Professional Documents
Culture Documents
Organic Geochemistry
journal homepage: www.elsevier.com/locate/orggeochem
a r t i c l e i n f o a b s t r a c t
Article history: The Upper Assam Basin in northeast India is a Tertiary sub-basin of the Assam-Arakan Basin. Hydrocar-
Received 20 October 2013 bons are present in the Langpar Formation (Upper Palaeocene), Lakadong member of the Sylhet Forma-
Received in revised form 9 June 2014 tion (Lower Eocene), and the Barail (Oligocene), Tipam (Lower Miocene) and Girujan (Middle Miocene)
Accepted 14 July 2014
formations in the basin. A detailed study to understand the nature and origin of the oils from different
Available online 26 July 2014
stratigraphic horizons using terrigenous and other biomarkers has been carried out. Further, the variation
in maturities of oils occurring in different stratigraphic horizons has also been studied. The study shows
Keywords:
that rearranged oleananes, oleananes and bicadinanes are present in these oils implying land plant input
Upper Assam Basin
Tertiary oils
to their source rocks. The oils have been classified into different groups, using ratios of rearranged olean-
Terrigenous biomarkers anes, oleananes, bicadinanes and steranes, indicating presence of multiple source rocks in the basin with
Rearranged oleananes subtle variation in characteristics. Maturity studies show that oils from younger horizons (Barail, Tipam
Bicadinanes and Girujan) are more mature than oils from older horizons (Langpar and Lakadong). There is an apparent
mismatch in maturity of oils as measured by different biomarker maturity parameters. This is due to the
mixing of two different charges of oils, having different maturities and generated from two different
source rock kitchens, in the same reservoir. Principal component analysis (PCA) of biomarker data has
also been able to classify the oils into various groups. A new parameter has been developed, using ratios
of rearranged oleananes, for determining maturity of these oils.
Ó 2014 Elsevier Ltd. All rights reserved.
1. Introduction oils is > 3. Thus, Lakadong and Langpar oils in the Upper Assam
Basin are derived from terrigenous organic matter (Hedberg,
The Upper Assam Basin is a Tertiary sub-basin of the 1968; Tissot and Welte, 1984).
Assam-Arakan geological province located in the northeastern part Mathur and Das (2013) carried out a study on the origin and
of the Indian subcontinent (Fig. 1). It has been a prolific hydrocar- maturity of Lakadong and Langpar oils in the basin using selected
bon producer for more than a century since oil was first discovered ion monitoring GC–MS analysis of biomarkers. They showed that
in Digboi in Upper Assam in 1889. The Digboi oilfield is still pro- these oils have high oleanane and low sterane contents. Further,
ducing from the Tipam Formation (Lower Miocene), although at a C29 steranes are predominant amongst C27, C28 and C29 steranes.
very low rate. Hydrocarbons were discovered in the Oligocene The oils are derived from terrigenous source rocks deposited under
Barail Formation (1950s) followed by Upper Miocene Girujan oxic to sub-oxic conditions. Also, the oils are early to mid-mature
Formation (1970s). More recently, in 1989, hydrocarbons were also and show evidence of migration contamination (Curiale and
discovered in deeper reservoirs in the Lakadong member of the Bromley, 1996).
Sylhet Formation (Lower Eocene) and the Langpar Formation An oil to source rock correlation study by Goswami et al. (2005)
(Upper Palaeocene). in the western part of the basin showed that oils from the Bokabil
Mathur et al. (2000) studied oils from Lakadong and Langpar (Early to Middle Miocene) and Sylhet (Middle to Late Eocene) for-
reservoirs from the Upper Assam Basin, using whole oil gas mations are derived from terrigenous organic matter. The oils have
chromatography. Their study has shown that these oils are waxy significant amounts of oleananes and bicadinanes, confirming their
with a predominance of n-alkanes in the carbon number range of terrigenous origin (Ekweozor and Udo, 1988; Alam and Pearson,
21–35 with maxima at C29. Moreover, pristane/phytane for these 1990; Ekweozor and Telnaes, 1990; van Aarssen et al., 1990,
1992a; Curiale et al., 1994; Murray et al., 1994; Nytoft et al., 2010).
⇑ Tel.: +91 9435039751; fax: +91 361 2262555. Several higher plant related C30 triterpanes have been observed
E-mail addresses: nmathur@oilindia.in, neeraj.nmathur@gmail.com in Late Cretaceous/Tertiary oils from Southeast Asia, New Zealand
http://dx.doi.org/10.1016/j.orggeochem.2014.07.007
0146-6380/Ó 2014 Elsevier Ltd. All rights reserved.
10 N. Mathur / Organic Geochemistry 76 (2014) 9–25
MANABHUM
KITCHEN
HAPJAN
SEALKATI
DIGBOI
KAMKHAT
NAHARKA
TIYA JORAJAN
KUSIJAN
SHALMARI
KHARSANG
NORTH TINALI
MADHAKALI
SAPEKHATI
NAGA
KITCHEN
and Nigeria (Ekweozor et al., 1979a,b; Ekweozor and Udo, 1988; range and the eastern Himalayan foothills region. The generalised
Curiale and Lin, 1991; van Aarssen et al., 1992a; Woodhouse stratigraphic succession of the Upper Assam Shelf along with the
et al., 1992; Murray et al., 1994; Sosrowidjojo et al., 1994). Detec- petroleum system is shown in Fig. 2 (Raju and Mathur, 1995;
tion of these compounds in oils and sediments requires a higher Mathur et al., 2001).
