International Journal of Coal Geology 178 (2017) 84–99

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International Journal of Coal Geology

journal homepage: www.elsevier.com/locate/coal

The effects of igneous dike intrusion on organic geochemistry of black shale MARK
and its implications: Late Jurassic Jhuran Formation, India
Ashwin Arora, Suryendu Dutta, Binod Gogoi, Santanu Banerjee⁎
Department of Earth Sciences, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India

A R T I C L E I N F O A B S T R A C T

Keywords: This study documents the effects of igneous dike intrusion on organic geochemical parameters of a shallow-
Black shale marine originated, Late Jurassic black shale (av. TOC = 2.2 wt%) in the Kutch rift basin in western India. The
Biomarker dike intrusion forms extremely to mildly altered, meter-scale zones around them. The primary wrinkled micro-
Maturation indicator texture of the shale is lost completely, and organic matter is charcoalized in the extremely altered zone recording
Palaeo-fire
a Rock-Eval Tmax > 458 °C. Immature type-III kerogen dominating the unaltered shale records abundant
Dike
Contact aureole
coniferal biomarkers such as retene, ent-beyerane, phyllocladane, ent-kaurane, abietane, labdane and norisopi-
Redox indicator marane, besides n-alkanes, hopanes and steranes. The transition from the unaltered (Rock-Eval Tmax < 432 °C)
PAHs to the altered zone involves a decrease in carbon preference index (CPI), pristane/n-C17, phytane/n-C18, C30
hopane/C29 ααα-sterane and gradual increase in C29 diasterane/sterane, trisnorneohopane/trisnorhopane (Ts/
Tm), Ts/C30 hopane, C29/C30 hopane and C29 20S/(20S + 20R) sterane ratios. Although most saturate
biomarkers disappear in the extremely altered zone, it records a high abundance of thermogenic polycyclic
aromatic hydrocarbons (PAHs), commonly found in palaeo-fire deposits. Besides the PAH ratios, methylphenan-
threne index-1, pristane/phytane, CPI and C29/C30 hopane ratios are found to be influenced significantly by
thermal maturation in the extremely altered zone. The fluoranthene/(fluoranthene + pyrene) ratio correctly
distinguishes different intensities of combustion products, while other PAH ratios behave differently at the
immediate contact of the dike. Pr/Ph ratio may correctly interpret the redox condition up to a Rock-Eval
Tmax ~ 520 °C, while it is ineffective at high maturity. The results of the investigation are significant for the
assessment of stability of biomarkers in highly matured source rocks, recording potential redox-sensitive
biomarkers in highly matured shales and detection of palaeo-fire deposits in ancient sedimentary succession.

1. Introduction 1979; Simonet et al., 1981; Murchison and Raymond, 1989; George,
1992; Raymond and Murchison, 1992; Santos et al., 2009; van de
Igneous dike intrusions are likely to alter physico-chemical char- Schootbrugge et al., 2009; Wang and Manga, 2015; Aghaei et al., 2015;
acteristics of an organic-rich shale drastically in a basin in both local Li et al., 2016). Although limitedly addressed, the rapid thermal stress
and regional scale. A clear understanding of this alteration can provide produced by dike intrusions possibly affects biomarkers significantly
clues to estimate hydrocarbon-generating potential of shales, to build (George, 1992; Svensen et al., 2004, 2009). Studies in this direction
up a maturation history of source rock and for organic matter may create a better perspective to understand changes in biomarker
characterization of sedimentary rocks (Galushikin, 1997; Meyers and composition in correspondence to the thermal aureole. Such a biomar-
Simoneit, 1999; Cooper et al., 2007; Aarnes et al., 2010, 2011; Wang ker record can be used to monitor geothermal maturation of hydro-
and Manga, 2015; Wang and Liu, 2015; Zanella et al., 2015; Aghaei carbon source rocks and also detect record of palaeo-fires (Killops and
et al., 2015; Varma et al., 2015; Li et al., 2016 and many others). The Massoud, 1992; Bojesen-Koefoed et al., 1997; Marynowski and
dimension of the dike, host rock conductivity, porosity, permeability as Simoneit, 2009; Marynowski et al., 2014). Polycyclic aromatic hydro-
well as the amount of pore fluid involved is considered significant in carbons (PAHs) are widely used as a proxy for recognition of ancient
determining the width of the altered zone (Iyer et al., 2013; Aghaei wildfires (Venkatesan and Dahl, 1989; Killops and Massoud, 1992;
et al., 2015). Several studies have recorded mineralogical and inorganic Kruge et al., 1994; Arinobu et al., 1999; Finkelstein et al., 2005;
geochemical changes in shale associated with dike intrusions (Meyers Marynowski and Filipiak, 2007; Marynowski and Simoneit, 2009; van
and Simoneit, 1999 and Aarnes et al., 2010; Perregaard and Schiener, de Schootbrugge et al., 2009; Hossain et al., 2009, 2013; Marynowski

⁎
Corresponding author.
E-mail address: [email protected] (S. Banerjee).

http://dx.doi.org/10.1016/j.coal.2017.05.002
Received 28 February 2017; Received in revised form 1 May 2017; Accepted 1 May 2017
Available online 03 May 2017
0166-5162/ © 2017 Elsevier B.V. All rights reserved.
A. Arora et al. International Journal of Coal Geology 178 (2017) 84–99

Fig. 1. Geological map of the outcrops of the Mesozoic Formations and Deccan Traps in Kutch Mainland (after Biswas, 1987). Map of India showing the study areas within inset (blue
solid circles mark sample positions). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Table 1
Stratigraphy of the Mesozoic succession of the Kutch Mainland with necessary elaborations of the Jhuran Formation (Biswas, 1977).

Age Biswas Members Description

(1977) (Jhuran Fm)
Albian to Greenish grey to yellow,
? Santonian Katesar massive cross-bedded
(Tithonian to sandstone with minor
Valanginian) intercalations of shales,
Aptian exposed only near western
Bhuj margin, near Katesar Temple
Formation
Predominantly arenaceous
Beriasian rocks. Red and yellow,
Upper
to massive cross bedded
(Tithonian)
Barremian sandstone with intercalations
of shales, siltstones
Predominantly shaley, dark
Middle grey to black shales,
Tithonian Jhuran
(M. Kimmeridgian interbedded with ferruginous
to Formation
to Tithonian) sandstones and laminated
Kimmeridgian
micaceous siltstone

Oxfordian Lower Alternating yellow and red

Jhumara
to (L. Kimmeridgian Sandstones, and shale beds in
Formation
Callovian and older) almost equal proportion with
some yellow fossiliferous,
calcareous sandstones
Jhurio
Bathonian
Formation

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zones, and d) sift out potential PAH ratios that may detect palaeo-fire
deposits.

