European Journal of Scientific Research ISSN 1450-216X Vol.25 No.3 (2009), pp.417-427 EuroJournals Publishing, Inc. 2009 http://www.eurojournals.com/ejsr.

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Aspect of Rock-Eval Studies of the Maastrichtian-Eocene Sediments from Subsurface, in the Eastern Dahomey Basin Southwestern Nigeria
M.E. Nton Department of Geology, University of Ibadan, Nigeria Email: ntonme@yahoo.com, matthew.nton@mail.ui.edu.ng P. R. Ikhane Department of Earth Sciences, Olabisi Onabanjo University, Ago- Iwoye, Nigeria M.N.Tijani Department of Geology, University of Ibadan, Nigeria Abstract Aspect of Rock-eval studies has been conducted on the Maastrichtian-Palaeocene sequence in the eastern Dahomey basin, southwestern Nigeria as penetrated by the Ibese and Aje-1 boreholes. The study aims at evaluating the hydrocarbon prospect of the associated shale and limestone within the basin. The Ibese well, with a depth of 100m, is made up of a lower to middle limestone, overlain by shale and sandstone in the upper part, while the Aje-1 well is 3,700m thick and made up of lower sandstone and shale with claystone interbed, middle limestone, upper shale and sandstone sequences successively. The limestones interval, which is assigned to the Ewekoro Formation, are grayish, fosslilferous and calcitic in places while the shales are dark in the lower intervals of the Afowo and Araromi Formations to grayish, concretionary with claystone interbeds in the Akinbo Formation at the top. Arising from Rock-eval pyrloysis, the total organic carbon (TOC) shows a range from 0.01-3.55 wt.%. This indicates that the organic matter is low to adequate, particularly within the dark shaly interval of Araromi and Afowo Formations in Aje-1 well. In both wells, the limestone intervals are low in organic matter. The Hydrogen Index (HI) and Genetic Potential (GP) show moderately low values Tmax ranges from 359oC to 465oCand indicate thermally immature to marginally mature sediments, while calculated vitrinite reflectance is 0.27% to 1.21%. Cross plots of rock-eval parameters such as HI versus TOC shows that the majority of the sediments plot within the gas prone source with some in the fair oil zone. HI versus Tmax shows samples plot mainly within type III kerogen. Arising from available data and from previous studies, it can be deduced that the sediments of the eastern Dahomey basin are terrestrial organic matter, immature to slightly mature, with prospect to generate gas rather than oil at appropriate maturity

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Introduction
The Dahomey (Benin) Basin covers much of the continental margin of the Gulf of Guinea, extending from Volta-delta in Ghana in the west to the Okitipupa Ridge in Nigeria in the east (Fig. 1).The basin is a marginal pull apart basin (Klemme, 1975) or marginal sag basin (Kingston et al., 1983) which developed in the Mesozoic due to the separation of African from south American plate in the Mesozoic era (Burke et at., 1971; Whiteman, 1982).
Figure 1: East -West Geological Section showing position, extent and sediment thickness variations in the onshore Dahomey Basin and the upper part of the Niger Delta (After Whiteman, 1982)

The eastern Dahomey basin or the Nigeria sector, contains extensive wedge of Cretaceous to Recent sediments, up to 3000m which thicken towards the offshore. The basin has been of much geological interest as a result of the reported occurrences of bitumen, limestones, glass sands and phosphates (Nton, 2001). It is of immense importance to note that exploration activity for hydrocarbon commenced in Nigeria in this basin in 1908, near Okitipupa, east of Lagos, where bituminous sands outcrop. With the discovery of oil in the Niger Delta in 1956, focus shifted from the eastern Dahomey basin to the Niger Delta and the wells earlier drilled, were termed ``dry and later abandoned. Recently, due to increased government incentives to prospectors and re-evaluation of data gathered from such unsuccessful attempts, there is a resurgence of interest in exploration activities in the eastern Dahomey basin. Also, it is relevant to note that conventional hydrocarbons in commercial quantity have been discovered offshore in the Republic of Benin (Billman, 1992). However, in comparison with the adjacent Niger Delta, few studies have been conducted in the eastern Dahomey basin in terms of hydrocarbon potential (Elueze and Nton, 2004; Nton, et al., 2006). The present study examines from bore hole data the hydrocarbon potential from two exploratory wells within this basin, in an attempt to provide additional geochemical information on the hydrocarbon potential of this frontier basin. Such information would be useful to researchers and explorationists.