selectivity method like metastable reaction monitoring (MRM)
GC–MS (Murray et al., 1994; Nytoft et al., 2010). 3. Experimental
In this paper, oils from Girujan, Tipam, Barail, Lakadong and
Langpar reservoirs from the Upper Assam Basin have been studied 3.1. Samples
using MRM GC–MS, for the analysis of biomarkers such as C30
triterpanes, oleananes, bicadinanes, hopanes and steranes, to Thirty-seven well head crude oil samples were collected from
understand their origin and maturity and to group them into wells producing from Girujan, Tipam, Barail, Lakadong and Langpar
different families. Further, a ratio using C30 triterpanes (rearranged reservoirs in Upper Assam Basin (Table 1) ensuring coverage of
oleananes) has been developed as a maturity parameter for these geographically dispersed oilfields. All the analyses were carried
oils. out in the laboratory of Oil India Limited operating under
ISO17025 standard.
2. Geological setting
3.2. Separation
The Upper Assam Basin is bounded in the northwest by the
eastern Himalayas, in the south by the Naga-Patkai Hills, in the Asphaltenes were precipitated from oils by adding 50 times
northeast by the Mishmi Hills and in the southwest by the Mikir excess n-hexane. The precipitated asphaltenes were Soxhlet
Hills and Shillong Plateau. The basin came into existence during extracted to remove any trapped hexane soluble fraction. The
the Cretaceous and Early Cenozoic period and was located in a pas- hexane soluble fraction was added to the maltenes obtained above.
sive continental margin facing an open sea. The Upper Assam Basin Maltenes were separated into saturated hydrocarbons, aromatic
had received clastic sediments in varied shallow marine to paralic hydrocarbons and resins fraction using the Radke et al. (1980)
and non-marine (deltaic, fluviatile) environmental conditions in medium pressure liquid chromatography method. n-Alkanes were
different geological times during Tertiary period. In the present removed from the saturated hydrocarbon fraction using Geokleen
day configuration of the basin, the basement dips both towards (GH Geochem, UK). The resulting fraction, enriched in biomarkers,
the southeast and northwest on the southern and northern flanks was subjected to MRM GC–MS analysis.
of the basement ridge, respectively. The basement ridge which
trends NE–SW is possibly the eastern continuation of the Mikir 3.3. GC–MS analysis
Hills and runs almost parallel to the present day Brahmaputra
River. The sedimentary thickness, which is < 4 km along the axis MRM GC–MS analysis was carried out using ThermoFisher
of the basement ridge, increases to > 7 km towards the Naga-Patkai Trace Ultra gas chromatograph connected to TSQ triple stage
N. Mathur / Organic Geochemistry 76 (2014) 9–25 11
quadrupole mass spectrometer. An Rtx-5 capillary column et al., 2010). Geochemical data interpretation software, pIGI (IGI
(30 m 0.25 mm i.d., 0.25 lm film thickness) from Restek Ltd, UK) was used for interpretation of data, plotting of diagrams
Corporation, USA was used. The injector and GC transfer line and statistical analysis.
temperatures were maintained at 300 °C. The GC oven temperature
programme was as follows: 100 °C (3 min), ramp rate 25 °C/min,
200 °C, ramp rate 2 °C/min, 300 °C (3 min). Helium was used as a 4. Results and discussion
carrier gas at a constant flow rate of 1 ml/min. The mass spectrom-
eter electron source was kept at temperature of 200 °C, and an ion- 4.1. Origin of oils
isation energy of 70 eV. Argon was used as the collision gas and the
collision energy was kept at 15 eV. The following parent-daughter Previously unpublished results from a study carried out using
transitions were used: 370 ? 191 for C27 hopanes, 398 ? 191 for MRM GC–MS on a different set of oils from Upper Assam Basin
C29 hopanes, 412 ? 191 for C30 hopanes and triterpanes, than the one used in this study show that oils from Girujan, Tipam,
412 ? 369 for C30 bicadinanes and 400 ? 217 for C29 steranes. Barail, Lakadong and Langpar reservoirs have predominant C29
The GC–MS was calibrated using standard C29 sterane and C30 steranes amongst C27, C28 and C29 steranes (Fig. 3). Therefore,
hopane obtained from Chiron, Norway. The other biomarker during this study, only the mass transition from 400 ? 217
compounds were identified by comparing the mass chromatogram corresponding to C29 steranes was monitored during MRM
with that available in the literature (Murray et al., 1994; Nytoft GC–MS analysis and C27 and C28 steranes were not determined.
12 N. Mathur / Organic Geochemistry 76 (2014) 9–25
(a)
(b)
Fig. 4. 412 to 191 and 412 to 369 MRM transitions for (a) Lakadong oil from Dikom oilfield, (b) Barail oil from Naharkatiya oilfield, (c) Tipam oil from Naharkatiya oilfield, (d)
Girujan oil from Kumchai oilfield. Relative intensities for the two transitions are also shown. Peaks 1–11: C30 triterpanes, T T1 and R: bicadinanes. Refer Table 2 for peak
identification.
