 052 071 091 090 065 063 164 075

OI 2

570

450 570

510 570

510 580

570B 620D

460B 550D

510

510B 580D

450B

510B ~ 580D °

570

A

630

--

595

600

--

600

590

590

590

--

--

EX

Xr~×

--

--

--

--

--

470

470

510

570

--

--

M.B

590

--

580

590

590

590

580

590

580

590

--

S

0.60

0.41 0.53

0.40 0.50

0.37 0.56

0.55 1.16

0.30 0.49

0.36

0.39

0.40 0.47

0.47 0.77

0.65

A

1.93

--

1.21

0.78

--

1.09

0.94

1.08

1.13

--

--

EX

--

--

--

--

--

0.49

0.58

0.58

0.67

--

--

M.B

R/GQ

1.11

--

0.65

0.72

0.83

0.73

0.64

0.71

0.64

0.90

--

S

66

62

126

168

116

175

96

185

197

29

66

Boron (ppm)

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Gb

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~:~

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q~

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% Roil % F I Red/Green Quotient Wavelength ( a m a x ) Figure 8 Depth versus maturity relationship for coal and oil shales in Grinnell Section based on: (a) vitrinite reflectance, (b) fluorescence intensity (I) at 546 nm, (c) wavelength of maximum intensity, and (d) red/green quotient (R/GQ) for alginite (O), exsudatinite (r-I), and sporinite (A)

The maceral composition for coal and oil shales

(Table 1) was determined using both white and fluorescent light (blue violet exitation filter 400-440, chromatic beam splitter 460, barrier filter 470 nm). Point counting of coal macerals was carried out under white light and when the nature of the maceral was in doubt, fluorescent light was employed, by contrast, the macerals composition of oil shales was determined under fluorescent light and when the nature of non fluorescent material was in doubt white light was employed. A total of 500 points, including the minerals was counted for each sample. Selected samples were also analysed using a RockEval/TOC pyrolysis apparatus (Espitali6 et al., 1979) in order to estimate the level of thermal maturity and to characterize the organic matter type. An aliquot of about 10 to 50 mg of powdered sample was analysed and the results recorded in Table 2. Boron concentrations (Table 1) were determined for coal and oil shale samples using sodium hydroxide fusion followed by inductively-coupled plasma emission spectrometry (Pollock, 1975).

Results

Organic petrology Organic materials in the Grinnell Peninsula section consist of coal and oil shales (Table 1). The oil shales contain both autochthonous and allochthonous materials. The autochthonous materials include kerogen Type I, alginite, bituminite, exsudatinite, and kerogen Type IV (Figure 4). The allochthonous materials consist of kerogen Type II, sporinite, kerogen Type III, vitrinite, kerogen Type IV, and inertinite of floral origin (Figure 5). The organic material in the Kleybolte section consists of kerogen Types III and IV (Figure 6). The variation in organic content of the samples from Grinnell versus depth is plotted in Figure 7. Reflectance of vitrinite and fluorescence properties of liptinite macerals versus depth for samples from the two sections are plotted in Figures 8 and 9, while the

relationship between the reflectance and fluorescence intensity (/) versus wavelength of maximum intensity Q.max) and Red/Green Quotient (Q) for samples from Grinnell sections are shown in Figures 10 and 11.

RockEval/TO C analysis The average Tmax value of about 432°C (Table 2) for the Grinnell Peninsula samples is approximately equivalent to a vitrinite reflectance value of 0.6% Ro (Durand et al., 1983) for Type III kerogen. Because the organic matter in this sample set is dominated by Type I and II material, it is probable that this Tmax Ro correlation may not be useful (see Espitali6 et al., 1984, Fig. 9). The low production index values (S1/[S1 + $2]) also indicate that the level of thermal alteration must be somewhat lower than 0.6% reflectance, that is, in good agreement with the measured reflectance values. The organic matter type in Grinnell Peninsula samples is quite variable according to the $2/$3 ratio and Van Krevelen type diagram of hydrogen index versus oxygen index (Figure 12). The H I - O I crossplot is also consistent with the interpreted low level of thermal maturation. Correlations between %FLI and %Ro with HI and OI and alginite content with HI are shown in Figure 13.

