A total of Twenty-one coal and carbonaceous shale samples were collected from four boreholes in Mamu and Awgu Formations of Lower and Middle Benue Trough, Nigeria. The samples were subjected to Elemental analysis using Gas Chromatography and Gas Chromatography- Mass Spectrometry (GC-MS).The saturated fraction was subjected to urea adduction to separate isoprenoids from n-alkanes and subjected to gas chromatography-mass spectrometry (GC-MS) using a CE 5980 GC coupled to an HP Finnigan 8222 MS held at 80oC for three minutes and raised to 310oC at 3oC min-1 and held isothermally for 10 minutes in order to assess some molecular parameters used in source rock characterization. The short chain/long chain saturated fatty acid (ATRFA) ratios for the samples which ranges from 0.85-1.00 and the carbon preference index (CPIFA) of the long chain n-fatty acids (C24-C30) ranging between 1.27 and 3.29 indicates both terrestrial and marine organic matter derived materials. The distribution of straight chain n-alkan-2-ones ranges from nC14 to nC33, maximizing at nC17 is an indication of contribution from higher plants.
2. Distribution of Possible Fatty Acids and Alkanones in some Thermally Immature Nigerian Coals
Uzoegbu et al. 104
to alkanes (Tuo and Li, 2005). The n-alkan-2-ones, n-
alkan-3-ones and n-alkan-4-ones have also been detected
in lipid fractions extracted from aerosol particulate matter
(Simoneit et al., 1988, 1991), hydrothermal petroleum and
sediment extracts from Guyama Basin (Leif and Simoneit,
1995). The higher alkenones (>C25) homologues with a
high odd carbon number predominance were interpreted
to originate from vegetation wax by oxidation while the
lower homologues (<C25) with no odd or even Carbon
number predominance were thought to originate from
anthropogenic sources by combustion or exposure to high
temperature (Leif and Simoneit, 1995). The C37 andC38
diunsaturated methyl and ethyl ketones are
biosynthesized by a limited number of haptophyte bacteria
like Prymnesiophyte algae (Volkman et al., 1980; 1995),
Emiliania huxleyi (Sonzogoni et al., 1997; Schouten et al.,
2000) and Gephyrocapsa oceanica (Schouten et al.,
2000). Their distributions are now widely used as specific
indicators of past sea surface temperature (SSTs) and the
unsaturation ratios can provide a reliable indicator of the
temperature at which they are biosynthesized (Brassel et
al., 1986; Phral and Wakeham, 1987).
The 6,10,14-Trimethylpentadecan-2-one is quite common
in nature, occurringwidely in sediments, water particulate
matter and recently in coals (Volkman et al.,1983, Rontani
et al., 1992, Tuo and Li, 2005).These isoprenoid ketones
could be produced from free phytol by bacteria
degradation and photosynthesized oxidation,
photosynthesized oxidation of some isoprenoids
hydrocarbons and during photo degradation of -
chlorophyll (Tuo and Li, 2005).
The homologous series of alkan-2-ones is generally found
with an odd carbon number predominance and its source
is likely microbial (Leif and Simoneit, 1995; Bai et al.,2006).
It has been proposed that n-alkan-2-ones are formed by
microbially mediated -oxidation of alkanes (Cranwell et
al., 1987; Rieley et al., 1991; Simoneit et al., 1998;) or from
-oxidation and decarboxylation of n-fatty acids (Volkman
et al., 1983). n-Alkan-2-ones maximizing at C25 or C27
have been reported in higher plants, microalgae and
phytoplankton (Gonzalez-Vila et al., 2003; Bai et al.,
2006). This research aims in determining the possible type
of lipid and alkanones in some thermally immature organic
matter and determining the environment of formation of the
organic matter of Nigerian coals.
STRATIGRAPHIC SETTING
The infilling of the Anambra and Afikpo started during the
Campanian to the Paleocene (Danian) under two major
eustatic cycles; the more pronounced Nkporo
transgression and the less active Nsukka transgression
with the Anambra basin showing the most complete
stratigraphic sections (Fig. 1). These cycles are also found
in the Afikpo syncline SE of the Abakaliki anticlinorium and
the Dahomey embayment, west of the Ilesha basement
spur, although both are incomplete (Murat, 1972).