Nytoft et al. (2010) observed that the ratio of the sum of C30 from Langpar and Lakadong reservoirs, in most parts of the basin,
triterpanes normalised to C30 triterpanes and oleananes increases are rich in both C30 triterpanes and diasteranes indicating an oxic,
with diasteranes content indicating that oxic, clay rich systems clay rich environment of deposition for the source rock for these
also favour the formation of C30 triterpanes. A similar relationship oils. Barail and Tipam oils are leaner in both C30 triterpanes and
has been observed for Assam oils (Fig. 8). It is observed that oils diasteranes compared to Langpar and Lakadong oils. However,
14 N. Mathur / Organic Geochemistry 76 (2014) 9–25
(c)
(d)
Fig. 4 (continued)
within Barail and Tipam oils, Tipam oils from the Digboi oilfield are in C30 triterpanes compared to Barail and Tipam oils while having
even further depleted in C30 triterpanes and diasteranes. similar diasteranes content.
Girujan oils from the Kumchai and Kharsang oilfields in the Thus, there is a variation in properties of the oils, in terms of
eastern and southeastern part of the basin and Lakadong oils from source input and depositional environment of their source rocks,
Madhakali and Moran in the southwest of the basin, are enriched across the basin and at different stratigraphic levels. Based on
N. Mathur / Organic Geochemistry 76 (2014) 9–25 15
Table 2
C30 triterpane compound used in this study (Fig. 4) and their correspondence with the peak assignments in a previous study (Nytoft et al. (2010)).
ND = Not determined.
the above, the characteristics of oils from the Upper Assam Basin diahopane content and are falling away from normal maturation
have been summarised in Table 6. trend (Fig. 10).
Four potential source rocks are present in the basin, viz. Langpar Bicadinane maturity index (BMI-1) is a very reliable maturity
shales, Lakadong shales, Kopili shales and Barail coals and shales parameter for terrigenous oils that contain bicadinanes (Murray
(Fig. 2). It is likely that Langpar and Lakadong oils are sourced from et al., 1994, 1997; Sosrowidjojo et al., 1996). BMI-1 continues to
Langpar and Lakadong shales whereas Barail, Tipam and Girujan increase in the oil window and is little affected by diagenetic
oils have sourced from Kopili shales and Barail coals and shales. effects and biodegradation. BMI-1 values are < 3 for Assam oils
Thus, oils in the Upper Assam Basin have sourced from multiple implying low maturity for these oils (Table 5). Further, BMI-1 val-
source rocks. ues are low even for higher maturity Tipam and Girujan oils.
The parameters Ts/(Ts + Tm) and C29 Ts/(C29 Ts + C29 hopane)
4.2. Maturity of oils have been widely used to determine maturity of oils and extracts
from low maturity to peak oil generation stage (Moldowan et al.,
Sterane maturity parameters (Seifert and Moldowan, 1986; 1986; Peters et al., 2005). These parameters show that Langpar
Peters et al., 2005) (Fig. 9) show that most of the oils from and Lakadong oils from Baghjan and Mechaki have higher maturity
Lakadong and Langpar reservoirs have low maturity, barring oils than most other oils (Table 5).
from Madhakali and Moran that have high maturity. Sealkati, Thus, there is an apparent anomaly among the maturities of the
Baghjan and Mechaki oils have very low maturity amongst oils, as measured by different parameters. This is further brought
Lakadong and Langpar oils. Oils from stratigraphically younger out by a crossplot of steranes maturity parameter C29 20S/(S + R)
reservoirs, viz. Barail, Tipam and Girujan, have higher maturity sterane and hopane maturity parameter Ts/(Ts + Tm) (Fig. 11). It
with Kumchai Girujan oils being highly mature. None of the oils can be seen that maturity of most of the oils increases in tandem,
seem to have suffered any migration–fractionation as both the as measured by these parameters. However, Baghjan, Barekuri,
sterane maturity parameters fall along the normal maturation Mechaki and Dikom oils show lower maturity based on C29 20S/
curve. (S + R) steranes compared to Ts/(Ts + Tm). On the other hand,
A plot of maturity parameters, C30 hopane/C30 moretane and Tipam oils from Digboi and Jorajan and Barail oil from Sapekhati
C30 diahopane/C29 moretane is used to determine the mixture of show higher steranes maturity.
early charge (containing C29 moretane) and late charge (containing Petroleum system modelling studies in the basin have shown
C30 diahopane), of oil in a reservoir (Cornford et al., 1983). These that there are two active source rock kitchens, namely the Naga
parameters (Fig. 10) also show that most of the Lakadong and Kitchen in the south and Manabhum Kitchen in the northeast
Langpar oils have low maturity with Sealkati, Baghjan and Mech- (Fig. 1). Different reservoirs have received charge from the both
aki oils having very low maturity. However, Lakadong oils from kitchens in different proportions (Mathur and Kumar, 2013). Since
the Moran and Madhkali fields have high maturity. Barail and the two charges could be of different maturities and having bio-
Tipam oils and Kharsang Girujan oils have higher maturity com- markers in different concentrations, the mixed oil accumulated
pared to Lakadong and Langpar oils. Kumchai Girujan oils are a in these reservoirs has an apparent mismatch of maturities based
mixture of early charge and late charge as they have high C30 on different parameters.
16
Table 3
Biomarker parameters used for correlation of oils.