Discussion The molecular structure of organic materials, specifically coal macerals, bitumens and organic fossils, changes with increasing thermal maturity. These changes are more or less continuous and irreversible and include an increase in the carbon content, reflectance and bireflectance, and a decrease in atomic H/C ratio. These changes can be observed by determination of optical properties and geochemical examination of organic materials (Goodarzi and Murchison, 1972; Teichm~ller, 1982; Goodarzi, 1985; Goodarzi and Norford, 1985). Solid fossil fuels include coal, natural bitumen and oil shales. Oil shales commonly are found in association M a r i n e and P e t r o l e u m G e o l o g y , 1987, Vol 4, M a y

137

Lower Carboniferous Emma Fiord Formation: F. Goodarzi et al. % Roil 2) is low; that is, this section has experienced little thermal stress. The vitrinite reflectance and RockEval Tmax for these oil shale samples remain almost constant 4 0 0 -max min over the entire section (Figure 8a, Tables 1 and 2). However, reflectance of vitrinite is lower in sediment with a high content of alginite, indicating that vitrinite reflectance is less sensitive as a thermal indicator for oil shale (Figure 14) than are the fluorescence properties of liptinite. Vitrinite, in some sections, fluoresces. This type of vitrinite has been defined as Type IIIa by Goodarzi (1986). The vitrinite reflectance for the Emma Fiord sequence on Grinnell Peninsula increases from 0.26 at the top to 0.50 at the base of the section measured. Figure 14 shows the relation between alginite content and reflectance of vitrinite. 300 -Three categories of reflectance can be observed: (a) high alginite content sediment (Table 1) in which the 5.48 3.74 reflectance of vitrinite (which often fluoresces, Figures 4 and 5) is about 0.26 and is the lowest in the section (Figure 8a); (b) moderate-alginite content sediment (Table 1) with reflectance values of 0.3 to 0.4; and (c) coal which contains little alginite (Table 1, Figure 14) and has a reflectance of 0.5.

5.00

3.58

u}

~,

In contrast with the Grinnell Peninsula section, the vitrinite reflectance in the section on Kleybolte Peninsula is > 5.0, indicating that it is overmature in a hydrocarbon-generation sense. Kerogen type III macerals have developed bireflectance (Figure 9). The reflectance and bireflectance remain almost constant throughout this section and the kerogen maturity is in the meta-anthracite stage, and past the dry gas zone of hydrocarbon generation (Teichm~iller, 1982). Comparing the Grinnell Peninsula section to the Kleybolte Peninsula section, it is evident that the former has undergone very little thermal stress, while the latter has been subjected to very high thermal alteration.

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Organic petrology

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with coal (particularly in the case of torbanite) (Moore, 1968) or with bitumen, as for example in the Uinta Basin (Khavari-Khorasani, 1984).

Maturity Samples of the Emma Fiord Formation, from two different areas and representing two different thermal histories, were examined (Figures 2 and 3): (I) The Grinnell Peninsula section The thermal maturity of the sediments in the section that was measured on Grinnell Peninsula (Figures 1 and 138

Marine and Petroleum Geology, 1987, Vol 4, May

The differences in thermal history of the samples from (I) Grinnell Peninsula and (II) Kleybolte Peninsula are evident in their organic petrographic composition: (I) The Grinnell Peninsula section is very interesting petrologically. It consists mainly of liptinite-group macerals. These rocks form one of the thickest Carboniferous oil shale deposits in Canada, yet they have not been described previously (Macauley et al., 1985). The organic material in section 1 of Grinnell Peninsula (Figure lb) has been examined closely. The organic-rich materials in this section include: (a) Coal. The Grinnell Peninsula coal is subbituminous (Table 1, Figure 5) and contains alginite, exudatinite and sporinite (Figure 5). The algal colonies in the coal are less abundant than those found in the Grinnell oil shale (Figure 5d). This is perhaps due to the high humic content of the coal. Stach (1982) has stated that growth of algal bodies is observed to be suppressed in the presence of high humic content (humic acid). The 'Bogen' structures of inertinite in the Grinnell coal are commonly filled with a fluid exsudate which leaked out and was partly vaporized upon light irradiation (Figure 15). Hydrogen to oxygen indices place the coal on the kerogen Type III track with high

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alginite (O) and exsudatinite (O) in Grinnell section