The first cycle which took place during the Lower
Campanian to the Maastrichian started with the deposition
of the Nkporo whose lateral (age) equivalents are the
Enugu and Owelli (Fig. 2). This is the basal unit of the
Campano-Maastrichian transgression and comprises of
dark mudstone, gray, fissile friable shales with thin beds of
marl, sandy shale and limestone overlying an angular
unconformity (Reyment, 1965).
The regressive phase was marked with the development
of a large offlap complex, starting with the paralic
sequence of the Mamu (Lower coal measure) overlying the
Nkporo (Reyment, 1965). It is thought to be lower
Maastrichian in age with a basal part that contains thin
marine intercalations, while the coal bearing part consist of
fresh water and low salinity sandstones, shale, mudstone
and sandy shales with coal seams occurring at several
levels (Simpson, 1955).
The Mamu formation is overlain by the continental
sequence of the Ajali. This sandstone unit has received
several names such as false bedded sandstone (Tattam,
1944), basal sandstone (Simpson, 1955) etc. iIts present
name was given by Reyment (1965) after establishing its
type locality at the Ajali. Virtually all exposures of the
formation are characterized by a lateritic profile at the top.
It was deposited during the regressive phase of the
Campano-Maastrichian transgression and the age is
Maastricthian.
The Ajali sandstone is overlain conformably by the Nsukka
Formation (Upper coal measures), and it consists of
alternating succession of gray sandy shales, sandstones,
plant bearing beds and thin beds of coal (Reyment, 1965).
Thin bands of marine limestone heralded the return of
marine sedimentation at the top of the formation. These
dark shales and the intensely bioturbated sandstones are
well exposed at Ihube, along the Enugu – Port Harcourt
expressway. The age range of the formation is late
Maastrichian to Danian based on the fossil record. This
formation bears the K/T boundary which is described by
Reyment (1965) as a period of transition in Nigeria. Mbuk
et al. (1985) identified this boundary in the Nsukka
Formation in Ozu Abam area of Abia State.
3. Distribution of Possible Fatty Acids and Alkanones in some Thermally Immature Nigerian Coals
Int. Res. J. Chem. Chem. Sci. 105
Fig. 1: Generalized geological map of Nigeria (boxed areas of inset) showing the geological map of the Anambra Basin.
Numbers indicate Cretaceous and Tertiary formations shown as follows: 1. Asu River Group; 2. Odikpani Formation; 3.
Eze-Aku Shale; 4. Awgu Shale; 5. Enugu/Nkporo Shale; 6. Mamu Formation; 7. Ajali Sandstone; 8. Nsukka Formation; 9.
Imo Shale; 10. Ameki Formation and 11. Ogwashi-Asaba Formation (after Akande et al., 2007).
Fig. 2: The Stratigraphy of the Anambra Basin Southeastern Nigeria (After, Ladipo, 1988 and Akande et al., 1992; Modified
in Uzoegbu et al., 2013b).
AGE
SEDIMENTARY
SEQUENCE
LITHOLOGY DESCRIPTION DEPOSITIONAL
ENVIRONMENT
REMARKS
ANKPA
SUB-
BASIN
ONITSHA
SUB-
BASIN
MIOCENE
OLIGOCENE
OGWASHI-
ASABA FM.
Lignites, peats,
Intercalations of
Sandstones &
shales
Estuarine
(off shore bars;
Intertidal flats)
Liginites
EOCENE AMEKE NANKA
FM. SAND
Clays,shales,
Sandstones
& beds of grits
Unconformity
Subtidal, intertidal
flats, shallow marine
PALEOCENE
IMO SHALE Clays, shales
& siltstones
Marine
MAASTRICHTIAN
Clays, shales, thin
sandstones & coal
seams
Coarse sandstones,
Lenticular shales,
beds of grits &
Pebbls.
Clays, shales,
carbonaceous
shale, sandy shale
& coal seams
NSUKKA FM.
AJALI SST.
MAMU FM.
? Estuarine
Subtidal, shallow
marine
Estuarine/ off-shore
bars/ tidal flats/
chernier ridges
CAMPANIAN
ENUGU/
NKPORO SHALE Clays & shales Marine
CONIACIAN-
SANTONIAN
AWGU SHALE
TURONIAN EZEAKU SHALE
Clays &
shales Marine
ODUKPANI FM.