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Stratigraphy of Eastern Dahomey Basin

The studied wells are located between latitudes 6o101 to 6o 401 N and longitudes 2o121 and 2o361, E and lie within the eastern Dahomey basin (Fig. 2). The stratigraphy of the eastern Dahomey basin has been discussed by various workers and several classification schemes have been proposed. These notably include those of Jones and Hockey (1964); Ogbe (1972); Omatsola and Adegoke (1981); Coker et al (1983); Billman (1992), Nton (2001); Elueze and Nton (2004); Nton et al. (2006) among others. Inspite of all these classification schemes, there are still controversies on age assignments and nomenclatures of the different lithological units within the basin. The different classification schemes are shown in Fig. 3.
Figure 2: Simplified Geological Map of South western Nigeria showing locations of ibese and Aje-1 wells

Aspect of Rock-Eval Studies of the Maastrichtian-Eocene Sediments from Subsurface, in the Eastern Dahomey Basin Southwestern Nigeria
Figure 3: Stratigraphy of eastern Dahomey basin
Jones & Hockey (1964)
Age Recent Formation Lithology Alluvium Coastal PleistoceneOligocene Plain Sands Ilaro Eocene Ososhun Paleocene Ewekoro Paleocene Akinbo Ewekoro Araromi

420

ERA
Quaternary

Omatsola & Adegoke (1981)

Age Formation Lithology

Pleistocene- Coastal Oligocene Plain Sands

Tertiary

Eocene

Ilaro

Late Cretaceous

Late Senonian

Abeokuta

Maastrichtian Neocomian

Afowo Ise

PRE - CAMBRIAN CRYSTALLINE BASEMENT

Alluvial sediments Siltstone/mudstone Unconsolidated sands and silty sands Poorly consolidated shale/clay Laminated fossiliferous shale Limestone, fossiliferous Basal conglomerate with grits and siltstone
Omatsola and Adegoke (1981) proposed the Cretaceous sequence in the eastern Dahomey basin as beginning with the Abeokuta Group, made up of three formations from oldest to the youngest namely; the Ise, Afowo and Araromi Formations. The Ise Formation unconformably overlies the basement complex of southwestern Nigeria and consists of conglomerates and grits at base and in turn overlain by coarse to medium grained sands with interbedded kaolinite. The conglomerates are unimbricated and at some locations, ironstones occur (Nton, 2001). The age is Neocomian to Albian. Overlying the Ise Formation is the Afowo Formation, which is composed of coarse to medium grained sandstones with variable but thick interbedded shales, siltstones and claystone. The sandy facies are tar-bearing while the shales are organic - rich (Enu, 1990). The lower part of this formation is transitional with mixed brackish t.o marginal horizons that alternate with well sorted, sub-rounded sands indicating a littoral or estuarine near-shore environment of deposition. Using palynological assemblage, Billman (1992) assigned a Turonian age to the lower part of this formation, while the upper part ranges into the Maastritchtian. The Araromi Formation overlies the Afowo Formation and has been described as the youngest Cretaceous sediment in the eastern Dahomey basin (Omatsola and Adegoke, 1981). It is composed of fine to medium grained sandstone at the base, overlain by shales, siltstone with interbedded limestone, marl and lignite. This Formation is highly fossiliferous containing abundant planktonic foraminifera,

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ostracods, pollen and spores. Omatsola and Adegoke (1981) assigned a Maastritchtian to Palaeocene age to this formation based on faunal content. The Ewekoro Formation overlies the Araromi Formation in the eastern Dahomey basin. It is an extensive limestone body, which is traceable over a distance of about 320km from Ghana in the west, towards the eastern margin of the Dahomey basin in Nigeria (Jones and Hockey, 1964). Elueze and Nton, (2004) has reported that the limestone is of shallow marine origin owing to abundance of coralline algae, gastropods, pelecypods, echnoid fragments and other skeletal debris . It is Palaeocene in age. Overlying the Ewekoro Formation is the Akinbo Formation, which is made up of shale and clayey sequence (Ogbe, 1972). The claystones are concretionary and are predominantly kaolinite (Nton and Elueze, 2005).The base of the formation is defined by the presence of glauconitic band with lenses of limestones (Ogbe, 1972; Nton, 2001). The formation is Palaeocene to Eocene in age. The Oshosun Formation overlies the Akinbo Formation and consists of greenish grey or beige clay and shale with interbeds of sandstones. The shale is thickly laminated and glauconitic. According to Okosun (1998), the basal beds consist of any of the following facies; sandstones, mudstones, claystones, clay-shale or shale. This formation is phosphate- bearing (Jones and Hockey, 1964; Nton, 2001). The Ilaro Formation overlies conformably the Oshosun Formation and consists of massive, yellowish poorly, consolidated, cross-bedded sandstones. The youngest stratigraphic sequence in the eastern Dahomey basin is the Benin Formation. It is also known as the Coastal Plain Sands (Jones and Hockey 1964) and consists of poorly sorted sands with lenses of clays. The sands are in parts crossbedded and show transitional to continental characteristics. The age is from Oligocene to Recent