Well Diasteranes/ Steranes/ C30 hopane/ Oleananes/ Bicadinanes/ Bicadinanes/ C30 diahopane/(C30
(diasteranes + steranes) (steranes + hopane) (C29 + C30 hopane) (oleananes + hopane) (bicadinanes + hopane) (bicadinanes + steranes) diahopane + C29 Ts)
Kharsang A 0.50 0.35 0.51 0.21 0.49 0.64 0.54
Kharsang B 0.50 0.33 0.52 0.19 0.49 0.66 0.53
Kumchai A 0.55 0.34 0.60 0.27 0.61 0.75 0.62
Kumchai B 0.55 0.35 0.59 0.28 0.61 0.74 0.63
Digboi A 0.50 0.16 0.48 0.10 0.24 0.62 0.46
Digboi B 0.51 0.15 0.49 0.11 0.23 0.63 0.46
Digboi C 0.53 0.15 0.55 0.11 0.27 0.68 0.51
Hapjan A 0.57 0.33 0.54 0.28 0.38 0.55 0.47
Jorajan A 0.55 0.34 0.52 0.22 0.35 0.52 0.42
Jorajan B 0.56 0.29 0.50 0.23 0.32 0.53 0.46
Naharkatiya B 0.62 0.31 0.48 0.21 0.34 0.53 0.41
Table 4
Ratio of C30 tritrpanes to oleananes used in this study.
Well Ratio 1 Ratio 2 Ratio 3 Ratio 4 Ratio 5 Ratio 6 Ratio 7 Ratio 8 Ratio 9 Ratio 10 Ratio 11
Kharsang A 0.40 0.42 0.29 0.13 0.09 0.80 0.25 0.16 0.09 0.08 0.15
Kharsang B 0.39 0.41 0.27 0.14 0.11 0.85 0.28 0.20 0.09 0.09 0.17
Kumchai A 0.43 0.43 0.29 0.12 0.16 0.97 0.30 0.21 0.10 0.10 0.15
Kumchai B 0.42 0.43 0.28 0.11 0.13 0.95 0.30 0.20 0.09 0.09 0.15
Digboi A 0.29 0.29 0.26 0.10 0.10 0.46 0.15 0.15 0.10 0.02 0.21
Digboi B 0.28 0.30 0.25 0.09 0.09 0.41 0.14 0.13 0.07 0.02 0.21
Digboi C 0.33 0.32 0.28 0.11 0.14 0.57 0.15 0.17 0.10 0.03 0.20
Hapjan A 0.36 0.34 0.35 0.08 0.13 0.70 0.19 0.17 0.10 0.05 0.12
Jorajan A 0.35 0.33 0.36 0.09 0.14 0.58 0.15 0.16 0.09 0.05 0.12
Jorajan B 0.36 0.31 0.37 0.08 0.15 0.68 0.18 0.16 0.09 0.05 0.13
Naharkatiya B 0.42 0.38 0.43 0.10 0.19 0.74 0.15 0.16 0.11 0.03 0.13
Naharkatiya C 0.38 0.34 0.41 0.10 0.18 0.62 0.15 0.15 0.12 0.04 0.15
Hapjan B 0.37 0.34 0.35 0.08 0.16 0.72 0.19 0.17 0.09 0.05 0.12
Kusijan A 0.37 0.31 0.33 0.07 0.15 0.70 0.20 0.16 0.08 0.05 0.12
Moran B 0.39 0.29 0.40 0.06 0.19 0.70 0.17 0.15 0.09 0.05 0.11
Naharkatiya A 0.34 0.32 0.36 0.08 0.19 0.72 0.17 0.17 0.10 0.05 0.12
Sapekhati A 0.33 0.28 0.38 0.07 0.18 0.58 0.15 0.15 0.11 0.03 0.20
Shalmari A 0.38 0.29 0.38 0.06 0.19 0.71 0.17 0.16 0.09 0.05 0.12
Baghjan J 0.42 0.25 0.44 0.08 0.44 1.71 0.24 0.31 0.19 0.11 0.18
Barekuri B 0.39 0.28 0.38 0.05 0.40 1.50 0.23 0.31 0.18 0.09 0.17
Bhogpara B 0.31 0.26 0.31 0.07 0.33 1.39 0.20 0.33 0.13 0.07 0.17
Dikom C 0.30 0.23 0.36 0.06 0.38 1.35 0.18 0.31 0.16 0.08 0.16
Dikom D 0.29 0.24 0.34 0.07 0.36 1.34 0.19 0.31 0.14 0.07 0.16
Kamkhat A 0.35 0.21 0.40 0.06 0.43 1.40 0.17 0.29 0.19 0.08 0.16
Kathalani B 0.32 0.28 0.31 0.09 0.33 1.41 0.21 0.33 0.13 0.06 0.17
Madhakali A 0.24 0.31 0.21 0.10 0.22 1.39 0.25 0.34 0.08 0.06 0.16
Mechaki B 0.41 0.22 0.45 0.06 0.46 1.70 0.23 0.32 0.20 0.11 0.18
Moran C 0.25 0.34 0.21 0.12 0.19 1.37 0.28 0.35 0.07 0.06 0.16
North Tinali A 0.24 0.24 0.32 0.06 0.36 1.27 0.16 0.32 0.14 0.06 0.18
Sealkati A 0.26 0.16 0.36 0.05 0.40 1.12 0.16 0.28 0.16 0.06 0.16
Shalmari B 0.20 0.19 0.31 0.05 0.37 1.15 0.16 0.32 0.13 0.05 0.18
Tengakhat F 0.33 0.28 0.36 0.06 0.36 1.59 0.18 0.32 0.16 0.08 0.16
Tengakhat G 0.35 0.26 0.35 0.09 0.39 1.35 0.18 0.32 0.13 0.08 0.17
Tengakhat H 0.28 0.23 0.33 0.06 0.37 1.29 0.18 0.30 0.15 0.08 0.16
Baghjan B 0.34 0.20 0.40 0.06 0.40 1.31 0.20 0.28 0.19 0.09 0.17
Baghjan G 0.36 0.22 0.42 0.07 0.41 1.50 0.22 0.29 0.20 0.10 0.18
Barekuri A 0.33 0.28 0.39 0.06 0.38 1.52 0.22 0.33 0.20 0.09 0.19
4.3. Principal component analysis The plot of principal component loadings (not shown here)
shows that maximum variance in principal component 1 comes
Principal component analysis (Davis, 1973) has been carried out from C30 triterpane-5/(C30 triterpane-5 + oleananes) and C30 triter-