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Figure 11 Fluorescence intensity (/) at 546 nm for liptinite macerals in Grinnell section versus their (a) wavelength of maximum intensity max and (b) red/green quotient, symbols as in Figure I0, except (A) is for sporinite

oxygen index (Figure 12). (b) Oil shales. The Grinnell samples comprise about 70 m of oil shales. They are divided into two groups based on liptinite content (particularly alginite), mineral matrix, hydrogen and oxygen indices: (i) Alginite-rich oil shales (Figure 4) with a clay-carbonate matrix. These shales contain 5-35% Pila-type algae (Table 1, Figure 4), about 2-4% of kerogen Type II, and up to 5% humic kerogens (Table 1, Figure 7). The liptinite content (including bituminite and exsudatinite) in these oil shales constitutes up to 93% of the organic matter (Table 1). Hydrogen/oxygen indices of these oil

shales indicate that they are intermediate between kerogen Types I and II (Figure 12). These samples are hydrogen rich and oxygen poor (Figure 13). (ii) Alginite-poor oil shales with a carbonate matrix. These samples are very low in organic matter and contain up to 5% alginite (Figure 4), very little Type II kerogen (sporinite), and humic kerogen (Table 1, Figure 4). Hydrogen/oxygen indices of these oil shales indicate that they are intermediate between kerogen Type II to Type III (Figure 12). These samples are relatively hydrogen poor and oxygen rich (Table 2, Figure 12). The main difference between the above two types of oil

Marine and Petroleum Geology, 1987, Vol 4, May

139

Lower Carboniferous Emma Fiord Formation: F. Goodarzi et al. (3) Exsudatinite is also present and often is observed shale is in the composition of their mineral matrix, filling the cracks and cavities of kerogen Types III and which appears to be associated with the alginite IV (Figures 4 and 5). It forms minor hydrogen-rich population and is related to the environment of components of the oil shales, has orange fluorescence deposition. colour, ~'max at longer wavelengths, and higher R/G The hydrogen-rich components of these oil shales values and lower fluorescence intensities (I) than are: alginites (Figure 8b-c). (1) Alginite. Two populations of alginite were observed in some of these oil shales. They display different Exsudatinite is a secondary product and is formed in fluorescence properties: the oil shales from seeping of bituminite into available free space (Figures 4 and 5), perhaps due to the (a) High intensity, greenish or fluorescing alginites compaction of the oil shales during diagenesis. This is with ~max occurring at shorter wavelengths, with low possibly a similar process to the expulsion of liquid R/G values (Figure 16) and high fluorescence intensity hydrocarbon from a petroleum source rock. Oil shales (I) (Table 1, Figure 16); and are considered to be immature source rocks and hence (b) low intensity, orange to light brown fluorescing could behave similarly to source rocks during alginites with )~.... occurring at longer wavelengths, diagenesis and catagenesis. higher R/G values (Figure 16), and lower fluorescence Exsudatinite in the Emma Fiord oil shales is mainly intensity (I) (Table 1). formed from alginite since alginite is the dominant The low-fluorescing type may represent slightly hydrogen-rich component of the oil shales. Different oxidized (reworked) alginite (Figures 4 and 5). The phases of transformation of alginite into exsudatinite interpretation of slight oxidation may be consistent can be observed in these sediments. Phase I includes with the high oxygen index values observed for several the bright alginite which always has the higher of the alginite samples (Figure 12). Experimental Fluorescence Intensity (FL I), low R/GQ and its ~'max results of Goodarzi (1986a) show that the fluorescence occurs at lower wavelengths (Figures 11 a and b). of resinite, which is a hydrogen-rich maceral similar to Phase II consists of dull alginite and perhaps is a alginite, shifts to longer wavelengths upon oxidation. transitional product. This type of alginite occupies an The fluorescence properties of alginite occurring in the intermediate position between bright alginite and coal are similar to alginite type (b) of the oil shales Phase III, exsudatinite (Figures 10 and 11). (Figures 4, 5 and 16). Exsudatinite has low FLI, high R/GQ and its ~'max occurs at longer wavelengths (Figures 10 and lla and (2) Bituminite is the dominant secondary hydrogen-rich b). component of the Emma Fiord oil shales and it occurs as a fluorescing ground mass (Figures 4 and 5). The (4) Sporinite forms a minor component in the oil shales bituminite is formed from algae, since the dominant (Figures 4 and 5) and is more abundant in oil shales hydrogen-rich primary component of these oil shales is with a clay/carbonate matrix than in the carbonate alginite. The bituminite in these oil shales thus can be matrix, and includes lycopod (fern) spores (Figure 4). classified as type I (Gormly and Mukhopadhyay, Sporinite has a lower fluorescence intensity (1) than the 1983). other hydrogen-rich kerogens (Figure 8b). (II) The Kleybolte samples consist only of kerogen Types III and IV due to high maturity of these samples. Kerogen Type III is strongly anisotropic and commonly shows original plant structure (Figure 6).

