CHAPTER VI

Maturity of Oils

6.1 Maturity of oils using physical and chemical properties

Kerogen is converted to crude oil during catagenesis stage of hydrocarbon

generation. As the source rock comprising of kerogen is buried deeper at higher
temperatures for longer periods of time, it is cooked to a higher level of maturity.
With increasing maturity, kerogen first liberates larger molecules of
hydrocarbons at the onset of oil generation (corresponding to equivalent vitrinite
reflectance (VRo of 0.6%). The larger molecules of oil consist of resins and
asphaltenes, polyaromatic compounds and long chain n-alkanes and
polycycloalkanes (saturates). At this stage, the saturates / aromatics ratio for the
generated oils is low. As the maturity of the source rock increases, the kerogen
generates smaller molecules that consist of shorter chain n-alkanes, cycloalkanes
and mono- & di-aromatics. Saturates/aromatics of the oils generated at higher
maturity of source rocks is higher (Tissot and Welte, 1984).

The saturates/aromatics ratio for the Eocene oils (Fig. 6.1; Table A.II) shows that
most of the oils have generated from source rocks in the main oil generation
window. Oils from Baghjan A and Samdang A have generated from source rocks
that are late mature whereas oils from Tengakhat C & F and Dikom-Kathalani D
& E have generated from low maturity source rocks. It is to be noted that
biodegraded oils and oils generated from immature source rocks plot in the same
region. However, as discussed earlier, Eocene oils are not biodegraded. Hence,
these oils are low maturity.

90
 20 Immature
biodegraded
esp Carbonates

16
Main oil window

Super mature
Frequency 12
Late mature

Area
Baghjan
Barekuri
8 Bhogpara
Borhapjan-Makum
Chabua
Dikom-Kathalani
Matimekhana
4 Mechaki
Moran-Haldibari
North Tinali
Samdang
Santi
Tengakhat
0
0 2 4 6 8 10 12
Saturates/Aromatics

Figure 6.1: Distribution of saturates / aromatics ratio for Eocene oils

(after pIGI, 2011)

A ternary plot of the bulk composition of oils (saturates, aromatics and resins
plus asphaltenes content) is used to differentiate between low maturity oils and
mature migrated oils. Low maturity oils that have not migrated long distance are
high in resins plus asphaltenes content. This is because during the hydrocarbon
generation process, initially large molecules, that are predominant in resins and
asphaltenes, are generated. With increasing maturity, progressively smaller
molecules, consisting of saturated hydrocarbons, are generated. Also, during
migration the molecules of resins and asphaltenes are progressively left behind
by the process known as “geochromatography”. Geochromatography refers to
preferential adsorption of polar molecules like resin and asphaltenes on the rock
surface during migration. Thus, mature and migrated oils are richer in saturates
compared to resins and asphaltenes. Further, biodegraded oils also have low
saturates and high resin plus asphaltenes content (Tissot and Welte, 1984).

Most of the oils from Eocene reservoir belong to mature migrated oils category
(Fig. 6.2; Table A.II). Oil from Dikom-Kathalani E well is low maturity whereas
oil from Baghjan A and Samdang A wells are high maturity in terms of its
composition. Further, none of the oils from Eocene reservoirs are biodegraded.

91
 Area
100 0 Baghjan
Barekuri
90 10 Bhogpara
Borhapjan-Makum
Chabua
80 20 Dikom-Kathalani
Matimekhana
Mechaki
70 30 Moran-Haldibari
North Tinali

Re
)

Samdang
(%

60 40

s+
Santi
cs

Tengakhat

As
ati

50 Dikom- 50 LithoStratigraphy

ph
om

Kathalani E Lakadong

(%
Ar

40 60 Langpar

)
30 70
Low Maturity /
20 Biodegraded Oils 80
Mature-Migrated
10 Oils 90
Baghjan A
0 100
100 90 80 70 60 50 40 30 20 10 0
Saturates (%)

Figure 6.2: Triangular distribution of saturates, aromatics and resins plus

asphaltenes for Eocene oils (after Tissot & Welte, 1984)

92
 As discussed earlier, a plot of saturates / aromatics ratio and API gravity for the
oils can give information about both the type of source rocks from which the oil
has generated and also the maturity and biodegradation of oils. It can be seen that
(Fig. 6.3, Table A.II) oils from Baghjan A, Samdang A and Tengakhat E are
showing high maturity. As has been previously established, the oils in Eocene
reservoirs are not biodegraded. Therefore, Dikom-Kathalani E oil has low
maturity and is not biodegraded.