CENOMANIAN
ALBIAN
L. PALEOZOIC
ASU RIVER GP.
B A S E M E N T C O M P L E X
Sub-
bituminous
Sub-
bituminous
3rd Marine
cycle
Unconformity
2nd Marine
cycle
Unconformity
1st Marine
cycle
Unconformity
NODEPOSITION
(? MINOR
REGRESSION
REGRESSION
(Continued
Transgression
Due to geoidal
Sea level rise)
TRANSGRESSION
(Geoidal sea level
Rise plus crustal
Movement)
Coal
Rank
~
~ ~
~
~
~ ~
~ ~
~ ~
~
~
~
~
~
~
~ ~
~
~ ~
~
~ ~
~ ~
~ ~
~ ~
~
~
~ ~
~~
~
~
~
~
~
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~~ ~ ~
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
.
. .
. ..
... .
... .
4. Distribution of Possible Fatty Acids and Alkanones in some Thermally Immature Nigerian Coals
Uzoegbu et al. 106
MATERIALS AND METHODS
A total of nine samples comprising of six coals, two
carbonaceous shales and one coaly shale were collected
from 2 boreholes (BH94 and BH120) from Awgu Formation
(BH). The coal seams and interbedded shale in BH94 and
BH120 were sampled between 218-431 m and 131- 289
m depths respectively. In Mamu Formation, twelve
samples consisting of nine coals and three carbonaceous
shales were collected from Okaba (OBA) and Onyeama
(AMA) with co-ordinates of 07o 28ˈN, 07o 43ˈE and 06o 28ˈ
N, 07o 26ˈE).
In the laboratory, the samples were reshaped using a
rotating steel cutter to eliminate surface that could be
affected by alteration. Chips were cut from the samples
and dried in an oven at 105oC for 24 hours. The dried
sample was pulverized in a rotating disc mill to yield about
50 g of sample for analytical geochemistry. The samples
were subjected to flame ionization detection (FID) for
hydrocarbons thermal conductivity detection (TCD) for
CO2. One milligram of bulk powder sample was added to
200 mg of KBr and the mixture homogenized using a
pestle in an agate mortar. Pressing the mixture using a
load of 10 t yielded a pellet for Fourier Transform Infrared
(FT-IR) Spectroscopy using a Nicolet Bench 505P
Spectrometer, with sample absorbance monitored using
256 scans with resolution of 4 cm-1 from a wave-number of
4000 – 400 cm-1. About 10 g of the sample was subjected
to sohxlett extraction using a solvent mixture of acetone,
chloroform and methanol (47: 30: 23 v/v) at 60oC for 24
hours to extract the soluble organic matter. The extract
was concentrated by evaporation to dryness using a
rotating vapour evaporator at 250 mb. The extract was
transferred to an 8 ml vial using the same solvent mixture
and allowed to evaporate to dryness in a vented hood. The
dried extract was fractionated by silica gel column
chromatography with a column prepared using 2 g of baker
silica gel calcined at 200oC for 24 hours to yield six
fractions ranging from saturate to polar.
The saturate fraction was subjected to urea adduction to
separate isoprenoids from n-alkanes and subjected to gas
chromatography-mass spectrometry (GC-MS) using a CE
5980 GC coupled to an HP Finnigan 8222 MS held at 80oC
for three minutes and raised to 310oC at 3oC min-1 and held
isothermally for 10 minutes in order to assess some
molecular parameters used in source rock
characterization.
RESULTAND DISCUSSION
The distributions of fatty acids in the polar fraction have
been successfully used to differentiate the biological
source of geological materials (Duan et al., 1997).The m/z
58 and m/z 74 mass chromatograms showing the
distributions of the saturated n-fatty acids and alkan-2-
ones in the coal extracts are shown in Figs.3,4,5,6,7 and 8
respectively. Parameters calculated from the fatty acids
and alkanones distribution in the coal extracts are listed in
Tables 1 and 2 respectively.