2. Geological background of the study area

The Kutch basin is situated in the westernmost fringe of the Indian

craton. The basin consists of Meso-Cenozoic litho-packages ranging in
age from Late Triassic to Lower Cretaceous sedimentary succession
(Biswas, 1981). The Late Jurassic (157–145 ± 4 Ma) Jhuran Forma-
tion was deposited in a pericratonic rift basin (Biswas, 1981) (Fig. 1).
The shallow marine Jhuran Formation rests unconformably on the
mixed carbonate-siliciclastic Jhumara Formation and is overlain by the
fluvio-deltaic Bhuj Formation (Biswas, 1993). The generalized Meso-
zoic lithostratigraphy of the mainland Kutch and detailed sub-divisions
of the Jhuran Formation is provided in Table 1. The entirely siliciclas-
tic, poorly fossiliferous Jhuran Formation is also referred to as Katrol
Formation by a few workers (Waagen, 1875; Rajnath, 1932; Krishna
et al., 1998). The Mesozoic succession is well exposed in the Kutch
Mainland and Khadir, Bela, Patcham and Wagad islands. The present
study is based on the outcrops of the Jhuran Formation in the Kutch
Mainland (Fig. 1).
The Jhuran Formation consists of three members, each exhibiting a
shallowing upward trend (Biswas, 1981). The study area exposes the
Middle Member of the Jhuran Formation, which consists of repeated
alternations between shale and sandstone. The Middle Member of the
Jhuran Formation represents a wave-dominated prograding shelf
succession (Arora et al., 2015). The TOC content of shale in the Middle
Member decreases from 4.9% at the base to 0.4% at the top (Arora
et al., op. cit.). HI and OI content of the shale varies between 2 and
174 mg HC/g TOC and 3 to 286 mg CO2/g TOC respectively, indicating
a dominantly continental source of organic matter (Arora et al., op.cit.).
Tmax of unaffected shale, far away from the contact aureole of dike
Fig. 2. Field photographs and marked sample positions at (a) Palara (b) Zara and (c) Ler intrusion varies from 435 °C to 429 °C.
localities of Kutch Mainland. Mesozoic rocks of the Kutch Basin are affected by magmatic
activities in many places in forms of dikes, sills, plugs, laccoliths and
ring dikes. The igneous dike intrusions, under focus, affected the lower
et al., 2011; Denis et al., 2012). However, PAHs may originate from to the middle part of the Jhuran Formation (Fig. 1). Karmalkar et al.
both combustion and diagenetic processes (Harvey, 1996; Yunker et al., (2014) provided 124 ± 4 Ma for the dikes emplaced within the Jhuran
2011; Hossain et al., 2013). The study of shale samples in the vicinity of Formation on the basis of U-Pb perovskite dating. This study investi-
dikes provides direct information about stability of different PAHs gates organic-rich shale samples in the vicinity of three dike intrusions
under high thermal stress. PAH ratios of samples in proximity to the within the Middle Member, around Palara, Zara and Ler villages.
contact aureole remain significant for assessment of the variable Thickness of dike in a vertical section varies between 1.7 m to 12 m.
intensities of palaeo-fires. The dike in the Ler section cut across the bedding at an oblique angle
The Mesozoic sedimentary succession of the Kutch basin witnessed while the other two dikes maintain orthogonal relationship with the
widespread igneous intrusions in various scales which include doleritic bedding (Fig. 2). At the contact of these dikes, the shale is extremely
dikes, sills, plugs, laccoliths and ring dikes (Biswas, 2005; Guha et al., altered with jet black appearance, which sharply passes over to the
2005; Paul et al., 2008; Sen et al., 2009; Karmalkar et al., 2014; Ray mildly altered shale and gradationally passes into the unaltered shale
et al., 2016). These igneous bodies have played a crucial role in the (Fig. 2). Average widths of the extremely altered and the mildly altered
maturation of organic matter (Biswas, 2005). This paper addresses in- zones vary from 1 m to 3 m and 3 m to 8 m respectively. These zones of
situ alteration of organic-rich shales in the proximity of three separate extremely altered, mildly altered and the adjacent unaltered shale are
meter-scale dike intrusions, two of which exhibits orthogonal and one hereafter referred to as zone-A, zone-B and zone-C respectively.
inclined relationship with the bedding plane. This study documents
organic-geochemical and micro-textural changes in systematically 3. Samples and methods
collected samples within the altered zone close to the dikes. Bulk
organic geochemical characterization by Rock-Eval pyrolysis records Outcrop samples of organic-rich shale were collected at the contact
variation of total organic carbon (TOC), Tmax, hydrogen index (HI) and of dikes from three localities namely, Palara, Zara and Ler (Figs. 1, 2).
oxygen index (OI) of samples. Systematically collected samples with Shale samples were collected at 1 m intervals successively moving away
respect to dike intrusion were analyzed by Gas Chromatography–Mass from the dike margins. The lateral extent of sampling was 20 m, 12 m
Spectrometry (GC–MS) for biomarkers. Changes in organic geochemical and 5 m for Palara, Zara and Ler outcrops respectively depending on
parameters such as carbon preference index (CPI), terpenoids, steranes, exposure limitations. In each case fresh samples were collected after
polycyclic aromatic hydrocarbons (PAHs) and several biomarker ratios excavating around 10 cm of an exposed portion of the shale.
were documented in relation to dike intrusion. This study intends to a) Chunks of shales were hardened by epoxy solutions (resin and
understand the factors that determine the width of contact aureole, b) hardener) in a Buehler vacuum impregnation unit for preparation of
determine stability of biomarkers in high temperature zones, c) thin sections. The samples were kept in vacuum chamber for 5–10 min
determine suitability of redox sensitive parameters in highly altered under −100 kPa and then cured for about 9 h to harden them for thin
section mounting on glass slides. Petrographic investigations were