1000

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Environment of deposition

200

Oil shales are deposited in subaqueous environments and are divided into two types: (a) continental oil shales, composed of torbanite which formed in swamps, and lamosite deposited in lacustrine environments; and (b) marine oil shales, composed of mixed and amorphous types of organic constituents (Macauley et al., 1985). The Grinnell Peninsula oil shales fall within the continental type on the basis of their organic composition. They contain only small amounts of humic debris (kerogen Types III and IV) and have no recognizable marine flora or fauna (dinoflagellates or acritarchs). The Grinnell Peninsula sediments (Section 1, Figure 2) can be divided into two zones, each rePresenting a particular sedimentological and organic-petrological environment of deposition (Figures 7 and 17).

Figure 12 V a n K r e v e l e n type diagram of RockEval p a r a m e t e r s - hydrogen i n d e x v e r s u s o x y g e n i n d e x . N u m b e r s refer to T a b l e I

(1) Coal-bearing zone, which includes a 1 m thick coal seam (Figure 2). The organic material in this zone represents peat

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INDEX

Marine and Petroleum Geology, 1987, Vol 4, May

Lower Carboniferous Emma Fiord Formation: F. Goodarzi et al. 08 68

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Figure 13 Variation of hydrogen and oxygen indices with fluorescence intensity of alginite and reflectance of vitrinite in Grinnell samples. Numbers refer to Table 1

accumulation in a stable environment with restricted oxygen input. The rate of accumulation of plant debris was probably regulated by slow and uniform subsidence. The concentration of boron in coal has been used to estimate the paleosalinity of the depositional environment (Swaine, 1962, 1971; Bohor and Gluskoter, 1973; Goodarzi 1987). Bohor and Gluskoter (1973) noted that Illinois coals with less than 125 ppm boron were deposited in fresh water environments. The coal at the base of the Grinnell section has a boron content of 66 ppm (Table 1, Figures 7 and 17), which indicates a fresh water environment (Swaine 1962, 1971). (2) Oil shales, which are about 70 m thick, were deposited in subaqueous lacustrine conditions after the drowning of peat-forming swamps. This zone represents a transition between the peatification (sapropelic coal) and the putrefaction (sapropelite) process of organic accumulation (Teichmiiller and Teichm/iller, 1982). The organic material in this zone

consists of autochthonous hydrogen-rich kerogen (Type I) with a minimum input of allochthonous humic kerogen (Types III and IV). The lithofacies changes from alginite-rich clay/carbonate matrix to alginite-poor lime muds. These changes are easily distinguished by organic petrologic analysis under a fluorescence microscope (Table 1, Figure 7). The oil shales were deposited in the following environments: (a) Alginite-rich oil shales which contain - 1 0 to 35 vol% of alginite and have a clay/carbonate matrix (Table 1). These oil shales contain a high percentage of bituminite type I (Gormly and Mukhopadhyay, 1983) and may represent an early stage of drowning of a peat-forming swamp by a lacustrine environment. These oil shales contain the highest hydrogen and the lowest oxygen indices of this suite of samples (Figures 12 and 13). Boron contents of these samples are >125 ppm (Table 1, Figure 17), indicating a more brackish environment of deposition (Bohor and Gluskoter, M a r i n e and P e t r o l e u m G e o l o g y , 1987, Vol 4, M a y