Materials and Methods of Study

Sampling Subsurface samples for this study were retrieved from Ibese and Aje-1 wells, within the eastern Dahomey basin, southwestern Nigeria (Fig. 2). The Ibeshe well extends up to a total depth of 100m while the Aje-1 well is from 178.8-3700 m ( Figs. 4 and 5). Field evidence shows that the sediments from Ibese well are made up of a thick sequence of limestone that is slightly sandy at base, grayish to dark in some part, fossiliferous towards the upper part. This is overlain by fissile shale sequence with some interbeds of claystone and capped by sandstone. In the Aje -1 well, the sequence begins with coarse to medium grained sandstone with claystone interbed. This is overlain by carbonaceous fissile shales of the Afowo-Araromi Formations. A thick sequence of limestone body overlies these lower sequences. The limestone is dark grey, fossiliferous and partly nodular. The whole sequence is capped by fissile dark shale that is partly concretionary and contains clayey sequence. Altogether, thirteen (13) samples, made up of six shales and seven limestones from both wells were sampled for this study. A detailed lithofacies study is in progress and will be reported elsewhere. Rock-Eval Pyrolysis The process of Rock-Eval Pyrolysis was described by Espitalie et al (1977) as a rapid method for the characterization of kerogen types and the determination of its maturity. About 80 100mg of each pulverized sample was heated initially at 3000C and followed by programmed pyrolysis at 25oCmin to 550oC in an atmosphere of helium. The analysis was determined by Rock-Eval II pyroanalyser which has a Total organic carbon (TOC) module. These analyses were conducted at the Humble Geochemical Services Division Houston, Texas USA.

Aspect of Rock-Eval Studies of the Maastrichtian-Eocene Sediments from Subsurface, in the Eastern Dahomey Basin Southwestern Nigeria

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Results and Discussion

Organic Richness The result of the total organic matter (TOC) is shown in Table 1. It is known that adequate amount of organic matter, measured as percentage total organic carbon (TOC), is a necessary pre-requisite for sediment to generate oil or gas ( Cornford, 1986). The samples from Ibeshe bore hole show TOC values between 0.01 0.53 wt % (average, 0.18). This shows that the total organic content in the Ibese well is inadequate for generation of organic matter. Within Ibese well, the TOC trend with depth does not show any perfect trend even though sample IB 4 shows slight enrichment which reduces drastically with depth. This enrichment may be attributed to migrated tars and not necessarily associated with adequate organic matter.
Table: Total organic carbon and Rock-eval pyrolysis data of analysed samples
S2 GP (kgHC/t) 0.11 0.16 0 0.02 0 0.01 0 0 0 0.02 4.45 6.99 0 0.03 0.98 23.67 0.13 0.91 1.02 21.09 1.49 3.12 11.82 16.88 4.48 8.13 Tmax (oC) 430 -1 -1 -1 -1 465 -1 363 413 373 432 429 431 Cal %Ro 0.58 -1 -1 -1 -1 1.21 -1 -1 0.27 -1 0.62 0.66 0.60 HI 37 -1 -1 -1 -1 310 -1 30 39 36 135 375 125 OI -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 S2/S3 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 S1/TOC 17 50 -1 0 -1 322 -1 705 236 712 146 161 103 PI 0.31 1 1 -1 1 0.51 1 0.96 0.66 0.95 0.52 0.32 0.45

Sample Code Formation TOC S1 IB1 Akinbo 0.30* 0.05 IB2 Ewekoro 0.04* 0.02 IB3 Ewekoro 0.01* 0.01 IB4 Ewekoro 0.53 0 IB5 Ewekoro 0.01* 0.02 YF1 Akinbo 0.79 2.54 YF2 Ewekoro 0.01* 0.03 YF3 Ewekoro 3.22 22.69 YF4 Ewekoro 0.03* 0.78 YF5 Araromi 2.82 20.07 YF6 Araromi 1.1 1.63 YF7 Afowo 3.15 5.06 YF8 Afowo 3.55 3.65 * Below threshold value to generate hydrocarbon

In the eight samples retrieved from Aje- 1 well, TOC values range between 0.01 3.55 wt percent. (av. 1.83 %). This imply that sediments of Aje-1 well is above the threshold limit of 0.5wt % TOC reported for the generation of organic matter from clastic sediments (Tissot and Welte, 1984). This suggests an adequate organic matter constituent for the generation of hydrocarbon particularly for the sequence penetrated by Aje-1 well. Average TOC values for the Ewekoro Formation penetrated by Ibese and Aje -1 wells are respectively, 0.15 and 1.05 wt 5% TOC. From the trend of TOC values within this formation and arising from previous studies ( Elueze and Nton, 2004; Nton et al., 2006), higher value of 3.22 wt % TOC for sample YF3 and 0.53 wt %, for sample IB 4 are not sustained with depth and may be attributed with contamination. Organic rich intervals of the Afowo and Araromi Formations as penetrated by Aje-1 well have average TOC values of 3.55 and 1.96 wt % respectively. The lithological section of Ibese and Aje-1 boreholes together with TOC variation with depths are shown in Figs 4 and 5.