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Fig. 3. (A–F) Micrographs of shales (in PPL) in different zones, extremely burnt zone-A (A–B), mildly burnt zone-B (C–D) and unaffected samples zone-C (E–F). Note the visible darkening,
fabric disorientation along with complete loss of micro-textures in zone-A.

carried out using Leica DM-4500P polarizing attached with a Leica aromatic fractions. The saturate was eluted using hexane and the
DFC450 camera at the Department of Earth Sciences, Indian Institute of aromatic required a solution of hexane and dichloromethane (9:1).
Technology Bombay. Powdered samples were analyzed by Rock-Eval 6 All samples were treated with activated copper chips to remove any
pyrolyzer, at the Department of Earth Sciences, Indian Institute of sulphur and sulphur bearing compounds. The saturate and aromatic
Technology Bombay for bulk organic geochemical characterization. fractions were analyzed using an Agilent 5975 mass spectrometer
The amount of hydrocarbons (HC) released during pyrolysis was interfaced to a 7890 gas chromatograph at the Department of Earth
detected with a flame ionization detector (FID), while online infrared Sciences, Indian Institute of Technology Bombay. The saturates were
detector measures continuously the released CO and CO2. The samples analyzed using a DB-1 capillary column (30 m × 0.25 mm i.d.,
were first pyrolyzed from 300 °C to 650 °C at a rate of 25 °C/min. The × 0.25 μm film thickness), while a HP-5 MS fused silica capillary
oxidation phase starts with an isothermal stage at 300 °C, followed by column (30 m × 0.25 mm i.d., × 0.25 μm film thickness) was used
an increase to 750 °C at a rate of 25 °C/min to incinerate all the residual for aromatics. Helium was used as a carrier gas with flow rate 1 ml/
carbon. min. Both fractions were analyzed in full scan mode over a mass range
Biomarker study was conducted on samples of the Zara locality of 50–600 Da. The samples were dissolved in n-hexane and injected by
because of its consistently high TOC (> 1 wt%) content. The bitumen autosampler in pulsed splitless mode. The ion source was operated in
content in the samples was extracted by sonicating powdered rocks in a the electron ionization mode at 70 eV. The temperature of GC oven was
solution of dichloromethane (DCM): methanol (9:1 ratio) for 45 min. held at 40 °C (for 5 min) and then ramped to 310 °C at 4 °C/min and
The bitumen was decanted into a separate beaker and left overnight for held for 5.5 min. Identification of compounds was based on comparison
evaporating the solvents. Asphaltene fraction was segregated by adding of elution pattern and mass spectra with those reported in the literature.
a few ml of DCM followed by ~50 ml n-pentane. Asphaltene was The data were processed using Chemstation software.
allowed to precipitate overnight. This was followed by decantation to
separate the asphaltene fraction. The solution was allowed to evaporate
till drying. A column was set up for the purpose of column chromato- 4. Results
graphy. The glassware used was fired at 300 °C for 4 h and thoroughly
sterilized using methanol and dichloromethane. The bitumen fraction The following section discusses the effects of igneous dike intrusion
was added to the column using dichloromethane and was kept on shale micro-texture, bulk organic geochemistry and biomarker
undisturbed till the solvent medium volatilized completely. Column ratios.
chromatography was performed in order to separate saturates from

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Table 2
Rock-Eval Pyrolysis data of the Jhuran shale samples.

S. no. Zone Sample Distance from Tmax [°C] TOC (wt%) S1 S2 HI OI Calculated*
name contact (m) [mg HC/g rock] [mg HC/g rock] [mg HC/g TOC] [mg CO2/g TOC] VRr%

1 A PB-1 0 601 2.88 0.03 0.22 8 27 3.66

2 A PB-2 1 589 2.25 0.03 0.28 12 13 3.44
3 A PB-3 2 458 2.4 0.02 0.07 3 20 1.08
4 B PB-4 3 441 2.4 0.04 0.93 39 36 0.78
5 B PB-5 4 446 1.89 0.03 1.23 65 54 0.87
6 B PB-6 5 440 1.1 0.03 0.45 41 109 0.76
7 B PB-7 6 444 2.41 0.04 1.75 73 49 0.83
8 B PB-8 7 443 1.65 0.04 1.07 65 48 0.81
9 B PB-9 8 442 1.6 0.09 0.96 60 51 0.8
10 C PB-10 9 434 1.37 0.02 0.61 45 50 0.65
11 B PB-11 10 440 2.58 0.11 0.97 38 43 0.76
12 B PB-12 11 445 2.08 0.03 1.1 53 41 0.85
13 B PB-13 12 441 1.77 0.01 0.69 39 68 0.78
14 C PB-14 13 434 2.63 0.02 1.02 39 51 0.65
15 B PB-15 14 437 2.1 0.04 0.96 46 46 0.71
16 C PB-16 15 433 1.97 0.03 0.84 43 87 0.63
17 C PB-17 16 431 1.94 0.02 0.92 47 57 0.6
18 B PB-18 17 436 1.67 0.02 0.85 51 92 0.69
19 C PB-19 18 428 1.48 0.02 0.87 59 80 0.54
20 C PB-20 19 433 1.95 0.02 0.78 40 76 0.63
21 C PB-21 20 433 1.62 0.02 0.75 46 72 0.63
22 C PB-22 21 432 2.22 0.03 1.22 55 62 0.62
23 A ZRB-0 0 578 1.73 0.02 0.18 10 25 3.24
24 A ZRB-1 1 518 0.98 0.01 0.03 3 55 2.16
25 B ZRB-2 2 455 2.74 0.03 2.54 93 30 1.03
26 B ZRB-3 3 445 2.4 0.05 2.28 95 45 0.85
27 C ZRB-4 4 433 2.58 0.04 2.59 100 27 0.63
28 C ZRB-5 5 434 2.67 0.06 3.15 118 36 0.65
29 C ZRB-6 6 433 2.8 0.03 2.46 88 35 0.63
30 C ZRB-7 7 433 2.88 0.05 3.23 112 35 0.63
31 C ZRB-8 8 435 2.48 0.05 2.4 97 37 0.67
32 C ZRB-9 9 433 3 0.06 3.65 122 30 0.63
33 C ZRB-10 10 433 2.93 0.06 3.57 122 31 0.63
34 C ZRB-11 11 432 2.83 0.07 3.46 122 34 0.62
35 A LER-a 0 547 1.17 0.03 0.11 9 57 2.69
36 A LER-b 1 546 0.87 0.03 0.9 10 79 2.67
37 A LER-c 2 500 1.31 0.11 0.61 47 47 1.84
38 B LER-d 3 454 0.43 0.04 0.31 72 112 1.01
39 C LER-e 4 432 0.5 0.02 0.1 20 108 0.62