141

Lower Carboniferous Emma Fiord Formation: F. Goodarzi et al. As discussed above, the concentration of boron in 1973). The boron content in normal marine sediment is the sediments further indicates their deposition in fresh 300 ppm (Frederickson and Reynolds, 1960). or brackish water environments. Figure 18 shows the (b) Alginite-poor oil shales which contain <5 vol% grouping of the samples according to their boron of alginite and have a carbonate matrix (lime muds). content; two major groups of oil shales are evident. These oil shales contain less bituminite than the One group is oxygen-rich and hydrogen- and alginite-rich oil shales (Figure 7) and may represent a boron-poor, consists mainly of alginite-poor oil shales less turbulent setting and complete drowning of the and coal (Figure 18); the other is oxygen-poor and swamp and deeper-water lacustrine sedimentation hydrogen- and generally boron-rich, and consists of (Figure 1 7). These oil shales contain less hydrogen than alginite-rich oil shales (Figure 18). Further division of alginite-rich sediment. A number of oil shales in this these sediments is illustrated (Figure 19) using group contain higher oxygen than other samples dendograph (Labonte and Goodarzi, 1985) or (Figure 13) indicating the possibility of slight correspondence analysis (Figure 20), performed using weathering. These oil shales contain <125 ppm boron data in Tables 1 and 2. (Table 1) indicating generally a more fresh water The alternation of alginite-rich oil shales with a clay environment (Bohor and Gluskoter, 1973). matrix with alginite-poor oil shales with a lime mud The occurrence of Botryococcus (Pila-type) algae in matrix (Figure 7) may further indicate possible both groups (a) and (b) of oil shales (Figures 4 and 5) contraction (alginite-poor oil shale) and expansion indicates a fresh-brackish water environment (alginite-rich oil shale) of a small basin, in which the (Zalessky, 1926; Moore, 1968;, Teichmfiller, 1982). water alternated from poorly to well aerated. Botryococcus braunii is a fresh or brackish water green Additional discussion of the depositional setting of alga (Blackburn and Temperley, 1936; Cook et al., the Emma Fiord Formation is presented by Davies and 1981). Nassichuk (in press). 40.0

Comparison with other Carboniferous oil shales in Canada

8 0

30.0

With the exception of the Emma Fiord Formation, Carboniferous oil shales in Canada occur mainly in New Brunswick and Nova Scotia (Macauley et al., 1985). The oil shales of the Albert Formation of New Brunswick are well documented and contain albertite bitumen (Khavari, 1983). These oil shales consist mainly of bituminite (Alginite B) with little input of alginite and other liptinite, although locally they may contain up to 10% sporinite (Kalkreuth and Macauley, 1984). The main differences betwen the Emma Fiord samples and the Albert Formation oil shales examined by Kalkreuth and Macauley (1984) are as follows: (a) Albert Formation oil shales generally are more mature than the Emma Fiord samples. (b) The Albert oil shales contain bituminite Types I and II (Teichmiiller and Ottenjan 1977) or Alginite B (Cook et al., 1980), in contrast with the Emma Fiord samples that contain normal alginite up to 35% Alginite A (Kalkreuth and Macauley, 1984).

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of alginite content in coals and oil shales in Grinnell Section to reflectance of associated vitrinite. Numbers refer to Table 1

142

Marine and Petroleum Geology, 1987, Vol 4, May

(1) Samples from the Emma Fiord Formation at Grinnell Peninsula on Devon Island are immature to marginally mature, while those from Kleybolte Peninsula on Ellesmere Island are overmature. (2) The samples from Grinnell Peninsula represent thin subbituminous coal seams and a thick succession of oil shales. (3) The kerogen in the oil shales consists of alginite, matrix bituminite, exsudatinite and sporinite (i.e. Types I and II). (4) Two types of oil shales are distinguished: the first is liptinite-rich, with a clay/carbonate matrix and relatively high hydrogen index and boron content; the second is liptinite-poor, with a carbonate matrix and relatively low hydrogen index and boron content.

L o w e r Carboniferous E m m a Fiord Formation: F. Goodarzi et al.

.3

Figure 15 Fusinite in coal showing 'Bogen' structure and bitumen staining. The cell lumens are filled with exsudatinite, (a) reflected white, (b) fluorescent [(c) and (d) are same light as (a) and (b), but after longer irradiation with fluorescent blue light (450 nm)], (c) note the extent of the bitumen staining on fragments of fusinite, and (d) extensive leakage of exsudatinite after long irradiation, magnification same as Figure 4

(5) The characteristics of the organic constituents and also the concentration of boron suggest a fresh to brackish water lacustrine environment for sediments from the Grinnell Peninsula section.

