Marine and Petroleum Geology xxx (2015) 1e17

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Marine and Petroleum Geology

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Research paper

Thermal maturity, source rock potential and kinetics of hydrocarbon

generation in Permian shales from the Damodar Valley basin, Eastern
India
Devleena Mani a, *, D.J. Patil a, A.M. Dayal a, B.N. Prasad b
a
CSIR-National Geophysical Research Institute, Hyderabad, India
b
Central Mine Planning & Design Institute Limited, Ranchi, India

a r t i c l e i n f o a b s t r a c t

Article history: This study investigates the source rock characteristics of Permian shales from the Jharia sub-basin of
Received 20 February 2015 Damodar Valley in Eastern India. Borehole shales from the Raniganj, Barren Measure and Barakar For-
Received in revised form mations were subjected to bulk and quantitative pyrolysis, carbon isotope measurements, mineral
12 August 2015
identification and organic petrography. The results obtained were used to predict the abundance, source
Accepted 14 August 2015
Available online xxx
and maturity of kerogen, along with kinetic parameters for its thermal breakdown into simpler
hydrocarbons.
The shales are characterized by a high TOC (>3.4%), mature to post-mature, heterogeneous Type IIeIII
Keywords:
Permian shales
kerogen. Raniganj and Barren Measure shales are in mature, late oil generation stage (Rr%Raniganj ¼ 0.99
Raniganj Formation e1.22; Rr%Barren Measure ¼ 1.1e1.41). Vitrinite is the dominant maceral in these shales. Barakar shows a
Barren Measure Formation post-mature kerogen in gas generation stage (Rr%Barakar ¼ 1.11e2.0) and consist mainly of inertinite and
Barakar Formation vitrinite. The d13Corg value of kerogen concentrate from Barren Measure shale indicates a lacustrine/
Source rock marine origin (24.6e30.84‰ vs. VPDB) and that of Raniganj and Barakar (22.72e25.03‰ vs. VPDB)
Geochemistry show the organic provenance to be continental. The d13C ratio of thermo-labile hydrocarbons (C1eC3) in
Barren Measure suggests a thermogenic source.
Discrete bulk kinetic parameters indicate that Raniganj has lower activation energies (DE ¼ 42
e62 kcal/mol) compared to Barren Measure and Barakar (DE ¼ 44e68 kcal/mol). Temperature for onset
(10%), middle (50%) and end (90%) of kerogen transformation is least for Raniganj, followed by Barren
Measure and Barakar. Mineral content is dominated by quartz (42e63%), siderite (9e15%) and clay (14
e29%). Permian shales, in particular the Barren Measure, as inferred from the results of our study,
demonstrate excellent properties of a potential shale gas system.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction main coal-bearing Formations in the basin. A marine/lacustrine

succession that deposited between the continental depositions
Damodar Valley is an important coal repository amongst the resulted in a coal-devoid Formation, the ‘Barren Measure’ (Gupta,
Gondwana basins of India. Located in the northeastern part of 1999). Shale formations occur extensively interbedded within the
Peninsular India, it comprises of series of east-west trending sub- coal-bearing horizons in the sub-basins. The PermianeCarbonif-
basins namely, Raniganj, Jharia, Bokaro, Ramgarh, Karanpura, Aur- erous Gondwana facies was deposited as basal glacial sediments,
anga, Daltonganj and Hutar (Fig. 1). Sediment deposition during overlain by coal measures across large regions of Australia,
early Permian in the Gondwana basin was primarily fluvio-glacial Antarctica, India, Arabia, Madagascar, Africa and South America. In
and lacustrine, leading to significant development of coal beds addition to the traditional mineable coal, the Permian basins in
(Gupta, 1999). Talchir, Barakar, Raniganj and Karharbari are the several of these regions also host major coal-seam gas and oil and/
or gas reserves.
The organic rich, thermally mature shales occurring in Indian
Gondwana's are likely source for the gaseous hydrocarbons. Wells
* Corresponding author.
E-mail address: devleenatiwari@ngri.res.in (D. Mani). drilled in the Damodar Valley basin have encountered gas flows in

http://dx.doi.org/10.1016/j.marpetgeo.2015.08.019
0264-8172/© 2015 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Mani, D., et al., Thermal maturity, source rock potential and kinetics of hydrocarbon generation in Permian
shales from the Damodar Valley basin, Eastern India, Marine and Petroleum Geology (2015), http://dx.doi.org/10.1016/j.marpetgeo.2015.08.019
2 D. Mani et al. / Marine and Petroleum Geology xxx (2015) 1e17

Fig. 1. Geological map of the Jharia sub-basin showing the locations of boreholes for shale sample collection (modified after; Chandra, 1992).

the Raniganj region (Padhy and Das, 2013). Thermal maturity data composition was ascertained by X-ray diffraction. The variation in
on coals surrounding the Barren Measure shale suggest it to be geochemical parameters in the sedimentary sequences enabled the
within gas window (Padhy and Das, 2013), making it a potential reconstruction of paleoenvironment and thermal conditions in
shale gas target. The qualitative and quantitative aspects of thermal which the organic rich sediments got preserved and matured, thus
transformation of shale organic matter can provide the much providing useful insights onto its generative potential.
needed information towards determining the presence and prop-
erties of hydrocarbons in potential source rocks (Tissot and Welte, 2. Geologic setting and stratigraphy
1984; Hunt, 1996; Peters et al., 2005). Geochemical attributes such
as organic richness, kerogen type and thermal maturity of sedi- The Gondwana basins occur within the suture zones of the
mentary organic matter are directly related to the hydrocarbon Precambrian cratonic blocks of the Peninsular India along some
generation potential of a source rock (Peters and Cassa, 1994; linear belts. These basins preserve a thick sedimentary pile
Rodriguez and Philp, 2010). deposited over nearly 200 million years from the Carboniferous to
The kinetic parameters for the kerogen decomposition in source the Lower Cretaceous (Mukhopadhyay et al., 2010). Occurring along
rocks provide quantitative estimates on the hydrocarbon genera- the major river valleys, the basins have been named after the
tion (Tissot and Welte, 1984; Ungerer et al., 1986; Braun and respective rivers flowing through the region. The EeW to
Burnham, 1987; Tissot et al., 1987; Ungerer and Pelet, 1987; WNWeESE trending DamodareKoel basin lies along the Damodar
Sweeney et al., 1990; Jarvie, 1991). river in the Trans-Indian basin belt (Mukhopadhyay et al., 2010).
In this paper, the abundance, source and maturity of organic The Jharia sub-basin forms part of the eastern end of the Damodar
matter has been investigated on the drill cores of shale from one of Valley. The Jharia coalfield is roughly sickle shaped, extending for
the sub-basins, Jharia, located in the eastern part of Damodar Valley about 38 km in an east-west direction and a maximum of 18 km in
basin to evaluate the hydrocarbon potential. Subsurface Permian north-south direction with an area of about 456 sq. km (Fig. 1;
shales (320e1050 m) from the Raniganj, Barren Measure and Bar- Chandra, 1992). It is marked by two prominent synforms and three
akar Formations were subjected to open system pyrolysis using high zones (Chandra, 1992).
Rock Eval 6. The pyrolysis results were further used to obtain the The basin is typically bounded by faults that developed along
kinetic parameters associated with the thermal maturation of shale the Precambrian lineaments during deposition, as well as affected
organic matter at varying heating rates (Tissot and Espitalie, 1975; by intrabasinal faults indicating fault-controlled synsedimentary
Ungerer and Pelet, 1987). Bulk and compound-specific carbon subsidence (Chakraborty et al., 2003). The Southern Boundary Fault
isotope measurements were performed on selected samples to is the most prominent and runs through the entire southern edge in
identify the source of organic matter using closed system pyrolysis. WSWeESE direction (Fig. 1). It is marked by a zone of parallel
The nature and proportion of organic constituents along with its fractures with a stratigraphic throw of about 1800 m towards the
rank were investigated using organic petrology, and the mineral north. A number of interbasinal faults having inter- and intra-