TOC = Total organic carbon [wt%]; S1 = Volatile hydrocarbon (HC) content [mg HC/g rock]; S2 = Remaining HC generative potential [mg HC/g rock]; Tmax = Temperature at
maximum of S2 peak; HI, Hydrogen index = S2 * 100/TOC [mg HC/g TOC]; OI, Oxygen index = S3 * 100/TOC [mg CO2/g TOC]; *calculated VRr% = (0.0180 * Tmax) − 7.16 (Wust
et al., 2013).

4.1. Changes in shale micro-texture decreases sharply to 518 °C at 1 m, and thereafter decreases gradually
to 431 °C at a distance of 10 m. In Ler section, Rock-Eval Tmax at contact
The unaltered shale in zone-C exhibits planar and wrinkled laminae of dike records 547 °C, which decreases to 432° over a distance of 4 m
(Fig. 3e,f). Carbonaceous matters within the shale appear as thin, from the dike.
continuous to discontinuous streaks, ranging in thicknesses from The hydrogen index (HI) values of studied samples in zone-A are
∼ 0.01 mm to 0.15 mm, which occasionally incorporate tiny pyrite close to 10 mg HC/g TOC. HI values of samples in zone-C for Zara,
crystals within them. Silt grains occur sporadically within the shale, Palara and Ler sections record 84, 122 and 72 mg HC/g TOC respec-
against which carbonaceous fragments are bent imparting a wavy tively (Fig. 4b,c). The HI of zone-B for the same sections are of
appearance (Fig. 3e,f). Samples of zone-B retain original microfabric intermediate values recording 93, 73 and 47 mg HC/g TOC respec-
of the unaltered zone, but its organic matter appears relatively darker tively. The oxygen index (OI) varies between 13 and 112 mg CO2/g
(Fig. 3c,d). The samples of extremely altered zone (zone-A), however, TOC, without showing any systematic change. While undisturbed HI
exhibit a complete loss of micro-textural details as silt grains appear to values of samples in zone-C relate them to type-III kerogen, the samples
float within a background carbonaceous matrix (Fig. 3a,b). of zone-A plot within type-IV kerogen field (Fig. 4b) on the HI vs OI
plot. The Rock-Eval Tmax values were converted to vitrinite reflectance
4.2. Results of Rock-Eval pyrolysis by using the formula VRr% = (0.0180 * Tmax) − 7.16 (Wust et al.,
2013) for comparison with published data on coals affected by similar
The TOC content of organic-rich shale varies from 0.5 wt% to 3.0 wt dike intrusion.
% (Table 2). Tmax exhibits a sharp fall from the zone-A to the zone-B,
and thereafter it records a gradual fall to the zone-C (Fig. 4a). Samples
of the Palara section records highly elevated Rock-Eval Tmax of 601 °C 4.3. Results of gas chromatography-mass spectrometry
at the immediate contact of the dike, which decreases sharply to 589 °C
at 1 m, 458 °C at 2 m, finally recording the background value (432 °C) Samples of the Zara locality, always containing > 1.5 wt% TOC
at a distance of 21 m (Fig. 4a). The samples of Zara section records were analyzed using GC–MS for detailed organic geochemistry. Salient
Rock-Eval Tmax of 578 °C at the immediate contact of the dike, which results of GC–MS analysis are as follows.

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Fig. 4. Relationship between Rock-Eval Tmax (°C) and distance from the contact of dikes
in different localities (A), HI vs Tmax (°C) plots of studied samples (B), hydrogen index (HI)
vs oxygen index (OI) plot of shale samples (C).