using all the biomarker parameters used in this study (Appendix pane-2/(C30 triterpane-2 + oleananes). Similarly, maximum
A). A plot of first two principal components (Fig. 12) is clearly able variance in principal component 2 comes from C30 triterpane-7/
to separate Assam oils into following groups (C30 triterpane-7 + oleananes) and C30 triterpane-3/(C30 triter-
Group I: Oils from Langpar and Lakadong reservoirs comprising pane-3 + oleananes). Thus, the ratios C30 triterpane-2/C30 triter-
of following sub-groups. panes-5 and C30 triterpane-7/C30 triterpane-3 can capture the
variance of principal components 1 and 2. C30 triterpane-3 corre-
Ia: Oils from Langpar and Lakadong reservoirs in central part of sponds to compound I (5(4 ? 3) abeo-3a (H),5b(H),18a(H)-olean-
the basin. ane) and C30 triterpane-7 corresponds to compound III (1(10 ? 5)
Ib: Oils from Moran and Madhakali Lakadong reservoirs in abeo-3b-methyl-24b-nor-18a(H)-oleanane) of Nytoft et al. (2010).
south–west of the basin. A plot of these ratios (Fig. 13) is able to differentiate among Lang-
Ic: Oils from Shalmari and North Tinali Lakadong reservoirs in par and Lakadong oils, Barail and Tipam oils and Girujan oils. Fur-
south–south–west of the basin. ther, it is also able to differentiate between Moran and Madhakali
Id: Oil from Baghjan, Barekuri and Mechaki Langpar and oils (Group Ib) and rest of the Langpar and Lakadong oils. However,
Lakadong reservoirs in north-east of the basin. these ratios are not able to separate Digboi Tipam oils from other
Tipam oils. Further, oils from Lakadong reservoirs from south–
Group II: Oils from Barail and Tipam reservoirs comprising of south–west (Group Ic) of the basin and from Langpar and Lakadong
following sub-groups. reservoirs from Baghjan, Barekuri and Mechaki (Group Id) are also
not separated from other oils from Langpar and Lakadong reser-
IIa: Oils from Barail and Tipam reservoirs in the central part of voirs in central part of the basin (Group Ia).
the basin. From the above, it is apparent that the ratio C30 triterpane-2/C30
IIb: Oils from Barail reservoir in Sapekhati and Tipam reservoir triterpanes-5 is dependent on the maturity of the oils. This is con-
in Digboi in southern part of the basin. firmed when this ratio is plotted against C29 20S/(20S + 20R) ster-
anes (Fig. 14). There is a good correlation between these two
Group III: Oils from Girujan reservoir in Kumchai and Kharsang parameters and the ratio C30 triterpane-2/C30 triterpane-5 contin-
in east and southeast of the basin. ues to increase into the peak oil generation stage when the sterane
18
Table 5
Biomarker maturity parameters used in this study.
General C29 steranes C29 steranes iso/ C29 hopane/(C29 C30 hopane/(C30 C30 diahopane/(C30 C29 Ts/(C29 Ts + C29 Ts/ BMI-1 18 a/(a + b)
20S/(S + R) (iso + reg) hopane + C29 moretane) hopane + C30 moretane) diahopane + C29 moretane) Hopane) (Ts + Tm) Oleanane
Kharsang A 0.54 0.59 0.90 0.90 0.70 0.18 0.34 2.42 0.61
Kharsang B 0.53 0.57 0.90 0.90 0.71 0.19 0.33 2.37 0.64
Kumchai A 0.57 0.58 0.89 0.91 0.83 0.26 0.42 2.31 0.58
Kumchai B 0.55 0.59 0.90 0.90 0.84 0.26 0.45 2.34 0.58
Digboi A 0.52 0.55 0.89 0.89 0.48 0.12 0.18 2.58 0.61
Digboi B 0.53 0.54 0.89 0.89 0.48 0.12 0.19 2.49 0.58
Digboi C 0.55 0.54 0.90 0.90 0.56 0.12 0.19 2.69 0.60
Hapjan A 0.53 0.55 0.88 0.89 0.60 0.18 0.27 2.64 0.54
Jorajan A 0.48 0.53 0.87 0.89 0.44 0.14 0.19 2.65 0.54
Kharsang Kumchai
Sapekhati
Digboi
Baghjan,
Barekuri,
Mechaki
Kumchai
Kharsang
Shalmari,
North Tinali
Digboi
Sapekhati
Moran,
Madhakali Kumchai
Kharsang
Digboi
Fig. 8. Diasteranes/(diasteranes + steranes) vs C30 triterpanes/(C30 triterpanes + oleananes) for Assam oils.