Please cite this article in press as: Mani, D., et al., Thermal maturity, source rock potential and kinetics of hydrocarbon generation in Permian
shales from the Damodar Valley basin, Eastern India, Marine and Petroleum Geology (2015), http://dx.doi.org/10.1016/j.marpetgeo.2015.08.019
 D. Mani et al. / Marine and Petroleum Geology xxx (2015) 1e17 3

formational nature have been identified in the basin. All major 2001). The pyrolysis oven was programmed with an initial
faults initiated as contemporaneous faults and extended their isothermal temperature of 300  C maintained for 3 min and fol-
strike length in subsequent times (Chandra, 1992). lowed by a ramp of 650  C at the rate of 25  C/min. Further, the
The general stratigraphic succession is given in Fig. 2 (after, samples were oxidized using a zero air flow of 300 ml/min. The
Chandra, 1992). The metamorphic rocks are overlain by the Talchir oxidation oven was programmed with an initial temperature of
Formation of fluvio-glacial origin, which is followed by the depo- 300  C maintained for 1 min and followed by a ramp at the rate of
sition of fluviatile coal-bearing Barakar Formation. Marine/Lacus- 20  Ce850  C. Hydrocarbons released from the pyrolysis of organic
trine Barren Measure Formation overlies Barakar and is coal- matter were detected by the flame ionization detector, which had a
devoid. Raniganj, the coal-bearing Formation overlies it. A combi- hydrogen flame at flow of 30 ml/min. The carbon dioxide and
nation of resurgent and block tectonism, with variable time lag in monoxide evolving from the decomposition of organic matter and
different parts of the reformed basin furnished a setting for cen- mineral matrix were detected by infrared detectors, two in
tripetal dispersed pattern with the streams flowing in from the numbers for the simultaneous pyrolysis and oxidation analyses.
surrounding upland areas into the basin (Chandra, 1992). With the The results were reported on a dry weight basis (Mani et al., 2014).
shifting of rivers, major parts of the depositional provinces were
transformed into the back swamp areas, which were the sites for
coal seam development (Chandra, 1992). It is generally known that 3.1.2. Optkin cycle
the Gondwana deposits in the Jharia coalfield are of fresh water The distribution of kinetic parameters for thermal cracking of
origin. However; marine incursions during Gondwana period have kerogen was obtained using the Optkin program (IFP/Beicip, Fran-
been indicated by the occurrence of lamellibranchs in Raniganj and lab). It uses the results of Rock Eval pyrolysis performed on source
Jharia as well as Bokaro, Karanpura, Sonhat and Wardha Valley rocks and calibrates the kinetic parameters of thermal cracking of
fields (Chandra, 1990; Chandra and Betekhtina, 1990) and Rajmahal organic matter into hydrocarbons (Espitalie et al., 1987; Ungerer
Group of coalfields (D'Rozario, 1988). and Pelet, 1987). Taking into account the amount of oil and gas
generated by primary cracking of kerogen when temperature in-
3. Materials and methods creases through time, the kerogen degradation is described by se-
ries of parallel chemical reactions, each of which obey the first-
Twenty-four subsurface drilled shale cores of ~30 cm length order kinetics, characterized by Arrhenius Law:
were collected from the three blocks of Jharia sub-basin, namely
kðTÞ ¼ A*expð  E=ðRTÞ (1)
West Mohuda (MMW-18), Singra (MSG-34) and Kapuria (MKP-29)
(Fig. 1). The sampled shale horizons occur interbedded between the
where k is the reaction rate parameter dependent on absolute
coal and sandstone lithology, in depths of ~150e1000 m. Litho-log
temperature (T, in Kelvin); E is the activation energy of the reaction
for the boreholes selected for shale sampling is shown in the
(J/mol) and R is the molar gas constant (J/mol/K); A is the pre-
Appendix. The shales were washed thoroughly with Milli-Q water
exponential frequency factor/Arrhenius constant (sec1).
and air-dried at room temperature. Homogeneously powdered
Eq. (1) is expressed as:
samples were used to carry out the geochemical analyses
comprising of Rock Eval pyrolysis (Basic and Optkin cycle), bulk and dXi=dt ¼ Aexpð  Ei=RTÞ$Xi (2)
compound-specific stable carbon isotope ratio determination,
organic petrology and X-ray diffraction. dXi/dt is the hydrocarbon generation rate and Xi is the residual
petroleum potential of the organic matter involved in reaction i. E is
3.1. Rock Eval pyrolysis the activation energy related to reaction i (Tissot and Espitalie,
1975; Ungerer et al., 1986; Braun and Burnham, 1987; Ungerer
3.1.1. Basic cycle and Pelet, 1987; Tissot et al., 1987). With increasing temperature,
About 50e70 mg of the shale sample was taken in a pre- the primary products break down to smaller molecules through
oxidized crucible and pyrolysed using the basic cycle of Rock Eval secondary cracking processes, and lead to gas and pyrobitumen as
6 pyrolyzer (Turbo version). Pyrolysis was carried out in an inert end products.
atmosphere of nitrogen with a flow of 100 ml/min (Behar et al., The amount Q of oil and gas formed is expressed by:

Fig. 2. Generalized stratigraphy of the Jharia sub-basin, Damodar Valley (modified after; Chandra, 1992).

Please cite this article in press as: Mani, D., et al., Thermal maturity, source rock potential and kinetics of hydrocarbon generation in Permian
shales from the Damodar Valley basin, Eastern India, Marine and Petroleum Geology (2015), http://dx.doi.org/10.1016/j.marpetgeo.2015.08.019
4 D. Mani et al. / Marine and Petroleum Geology xxx (2015) 1e17