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Figure 16 Depth versus relationship in Grinnell Section for bright (O) and dull (0) alginite in coal and oil shales; (a) wavelength of maximum intensity km~×, (b) red/green quotient

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Figure 17 Variation of boron in Grinnell sub-section Marine

and Petroleum

Geology,

1 9 8 7 , V o l 4, M a y

143

Lower Carboniferous 40

Emma

Fiord Formation:

F. G o o d a r z i et al.

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Figure 19 Dendograph showing the similarity index between the

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Figure 18 Variation in concentration of boron with (a) alginite content, (b) hydrogen index, and (c) oxygen index in coal and oil shales. Numbers refer to Table 1

References

Blackburn, K. B. and Temperley, B. N. (1936) Botryococcus and algal coals, Trans. Roy, Soc. Edinburgh 58, (3), 841-868 Bohor, B. F. and Gluskoter, H. J. (1973) Boron in illite as a paleosalinity indicator of Illinois coal, J. Sed. Petrol 43, (4), 945-956 Brooks, J. (1981) Organic maturation and sedimentary organic matter and petroleum exploration. A review in: Organic maturation studies and fossil fuel exploration (Ed. J. Brooks), Academic Press, New York, pp. 1-38 Brooks, P. W., Embry, A. F., Goodarzi, F., and Stwart, R. (1987) Organic maturation and biomarker geochemistry of Schei Point Group, Sverdrup Basin, Arctic Canada, in press - Canadian Society of Petroleum Geologists. Bustin, R. M. (1985) Organic maturity of late Cretaceous and Tertiary coal measures, Canadian Arctic Archipelago, Int. J. Coal GeoL 6, 71-106 144

M a r i n e a n d P e t r o l e u m G e o l o g y , 1987, V o l 4, M a y

Cook, A. C., Hutton, A. C. and Sherwood, N. R. (1981) Classification of oil shales, Bull. Centres Research Exploration, Production Elf-Aquitaine, 5, 353-381 Davies, C. R. and Nassichuk, W. W. (1987) A Lower Carboniferous (Vis6an) lacustrine oil shale in the Canadian Arctic Archipelago, Am. Assoc. Petrol GeoL Bull. in press Durand, B., Paratte, M. and Bertrand, P. (1983) Le potential en huile des charbons: une, approche geochimique, Revue de I'lnstitut Fran~ais du P~trole, 38, 709-721 Espitali6, J., Laporte, J. L., Madec, M., Marquis, F., Leplat, P., Paulet, J. and Boutefeu, A. (1979) M~thode rapide de caract6rization des roches m6res de leur potential p~trolier et de leur degr~ d'~volution, Revue de I'lnstitut Fran¢ais du P~trole, 32/1, 23-42 Espitali~, J., Marquis, F. and Barsoug, I. (1984) Geochemical logging; Proceedings of the 5th International Symposium on Analytical Pyrolysis, Vail, Colorado, September, 1983 (Ed. K. J. Voorhis), 276-304 Frederickson, A. F. and Reynolds, R. C. (1960) Geochemical method for determining paleosalinity: clays and clay minerals, Proc. 8th Nat/. Conf., Pergamon Press, Oxford, 203-213 Goodarzi, F. and Murchison, D. G. (1972) Optical properties of carbonized vitrinite, Fuel 51,322-328 Goodarzi, F. (1985) Preservation and characteristics of plant remains in Iranian natural bitumens, Int. J. Coa/ GeoL, 4, 321-334 Goodarzi, F. and Norford, B. S. (1985) Graptolites as indicators of the temperature histories of rocks, J. GeoL Soc. London, 142, 1089-1099 Goodarzi, F. (1986) Comparison of reflectance data from various macerals from subbituminous coals, J. Pet. Geol., in press