a) Chromatograms of samples corresponding to each zone exhibit a

general predominance of even numbered n-alkanes over odd
(Fig. 5). While the odd-even effect is conspicuous in zone-C, the
same is insignificant in samples of zone-A (Fig. 5). Saturates are
nearly absent in zone-A (Fig. 5). Odd carbon straight chain saturates
as well as triterpenoids and steranes are found in zone-B and zone-C
(Fig. 6). The CPI sharply increases from 0.24 in zone-A to ~2 in
zone-B, and it remains more or less same in zone-C (Table 3,
Fig. 7a). The pristane/phytane ratio sharply increases from 0.20
(zone-A), reaches to 1.15 (zone-B) and further increases to 1.36
(zone-C) (Fig. 7a). The pristane/n-C17 ratio records an overall
increase from 0.26 at the contact of dike to zone-C (1.18)
(Fig. 7a). The phytane/n-C18 ratio remains ~0.11 in zone-A and
zone-B and it sharply increases to 2.59 in zone-C (Fig. 7a).
b) Trisnorneohopane/trisnorhopane (Ts/Tm) decreases gradually from
0.62 in zone-B to 0.47 in zone-C (Fig. 7b). C29 Diasterane/sterane
ratio also records a gradual decrease from 0.51 in zone-B to 0.25 in
zone-C (Figs. 7b, 8). Ts/C30 hopane ratio records a minor decrease
from 0.20 in zone-B to 0.14 in zone-C (Fig. 7b). C30 hopane/C29
ααα-sterane ratio gradually increases from 1.28 in zone-B to 1.44 in
zone-C (Fig. 7c). The C29 sterane (20S and 20R) epimer ratio
decreases marginally from 0.15 in zone-B to 0.13 in zone-C
(Tables 3, 4). Hopanoids are rare in samples of zone-A. These
terpenoids, however, occur in high abundance in zone-B and zone-C.
22S to 22R isomers of C31 homohopane fails to reveal a systematic
trend across these zones (Figs. 6, 7d), but, isomer ratios of C32
homohopane show stable values near 0.58 (Table 3). The C29/C30
hopane ratio decreases sharply from zone-A to zone-B and further
records a gradual decrease (Fig. 7d).
c) Methylphenanthrene index-1 (MPI-1) value sharply decreases from
1.28 in zone-A to 0.46 in zone-B, followed by a gradual decrease to
0.42 in zone-C (Fig. 7e, 9). Coniferal diterpenoid such as phyllocla-
dane, abietane, ent-beyerane, ent-kaurane, labdane and norisopi-
marane occur in high abundance in samples of zone-B and C, while
these biomarkers are completely absent in zone-A (Fig. 10). How-
ever, aromatic diterpenoid such as retene occurs in samples of zone-
A. Dia/(Dia + Reg) for C29 steranes increases with increasing Ts/
(Ts + Tm) (Fig. 7f).
d) Fourteen PAHs were identified from the aromatic fraction using
characteristic mass chromatograms (Fig. 11,Table 5). The zone-A is
dominated by fluoranthene, pyrene and chrysene. The zone-A also
exhibits high abundance of benzo[b]fluoranthene, benzo[e]pyrene
and benz[a]anthracene and insignificant phenanthrene, retene,
benzo[a]pyrene, perylene, indeno[1,2,3-c,d]pyrene, dibenz[a,h]an-
thracene and benzo[ghi]perylene. The zone-B is rich in perylene,
followed by fluoranthene and pyrene in almost equal abundance,
besides retene. The zone-C is rich in fluoranthene, pyrene, retene
and perylene. The transition from zone-A to zone-C through zone-B
exhibits a systematic increase in relative abundances of phenan-
threne, retene and perylene and an decrease in relative abundances
of benz[a]anthracene, chrysene, benzo[b]fluoranthene and benzo[e]
pyrene. Traces of Indeno[1,2,3-c,d]pyrene, dibenz[a,h]anthracene
and benzo[ghi]perylene are recognized in samples of zone-B and
zone-C. Retene and perylene survive, while most saturate land-plant
derived biomarkers disappear in zone-A. Ratios of PAHs involving
fluoranthene (Fla), pyrene (Py), benz[a]anthracene (BaAn), indeno
[1,2,3-cd]pyrene (InPy), benzo[ghi]perylene (BghiP), retene (Ret)
and chrysene (Chry) are plotted to evaluate their thermal stability
(Fig. 12). The Fla./(Fla + Py) ratio decreases from 0.62 in zone-A to
0.53 in zone-B and 0.52 in zone-C (Fig. 12a). The InPy/(InPy
+ BghiP) ratio reveals a decrease from 0.43 in zone-A to 0.35 in
zone-B and 0.34 in zone-C (Fig. 12b). The Ret/(Ret + Chry) ratio is
(caption on next column)

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Fig. 5. Partial mass chromatograms at m/z 57 showing the variations of n-alkanes and isoprenoid distribution in samples of different zones.

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Fig. 6. Partial mass chromatograms at m/z 191 in samples of different zones.

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Table 3
Biomarker parameters of selected samples of Zara.

Biomarker parameters Zone-A Zone-B Zone-C

ZRB-0 ZRB-1 ZRB-2 ZRB-3 ZRB-4 ZRB-6 ZRB-7

Distance (m) 0 1 2 3 4 6 7
CPI 0.24 0.25 2.12 1.96 2.03 1.86 2.1
Pr/Ph 0.20 1.13 1.15 1.24 1.15 1.11 1.36
Pr/n-C17 0.26 0.40 1.10 0.67 1.23 1.11 1.18
Ph/n-C18 0.11 0.04 0.07 0.05 1.02 1.08 2.59
Ts/Tm * * 0.62 0.54 0.54 0.50 0.47
C31 22S/22S + 22R * * 0.18 0.21 0.20 0.22 0.19
C32 22S/22S + 22R * * 0.59 0.58 0.57 0.58 0.57
Hopane/sterane * * 1.28 1.38 1.44 1.46 1.44
Ts/C30 Hopane * * 0.20 0.18 0.18 0.18 0.14
Ts/Ts + Tm * * 0.38 0.34 0.34 0.33 0.32
Tmax (°C) 578 518 455 445 433 433 433
VRr%** 3.24 2.16 1.03 0.85 0.63 0.63 0.63
C29 20S/20S + 20R * * 0.15 0.15 0.15 0.14 0.13
C29 diasterane/sterane * * 0.51 0.47 0.40 0.34 0.25
C29H/C30H 1.10 0.95 0.85 0.83 0.82 0.80 0.78
MPI-1 1.28 0.73 0.46 0.45 0.42 * *
Fla/(Fla + Py) 0.62 0.61 0.53 0.52 0.52 * 0.53
InPy/(InPy + Bghip) 0.43 0.42 0.35 0.35 0.36 * 0.34
Ret/(Ret + Chry) 0.10 0.25 0.67 0.60 0.66 * 0.74
BaAn/(BaAn + Chry) 0.18 0.21 0.26 0.23 0.27 * 0.27

MPI-1 = Methylphenanthrene index = 1.5 * [2MP + 3MP]/[P + 1MP + 9MP]; CPI = Carbon preference index = {2(C23 + C25 + C27 + C29)}/{C22 + 2(C24 + C26 + C28) + C30};
Pr = pristane; Ph = phytane; Ts = 18α(H)-22,29,30-trisnorneohopane; Tm = 17α(H)-22,29,30-trisnorhopane; C29H = C29 17α (H)-norhopane; C30H = C30 17α(H)21β(H)-hopane;
hopane/sterane = C30 hopane/C29 ααα sterane; *indeterminable ratios; **calculated VRr% = (0.0180 * Tmax) − 7.16 (Wust et al., 2013); Fla = fluoranthene; Py = pyrene;
InPy = indeno[1,2,3-cd]pyrene; BghiP = benzo[ghi]perylene; Ret = retene; Chry = chrysene; BaAn = benz[a]anthracene.