absorbing the CO2 coming out during the pyrolysis of shale organic
X
N
matter. 1 ml of the desorbed gas was injected into the Agilent 6890
Q¼ ðXio  XiÞ (3)
GC, equipped with “Pora Plot Q” capillary column, 25 m in length
i¼1
and a diameter of 0.32 mm, in splitless mode with helium as carrier
where Xio is the value of Xi at t ¼ 0. gas at a fixed oven temperature of 28  C. The chromatographically
Pyrolysis curves for the Raniganj (R-4), Barren Measure (MKP- separated hydrocarbon gases eluted from GC column entered a pre-
29/BM-II, MSG-34/BM-II) and Barakar (MKP-29/B-2) shales were oxidized CueNiePt combustion reactor maintained at 960  C,
generated. Ideally, immature samples are used for kinetic analysis, where they were converted into carbon dioxide and water. Water
however; in Damodar Valley basin, majority of Permian shales was removed using a Nafion membrane tube prior to entry into the
(n ~ 300) from studied formations exhibit a Tmax greater than mass spectrometer. The purified CO2 after combustion entered the
435  C (NGRI unpublished data; Varma et al., 2015), due to which mass spectrometer for 13C/12C ratio measurement of the individual
very early/least mature (lower Tmax values) shales were selected. hydrocarbon components. GCeC-IRMS was calibrated using Natu-
Also, the variation in mineral matrix and the amount and type of ral Gas Standard (NGS-1) mixture and reported to the Vienna
organic matter were taken into consideration, and representative PeeDee Belemnite (VPDB). The precision was found to be within
shales from the selected intervals of core were used for the kinetic ±0.3‰ of the reported value for NGS-1 (Mani et al., 2011).
analysis. Pyrolysis was conducted on ~50 mg of shale samples using
three different heating rates of 5, 15 and 30 /minute with initial 3.3. X-ray diffraction
temperature of 300  C to a final of 700  C. The input file for opti-
mization was created for the parallel reactions of first-order using XRD analysis was carried out using Siemens D 500 diffractom-
an activation energy step of 2 kcal/mole. Utilizing the Rock Eval eter at XRD Laboratory, Atomic Mineral Directorate (AMD),
pyrolysis time, temperature and heating rates and hydrogen index Hyderabad. An accelerating voltage was maintained at 35 kV and
(HI), best fitting kinetic parameters (activation energies E, Arrhe- the tube current at 22 mA. CuK a radiation (1.5418 A), mono-
nius constants A, and initial petroleum potentials Xio) for the chromatised using curved graphite monochromator, was used for
observed S2 (hydrocarbon peak obtained during cracking of diffraction. For identification, a scanning speed of 0.03 2q/s, over a
kerogen) were calculated. The best adjustment corresponded to the long angular range (4e90 2q), with a sampling time of 2 s, was
minimum of the error function (summation of the quadratic dif- selected. Mineral identification was done from the powder
ferences) calculated between measured and computed values. diffraction data so obtained by comparing the same with the rele-
vant International Centre for Diffraction Data (ICDD) card.
3.2. Carbon isotope analysis
3.4. Organic petrography
3.2.1. Kerogen isolation
The microscopic examination of the organic matter in shales
Kerogen was isolated from the selected shale rocks by treating
was carried out in the Coal Petrology laboratories of Central Mine
~1 g of powdered sample with 20% HCl and stirring at 50  C for 6 h.
Planning & Design Institute Limited (CMPDIL), Ranchi and Indian
The acid treated sample was washed thrice with Milli-Q water.
School of Mines, Dhanbad. Maceral analysis and reflectance mea-
Further, it was soaked in 20% HCl þ48% HF (1:4) acid mixture
surement of vitrinite grains in oil (Random; Rr% oil) was carried out
overnight. The acid treated samples were washed thoroughly with
on polished pellets under normal reflectance (incident light) and
MilliQ water and dried at 50  C (Horvath and Jackson, 1981).
fluorescence modes using advanced polarizing microscope with
photometer, following the standard protocol by ICCP (International
3.2.2. Bulk carbon isotope analysis Committee for Coal Petrography).
Bulk carbon isotope analysis (d13Corg) of the kerogen concen-
trate was performed on a Thermo Finnigan Flash-Elemental 4. Results
Analyzer (TC/EA) connected to Delta plusXP isotope ratio mass
spectrometer (IRMS). The samples, held in tin containers, were The shales (MMW-18/R-1 to MMW-18/R-9) from the Raniganj
placed inside the auto-sampler drum, where they were purged Formation, West Mohuda, show high Total Organic Carbon (TOC)
with a continuous flow of helium and then dropped at preset in- content in the range of 2.86e23.09% (Table 1, Fig. 3). The S1 (ther-
tervals into a vertical quartz tube maintained at 1020  C (com- mally liberated free hydrocarbon) and S2 (hydrocarbon from
bustion reactor). Flash combustion of sample took place in the cracking of kerogen) values range between 0.27e2.77 mg HC/g rock
helium stream temporarily enriched with pure oxygen. The and 2.15e68.69 mg HC/g rock, respectively. The hydrogen index
resulting gas mixture was directed to the chromatographic column (HI) ranges between 75 and 297 mg HC/g TOC. The oxygen index
(Porapak PQS) where the individual components were separated. (OI) is fairly low, ranging between 1 and 6 mgCO2/TOC (Table 1).
The isotopic composition of evolved carbon dioxide (CO2) was The Tmax (temperature at highest yield of S2) ranges between 442
measured using IRMS. The Flash EA-IRMS was calibrated using in- and 461  C, suggesting a mature stage for hydrocarbon generation
ternational standards, NBS-20 and graphite, and the precision was (Fig. 4). Organic matter is characterized by mixed Type IIeIII oil/
found to be within ±0.3‰ of the reported value. gas-prone kerogen (Fig. 5).
The Barren Measure shales from MSG-34 and MKP-29 boreholes
3.2.3. Compound-specific carbon isotope analysis from Singra and Kapuria blocks, respectively show a TOC content in
An offline, closed system pyrolysis of shales was performed at the range of 4.36e4.48% with an average value of ~4.5% (Table 1).
300  C to desorb the thermo-labile gases present in it. 500 mg of The S1 and S2 values range between 0.35e0.76 and 3.63e6.95 mg
powdered shale was heated in the pre-evacuated pyrolysis as- HC/g rock, respectively. The Tmax values range between 452 and
sembly for 3 min. Saturated KOH solution was added externally to 455  C, suggesting a mature kerogen in oil-condensate window
glass ampoule and the thermally-desorbed gases released during (Table 1; Fig. 4). The HI values are between 83 and 143 mg HC/g
the pyrolysis were collected by upward displacement in the grad- TOC, and the OI values are <10 mg CO2/TOC (Fig. 5).
uated limb of apparatus fitted with silicone septum. KOH solution The Barakar Formation shows TOC values ranging between 5.95
served the dual purpose of displacing the gases, as well as and 16.42% (Table 1). The S1 and S2 values range between 0.12 and

Please cite this article in press as: Mani, D., et al., Thermal maturity, source rock potential and kinetics of hydrocarbon generation in Permian
shales from the Damodar Valley basin, Eastern India, Marine and Petroleum Geology (2015), http://dx.doi.org/10.1016/j.marpetgeo.2015.08.019
 D. Mani et al. / Marine and Petroleum Geology xxx (2015) 1e17 5

Table 1
Rock Eval pyrolysis results of shales from the Jharia sub-basin, Damodar Valley.

Block Borehole/Depth (m) S1 S2 PI Tmax S3 PC (%) RC (%) TOC(%) HI OI MINC (%)

W. Mahuda MMW-18
R-1 151.8e152.2 0.61 15.43 0.04 442 0.29 1.4 6.35 7.75 199 4 0.79
R-2 193.8e194.2 0.95 24.75 0.04 444 0.13 2.17 9.12 11.29 219 1 0.52
R-3 226.9e227.2 0.42 3.54 0.11 450 0.15 0.41 3.76 4.17 85 4 0.88
R-4 272.1e272.4 1.19 68.69 0.02 439 0.2 5.86 17.23 23.09 297 1 4.59
R-5 330.1e330.5 0.29 2.67 0.1 455 0.07 0.36 3.04 3.4 79 2 1.29
R-6 369.1e369.4 0.27 2.15 0.11 452 0.16 0.25 2.62 2.87 75 6 0.81
R-7 416.5e416.8 2.47 17.01 0.13 445 0.24 1.76 10.21 11.97 142 2 1.69
R-8 416.0e416.5 2.76 19.71 0.12 450 0.34 2.02 10.78 12.8 154 3 1.6
R-9 450.1e450.6 1.47 8.45 0.15 464 0.35 1 6.88 7.88 107 4 2.11
Singra MSG-34
BM-1 409.8e410.1 0.35 3.63 0.09 455 0.19 0.37 3.99 4.36 83 4 0.54
BM-2 421.8e422.1 0.58 6.39 0.08 452 0.11 0.6 3.88 4.48 143 2 0.33
B-I 605.1e605.4 0.76 33.2 0.02 461 0.11 2.85 13.57 16.42 202 1 6.77
B-II 629.4e629.7 0.6 3.96 0.13 470 0.33 0.67 5.28 5.95 67 6 2.57
B-III 664.2e664.5 0.35 3.95 0.08 467 0.22 0.43 5.79 6.22 64 4 1.24
B-VA 1012.8e1013.2 0.87 7.3 0.11 485 0.21 0.76 10.55 11.31 65 2 7.34
B-VB 1048.8e1049.1 0.63 6.28 0.09 492 0.21 0.7 10.49 11.19 56 2 8.34
Kapuria MKP-29
BM-1 320.3e320.6 0.76 4.7 0.14 459 0.15 0.5 3.89 4.39 107 3 0.94
BM-2 351.0e351.3 0.66 4.08 0.14 457 0.25 0.48 3.8 4.28 95 6 1.42
B-I 540.3e540.7 0.56 6.15 0.08 473 0.19 0.6 7.51 8.11 76 2 1.57
B-II 572.9e573.2 0.69 3.31 0.17 473 0.21 0.43 4.67 5.1 65 4 1.57
B-III 641.3e641.6 0.42 6.48 0.06 476 0.18 0.62 8.24 8.86 73 2 1.22
B-V 876.3e876.7 0.19 2.9 0.06 493 0.16 0.32 7.16 7.48 39 2 1.47
B-VII 958.6e959.0 0.13 5.55 0.02 493 0.18 0.66 12.31 12.97 43 1 4.44
B-IX 1009.0e1009.3 0.12 2.99 0.04 509 0.27 0.38 8.34 8.72 34 3 5.55

S1 ¼ mgHC/gTOC; S2 ¼ mgHC/gTOC; PI ¼ S1/S1 þ S2; Tmax ¼  C; PC ¼ Pyrolysable carbon (%); RC ¼ Residual carbon (%); HI ¼ mgHC/g TOC; OI ¼ mg CO2/g TOC; MINC ¼ mineral
carbon (%); R ¼ Raniganj Formation; BM ¼ Barren Measure Formation; B ¼ Barakar Formation.