Table 6
Summary of characteristics of Assam oils and the source input/depositional environment of their source rocks.
Moran,
Madhakali
Sealkati
Baghjan,
Mechaki
Fig. 9. Sterane maturation parameters C29 steranes iso/(iso + reg) and C29 steranes 20S/(S + R) for Assam oils (maturation curve from pIGI software).
N. Mathur / Organic Geochemistry 76 (2014) 9–25 21
Moran
Madhakali
Kumchai
Baghjan,
Mechaki
Sealkati
Fig. 10. Maturity parameters C30 diahopane/C29 moretane and C30 hopane/C30 moretane for Assam oils (maturation curve from pIGI software).
Baghjan,
Barekuri,
Mechaki,
Dikom
Digboi,
Jorajan,
Sapekhati
Fig. 11. Cross plot of maturity parameters C29 steranes 20S/(S + R) and Ts/(Ts + Tm) for Assam oils.
Group IIb
Group Ia
Group Ic
Group IIa
Group Id
Group Ib
Group III
Group Ib
Group III
Groups IIa+IIb
Groups Ia+Ic+Id
Fig. 13. Plot of ratio of C30 triterpane compounds 2 and 5 vs 7 and 3 (see Fig. 4) for grouping of Assam oils.
Fig. 14. Correlation of the ratio C30 triterpanes 2 and 5 with maturity parameter C29 steranes 20S/(S + R).
maturity parameter has reached its maximum value. Thus, the source rock kitchens, namely, the Naga kitchen in the south and
ratio C30 triterpane-2/C30 triterpane-5 can be used as a maturity Manabhum kitchen in the east.
parameter for Tertiary terrigenous oils from Upper Assam Basin. Principal component analysis of biomarker data has classified
the oils into following groups.
5. Conclusions
Group I: Oils from Langpar and Lakadong reservoirs with four
sub-groups.
In the Upper Assam Basin, oil is present in the Langpar Forma-
Group II: Oils from Barail and Tipam reservoirs with two
tion (Upper Palaeocene), the Lakadong member of the Sylhet For-
sub-groups.
mation (Lower Eocene), and the Barail (Oligocene), Tipam (Lower
Group III: Oils from the Girujan reservoir.
Miocene) and Girujan (Middle Miocene) formations. The presence
of rearranged oleananes and other similar land plant components
A new maturity parameter has been developed, based on the
(collectively referred to as C30 triterpanes), oleananes and bicadin-
ratio of C30 triterpane compounds that can be used to evaluate
anes in these oils shows that they are derived from Tertiary terrig-
the maturity of Assam oils from low to peak maturity range.
enous source rocks that have received significant land plant input.
However, there are subtle differences in the characteristics of these
oils that are brought out by parameters based on the ratios of C30 Acknowledgements
triterpanes, oleananes, bicadinanes and steranes. This implies that
multiple source rocks are present in the basin. Further, oils from The author would like to thank the reviewers Dr. Asif and an
younger Barail, Tipam and Girujan horizons are more mature than anonymous reviewer for their suggestions that have significantly
oils from older Langpar and Lakadong horizons. There is an appar- improved the paper. The author is grateful to the Management of
ent mismatch in maturity, as measured by different maturity Oil India Limited for permission to publish this work. Help in
parameters, among oils in Langpar and Lakadong reservoirs. This analytical work by Dr. M.K. Sarmah and Mr. S. Borthakur is grate-
is due to the mixing of two different charges of oils from separate fully acknowledged.
N. Mathur / Organic Geochemistry 76 (2014) 9–25 23
Appendix A
Parameter Description
Diasteranes/(diasteranes + steranes) 13b(H),17a(H)-Diastigmastane 20S + 20R/(13b(H),17a(H)-
Diastigmastane 20S + 20R + 5a,14b,17b(H)-stigmastane
20S + 20R + 5a,14a,17a(H)-stigmastane 20S + 20R)
Steranes/(steranes + hopane) (5a,14b,17b(H)-stigmastane 20S + 20R + 5a,14a,17a(H)-
stigmastane 20S + 20R)/(5a,14b,17b(H)-stigmastane
20S + 20R + 5a,14a,17a(H)-stigmastane
20S + 20R) + 17a(H),21b(H)-hopane)
C30 hopane/(C29 + C30 hopanes) 17a(H),21b(H)-hopane/(17a(H),21b(H)-
norhopane + 17a(H),21b(H)-hopane)
Oleananes/(oleananes + hopane) (18 a + 18 b-oleananes)/(18 a + 18 b-oleananes + 17a(H),21b(H)-
hopane)
Bicadinanes/(bicadinanes + hopane) (Bicadinanes T + T1 + R)/(Bicadinanes T + T1 + R + 17a(H),21b(H)-
hopane)
Bicadinanes/(bicadinanes + steranes) (Bicadinanes-T + T1 + R)/(bicadinanes-T + T1 + R + 5a,14a,17a(H)-