extremely low 0.01 in zone-A, but it sharply increases to 0.67 in Eval Tmax of 442 °C at 7.5 m. Agirrezabala et al. (2014) reported ~2 m
zone-B and 0.74 in zone-C (Fig. 12c). The BaAn/(BaAn + Chry) wide thermal aureole for a 5 m thick magmatic sill. Aarnes et al. (2010)
ratio exhibits a gradual increasing trend from 0.18 to 0.21 in zone-A, documented that the width of the contact aureole may vary from 30%
followed by a sharp increase to about 0.26 in zone-B and 0.27 in to 250% of magmatic sill thickness, depending on the host rock and the
zone-C (Fig. 12d). temperature of intrusion. The Jhuran samples at the direct contact of
dikes record Tmax values between 601 °C and 547 °C in zone-A which
5. Discussion reduces sharply to 450 °C within a few meter distance in zone-B. The
zone-A records the complete loss of micro-texture of shales because of
Effects of igneous dike intrusions on biomarker ratios are scarcely charcoalization of organic matter (Scott, 1989; Jones et al., 2002;
investigated. Earlier works primarily focused on bulk organic geochem- Ascough et al., 2010). Micro-textural details of the background shale
ical signatures. Multiple dike intrusions around 124 Ma within the remain unaffected in zone-C while zone-B records minor modifications
Jhuran Formation provides an excellent opportunity to explore the of the texture. Factors like thermal conductivity of sediments, pore
changes in bulk organic geochemical characteristics and biomarker water volume, development of convection cell and background tem-
ratios caused by high thermal stress around dike intrusions. Studies perature in host rock may affect thickness of contact aureole (Barker
suggest emplacement tempreatures of dolerite dikes may range from et al., 1998; Suchý et al., 2004; Aarnes et al., 2010, 2011). The volume
950 to 1160 °C (Holness and Humphreys, 2003; Monreal et al., 2009; of pore fluid is crucial for developing a thermal convective cell. Lack of
Iyer et al., 2013). Dike intrusions are likely to affect organic matters by pore fluids possibly results a constricted zone of thermal alteration. The
geologically instantaneous thermal stress, which is different from time- time gap between the deposition of Jhuran shale (~ 150 Ma) and the
dependent maturation of kerogen during diagenesis. Although the TOC dike intrusion (~ 125 Ma) involves expulsion of most pore fluids
content of shale have been reported to fall in relation with distance (Cartwright, 1994). The narrowness of thermal aureole in the present
from dykes (Svensen et al., 2009; Aarnes et al., 2015), but present study case is, therefore, linked to the low volume of pore fluid, low
does not record any systematic change. This may be attributed to the permeability of shale and a small dimension of the dike intrusions.
lateral variability in the relative silt content within shale bed. However,
the biomarker ratios do show a systematic change (Tables 2,3). 5.2. Stability of biomarkers in zones of high thermal stress
The following section discusses how meter-scale dike intrusions
affect the width of the altered zone in shale, alters biomarker ratios in C27 18α-trisnorneohopane (Ts)/C27 17α-trisnorhopane (Tm) de-
the heat-affected zone, and form PAHs at the thermal aureole. It also creases gradually from the zone-B to zone-C (Fig. 7b). This ratio is
discusses the broader geological implications of the systemic changes of not estimated in the zone-A because of absence of both biomarkers. Ts/
the biomarker ratios at the contact zone of igneous dikes. Tm ratio is considered as an excellent indicator of thermal maturation
as C27 18α-trisnorneohopane (Ts) is more stable at a high temperature
5.1. Width of altered zone compared to C27 17α-trisnorhopane (Tm) (Seifert and Moldowan, 1978,
1980; Kolaczkowska et al., 1990; Jiang and Zhang, 2015; Li et al.,
A few studies document the relationship between the thickness of 2015). This ratio may be affected by the type of organic matter and
intrusive and the thickness of contact aureole (Meyers and Simoneit, lithology (Moldowan et al., 1986; Peters et al., 2005). Ts/Tm decreases
1999; Aarnes et al., 2010; Agirrezabala et al., 2014). George (1992) from the zone-B to the zone-C in Jhuran Shale only because of
reported a Rock-Eval Tmax ~ 475 °C near the contact of igneous temperature, as other controlling factors remain same.
intrusion (at 2.5 m distance) which reduces to the background Rock- The ratio Ts/C30-hopane decreases gradually from zone-B to zone-C

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Fig. 7. Cross-plots of important biomarker parameters in different samples. Positions of samples in relation to dike are indicated. (A–D) Variation of selective n-alkane and isoprenoid,
terpane and sterane parameters in different zones, (E) variation of MPI-1 and Pr/Ph with Tmax, (F) cross-plot between Ts/(Ts + Tm) and Dia/(Dia + Reg) C29 Sterane.

(Fig. 7b). This ratio is not estimated in the zone-A as Ts is absent. This
ratio provides an estimation of maturation of organic matter as Ts has a
lower stability than C30-hopane at a high temperature (Seifert and
Moldowan, 1978; Volkman et al., 1983; Huang et al., 2015). The
decrease in C29/C30 hopane ratio from zone-A to zone-C relates to the
C30 hopane demethylation caused by a high temperature (Philip and
Gilbert, 1984; van Graas, 1986; Pan et al., 2005). Our observation
corroborates Peters et al. (2005), who found C29 hopane more stable
than C30 hopane at a higher level of thermal maturity. The increase in
C30 hopane/C29 ααα-sterane ratio from 1.28 in zone-B to 1.44 in zone-C
relates to higher stability of sterane at a higher temperature (Requejo,
1994; Love et al., 1996; Rabbani, 2008; Mißbach et al., 2016).
The 22S/(22S + 22R) ratio of C31 homohopane is almost same in
zone-B (0.18) and zone-C (0.19) (Fig. 7d). Both the isomers are low in
abundance within zone-B and zone-C and these are completely absent
in zone-A. Although this ratio is the most widely used hopanoid
maturity parameter (Peters et al., 2005), it is found to be ineffective
in zones of high thermal alteration due to the leaching and/or
Fig. 8. Representative partial mass chromatograms (m/z 217) showing the distribution of solubilizations of homohopane isomers (Philp, 1982). However, the
steranes and diasteranes (peak assignments in Table 4). 22S epimer of C32 homohopane is dominant than its 22R counterpart.
The C32 epimer ratio values (0.57–0.59) remain near consistent due to

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Table 4
List of steranes and diasteranes detected in the shale samples of Zara.