0.76 mg HC/g rock and 2.9e33.2 mg HC/g rock, respectively. HI desorption at 300  C of the one shale sample belonging to the
ranges between 34 and 76 mg HC/g TOC. Organic matter is char- Barren Measure Formation is as follows: d13C1 ¼ 40.38e44.82‰;
acterized by Type III gas-prone kerogen (Fig. 3). Tmax ranges be- d13C2 ¼ 29.62e30.3‰; and d13C3 ¼ 27.0e29.21‰. The values,
tween 461 and 509  C, showing a post-mature kerogen, between variable in a narrow range, indicate a thermogenic source for the
condensate-wet gas and dry gas window (Figs. 4 and 5). matrix adsorbed gaseous hydrocarbons.
Bulk and compound-specific (C1eC3) carbon isotope ratios of The results of petrographic examination of the shale samples are
the organic matter and thermo-labile gases obtained from the given Table 3. Photomicrographs of the macerals recorded from the
combustion-IRMS and offline pyrolysis of shales from Jharia coal three formations are shown in Plates IeIII. The Raniganj (Rr
field are shown in Table 2. The d13Corg values of the Barren Measure % ¼ 0.99e1.22) and Barren Measure (Rr% ¼ 1.1e1.41) shales show
shales lie in the range of 24.6e30.84‰, indicating a lacustrine/ vitrinite and inertinite macerals, with lesser occurrence of liptinite.
marine source for the shale organic matter. One sample from the The Barakar shales (Rr% ¼ 1.11e2.0) consist mainly of inertinite and
Raniganj Formation shows a d13Corg of 24.28‰, whereas those of vitrinite. Abundant clay minerals along with siderite and pyrite are
Barakar have a value of 22.72e25.03‰, suggesting the organic present.
provenance to be continental. The d13C ratios for the individual The X-ray diffraction results (Table 4) on nine selected samples
compounds (C1eC3) obtained from the repeated (n ¼ 5) thermal representing the three formations show quartz (42e63%), siderite
(9e15%), and albite (2e13%) to be the main minerals. Clay content is
dominated by Kaolinite (4e17%) and illite (9e13%). Traces of chlo-
rite and chloritoid, minute traces of almandite, anatase, microcline,
rutile and zircon are also observed.

5. Discussion

5.1. Organic richness and thermal maturity

Organic matter in the shales from Jharia sub-basin, Damodar

Valley show excellent organic richness (TOC ¼ 2.86e23.09%),
characterized by Type II/III and Type III kerogen with thermal
maturities spanning the mature (oil window-gas condensate) to
post mature (dry gas) zone for hydrocarbon generation. While the
Raniganj and Barren Measure shales are in late oil generation
window, the Barakar shales show post-mature stage for oil (Fig. 4).
Raniganj (Rr% ¼ 0.99e1.22) and Barren Measure (Rr% ¼ 1.1e1.41)
Fig. 3. TOC versus S2 variation (after, Langford and Blanc-Valleron, 1990) in shales from
shales show vitrinite and inertinite as dominant macerals, with
MMW-18, MSG-34, MKP-29 borewells, Jharia sub-basin, Damodar Valley. RNG¼Rani- sparse occurrence of liptinite. Barakar shales (Rr% ¼ 1.11e2.0)
ganj; BM¼Barren Measure; BRK¼Barakar consist mainly of inertinite and vitrinite. Thermal maturities of the

Please cite this article in press as: Mani, D., et al., Thermal maturity, source rock potential and kinetics of hydrocarbon generation in Permian
shales from the Damodar Valley basin, Eastern India, Marine and Petroleum Geology (2015), http://dx.doi.org/10.1016/j.marpetgeo.2015.08.019
6 D. Mani et al. / Marine and Petroleum Geology xxx (2015) 1e17

Fig. 4. HI vs Tmax plots (after Espitalie et al., 1987) indicating the kerogen type and thermal maturity of shales from the Jharia sub-basin, a) Raniganj, b) Barren Measure c) Barakar
Formations.

Please cite this article in press as: Mani, D., et al., Thermal maturity, source rock potential and kinetics of hydrocarbon generation in Permian
shales from the Damodar Valley basin, Eastern India, Marine and Petroleum Geology (2015), http://dx.doi.org/10.1016/j.marpetgeo.2015.08.019
 D. Mani et al. / Marine and Petroleum Geology xxx (2015) 1e17 7

Fig. 5. Modified van Krevelen diagram (Peters, 1986) indicating the kerogen type in the shales from Jharia sub-basin, Damodar Valley.

shales are also reflected in correlation plot of Rock Eval Tmax and et al., 2003; Hamblin, 2006; Tan et al., 2015). The kerogen quan-
Vitrinite reflectance (Fig. 6). Barakar shales have experienced tity and quality of Permian shales from Damodar Valley basin are
highest maturity. The Raniganj shales are comparatively less very much in agreement with these requirements.
mature and Barren Measure is in late mature stage.
Organic matter typing or the kerogen classification is directly
5.2. Stable carbon isotope compositions
related to total hydrocarbon potential, oil chemistry, and hydro-
carbon generation kinetics (van Krevelin, 1961; Obermajer et al.,
Bulk and individual carbon isotope ratios of hydrocarbon gases
1997; McCarthy et al., 2011; Hartwig et al., 2012; Rippen et al.,
obtained from the flash-combustion and thermal desorption,
2013; Abbassi et al., 2014). With relatively lesser thermal matu-
respectively of the shales indicate a thermogenic gas from the
rity, the HI of Raniganj is highest (75e297 mg HC/g TOC), followed
continental/terrestrial organic matter, except for Barren Measure,
by Barren Measure (83e147 mg HC/g TOC) and Barkar (34e95 mg
wherein a lacustrine/marine source is inferred. Stable carbon
HC/g TOC; except, B-1 ¼ 202 mg HC/g TOC from MSG-34), respec-
isotope ratios have been utilized for the identification of varied
tively. The HI values correlate well with the Tmax. The shales with
locations or origins of diverse potential sources of the hydrocarbon
increasing maturity (higher Tmax) have lower HI. This is in
gases, particularly methane (Schoell, 1983). The depositional
particular for the Barren Measure and Barakar shales; except for
environment of shales - marine versus non-marine, has a direct
two samples (MGS-34/BM-II & B-III), where the variation is in
influence on the type and amount of organic matter that they
narrow range (Table 1). For the Raniganj shales (MMW-18), the
contain. The marine and continental (terrestrial and freshwater)
variation of HI is not consistent with Tmax. HI and Tmax are
plants show different d13C signatures in land plants as compared
functions of both the kerogen composition and burial and thermal
with marine plants due to the difference in the isotopic composi-
history, which can possibly influence the correlation between these
tion of carbon sources. As a result, the gas systems originating from
parameters. The OI for all of these shales is <10 mg CO2/g TOC
respective source organic matter have been classified into two
(Fig. 5). The OI values vary in very narrow range (1e6 mg CO2/g
distinct types namely biogenic (or microbial) and thermogenic
TOC). Raniganj shales show Type IIeIII oil and gas-prone kerogen,
(Whiticar, 1996; Martini et al., 2003; Tian et al., 2010). There can
whereas Barren Measure and Barakar consist of Type III kerogen
also be mixtures of the two gas types (Jarvie et al., 2007).
(Fig. 5). The production index (PI) ranges from 0.02 to 0.11 and
Occurrence of thermogenic gas establishes the presence and/or
tends to gradually increase linearly with depth for the Raniganj and
possibility of a source rock in the subsurface and gives information
Barren Measure shales. The exploration targets comprise of sig-
on the elements of petroleum or gas system, which otherwise lacks
nificant Type II organic matter in thermally over-mature stage and
in biogenically produced gases. Thermogenic signature of hydro-
Type III organic matter in mature to overmature stage (Martini
carbon gases from the Barren Measure shale indicates the