stigmastane 20S + 20R + 5a,14b,17b(H)-stigmastane 20S + 20R)
C30 diahopane/(C30 diahopane + C29 Ts) 17a(H)-diahopane/(17a(H)-diahopane + 18a-30-norneohopane)
C30 triterpanes/(C30 triterpanes + oleananes) (Sum of C30 triterpanes 1 to 11)/(sum of C30 triterpanes 1 to 11 + 18
a + 18 b-oleananes)
C29 steranes 20S/(S + R) 5a,14a,17a(H)-stigmastane 20S/(5a,14a,17a(H)-stigmastane
20S + 20R)
C29 steranes iso/(iso + reg) (5a,14b,17b(H)-stigmastane 20S + 20R)/(5a,14b,17b(H)-
stigmastane 20S + 20R + 5a,14a,17a(H)-stigmastane 20S + 20R)
C29 hopane/(C29 hopane + C29 moretane) 17a(H),21b(H)-norhopane/(17a(H),21b(H)-
norhopane + 17b(H),21a(H)-normoretane)
C30 hopane/(C30 hopane + C30 moretane 17a(H),21b(H)-hopane/(17a(H),21b(H)-hopane + 17b(H),21a(H)-
moretane)
C30 diahopane/(C30 diahopane + C29 moretane 17a(H)-diahopane/(17a(H)-diahopane + 17b(H),21a(H)-
normoretane)
C29 Ts/(C29 Ts + C29 Hopane) 18a(H)-30-norneohopane/(18a(H)-30-
norneohopane + 17a(H),21b(H)-norhopane)
Ts/(Ts + Tm) 18a(H)-22,29,30-trisnorneohopane/(18a(H)-22,29,30-
trisnorneohopane + 17a(H)-22,29,30-trisnorhopane)
BMI-1 trans-trans-trans Bicadinanes-T/(T1 + R)
18a/(18a + b) oleananes (18 a-oleanane)/(18 a + 18 b-oleananes)
Ratio 1 C30 triterpane-1/(C30 triterpane-1 + 18 a + 18 b-oleananes)
Ratio 2 C30 triterpane-2/(C30 triterpane-2 + 18 a + 18 b-oleananes)
Ratio 3 C30 triterpane-3/(C30 triterpane-3 + 18 a + 18 b-oleananes)
Ratio 4 C30 triterpane-4/(C30 triterpane-4 + 18 a + 18 b-oleananes)
Ratio 5 C30 triterpane-5/(C30 triterpane-5 + 18 a + 18 b-oleananes)
Ratio 6 C30 triterpane-6/(C30 triterpane-6 + 18 a + 18 b-oleananes)
Ratio 7 C30 triterpane-7/(C30 triterpane-7 + 18 a + 18 b-oleananes)
Ratio 8 C30 triterpane-8 (C30 triterpane-8 + 18 a + 18 b-oleananes)
Ratio 9 C30 triterpane-9/(C30 triterpane-9 + 18 a + 18 b-oleananes)
Ratio 10 C30 triterpane-10/(C30 triterpane-10 + 18 a + 18 b-oleananes)
Ratio 11 C30 triterpane-11/(C30 triterpane-11 + 18 a + 18 b-oleananes)
24 N. Mathur / Organic Geochemistry 76 (2014) 9–25
Appendix B
Associate Editor—Andrew Murray Ekweozor, C.M., Udo, O.T., 1988. The oleananes: origin, maturation and limits of
occurrence in Southern Nigeria sedimentary basins. In: Mattavelli, L., Novelli, L.
(Eds.), Advances in Org. Geochem 1987. Proceedings of the 13th International
References Meeting on Organic Geochemistry, Venice. Pergamon Press, Oxford, pp. 131–
140.
Alam, M., Pearson, M.J., 1990. Bicadinanes in oils from the Surma Basin, Bangladesh. Ekweozor, C.M., Okogun, J.I., Ekong, D.E.U., Maxwell, J.R., 1979a. Preliminary organic
Organic Geochemistry 15, 461–464. geochemical studies of samples from the Niger delta (Nigeria): II. Analyses of
Cornford, C., Morrow, J.A., Turrington, A., Miles, J.A., Brooks, J., 1983. Some shale for triterpenoid derivatives. Chemical Geology 27, 29–37.
geological controls on oil composition in the UK. North Sea. In: Brooks, J. Ekweozor, C.M., Okogun, J.I., Ekong, D.E.U., Maxwell, J.R., 1979b. Preliminary organic
(Ed.), Petroleum Geochemistry and Exploration of Europe. Geol. Soc. Sp. Publ. geochemical studies of samples from the Niger Delta (Nigeria). 1. Analyses of
No. 12. Blackwell Scientific Publications, Oxford, pp. 175–194. crude oils for triterpanes. Chemical Geology 27, 11–28.
Curiale, J.A., Bromley, B.W., 1996. Migration of petroleum into Vermilion 14 field, Goswami, B.G., Bisht, R.S., Bhatnagar, A.K., Kumar, D., Pangtey, K.L., Mittal, A.K., Goel,
Gulf Coast, USA – molecular evidence. Organic Geochemistry 24, 563–579. J.P., Datta, G.C., Thomas, N.J., 2005. Geochemical characterization and source
Curiale, J.A., Lin, Rui., 1991. Tertiary deltaic and lacustrine organic facies: investigation of oils discovered in Khoraghat-Nambar structures of the Assam-
comparison of biomarker and kerogen distributions. Organic Geochemistry Arakan Basin, India. Organic Geochemistry 36, 161–181.
17, 785–803. Hedberg, H.D., 1968. Significance of high-wax oils with respect to genesis of
Curiale, J.A., Kyi, Pe, Collins, I.D., Din, Aung, Nyein, Kyaw, Nyunt, Maung, Stuart, C.J., petroleum. American Association of Petroleum Geologists Bulletin 52, 736–750.