Peak no. Compound name Base peak Molecular ion

1 C27 13β,17α(H)-diasterane 20S 259 372

2 C27 13β,17α(H)-diasterane 20R 259 372
3 C29 13β,17α(H)-diasterane 20S 217 400
4 C27 5α,14α(H),17α(H)-sterane 20R 217 372
5 C29 13β,17α(H)-diasterane 20R 259 400
6 C28 5α,14α(H),17α(H)-sterane 20S 217 386
7 C28 5α,14α(H),17α(H)-sterane 20R 217 386
8 C29 5α,14α(H),17α(H)-sterane 20S 217 400
9 C29 5α,14β(H),17β(H)-sterane 20R 217 400
10 C29 5α,14β(H),17β(H)-sterane 20S 217 400
11 C29 5α,14α(H),17α(H)-sterane 20R 217 400

crease from 0.15 in zone-B to 0.13 in zone-C. This ratio usually

increases with increasing thermal maturity (Difan et al., 1990). The
sterane C29-20S/(20S + 20R) value may be influenced by factors like
salinity, anoxia and/or maturity within sediments. The original R
configuration at C-20 (20R) gradually converts to a mixture of R and
S configurations in response to increased heating (Mackenzie et al.,
1980; Peters et al., 2005).
The MPI-1 ratio is calculated at m/z 178 and 192 mass chromato-
grams for a few aromatic fractions in samples of different zones using
peak areas of phenanthrene and methylphenanthrene isomers. The
steady decrease of MPI-1 from 1.28 in zone-A to 0.46 in zone-B
identifies it is as a sensitive maturation indicator in zones of high
thermal stress. The observed decrease of MPI-1 is related to volatiliza-
tion and/or concomitant restructuring of side chains of compounds
because of rapid thermal stress created by the dike intrusion. Pr/Ph
increases from zone-A to zone-B, up to a Rock-Eval Tmax 520 °C and it
remains more or less consistent in the Rock-Eval Tmax range between
520 °C to 430 °C (Fig. 7e, Table 3). Retene is a prominent aromatic land
plant biomarker in all the zones. Retene forms either as a diagenetic
product of abietic acid in conifer resins or combustion of conifer wood
(Aizenshtat, 1973; Laflamme and Hites, 1978; Simoneit et al., 1993;
Jiang et al., 1998, 2000; Paul and Dutta, 2015). Retene has a high
thermal stability compared to other coniferal biomarkers (Standley and
Simoneit, 1994; Dutta and Schobert, 1993; Zhang et al., 1999;
Tudorachi et al., 2012; Hossain et al., 2013; Li et al., 2016). Presence
of retene in all zones, and disappearance of most coniferal biomarkers
in zone-A supports its high thermal stability.
The Dia/(Dia + Reg) ratio for C29 steranes increases with increasing
Ts/(Ts + Tm) in samples of zone-B and zone-C exhibiting moderate
Fig. 9. Representative partial mass chromatograms (m/z 178 + 192) showing the correlation (Fig. 7f). These ratios are influenced by thermal maturity,
distribution of phenanthrene (P) and methylphenanthrene (MP) isomers. host lithology and redox potential (Moldowan et al., 1986; Rabbani,
2008). In the present case, the moderate correlation between these
an apparent equilibration of individual epimers with thermal stress ratios is related to decreasing thermal maturation from zone-B to zone-
(Seifert and Moldowan, 1980; Peters et al., 2005). C. Moldowan et al. (1986) and Peters (1999), however, used C27 sterane
C29 ααα 20S/(20S + 20R) sterane ratio exhibits a marginal de- in lieu of C29 sterane in the ratio Dia/(Dia + Reg).

Fig. 10. Representative partial mass chromatograms (m/z 123) of an unaltered shale sample showing the distribution of various coniferal diterpenoids.

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A. Arora et al. International Journal of Coal Geology 178 (2017) 84–99

Fig. 11. Representative partial mass chromatograms (m/z 178 + 202 + 219 + 228 + 252 + 276 + 278) showing the distribution of PAHs for zone-A (A), zone-B (B) and zone-C (C)
(peak assignments in Table 5).

5.3. Alteration of redox-sensitive biomarker ratios related to thermal stress et al., 1987). The Pr/Ph ratio may also be influenced by a pristane
precursor in the source (Koopmans et al., 1999) and the release of more
The pristane/phytane (Pr/Ph) ratio sharply increases from zone-A to pristane compared to the phytane at the oil window range (Albrecht
zone-B up to a Rock-Eval Tmax 520 °C but further from zone-B to zone-C et al., 1976). The decrease in Pr/Ph ratio to an abnormally low value in
it shows inconsistent trends (Fig. 7a). The pristane/phytane (Pr/Ph) zone-A in Jhuran shales is related to the preferential destruction of
ratio plots at the boundary between sub-oxic and oxic fields in zone-B pristane, rather than increased production of phytane in zone-A (cf.
and zone-C, while it is abnormally low (~ 0.20) in zone-A. The Pr/Ph Radke et al., 1980). The abnormally low Pr/Ph value in zone-A
ratio serves as an excellent indicator of redox condition of depositional apparently indicates strongly reducing condition. Therefore, the Pr/
environment in several cases (Powell and McKirdy, 1973; Didyk et al., Ph ratio can be used as an effective indicator of redox condition below a
1978; Naeher and Grice, 2015; Dutta et al., 2013; Mohialdeen and Rock-Eval Tmax of 520 °C.
Hakimi, 2016). Pristane and phytane originate from the phytol side The Pr/n-C17 ratio gradually increases from zone-A to the transition
chain of chlorophyll (Hughes et al., 1995). A combination of a slow rate of zone-B, and it further records an overall marginal increase. The Ph/n-
of sedimentation and strongly oxidizing depositional condition favours C18 ratio is very low in zone-A and zone-B but it sharply increases in
the conversion of phytol into pristane over phytane (Didyk et al., 1978). zone-C. This increasing trend of Pr/n-C17 and Ph/n-C18 from zone-A to
Some researchers, however, reported archaebacteria as an alternate zone-C indicates a preferential formation of n-alkanes from kerogen at a
source of phytane (Brassell et al., 1981; Risatti et al., 1984) and high thermal stress than isoprenoids (Tissot et al., 1971).
tocopherols as a source of pristane (Goossens et al., 1984; ten Haven Although the C29 diasterane/sterane ratio in samples of zone-C is

Table 5
List of PAHs detected in the shale samples of Zara.