Table 2
Bulk (combustion-IRMS) and compound-specific (offline pyrolysis-IRMS) carbon isotope ratios of the organic matter and thermo-labile desorbed gases, respectively, from the
shales, Jharia sub-basin.

Sample ID Bulk d13C ratio (‰) Sample d13C1 (‰) d13C2 (‰) d13C3 (‰)
MKP-29/BM-2 30.8 MSG-34 BM-II 40.4 e 28.9
MKP-29/B-3 25.0 MSG-34 BM-II 42.5 e 27.0
MMW-18/R-4 24.3 MSG-34 BM-II 43.0 e 26.9
MSG-34/BM-1 24.6 MSG-34 BM-II 44.6 29.7 29.2
MSG-34/B-VA 22.7 MSG-34 BM-II 44.8 30.3 27.0

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8 D. Mani et al. / Marine and Petroleum Geology xxx (2015) 1e17

Table 3
Petrographic analysis of the shales from Jharia sub-basin, Damodar Valley.

Sample Lithology Rr% Remarks

West Mohuda Block, MMW-18, R ¼ Raniganj Formation

R-1 Sandy shale 0.99 Liptinite is abundant. Shows orangeeyellow color under fluorescence light. Clay minerals are dominant. Abundance of
macerals: Liptinite > Vitrinite > Inertinite.
R-2 Sandy shale 1.11 Vitrinite is common. Liptinite is sparse. Mineral matter abundant. Abundance of macerals: Vitrinite > Liptinite > Inertinite.
R-3 Sandy shale 1.24 Vitrinite is common. Liptinite rare and Inertinite rare to sparse. Abundance: Vitrinite > Inertinite > Liptinite. Mineral
matter dominant.
R-4 Sandy shale 1.24 Vitrinite > Inertinite > Liptinite. Abundant mineral matter.
R-5 Sandy shale 1.13 Inertinite common, Vitrinite sparse. Abundance: Inertinite > Vitrinite > Liptinite. Mineral matter abundant.
R-6 Sandy shale 1.29 Vitrinite > Inertinite > Liptinite. Abundant mineral matter, clay minerals present.
R-7 Shale 1.22 Inertinite > Vitrinite > Liptinite. Abundant mineral matter. Clay minerals and siderite observed.
Singra Block, MSG-34; BM ¼ Barren Measure; B ¼ Barakar Formation
BM-I Intercalation of 1.1 Grains of vitrinite and inertintes are large. Fusinite present. Inertinite > Vitrinite > Liptinite. Pyrite, siderite and clay
shale and sandstone minerals present.
BM-II Grey shale 1.15 Inertinite > Vitrinite > Liptinite. Mineral matter dominant. Siderite and pyrite observed.
B-I Dark grey shale 1.41 Inertinite abundant, Vitrinite common and Liptinite rare. Abundance of macerals: Inertinite > Vitrinite > Liptinite.
Siderite is common.
B-II Intercalation of 1.11 Inertinite > Vitrinite > Liptinite.
shale and sandstone
B-III Shale 1.3 Vitrinite and Inertinite abundant. Liptinite rare. Mineral matter abundant, Pyrite common.
B-VA Sandy shale 1.58 Inertinite > Vitrinite > Liptinite. Fusinite common, Siderite, pyrite abundant.
B-VB Gray shale 1.6 Organic constituent abundant in ground mass, Inertinite > Vitrinite. Siderite abundant, Clay, quartz and few pyrites observed.
Kapuria Block, MKP-29, BM ¼ Barren Measure; B ¼ Barakar Formation
BM-1 Gray shale 1.41 Organic constituent sparse to common. Vitrinite > Inertinite. Liptinite rare. Abundant mineral matter. Some pyrite observed.
Inertinite > Vitrinite > Liptinite.
BM-2 Gray shale 1.32 Organic constituent sparse to common. Vitrinite > Inertinite. Liptinite rare. Abundant mineral matter. Some pyrite observed.
Inertinite > Vitrinite > Liptinite
B-1 Intercalation of 1.41 Vitrinite > Inertinite. Liptinite rare. Mineral matter Abundant. Clay & quartz > siderite > pyrite present.
shale & sandstone
B-2 Gray shale 1.24 Large grains of vitrinite and Inertinite. Vitrinite > Liptinite > Inertinite. Mineral matter abundant. Siderite and pyrite observed.
B-3 Sandy shale 1.23 Vitrinite sparse, Inertinite common. Mineral matter dominant.
B-5 Gray shale 1.32 Abundant Inertinite. Liptinite shows orangish color under fluorescence light. Mineral matter abundant. Some pyrite observed.
B-7 Intercalation 1.20 Vitrinite grains are rare, Inertinite common to abundant. Organic constituents sparse.
B-9 Gray shale 2.0 Vitrinites grains are altered. Inertinite abundant.

Table 4
Mineral identification in the shales from Jharia sub-basin using XRD technique.

Sample id Minerals identified Clay minerals identified

MMW-18/R-2 Quartz (63%), siderite (10%), albite (3%), traces of chlorite, chloritoid, minute traces of almandite, microcline, rutile, zircon Kaolinite (10%), illite (13%)
MMW-18/R-4 Quartz (42%), siderite (15%), albite (13%), traces of chlorite, chloritoid, minute traces of microcline Kaolinite (14%), illite (13%)
MMW-18/R-7 Quartz (55%), siderite (13%), albite (5%), pyrite (4%), traces of chlorite, minute traces chloritoid and microcline Kaolinite (10%), illite (10%)
MMW-18/R-8 Quartz (55%), siderite (12%), albite (6%) Kaolinite (12%), illite (13%)
MSG-34/BM-I Quartz (59%), siderite (09%), albite (2%), minute traces of almandite, anatase, microcline, rutile, zircon Kaolinite (17%), illite (12%)
MSG-34/BM-II Quartz (65%), siderite (10%), pyrite (2%), albite (3%), traces of chlorite, minute traces of almandite, microcline, rutile, zircon Kaolinite (06%), illite (13%)
MSG-34/B-VA Quartz (62%), siderite (13%), albite (2%), traces of chlorite, chloritoid, minute traces of zircon Kaolinite (11%), illite (10%)
MKP-29/BM-I Quartz (65%), siderite (10%), pyrite (9%), traces of chlorite and chloritoid, minute traces of albite, almandite and microcline Kaolinite (10%), illite (09%)
MKP-29/BM-II Quartz (65%), siderite (14%), albite (4%), minute traces of anatase, chlorotoid, microcline, pyrite, titanite and zircon Kaolinite (04%), illite (11%)
MKP-29/B-2 Quartz (63%), siderite (12%), albite (3%), minute traces of chlorite, rutile, zircon Kaolinite (10%), illite (10%)

Fig. 6. Correlation plot of Rock Eval Tmax and Vitrinite reflectance data (Espitalie, 1986) from the shales of Jharia sub-basin, Damodar Valley.