Lower Carboniferous Emma Fiord Formation: F. Goodarzi et al. Goodarzi, F. (1986a) Optical properties of oxidized resinite, Fuel 65, 260-265 Goodarzi, F. (1987) Elemental distribution in Canadian coals 2, Byron Creek Collieries, British Colombia, Canada, Fuel 60, 250-254 Goodarzi, F., Harrison, C, and Wall, J, H. (1987) Stratigraphy and petrology of Lower Cretaceous coal, southeast Melville Island, District of Franklin, Northwest Territories, Canada, Geol. Survey of Canada paper, in press Gormly, J. R. and Mukhopadhyay, P. K. (1983) Hydrocarbon potential of kerogen types of pyrolysis-gas chromatography, in: Advances in Organic Geochemistry (Ed. M. Bjoroy et al.), John Wiley and Sons, Oxford, pp. 597-606 Jacob, H. (1975) Mikroskopphotometrische analyse naturlicher fester Erdolbitumina, in: P~trographie Organique et Potential P~trolier (Ed. B. Alpern), Centre National de la Recherche Scientifique, Paris, pp. 103-113 Kalkreuth, W. and Macauley, G. (1984) Organic petrology of selected oil shale samples from the Lower Carboniferous Albert Formation, New Brunswick, Canada, Bull. Can. Petrol. GeoL, 32, (1), 38-51 Khavari-Khorasani, G. (1983) Structure of albertite from New Brunswick, Canada, Bull. Can. Petrol. Geol., 31 (2), 123-126 Khavari-Khorasani, G. (1984) Free hydrocarbon in Uinta Basin, Utah, AAPG, Bull., 68, (9), 1193-1197 Labonte, M. and Goodarzi, F. (1985) Use of the dendograph for data processing in fuel science, Fuel 64, 1177-1179 Macauley, G. (1984). Geology of the oil shale deposits of Canada, Geol. Survey of Canada, Paper 81-25, 65 p Macauley, G., Snowdon, L, R. and Ball, F. D. (1985) Geochemistry and geological factors governing exploration of selected Canadian oil shale deposits, Geol. Survey of Canada, Paper 86-13, 65 pp Mackowsky, M. Th. (1982) Rank determination by measurement of reflectance on vitrinites, in: Stach's Textbook of Coal Petrology (Eds: E. Stach et al.), GebrL~der Borntraeger, Berlin, pp. 31 9-329 Millaid, R. and Murchison, D. G. (1969). Properties of the coal macerals, infrared spectra of alginites, Fuel 48, 247-258

Moore, L. R. (1968) Cannel coals, bogheads and oil shales, in: Coal and coal bearing strata (Eds: D. Murchison and T. S. Westoll), Oliver and Boyd, Edinburgh, pp. 19-29 Pollock, E.N. (1975) Trace impurities in coal by wet chemical methods, Adv. Chem. Ser., 141, 23 Ricketts, B. D. and Embry, A. F. (1984) Summary of geology and resource potential of coal deposits in the Canadian Arctic Archipelago, Bull. Can. Petrol. Geol., 32, (4), 359-371 Ricketts, B. D. and Embry, A. F. (1986) Coal in Canadian Arctic Archipelago, GEOS, 15, (1), 16-18 Snowdon, L. R., Brooks, P. W. and Goodarzi, F. (1986) Chemical and petrological properties of some liptinite-rich coals from British Columbia, Fuel 65, 459-472 Stach, E. (1982) The lithotypes of humic and sapropelic coals, in: Coal petrology (Eds. E. Stach et aL), Gebr(ider Borntraeger, Berlin, pp. 171-177 Swaine, D. J. (1962) Boron in New South Wales Permian coals, Australian J. Earth Sci., 26, (6), 265 Swaine, D. J. (1971) Boron in coals of the Bowen Basin, an environmental indicator, GeoL Survey of Queensland, Report 62 TeichmOller, M. and Wolf, M. (1977) Application of fluorescence microscope in coal petrology and oil exploration, J. Microscopy, 109, (1), 49-73 TeichmOller, M. and Ottenjann, K. (1977) Art und diagenese von liptiniten und lipoiden stoffen in einem Erd61muttergestein auf grund fluorezenzmikroskopischer untersuchungen, ErdSI u. Kohle, 30, 387-398, Leinfelden Teichm~ller, M. (1982) Origin of the petrographic constituents of coal. in: Coal petrology (Eds. E. Stach et aL), Gebr~der Borntraeger, Berlin, pp. 219-283 Teichm~iller, M. and TeichmLiller, R. (1982) The geological basis of coal formation, in: Coal petrology (Eds. E. Stach et aL), GebrOder Borntraeger, Berlin, pp. 5-82 Williams, P. F. V. (1983) Oil shales and their analysis, Fuel, 62, 756-771 Zalessky, M. D. (1926) Sur les nouvelles algues d~q.ouvertes dans le saprop~log~ne du lac B~loc et sur une algae saprop~log6ne, Botryococcus braunii (kutzing), Bull. G~n. Bot., 8, 30-34

Marine and Petroleum

G e o l o g y , 1987, V o l 4, M a y

145