Baghjan A
6 High Maturity

5
Saturates/Aromatics

Samdang A Area
4 Baghjan
Barekuri
Bhogpara
Borhapjan-Makum
3 Chabua
TYPICAL Clastic OILS Dikom-Kathalani
Tengakhat E Matimekhana
Mechaki
2 Moran-Haldibari
North Tinali
Samdang
Dikom- Santi
1 Tengakhat
Kathalani E LithoStratigraphy
TYPICAL Carbonate OILS Lakadong
Low Maturity or Biodegradation
Langpar
0
10 20 30 40 50 60
Oil Gravity (API°)

Figure 6.3: Plot of saturates / aromatics ratio and API gravity for
Eocene oils (after pIGI, 2011)

93
6.2 Maturity of oils using biomarkers

With increasing thermal maturation, more and more n-alkanes are generated
compared to isoprenoid compounds like pristane and phytane (Shanmugam,
1985). Therefore, with increasing maturity, pr / n-C17 and ph / n-C18 decrease. A
plot of pr / n-C17 and ph / n-C18 (Fig. 6.4, Table A.III) shows that the Eocene oils
are early mature and are not biodegraded. Amongst these oils, Samdang A and
Mechaki A oils have slightly higher maturity and oil from Tengakhat G has
lower maturity than other oils.

10.00
Terrestrial organic matter Biodegraded/
Mixed sources Immature
Marine organic matter

1.00 Oxidising Area

Baghjan
Pr/nC17

Early Mature Barekuri

Bhogpara
Borhapjan-Makum
Chabua
Dikom-Kathalani
Matimekhana
Mechaki
0.10 Reducing
Moran-Haldibari
North Tinali
Mature Samdang
Santi
Tengakhat
LithoStratigraphy
Lakadong
Langpar
0.01
0.01 0.10 1.00 10.00 100.00
Ph/nC18

Figure 6.4: Plot of pr / n-C17 and ph / n-C18 ratios for Eocene oils
(after Shanmugam, 1985)

94
 Each of the homohopanes from C31 to C35 show isomerization C-22 position.
Two isomers 22S and 22R are possible. The biologically produced hopane has a
22R configuration that is gradually converted to a mixture of 22S and 22R
during catagenesis. The ratio 22S/(22S+22R) hopane, therefore, increases from
zero to an equilibrium values of approximately 0.6 by the top of the oil window
(0.6% Ro) (Peters et al., 2005; Seifert and Moldowan, 1980). It is usually
measured from the C32 components because they are generally the most abundant
peaks in the m/z 191 fragmentogram that do not suffer from potential co-elution
problems with other triterpanes.

Most of the Eocene oils have C32 S/(S+R) Hopane between 0.55-0.60 (Fig. 6.5;
Table A.IVb). This implies that these oils have generated from source rocks that
have already entered the oil window. However, oils from Mechaki B (5460m &
5560m), are showing lower maturity than other oils.

15

10
Frequency

Area
Baghjan
Barekuri
Bhogpara
Borhapjan-Makum
5
Chabua
Dikom-Kathalani
Matimekhana
Mechaki
Moran-Haldibari
North Tinali
Samdang
Santi
Tengakhat
0
0.40 0.44 0.48 0.52 0.56 0.60 0.64 0.68
Hop32( S/S+R)

Figure 6.5: Distribution of C32 S/(S+R) hopane for Eocene oils

95
 C29 20S/(S+R) sterane is a useful maturity parameter used in conjunction with
C29 iso / (iso + regular) sterane which is another maturity parameter. At the end
of diagenesis the biologically preferred 20R configuration is universally present
in immature oils. With heating the 20R configuration is converted to 20S
configuration

heating
C29 Sterane 20R C29 Sterane 20S

Similarly, C29 regular steranes dominate immature bitumens. With thermal

stress, the regular configuration converts to iso configuration.

heating
C29 regular Sterane C29 iso Sterane

C29 iso / (iso + regular) steranes when used along with C29 20S/ (S+R) is a very
useful parameter for determining maturity in the immature to peak mature range.
The ratio C29 20S/(S+R) sterane varies from 0 at immature stage to a maximum
value of 0.55 in the early mature stage whereas C29 iso / (iso + regular) sterane
varies from a very low value at immature stage to 0.70 in the peak mature stage
(Peters et al., 2005; Seifert and Moldowan, 1986).