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 D. Mani et al. / Marine and Petroleum Geology xxx (2015) 1e17 9

possibility of it being organic rich and thermally mature (Table 2). Measure shale indicate a marine/lacustrine source for the organic
Under given conditions of sufficient burial and exposure to heat, matter.
the organic matter matured to generate the hydrocarbons, which Pyrolytic yields of the hydrocarbons and carbon dioxide are
might have been retained in the shale matrix. Upon desorption at affected by associated mineral matrix (Espitalie et al., 1980;
300  C, the thermo-labile components having petrogenic signature Horsfield and Douglas, 1980; Katz, 1983; Dembicki, 1992). Clay
were liberated. Such isotopic signatures are essential for natural gas minerals have been shown to retain the heaviest hydrocarbon
exploration and production strategies, maturity predictions and compounds and amount of adsorbed gases increase with the spe-
resource estimations (Osborn and McIntosh, 2010). cific surface area of the argillaceous minerals. Similarly, higher OI
The stable carbon isotope ratios have been shown to be sus- has been observed for the shales containing carbonate minerals,
ceptible towards fractionation due to migration, bacterial oxidation which mainly results from the carbonate matrix-derived CO2
and thermal maturation of hydrocarbons (Prinzhofer and Huc, liberated during pyrolysis. Such relative differences in yields are
1995; Rangel et al., 2003). The shale cores studied here are not most pronounced in organically leaner, immature samples. Low to
contaminated by weathering and oxidation processes, hence, the moderate clay content (4e17%), low abundance of carbonates
thermally desorbed gases upon their pyrolysis reflect the pristine (0.33e8.34%) and minute traces of heavy minerals, characterize the
signature of gases derived from the thermal cracking of kerogen. mineralogy of Jharia shales (Table 4). The shales contain very high
Isotopic compositions tend to show enrichments with increasing organic matter content (TOC ¼ 2.86e23.09%) in mature stage with
thermal maturity (Burruss and Laughrey, 2010). The Damodar very low OI (<10). Thus, any substantial effect of mineralogy on
Valley shales are in thermally mature and post-mature stage of pyrolytic yield is not apparent and the high concentration of
hydrocarbon generation, however; the exposure of organic matter released hydrocarbons represent the ones that are free (S1) and
to higher temperatures has not altered or enriched the d13C values those derived from the cracking of kerogen (S2), with low to
significantly. The isotopic compositions vary in a narrow range and negligible retention on the mineral matrix.
are nearly similar for all the studied samples (40.4e44.8‰;
Table 2). 5.4. Hydrocarbon generative potential

5.3. Maceral composition and mineralogy The cracking of kerogen into simpler hydrocarbons is highly
complex, as a result discrete bulk kinetic concepts, based primarily
Maceral constituents in the Jharia shales are dominated by vit- on the Arrhenius law (Eqs. (1)e(3)) are used (Tissot and Espitalie,
rinite and inertinite with sparse occurrence of liptinite (Table 3; 1975; Schenk and Horsfield, 1998). The A and E (Eqs. (1) and (2))
Plates IeIII). The organic precursors are mainly woody tissues, are properties of a specific reactant, and are related to the degree of
derived from higher terrestrial land plants. Liptinite is more in the vibrational frequency of an activated complex formed in tran-
Raniganj shales, and is marked by the presence of alginite and sition state of a reaction, thus are dependent on the type of organic
sporinite (Plate I). Vitrinite sub-type, collotelinite, is recorded in matter (Dieckmann, 2005; Mahlstedt, 2012). The best fit between
abundance. The organic matter assemblage is consistent with Type calculated and measured hydrocarbon generation rates were ob-
II/III organic matter in the Raniganj Formation. Kerogen pyrolysis of tained with the activation energy distribution (Ea) and single pre-
these shales also shows a lower Tmax and higher HI, and a Type II/ exponential factor (A) for the shales from each formation (Fig. 7).
III kerogen in maure, oil generating stage. However; with increasing In general, broad distribution of activation energies (40e70 kcal/
depth and maturation, vitrinite is the dominant constituent. In mol) are observed, which are typical for the heterogeneous
Barren Measure shales, collotelinite is recorded in the form of thick terrestrial organic matter derived from higher land plants
and thin bands (Plate II). Presence of framoboidal pyrites suggests (Mahlstedt and Horsfield, 2012). Raniganj shales, which are
the anoxic depositional environments (Plate II). Barakar shales comparatively less mature, show the chemical bonds with activa-
show vitrinite and inertinite macerals with subtypes as collotelinite tion energies between 42 and 62 kcal/mol, with peak energy for the
and inertodetrinite, respectively (Plate III). In general, the maceral hydrocarbon bond breaking at 48 kcal/mol (Fig. 7). Activation en-
composition is mainly a function of kerogen type (organic pre- ergy distribution is governed largely by the structure of kerogen.
cursors) and is also dependent on extent of thermal exposure The rupture energy is attributable to variety of hydrocarbons bonds
witnessed by the sediments. Damodar Valley is a Permian Gond- that are present in the kerogen, and is also influenced by the
wana basin and large percentage of organic matter is derived from neighboring functional groups and length of hydrocarbon chains
higher terrestrial plants, wherein vitrinite dominates. Higher heat (Tissot and Espitalie, 1975). With increasing depth and tempera-
flow and effect of temperature on the liptinite rich sediments in the ture, various bonds corresponding to the successive activation en-
basin might result in cracking of it to oil and gas. The vitrinoid type ergies are progressively broken, roughly in the order of increasing
(Vtype) distribution for the Raniganj and Barren Measure shales activation energies. Thus, the differences in Ea distribution are
indicate large percentage of high to medium-volatile carbon, actually significant, which depict the variation in source rock
whereas for Barakar, low-volatile form is present. The vitrinite organofacies and compositions, irrespective of the levels of thermal
reflectance for Barakar shales (Rr% ¼ 1.1e2.0) suggests a post- maturation attained by the kerogen. In the present study, the
mature stage, where any residual oil or oil-prone kerogen will activation energy determined is for early mature to late and post
likely be cracked to gas. The Tmax values for these shales are high mature samples, which might have experienced a partial conver-
(460  Ce509  C). The variation of vitrinite (Rr%) with depth is sion of organic matter into oil and gas. Lower activation energies for
almost linear for all the samples. the Raniganj implicate towards the distinctive organic material,
Mineral content is dominated by detrital quartz (42e63%), comparatively more homogenous and capable of generating the
siderite (9e15%) and clay (14e29%). Minute traces of heavy min- gas, in addition to having the oil prone character. This is also re-
erals are also observed (Table 4). Barren Measure shows the pres- flected in the organic matter quality of these shales, which is
ence of pyrites (2e9%). It is mainly in framboidal form (Plate II). The marked by presence of alginite and sporinite with oil & condensate-
formation of siderite is favored by alkaline reducing conditions, wet gas-prone Type IIeIII kerogen (Fig. 4). The thermal degradation
whereas the pyrite deposition commonly takes place in marine, of kerogen in Barren Measure (44e68 kcal/mol) and Barakar (42-
reducing depositional environments in presence of organic mate- 68kal/mol) shows higher activation energies, with mean value of
rial (Berner, 1981). The carbon isotope signatures of the Barren 52 kcal/mol. The Barren Measure shales are in late mature, gas

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shales from the Damodar Valley basin, Eastern India, Marine and Petroleum Geology (2015), http://dx.doi.org/10.1016/j.marpetgeo.2015.08.019
10 D. Mani et al. / Marine and Petroleum Geology xxx (2015) 1e17

Fig. 7. Frequency factors and activation energy distribution for the thermal cracking of organic matter in shales from the Jharia sub-basin, Damodar Valley.

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shales from the Damodar Valley basin, Eastern India, Marine and Petroleum Geology (2015), http://dx.doi.org/10.1016/j.marpetgeo.2015.08.019
 D. Mani et al. / Marine and Petroleum Geology xxx (2015) 1e17 11

generating stage with abundant vitrinitic, Type III organic matter.