Awgu samples have n-fatty acids ranging from C14 to C30,
maximizing at nC16 ornC18(Fig. 3). The short chain/long
chain saturated fatty acid (ATRFA) ratios for the samples
which range from 0.97-1.00, indicate both terrestrial and
marine organic matter derived material (Wilkes et al.,
1999). Abundance of short chain saturated n-fatty acids
(<nC20) in the samples reflects mixed input of
microorganisms and algae (Duan et al., 1997; Killops and
Killops, 2005). The nC16and nC18 are prominent in all the
samples. These compounds are ubiquitous and can also
reflect higher plant input e.g. seed and leaf oils of
gymnosperms (Volkman et al.,1998). The appreciable
amount of long chain saturated n-fatty acids(>C20) in the
samples can be attributed to curticular waxes of higher
plants (Cranwell,1974).
The carbon preference index (CPIFA) of the long chain n-
fatty acids (C24-C30) range between 1.98 and 3.29 (Table
1), indicating a strong even over odd predominance.
These values inferred high maturity status for the samples
(Wilkes et al., 1999). The distribution of straight chain n-
alkan-2-ones ranges from nC14 to nC33,maximizing at
nC17(Fig. 4). Similar distribution has previously been
observed in stalagmites (Xie et al., 2003; Bai et al., 2006).
However, some of the samples maximize at nC23 or
nC25(Fig. 4), an indication of contribution from higher
plants, microalgae and phytoplankton organic matter
inputs (Hernandez et al., 2001;Gonzalez-Vila et al., 2003).
Fig. 3: m/z 74 mass chromatogram showing the
distribution of n-fatty acids in Awgu samples (Numbers
refer to carbon chain lengths of n-fatty acids).
Fig. 3: (contd.): m/z 74 mass chromatogram showing the
distribution of n-fatty acids in Awgu samples (Numbers
refer to carbon chain lengths of n-fatty acids).
5. Distribution of Possible Fatty Acids and Alkanones in some Thermally Immature Nigerian Coals
Int. Res. J. Chem. Chem. Sci. 107
Table 1: Parameters calculated from n-Fatty acids and alkanones composition of Awgu Formation.
Sample N0 Depth (m) Lithology ATRFA CPILFA Pr-2-one/C17 CPI (alkanone)
BH218 218.5-222.5 Carbonaceous shale 0.99 nd 0.58 0.84
BH407 407.4-412.5 Coaly shale 0.99 nd 0.80 0.85
BH417 417.0-422.0 Coal 1.00 nd 1.09 1.14
BH131 131.7-136.6 Coal 0.99 nd 0.51 0.89
BH148 148 Coal 0.99 2.46 0.60 0.76
BH168 168.8-173.7 Coal 0.99 1.98 0.39 1.01
BH212 212.1-216.2 Coal 0.99 3.29 1.59 0.76
BH247 247 Carbonaceous shale 0.97 3.20 0.86 0.93
BH286 286.0-289.0 Coal 0.98 nd 0.82 1.20
ATRFA = Short chain/long chain saturated fatty acid
CPILFA= Carbon Preference Index (Longchain fatty acids)
CPI (alkanones)= Carbon Preference Index (alkan-2-ones).
ATRFA = C14 + C16 + C18 / C14 + C16 + C18 + C26 + C28 + C30
CPILFA=½{(C24+C26+C28+C30/C21+C23+C25+C27)+(C24+C26+C28+C30/C23+C25+C27+C29)}
CPI(alkanones)=1/2{(C25+C27+C29+C31+C33)/(C22+C24+C26+C28+C30+C32)
+(C25+C27+C29+C31+C33)/ C24+C26+C28+C30+C32+34}}
nd – Not determined
Fig. 4: m/z 58 mass chromatograms showing the
distributions of alkan-2-ones in Awgu samples (Numbers
refer to carbon chain lengths of alkan-2-ones).
Mamu samples have saturated n-fatty acids ranging from
C8 to C32 , maximizing at nC16 or nC18(Fig. 5 and 7). These
distributions reflect organic matter from both marine and
terrestrial materials (Volkman et al., 1998). However, the
dominance of short chain (<C20) saturated n-fatty acids
maximizing at C16 is an indication of substantial
contribution of microorganism/algal to the organic matter.
The appreciable quantity of long chain saturated n-fatty
acids (>nC22) in the samples canbe attributed to the
contribution of higher plants to the organic matter
(Cranwell, 1974). The short chain/long chain saturated
fatty acid (ATRFA) ratios range from 0.85 to 0.96. These
values indicate organic matter derived from mixed origin
(Wilkes et al., 1999). The carbon preference index
(CPILFA)for the long chain saturated n-fatty acids range
between 1.25 and 2.78, indicating a slight even over odd
predominance (Table 2). These values indicate low
maturity(Wilkes et al., 1999).