Peak no. Compound Base peak Molecular ion

1 Phenanthrene 178 178

2 Fluoranthene 202 202
3 Pyrene 202 202
4 Retene 219 234
5 Benz[a]anthracene 228 228
6 Chrysene/Triphenylene 228 228
7 Benzo[b]fluoranthene 252 252
8 Benzo[k]fluoranthene 252 252
9 Benzo[e]pyrene 252 252
10 Benzo[a]pyrene 252 252
11 Perylene 252 252
12 Indeno[1,2,3-cd]pyrene 276 276
13 Diebenz[a,h]anthracene 278 278
14 Benzo[ghi]perylene 276 276

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Fig. 12. Variation of important PAHs diagnostic ratios in samples of different zones (A–D).

significantly low (0.25), it increases to 0.51 in the zone-B and it is phenanthrene and chrysene form either during combustion of organic
indeterminable in zone-A because of volatilization of sterol derived matter or by diagenetic processes (Laflamme and Hites, 1978; Hites
products. This ratio is an indirect redox indicator under lithology and et al., 1980; Tan and Heit, 1981; Gschwend and Hites, 1981; Jiang
thermal constraints. A relatively high value (> 0.5) of this ratio et al., 1998, 2000; Grice et al., 2009).
suggests oxic and a low value (< 0.05) indicates anoxic depositional Recently Hossain et al. (2013) considered several ratios to distin-
conditions. The ratio is, however, affected by background lithology guish combustion related and diagenetically altered, land plant derived
(Moldowan et al., 1986, 1994; Brincat and Abbott, 2001; Peters et al., PAHs. They used PAH ratios such as Fla/(Fla + Py), InPy/(InPy
2005; Pei et al., 2016) as well as thermal stress (Seifert and Moldowan, + BghiP), Ret(Ret + Chry) and BaAn/(BaAn + Chry) to distinguish
1978; van Graas, 1990; Peters et al., 2005). A combination of thermal between combustion/pyrogenic and diagenetic sources. The Fla/(Fla
stress and redox conditions reduce its efficacy as a pure redox indicator. + Py) ratio in zone-A (0.62) corresponds to the combustion of solid
Hence, this ratio must be cautiously used for the present case. The C29 fossil fuel. This ratio decreases to ~0.52 in samples of zone-B and zone-
diasterane/sterane ratio increases sharply after the oil window as the C. The ratio value represents the transition from solid fossil fuel to
diasterane is more stable than sterane at elevated temperature (Peters liquid fossil fuel combustion. The Ret/(Ret + Chry) ratio exhibits a
et al., 1990, 2005). Rullkötter et al. (1984) reported that rearrangement sharp fall from ~0.67 in zone-B to 0.1 at the contact of dike. A high
of sterane to diasterane may take place at a high temperature because of Ret/(Ret + Chry) ratio (> 0.80) usually indicates combustion of con-
hydrogen-exchange reactions. The unaltered shale in zone-C, therefore, ifer wood while a low value in the range between 0.15 and 0.50
suggests a sub-oxic to dys-oxic depositional regime while an apparent suggests petroleum/coal combustion (Yan et al., 2005; Kuo et al.,
oxic value in zone-B (0.51) is related to the proximity of dike. 2011). The sharp fall in Ret/(Ret + Chry) in zone-A relates to the
destruction of retene in response to intense heating. This study,
therefore suggests that palaeo-fire deposits may show a very low Ret/
5.4. Applications of biomarkers for recording palaeo-wild fire deposits (Ret + Chry) ratio, similar to that in zone-A, in case of high-intensity
fire.
Polycyclic aromatic hydrocarbons (PAHs) are extensively studied The ratio BaAn/(BaAn + Chry) decreases from 0.26 in zone-B to
for recording palaeo-wild fire deposits as they can distinguish the high 0.18 at the contact of dike. The observed decrease in this ratio is similar
temperature, combustion related fossil fuels from diagenetic fossil fuels to that of Ret/(Ret + Chry). A high BaAn/228 ratio (> 0.35) indicates
formed at low temperature. The combustion/pyrogenic derived PAHs combustion source, an intermediate range between 0.2 and 0.35 implies
are primarily represented by a dominance of unsubstituted PAHs over a mixed petrogenic/combustion source, while a low value < 0.2
their alkylated homologues, whereas PAHs formed during diagenesis indicates diagenetic source. A very high thermal stress at the immediate
are dominated by alkyl-substituted compounds with 2–4 rings contact of the dike results in the destruction of BaAn in zone-A
(Venkatesan and Dahl, 1989; Killops and Massoud, 1992; Liu et al., (Fig. 12d). Therefore Palaeo-fire deposits may show a very low BaAn
2005). Unsubstituted PAHs indicate pyrolytic origin (Murchison and ratio in case of high-intensity fire. The variation of the ratio InPy/(InPy
Raymond, 1989; Kawka and Simoneit, 1990; Simoneit and Fetzer, + BghiP) from zone-C to zone-A mimics that of Fla/(Fla + Py) ratio
1996). Combustion/pyrolytic derived PAHs include fluoranthene, pyr- (Fig. 12b). An InPy/(InPy + BghiP) > 0.50 indicates solid fuel com-
ene, benz[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, bustion sources, whereas an intermediate ratio in the range 0.20 to 0.50
benzo[e]pyrene, benzo[a]pyrene, dibenz[a,h]anthracene, indeno implies liquid fuel combustion/mixed sources; a low ratio < 0.20
[1,2,3-cd]pyrene, benzo[ghi]perylene and coronene (Youngblood and suggests petrogenic origin (Fig. 12b, Yunker et al., 2002). The ratio
Blumer, 1975; Blumer, 1976; Hites et al., 1977; Laflamme and Hites, value is high in zone-A (0.43) fails to indicate solid fuel combustion
1978; Wakeham et al., 1980; Tan and Heit, 1981; Killops and Massoud, unlike the Fla/(Fla + Py). One possible explanation is that both InPy
1992; Jiang et al., 1998; Grice et al., 2007). Retene, perylene,

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and BghiP are present in very low concentrations in zone-A. The present terrestrial biomarker at the Cretaceous-Tertiary boundary at Caravaca, Spain.
Geology 27, 723–726.
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Institute of Technology Bombay for infrastructure facilities. S.B. and George, S.C., 1992. Effect of igneous intrusion on the organic geochemistry of a siltstone
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