0.8
Area
Baghjan
Barekuri
Bhogpara Bacterial degradation Most oils
Borhapjan-Makum
Chabua
0.6 Dikom-Kathalani
Matimekhana High maturity oil
Mechaki
Moran-Haldibari
North Tinali Mechaki B
St29S/S+R

Samdang
Santi Matimekhana A
0.4 Tengakhat
Low maturity oil
LithoStratigraphy
Lakadong
Langpar Tengakhat
Migrational fractionation
B&E
Baghjan A
0.2
Borhapjan-
Makum B
Immature source rock
0.0
0.0 0.2 0.4 0.6 0.8
St29I/I+R

Figure 6.6: Plot of sterane maturity parameters C29 20S/(S+R) and C29 iso / (iso +
regular) for Eocene oils (after Seifert & Moldowan, 1986)

96
Sterane maturity parameters (Fig. 6.6, Table A.VI)) shows that most of the
Eocene oils are early mature. Oils from Baghjan A and Borhapjan-Makum B
have very low maturity that corresponds to immature source rock. The extremely
low maturity shown by oils is discussed under migration-contamination, later in
this section. Oils from Tengakhat B & E, Mechaki B, Matimekhana A and
Dikom-Kathalani E are showing low maturity. Oils from Moran-Haldibari A &
B, Santi A, Samdang A and Bhogpara A are peak mature.

The 20S isomer is slightly more resistant towards biodegradation. With

increasing biodegradation, the concentration of 20R isomer decreases faster than
20S isomer, thereby increasing the 20S/(S+R) ratio. None of the Eocene oils are
biodegraded (Fig. 6.6).

During migration, the isomers of steranes move at different rates. This results in
the fractionation of isomers. The regular isomers move at a slower rate than iso
isomers resulting in increase in iso / (iso + regular) isomers with increasing
migration. This phenomenon is called migration-fractionation or
geochromatography. It can be seen that (Fig. 6.6) Eocene oils have not suffered
significant migration-fractionation.

97
 The ratio Ts/Tm is used as a maturity indicator, because C27 18α-trisnorhopane
or Ts exhibits greater thermal stability than its regular hopane counterpart, C27
17α-trisnorhopane or Tm. But the ratio is also source dependent. The value of
this ratio varies from low in immature range to 1.0 in late oil generation stage
(Moldowan et al., 1986; Peters et al., 2005). The ratio 29Ts/29Tm is defined as
the abundance of the C29 neohopane, commonly called C29Ts relative to the C29
regular hopane. The ratio measures the relative abundance of the neohopane to
the regular hopane and can be used in a similar fashion to the Ts/Tm ratio
(Cornford et al., 1988; Hughes et al., 1985). Both ratios increase with thermal
maturity. Most of the Eocene oils are falling in early to mid-mature range (Fig.
6.7; Table A.IV). Oil from Samdang A is showing high value for the ratio Ts/Tm
compared to other oils. This could be because the ratio Ts/Tm is also source
dependent and, as discussed earlier, Samdang A oil has been derived from a
source different than those for other Eocene oils.

0.60

Early m ature
0.50 Mid m ature

Late mature

0.40
Area
29Ts/29Tm

Baghjan
Barekuri
Bhogpara
0.30
Borhapjan-Makum
Chabua
Dikom-Kathalani
Matimekhana
0.20 Mechaki
Samdang A Moran-Haldibari
North Tinali
Samdang
Santi
0.10
Tengakhat
LithoStratigraphy
Lakadong
Langpar
0.00
0.0 0.3 0.6 0.9 1.2 1.5 1.8 2.1 2.4 2.7 3.0
Ts/Tm

Figure 6.7: Plot of Ts/Tm and C29 Ts/Tm for Eocene oils (after Cornford et al. 1988)

98
 As discussed earlier, source parameters bicadinane / hopane and oleanane index
also have some maturity effect i.e. both of them increase with increase in
maturity of the source rock from which the oil has generated. A plot of
bicadinane / hopane and oleanane index (Fig. 6.8, Table A.IV & A.VI) (Rangel
et al., 2000) shows that there is significant variation in maturity of oils.
However, due to strong effect of source rock characteristics on these ratios, it is
difficult to assess the relative maturity unless it is certain that the oils are derived
from the same source rock.