1994. The central Myanmar (Burma) oil family – composition and implications Mathur, N., Das, D.N., 2013. Origin and maturity of oils from Eocene reservoirs from
for source. Organic Geochemistry 22, 237–255. a part of Upper Assam Basin, India. Journal of Applied Geochemistry 15, 1–17.
Davis, J.C., 1973. Statistics and Data Analysis in Geology. Wiley, New York. Mathur, N., Kumar, S.T., 2013. Petroleum System Modelling of Upper Assam Basin.
Ekweozor, C.M., Telnaes, N., 1990. Oleanane parameter: verification by quantitative Internal Report.
study of the biomarker occurrence in sediments of the Niger Delta. Organic Mathur, N., Das, H.C., Kulkarni, T.G., 2000. Light hydrocarbon geochemistry of oils
Geochemistry 16, 401–413. from Upper Assam Basin, India. In: Garg, A.K., Banerjie, V., Swamy, S.N.,
N. Mathur / Organic Geochemistry 76 (2014) 9–25 25
Dwivedi, P. (Eds.), AAAPG 2000. Proceedings of the Fifth International Magdalena Basin oil, Colombia. American Association of Petroleum Geologists
Conference and Exhibition on Petroleum Geochemistry and Exploration in the Bulletin 86, 2069–2087.
Afro-Asian Region. B.R. Publishing Corporation, Delhi, New Delhi, pp. 389–394. Seifert, W.K., Moldowan, J.M., 1986. Use of biological markers in petroleum
Mathur, N., Raju, S.V., Kulkarni, T.G., 2001. Improved identification of pay zones exploration. In: Johns, R.B. (Ed.), Biological Markers in the Sedimentary
through integration of geochemical and log data: a case study from Upper Record. Methods in Geochemistry and Geophysics. Elsevier Science Publishers
Assam Basin, India. American Association of Petroleum Geologists Bulletin 85, BV, Amsterdam, pp. 261–290.
309–324. Sosrowidjojo, I.B., Alexander, R., Kagi, R.I., 1994. The biomarker composition of some
Moldowan, J.M., Sundararaman, P., Schoell, M., 1986. Sensitivity of biomarker crude oils from Sumatra. Organic Geochemistry 21, 303–312.
properties to depositional environment and/or source input in the Lower Sosrowidjojo, I.B., Murray, A.P., Alexander, R., Kagi, R.I., Summons, R.E., 1996.
Toarcian of SW. Germany. Organic Geochemistry 10, 915–926. Bicadinanes and related compounds as maturity indicators for oils and
Murray, A.P., Summons, R.E., Boreham, C.J., Dowling, L.M., 1994. Biomarker and n- sediments. Organic Geochemistry 24, 43–55.
alkane isotope profiles for Tertiary oils: relationship to source rock depositional Tissot, B.P., Welte, D.H., 1984. Petroleum Formation and Occurrence, second ed.
setting. Organic Geochemistry 22, 521–542. Springer-Verlag, Berlin.
Murray, A.P., Sosrowidjojo, I.B., Alexander, R., Kagi, R.I., Norgate, C.M., Summons, van Aarssen, B.G.K., Cox, H.C., Hoogendoorn, P., de Leeuw, J.W., 1990. A cadinene
R.E., 1997. Oleananes in oils and sediments: evidence of marine influence biopolymer in fossil and extant dammar resins as a source for cadinanes and
during early diagenesis? Geochimica et Cosmochimica Acta 61, 1261–1276. bicadinanes in crude oils from SE. Asia. Geochimica et Cosmochimica Acta 54,
Nytoft, H.P., Kildahl-Andersen, G., Samuel, O.J., 2010. Rearranged oleananes: 3021–3031.
structural identification and distribution in a worldwide set of Late van Aarssen, B.G.K., Hessels, J.K.C., Abbink, O.A., de Leeuw, J.W., 1992a. The
Cretaceous/Tertiary oils. Organic Geochemistry 41, 1104–1118. occurrence of polycyclic sesqui-, tri-, and oligoterpenoids derived from a
Peters, K.E., Walters, C.C., Moldowan, J.M., 2005. The Biomarker Guide, second ed. resinous polymeric cadinene in crude oils from Southeast Asia. Geochimica et
Cambridge University Press, Cambridge. Cosmochimica Acta 56, 1231–1246.
Radke, M., Willsch, H., Welte, D.H., 1980. Preparative hydrocarbon group type van Aarssen, B.G.K., Quanxing, Zhang., de Leeuw, J.W., 1992b. An
determination by automated medium pressure liquid chromatography. unusual distribution of bicadinanes, tricadinanes and oligocadinanes in
Analytical Chemistry 52, 406–411. sediments from the Yacheng gasfield, China. Organic Geochemistry 18, 805–
Raju, S.V., Mathur, N., 1995. Petroleum geochemistry of a part of Upper Assam 812.
Basin, India: a brief overview. Organic Geochemistry 23, 55–70. Woodhouse, A.D., Oung, J.-N., Philp, R.P., Weston, R.J., 1992. Triterpanes and ring-A
Rangel, A., Moldowan, J.M., Nino, C., Parra, P., Giraldo, N., 2002. Umir Formation: degraded triterpanes as biomarkers characteristic of Tertiary oils derived from
organic geochemical and stratigraphic assessment as cosource for Middle predominantly higher plant sources. Organic Geochemistry 18, 23–31.