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Figure 4: Lithological section and variation of Total Organic carbon with depth in ibese bore hole
DEPTH (m)
FORMATION
SAMPLE NO LITHOLOGY AGE DEPTH

TOC (wt %)

AKINBO OSHOSUN

EOCENE

1B1 20

40

1B2

PALEOCENE

EWEKORO

1B3 60

Sandstone Shale Glauconite band Limestone , Fossiferous Sampled points

80

1B4

1B5
20m

Figure 5: Lithological section and variation of Total organic Carbon with depth in Aje-1 borehole

Organic Matter Type Cross plot of hydrogen index (HI) versus Tmax, (Fig. 6) shows that majority of the samples plot within Types III kerogen with the exception of sample YFSI, which lies within the oil zone. Type III organic matter is usually derived from terrestrial plants, and is dominated by vitrinite and lesser amounts of inertinite macerals. Type IV organic matter can be derived from other kerogens types that have been

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reworked and oxidized (Peters and Moldowan 1993). Source richness plots of HI versus TOC ( Fig. 7) ( adapted from Jackson et al., 1985) indicate that the majority of the sediments plot within gas source rocks, however few plot in fair oil field which may be attributed to contamination from migrated tars. It can be implied that the sediments of eastern Dahomey basin are terrestrial and reworked immature organic matter with prospect to generate gas rather than oil at appropriate maturity. This corroborates the findings of (Elueze and Nton 2004; Nton et al., (2006).
Figure 6: Classification of Kerogens on HI-Tmax diagrams

Figure 7: Source Richness plots for sediments of eastern Dahomey Basin( Adapted from Jackson et al., 1985)
B
10000

HI (mg HC/g TOC)

RY VE
1000

D OO

OIL

OIL OD O G

IR FA

OIL

100

POOR/ BARREN SOURCE

10 0.1 1

N SA A G GAS SOURCE

E OM S D

OIL

TOC (%)

10

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M.E. Nton, P. R. Ikhane and M.N.Tijani

Tmax for the selected samples range from 363-463C and portray immature to slightly mature organic matter . Higher value of 463C for sample YF1, may not really connote maturity more so with a TOC quantity of 0.79 wt %. The production index (PI) is used to assess the generation status of source rocks but is often useful when homogenous source rocks of different ranks are compared, in which case it is characterized as the transformation ratio. Hunt (1979) suggested that PI from 0.08 to 0.4 is characteristic of source rock in the oil window after which gas is the main hydrocarbon phase produced (Dow, 1977). The maturity indicator as shown by calculated vitrinite reflectance (Ro %) values range from 0.27 % to 1.21%, portrays thermally immature to marginally mature source rock considering the depth of burial of the samples involved. This is further supported by Tmax values ranging from 363C -465C. Some of the shale samples retrieved at the depth shows contamination. The hydrogen index (HI) values range between 30 and 375mgHc/g TOC. The samples with a range of 15-86mgHC/TOC have Type IV kerogen (IB1, YF3, YF4 and YF5) which are terrestrially derived. Samples with HI values range between 86-135mg Hc/g TOC ( YF8) fall within type III kerogen (middle of the Afowo Formation). This organic matter displays gas-prone characteristics indicating a woody or herbaceous origin. Those samples within the range of 135-375mg HC/g TOC ( YF1, YF6 and YF7 )consists of Type II-III Kerogens however judging from the majority of the samples and arising from other parameters, the sediments are mainly gas prone ( Type III and IV) which are immature. More mature strata may likely be intercepted at depth

Sumary and Conclusions

Rock eval pyroylsis studies of subsurface samples from Ibese and Aje-1 bore holes within the eastern Dahomey basin, southwestern Nigeria show that the sediments have low to adequate organic matter mainly from the shaly intervals of the Araromi and Afowo Formations. The hydrocarbon source potential indicates predominantly immature sediments that are gas prone. It can be deduced that the sediments were derived from mainly terrestrial biota with immature to fairly mature status, having prospects to generate gas rather than oil at appropriate maturation.

Acknowledgment
The authors are grateful to the management of Yinka Folawiyo Oil Company Ltd, Lagos and Dangote Nigeria Ltd, for the provision of well samples for this study. We acknowledge the invaluable technical assistance of Dr. Dan Jarvie of Humble Geochemical Laboratory, Texas in sample analysis. The role played by Messrs Joseph Asanga and Patrick Obot of Global Energy Company, Lagos in facilitating the technical arrangement is appreciated. We also extend our gratitude to Mr Nneli Onyeka, a Post graduate student in our Department, for support.

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