The total petroleum potential is higher for Raniganj (HI ¼ 257 mg/g
TOC) compared to Barren Measure (HI ¼ 102e158 mg/gTOC) and
Barakar (HI ¼ 78 mg/g TOC).
In temperature span (DT) of 380e540  C, the Raniganj shales
show the generated hydrocarbons to be 240 mg HC/g TOC, which is
highest, compared to the Barren Measure (90e140 mg HC/g TOC)
and Barakar (78 mg HC/g TOC). The generation rate per degree C for
the different samples is shown in Fig. 8. Rate curves for each of the
product groups shift towards higher Tmax with increasing rates.
The effective interval of hydrocarbon generation is represented by a
10e90% kerogen conversion ratio and the temperature span DT of
the effective interval of hydrocarbon generation. The temperatures
have been described for onset (10% transformation), middle (50%
transformation), and end (90% transformation) of hydrocarbon
generation. The temperature for onset (10% KTR) of hydrocarbons is
highest for the Barakar shales (400  C) when compared to Raniganj
(370  C) and Barren Measures (380  C) (Fig. 9). At 50% and 90%
conversions, Barakar shales exhibit effective temperature greater
than that shown by the Raniganj shale (420  C and 460  C,
respectively). The Barren Measure shows intermediate character-
istics. The organic matter in Raniganj shales demonstrates a faster
hydrocarbon generation rate compared to the other two
formations.
It is generally accepted that a reaction occurring in a natural
sedimentary environment has the same chemical kinetic properties
(E and A) as the reaction occurring under controlled conditions of
laboratory, and the thermal cracking of kerogen under geological
condition can be reproduced by integrating kinetic parameters
with the burial and thermal history of a sedimentary basin (Tissot
and Welte, 1984; Braun and Burnham, 1987; Ungerer and Pelet,
1987). Maturation of organic matter in Jharia shales has been
significantly affected by its burial and thermal history. During early
Barakar deposition, the entire basin subsided. Contemporaneous
faulting took place by the time middle Barakar deposited (Ghosh
and Mukhopadhyay, 1985). During Upper Barakar times, the
Southern Boundary fault was initiated, which got extended along
the present southern boundary with the deposition of Barren
Measure (Ghosh and Mukhopadhyay, 1985). The center of
maximum subsidence was around Mohuda (Chandra, 1992). By end
of the Barren Measure deposition, subsidence and faulting led to an
elliptical basin. The deep syn- and post sedimentary burial and
related tectonic activity might have led to the increased maturity
and thermal alteration of organic matter in the shales. According to
Mishra and Cook (1992), the Permian sections of the basin suffered
a major PermianeTriassic thermal event and a tensional tectonic
regime probably prevailed in India, possibly centred in Jharia. This
might have led to extensive subsidence and, consequently, a thicker
sedimentary sequence was deposited in the sub-basin than in the
other Gondwana basins of India. However; high rank Permian coals
(mean maximum reflectance of vitrinite; Rv ¼ 0.93e1.27%) occur
near the surface of the sub-basin and comparisons of the vitrinite
reflectance versus depth profiles from the region indicate that
2.5e3.5 km of cover was eroded (Mishra and Cook, 1992). This is Fig. 8. Hydrocarbons generation rate with increasing temperature during pyrolysis of
shales from the Jharia sub-basin, Damodar Valley.
also corroborated from other works (Chandra and Chakraborti,
1989; Bardhan and Ghosh, 1999) in Jharia, where the estimated
temperature attained is in range of about 160e220  C and corre- 1992). The thermal maturity data on coals adjoining the Barren
sponding paleodepth is reported to be ~1600e4000 m. Measure suggest the shale to be thermally late mature within the
Using a Time-Temperature Index (TTI) type reconstruction on wet gas/condensate (Ro of 1.0%e1.3%) window (Padhy and Das,
coals, Mishra and Cook (1992) suggested that the hydrocarbon 2013). The basin has a present-day temperature ranging from
generation within the Permian section had commenced by the Late 34  C/km to 39  C/km (Rao and Rao, 1980; Mishra and Cook, 1992).
Jurassic. The Early Permian Barakar Formation produced significant Maturation data for Jharia boreholes indicate relatively high tem-
amounts of oil while passing through the zone of oil generation, perature levels during the Mesozoic and the main phase of oil
probably during the Jurassic to Cretaceous, and the Late Permian generation occurred during the Late Cretaceous and oil generation
Raniganj Formation is presently in mature stage (Mishra and Cook, from the lower part of the Permian ceased before the early Tertiary

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12 D. Mani et al. / Marine and Petroleum Geology xxx (2015) 1e17

Plate I. Photomicrograph of Raniganj shale (MMW-18/R-2) showing the presence of

macerals- collotelinite (Co) alginite (Al) e (Plate I a); pyrofusinite (Pf) and collotelinite
(Co) e (Plate Ib); sporinite (Sp), clay (Cy) e (Plate I c), under reflected light (magni-
fication 625).

typical of a Type II/III kerogen, while the Early Permian Barakar

shales are over mature. The kinetic parameters and organic prop-
erties of Middle Permian Barren Measure shale show it to be
thermally late mature, in the gas generating window.
Fig. 9. Kerogen transformation ratio (%) with increasing temperature during pyrolysis
of the shales from the Jharia sub-basin, Damodar Valley.
5.5. Permian gas shales in Jharia?

Increasing research activities on shale gas have led to estab-

(Mishra and Cook, 1992). The kerogen quality suggests that it has lishment of certain characteristics of potential plays. The produc-
passed the oil window; however it possesses excellent properties tive gas shales are in general >200 ft (65 m) thick, have TOC content
for the gas generation. This is also supported by the pyrolysis re- > 3 wt % and HI >350 mg HC/gTOC, and contain type II marine
sults of the shales from these formations. Late Permian Raniganj kerogen of organic maturity >1.10% Ro (Curtis, 2002; Montgomery
shale has lower activation energy with relatively higher potential, et al., 2005; Boyer et al., 2006; Jarvie and Lundell, 1991; Jarvie et al.,

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shales from the Damodar Valley basin, Eastern India, Marine and Petroleum Geology (2015), http://dx.doi.org/10.1016/j.marpetgeo.2015.08.019
 D. Mani et al. / Marine and Petroleum Geology xxx (2015) 1e17 13

Plate II. Photomicrographs of Barren Measure shale (MKP-29/BM-1) showing the macerals e collotelinite (Co), pyrite (py) e (Plate II a); collotelinite (Co), clay (Cy), pyrofusinite (Pf)
e (Plate II b); clay (Cy), sporinite (Sp)- (Plate II c); vitrodetrinite (Vd), collotelinite (Co), clay (Cy), e (Plate II d); clay (Cy), pyrofusinite (Pf)- (Plate II e); pyrite (Py) e (Plate II f) under
reflected light (magnification of 625).