0.6
Area
Baghjan
Barekuri
Bhogpara
0.5 Borhapjan-Makum
Chabua Santi A
Dikom-Kathalani
Matimekhana
Mechaki
Bicadinane/Hopane

0.4
Moran-Haldibari
North Tinali
Samdang
Increasing Maturity
Santi
0.3 Tengakhat
LithoStratigraphy
Lakadong
Langpar Mechaki B
0.2
Moran-
Baghjan C Haldibari B
0.1 Borhapjan-
Makum B
Tengakhat G
0.0
0.0 0.3 0.6 0.9 1.2
OleanIndex

Figure 6.8: Plot of OleananeIndex and Bicadinane/hopane for Eocene oils (after
Rangel et al., 2000)

99
 The ratio Dia/NorM is a sensitive maturity parameter and can reveal the possible
presence of mixtures of early charge (containing normoretane) and late charge
(containing diahopane) oils (Cornford et al., 1983). Moretane is thermally less
stable than hopane. On heating, moretane gets converted to hopane. Therefore,
the ratio Hopane / Moretane can be used as a maturity parameter. The value of
this ratio varies from low values in the immature range to 20 in the early mature
range (Seifert and Moldowan, 1980).

A plot of Hopane/Moretane and Diahopane/Normoretane (Fig. 6.9) shows that

some of the Eocene oils are falling close to the normal maturation curve in early
to mid-mature range. However, most of the oils, particularly from Santi A,
Moran-Haldibari A & B, Mechaki A and Borhapjan-Makum C appear to have
higher maturity based on diahopane/normoertane ratio (Table A.IVa). This could
happen if the oil is a mixture of early charge and late charge. The late charge oil,
which is more mature, contains significant amount of diahopane thus increasing
the diahopane / normoretane ratio. Oils from Tengakhat G and Dikom-Kathalani
E are low maturity. Borhapjan-Makum B oil, however, is mature and is not
showing very low maturity as it is showing in the case of sterane maturity
parameters (Fig. 6.6).
20

High maturity

15
Hopane/Moretane

Area
Baghjan
Barekuri
10 Bhogpara
Borhapjan-Makum
Chabua
Borhapjan- Dikom-Kathalani
Makum B Moran-Haldibari Matimekhana
Mechaki
A&B Moran-Haldibari
5 North Tinali
Samdang
Borhapjan- Santi A Santi
Makum C Tengakhat
LithoStratigraphy
Lakadong
Low maturity Langpar
0
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0
Dia-hopane/Nor-Moretane

Figure 6.9: Plot of diahopane / normoretane and hopane / moretane for Eocene oils
(after Cornford et al., 1988)

100
There is an apparent anomaly when one looks at the sterane maturation plot (Fig.
6.6) and Ts/Tm vs 29Ts/Tm (Fig. 6.7) maturity plot. Oils from Baghjan A and
Borhapjan-Makum B appear to have extremely low maturity according to sterane
maturation plot. It is not possible to have such low maturity for oil because at
that level of maturity the source rock cannot expel hydrocarbons. However, these
oils are early to mid-mature based on the plot of maturity parameters Ts/Tm and
29Ts/Tm. Tengakhat B & E oils also have lower maturity compared to other oils
from Tengakhat oilfield.

In order to understand this anomaly, maturity parameter Ts/(Ts+Tm)) has been

plotted against one of the sterane maturity parameter C29 S / (S+R) steranes (Fig.
6.10, Tables A.IVa & A.VI). It is seen that the Baghjan A and Borhapjan-
Makum B oils are showing very low maturity based on sterane maturity
parameter even though the maturity does not appear to be very low based on
Ts/(Ts+Tm) ratio. Tengakhat B & E oils are also showing slightly lower maturity
based on sterane maturity parameter compared to hopane maturity parameter.
Further, Tengakhat G and Dikom-Kathalani E oils are showing low maturity
based on Ts/(Ts+Tm) ratio, even though sterane maturity parameters show that
the oils are early mature.
0.8

0.6

Tengakhat G
St29S/(S+R)