The n-alkan-2-ones range from nC12 to nC33, maximizing
at nC17 or nC29 (Fig. 6 and 8). These distributions reflect
higher plants and algae inputs to the organic matter (Bai
et al., 2006). The CPI values range from 1.27 to 1.69 and
2.10 to2.66 in Onyeama and Okaba samples respectively
(Table 2). These values indicate low maturity status for all
the samples (Tuo et al., 2007).
Fig. 5: m/z 74 mass chromatogram showing the
distribution of n-fatty acids in Mamu samples (Okaba)
(Numbers refer to carbon chain lengths of n-fatty acids).
Fig. 6: m/z 58 mass chromatograms showing the
distributions of alkan-2-ones in Mamu samples (Okaba)
(Numbers refer to carbon chain lengths of alkan-2-ones).
6. Distribution of Possible Fatty Acids and Alkanones in some Thermally Immature Nigerian Coals
Uzoegbu et al. 108
Table 2: Parameters calculated from n-Fatty acids and alkanones composition of Mamu Formation.
Sample N0 Depth (m) Lithology ATRFA CPILFA Pr-2-one/C17 CPI (alkanone)
AMA5 4.6-5.8 Carbonaceous shale 0.95 1.47 4.39 1.27
AMA4 6.0-6.8 Coal 0.91 1.37 10.54 1.45
AMA3 6.8-7.3 Coal 0.92 1.61 8.69 1.51
AMA2 7.6-8.4 Coal 0.92 2.07 12.18 1.69
AMA1 8.4-8.8 Coal 0.96 1.25 7.45 1.30
AMA6 9.0-9.5 Carbonaceous shale 0.94 1.61 4.10 1.60
OBA4 16.5-17.6 Carbonaceous shale nd nd nd nd
OBA3 18.0-18.5 Coal 0.85 2.78 8.68 2.66
OBA2 18.6-18.9 Coal 0.93 1.37 7.69 2.25
OBA1 18.9-19.3 Coal 0.94 1.95 12.69 2.59
OBA5 19.3-19.6 Coal 0.96 1.44 13.71 2.49
OBA6 19.6-20.0 Coal 0.91 2.51 21.43 2.10
ATRFA = Short chain/long chain saturated fatty acid
CPILFA= Carbon Preference Index (Longchain fatty acids)
CPI (alkanones)= Carbon Preference Index (alkan-2-ones).
ATRFA = C14 + C16 + C18 / C14 + C16 + C18 + C26 + C28 + C30
CPILFA=½{(C24+C26+C28+C30/C21+C23+C25+C27)+(C24+C26+C28+C30/C23+C25+C27+C29)}
CPI(alkanones)=1/2{(C25+C27+C29+C31+C33)/(C22+C24+C26+C28+C30+C32)
+(C25+C27+C29+C31+C33)/ C24+C26+C28+C30+C32+34}}
nd – Not determined
Fig. 7: m/z 74 mass chromatogram showing the
distribution of n-fatty acids in Mamu samples (Onyeama)
(Numbers refer to carbon chain lengths of n-fatty acids).
Fig. 7: (contd.): m/z 74 mass chromatogram showing the
distribution of n-fatty acids in Mamu samples (Onyeama)
(Numbers refer to carbon chain lengths of n-fatty acids).
Fig. 8: m/z 58 mass chromatograms showing the
distributions of alkan-2-ones in Mamu samples (Onyeama)
(Numbers refer to carbon chain lengths of alkan-2-ones).
CONCLUSION
Coal and coaly organic matter samples were collected
from coal bearing measures of Lower and Middle Benue
Trough, Nigeria. These samples were subjected to Gas
Chromatography and Gas Chromatography-Mass
Spectrometry analyses. The distributions of fatty acids and
n-alkan-2-ones showed that Awgu samples were formed
from organic matter derived from both terrestrial and
marine organic matter while Mamu samples were derived
from terrestrial organic matter.
7. Distribution of Possible Fatty Acids and Alkanones in some Thermally Immature Nigerian Coals
Int. Res. J. Chem. Chem. Sci. 109
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