2007; Loucks and Ruppel, 2007; Romero and Philip, 2012; Horsfield intrusives, which might be responsible for the cooking of the Type
and Schulz, 2012; Slatt and Rodriguez, 2012 and several others). IIeIII kerogen in Raniganj shales (Verma et al., 1979; Paul and
The organic richness and thermal maturity of Permian shales from Chatterjee, 2011). Highly mature kerogen in the Barren Measure
Jharia sub-basin suggest these to be possible targets for shale gas. and Barakar Formations could be attributed to the dolerite dykes
The thermogenic source, deduced from the carbon isotope ratios of occurring in vicinity of the Singra and Kapuria boreholes in the
these gases, further corroborates the occurrence of organic rich, central part of sub-basin (Verma et al., 1979; Paul and Chatterjee,
thermally mature source beds in the region. 2011). The vitrinite reflectance for these shales is 1% Rr. The late
The gas-prone shale formations are wide spread in the basin and to post-mature stage of organic matter is attributed to the signifi-
have sufficient thicknesses at depth. About 58 km2 of the area is cantly higher heat flow in the basin, apart from the increasing
occupied by the Raniganj series, 218 km2 by the Barakar series and burial depths of these formations. The mean heat flow value re-
181 km2 comprise rocks of Barren-Measures and the Talchir series ported from the main synclinal region, which forms the major part
in the Jharia sub-basin (Verma et al., 1979). The thickness of Rani- of the Jharia sub-basin, is 1.9 HFU (Heat Flow Unit; about
ganj is about 800 m, whereas the Barren Measure varies from 600 79 mWm2) (Rao and Rao, 1980). This is notably higher than the
to 730 m (Chandra, 1992). The thickness of Barakar Formation continental mean of 1.5 HFU and is nearly twice the value of 1.0
varies from 800 to 1250 m. The variability in organic matter content HFU, generally quoted for shields.
and quality with increasing depths is attributed to the depositional When considering the source rocks in terms of gas shales, be-
facies, burial depths and partly to the igneous intrusive (Rullkotter sides organic properties, factors such as mineralogy, matrix
et al., 1988; Huang et al., 2013) occurring all over the Jharia sub- porosity/permeability and geological complexity become vital in
basin. West Mohuda block has extensive mica-peridotite assessment of the generation potential (Loucks and Ruppel, 2007;

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14 D. Mani et al. / Marine and Petroleum Geology xxx (2015) 1e17

Plate III. Photomicrograph of Barakar shale (MKP-29/B-2) showing the presence of collotelinite (Co)-(Plate III a); alginite (Al), inertodetrinite (Ind), clay (Cy)- (Plate III b); collo-
telinite (Co), clay (Cy)- (Plate III c); collotelinite (Co), vitrodetrinite (Vd), pyrofusinite (Pf)- (Plate III d), alginite (Al), clay (Cy)- (Plate III e); collotelinite (Co)-(Plate III f), under
reflected light (magnification 625).

Ross and Bustin, 2009; Horsfield and Schulz, 2012; Slatt and hydraulic stimulation (EIA, 2015). With known gas shales mostly
Rodriguez, 2012; EIA, 2015). Shales with a high percentage of aquatic (marine/lacustrine) in origin, the Barren Measure has sub-
quartz, when fracked lead to a vast array of small-scale induced stantial geochemical and geological attributes to be a promising
fractures providing numerous flow paths from the matrix to the target. Bulk organic carbon isotopes show lacustrine/marine
wellbore, when hydraulic pressure and energy are injected into the dominated signatures for the Barren Measure. Its Lower Member,
shale matrix (Loucks and Ruppel, 2007; EIA, 2015). This is opposed the Shibabudih shale has the thickness of 148 m and is of lacustrine
to that of shales with a high clay content, which being ductile are origin (Dasgupta, 2005). Shale having Type III organic matter in
deformed instead of shattering leading to relatively few induced thermally mature to over mature states generates gas (Martini
fractures. The XRD studies on shales from the Jharia sub-basin show et al., 2003; Hamblin, 2006; Tan et al., 2015). Gas shows at the
them to be dominantly containing quartz, with low to moderate clay depth of 985e1843 m in Barren Measures Formation have been
content. The quartz is largely detrital in nature (Dutta and Suttner, observed from the Raniganj sub-basin of the Damodar Valley.
1986; Dasgupta, 2006), and has higher porosity and permeability Central Mine Planning and Design Institute (CMPDI) has reported
than the biogenic silica-rich quartz (Bustin and Bustin, 2012). 45 TCF of shale gas in six sub-basins (Jharia, Bokaro, North Kar-
In general, marine-deposited shales tend to have lower clay anpura, South Karanpura, Raniganj & Sohagpur) of Damodar Valley
content and high brittle minerals such as quartz, feldspar and (MoP and NG, 2015).
carbonates. Shales deposited in non-marine settings (lacustrine, The gas recovery efficiency from a shale gas basin/formation is
fluvial) tend to be higher in clay, more ductile and less responsive to largely dependent on the complex geologic features. Areas with

Please cite this article in press as: Mani, D., et al., Thermal maturity, source rock potential and kinetics of hydrocarbon generation in Permian
shales from the Damodar Valley basin, Eastern India, Marine and Petroleum Geology (2015), http://dx.doi.org/10.1016/j.marpetgeo.2015.08.019
 D. Mani et al. / Marine and Petroleum Geology xxx (2015) 1e17 15

extensive faults, deep seated, vertical or thrust faults can hinder

gas recovery by limiting the productive length of the horizontal
well, reducing the relative permeability and gas flow capacity
(Curtis, 2002; EIA, 2015). In Damodar Valley basin, the transverse
normal faults are distributed along the basin margin (Ghosh,
2002; Chakraborty et al., 2003). Conjugate sets of intrabasinal
normal faults transverse to the basinal trend are common, and
have truncated the entire Gondwana sediment package as well as
the basement rocks. Other intrabasinal normal faults parallel to
the basin margin are thought to have been active during the
sedimentation (Ghosh, 2002). Compared to other sub-basins of
Damodar Valley such as Bokaro, Raniganj etc., where the sedi-
mentary overburden is substantial, the shallow depth of shale
occurrences and structure complexities of Jharia require careful
consideration in deciding upon the exploration methodologies in
the basin.

6. Conclusion

The organic richness, thermal maturity and kerogen type in

Permian shales from Jharia sub-basin of Damodar Valley show
excellent potential for the generation of gas. The carbon isotope
ratios of the thermo-labile components suggest the source of the
gaseous hydrocarbons to be thermogenic. The Raniganj and
Barren Measure Formation are thermally mature in late gas gen-
eration stage, where as the Barakar shales are post-mature. The
vitrinite reflectance also follows the corresponding pattern of
organic matter abundance and maturity. Kinetic analysis of the
thermal cracking of kerogen demonstrates the Raniganj shales to
be more capable of generating gas and at a faster hydrocarbon rate
compared to the Barren Measure and Barakar. With a lacustrine/
marine origin and sufficient thermal maturity for gas generation,
the Barren Measure is a potential candidate for shale gas. Besides
providing high rank coals, the Permian Gondwana shales can be a
source of unconventional shale gas. These shales tend to have
lower clay content and high brittle minerals such as quartz and
siderite, owing to which the response to hydraulic stimulation
could be favorable. With the surge in shale gas activities world-
wide, the results of this study provide new information on the
organic, mineralogical and kinetic properties of source rocks of
Jharia sub-basin and have encouraging implications towards its
exploration.

Acknowledgments

The Oil Industry Development Board, New Delhi (4/5/2009-

OIDB) is acknowledged for the financial support towards estab-
lishment of laboratory facility. Officials of Central Mine Planning &
Design Institute (CMPDI), Ranchi (Grant no. GAP-673-28(DJP)) are
thanked for extending their support during field visits. The authors
are grateful to The Director, Atomic Mineral Directorate (AMD) and
Dr.Y.Singh for the XRD analysis. Prof. A. Varma and his research
students, ISM, Dhanbad are acknowledged for the support
extended towards micropetrographic analysis. Prof. M. K. Sen, UT,
Austin is acknowledged for his support towards project activities.
The manuscript was immensely benefited from comments of Profs.
Barry J. Katz, Tongwei Zhang and Hui Tian. The Director, NGRI is
thanked for permitting the publication of this work.

Appendix

Litho-log of the boreholes selected for shale sampling.

Please cite this article in press as: Mani, D., et al., Thermal maturity, source rock potential and kinetics of hydrocarbon generation in Permian
shales from the Damodar Valley basin, Eastern India, Marine and Petroleum Geology (2015), http://dx.doi.org/10.1016/j.marpetgeo.2015.08.019
16 D. Mani et al. / Marine and Petroleum Geology xxx (2015) 1e17

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shales from the Damodar Valley basin, Eastern India, Marine and Petroleum Geology (2015), http://dx.doi.org/10.1016/j.marpetgeo.2015.08.019