Area
Baghjan
0.4 Barekuri
Dikom- Bhogpara
Borhapjan-Makum
Kathalani E Chabua
Dikom-Kathalani
Tengakhat B & E Matimekhana
Mechaki
0.2
Baghjan A Moran-Haldibari
North Tinali
Santi
Borhapjan- Tengakhat
Makum B LithoStratigraphy
Lakadong
Langpar
0.0
0.0 0.1 0.2 0.3 0.4 0.5
Ts/(Ts+Tm)

Figure 6.10: Plot of C29 S/(S+R) steranes and Ts/(Ts+Tm) for Eocene oils

101
The anomalous behaviour of sterane maturity parameters is further confirmed
when one of the parameters, C29 S/(S+R) sterane, has been plotted against
another maturity parameter saturates / (saturates + aromatics) (Fig. 6.11, Tables
A.II & A.VI). It can be seen that Baghjan A and Borhapjan-Makum B oils are
not falling on normal maturity line and their maturity, as determined by C29
S/(S+R) sterane, is very low. Further, oils from Samdang A and Tengakhat B &
E also have lower maturity based on sterane maturity parameter.

0.8

0.6 Tengakhat B & E

Area
St29S/S+R

Baghjan
Barekuri
0.4
Samdang A Bhogpara
Borhapjan-Makum
Chabua
Dikom-Kathalani
Matimekhana
Mechaki
Moran-Haldibari
0.2 North Tinali
Samdang
Baghjan A Santi
Tengakhat
Borhapjan- LithoStratigraphy
Lakadong
Makum B Langpar
0.0
0.2 0.4 0.6 0.8 1.0 1.2
Sats/Sat+Arom

Figure 6.11: Plot of C29 S/(S+R) steranes and saturates / (saturates + aromatics)
ratio for Eocene oils

102
In order to understand the mismatch between sterane maturity parameters and
maturity parameters based on other hopanes, the maturity parameter C29 S/(S+R)
has been plotted against steranes / steranes + triterpanes ratio. This ratio
determines the relative amount of steranes present in oil. It can be seen (Fig.
6.12, Table A.VI) that the maturity of oil, as determined by the sterane maturity
parameter, C29 S/(S+R) steranes, decreases with increasing steranes content. This
can be explained by invoking the process of migration-contamination or leeching
of source rocks. In this process, normal oil is generated by mature source that are
buried sufficiently deep. This oil is homogenous and the maturity of the oil, as
measured by different maturity parameters, is consistent. On expulsion by the
source rock, this oil migrates to reservoir rocks, where it gets accumulated.
However, the migrating oil encounters organically rich, immature source rocks
that have generated oil but that have not yet expelled it. The migrating oil
leeches immature oil from these source rocks and thus these oils get
contaminated with immature oil during migration. Hence, this process is referred
to as migration-contamination (Curiale and Bromley, 1996).

It is envisaged that the depositional environment and source input of the source
rocks that have generated these oils are slightly different from the source rocks
that these oil have encountered during migration. The steranes / steranes +
triterpanes ratio for the original oil is quite low. However, this ratio is higher for
the source rocks in the migration pathway of these oils.

Due to leeching of immature oil in the source rock by the migrating oil, the
steranes / steranes + triterpanes ratio of the migrating oil significantly increases
and the maturity of the oil, as determined by sterane maturity parameter,
significantly decreases. Thus, the oils that are showing low maturity based on
sterane maturity parameter, have suffered significant migration-contamination.

Borhapjan-Makum B and Baghjan A oils have picked up significant amount of

steranes during migration and are therefore, contaminated. Tengakhat G oil has
not picked up any steranes during migration. Therefore, its maturity parameter
has not been affected due to sterane contamination.

103
 0.6
Borhapjan-
Makum B
0.5

0.4
St29/St29+Tt30

Area
Baghjan
Barekuri
Baghjan A Bhogpara
0.3 Samdang A Borhapjan-Makum
Chabua
Baghjan C Dikom-Kathalani
Matimekhana
0.2 Mechaki
Moran-Haldibari
Tengakhat B North Tinali
Samdang
&E Santi
0.1
Tengakhat
LithoStratigraphy
Tengakhat G Lakadong
Langpar
0.0
0.0 0.2 0.4 0.6 0.8
St29S/S+R

Figure 6.12: Plot of C29 S/(S+R) steranes and steranes /(steranes +

triterpane) ratio for Eocene oils

104