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CUTSE International Conference 2008, 24-27 November 2008, Miri, Sarawak, Malaysia

Geochemistry and Diagenesis of Neo-


Proterozoic limestones of Bhima Basin,
Southern India

Ramasamy Nagarajan Raghavendra Nagendra


Department of Applied Geology, School of Department of Geology, Anna University,
Engineering and Science, Curtin University of Chennai – 600 025, Tamil Nadu, India
Technology, 98009, Miri, Sarawak, Malaysia. geonag@annauniv.edu
Email: nagarajan@curtin.edu.my

Abstract: Geochemistry (Major, Trace elements,


Stable isotopes (Carbon, Oxygen and 87Sr/86Sr) are I. INTRODUCTION
reported for Limestones of Shahabad Formation,
Bhima Basin, Karanataka, South India. The Study of bulk chemical composition of
limestones show variation in geochemical and
sedimentary rocks can be an effective tool to infer
petrologic signatures according to the effects of
diagenesis in the sedimentary system.
the factors that controlled sediment
Petrographically limestones of Shahabad characteristics during and after their deposition.
Formation are micritic (calmicrite) and stylolites Bulk chemical composition of sedimentary rocks
and pressure solution structures are present. Some has been widely used to delineate specific units of
of the pressure solution structures are related to clastic and carbonate strata (Premmer et al 1990).
horizontal compressional forces (probably Chemical studies of ancient carbonate rocks have
resulting from tectonism). Terrigenous particles shown that their composition is facies controlled,
like quartz and feldspar occur as aggregates and and this is particularly for elements and isotopes
lenses in the inter-laminar areas. Major and trace associated with carbonate lattice (Veizer et al
elements signatures are varying minimally, 1978). Such chemical criteria may only be of
according to the lithological variations within the supplementary importance in Phanerozoic rocks
Shahabad Formation. A positive carbon and with abundant biota, but they may be
negative Oxygen isotopic signatures are recorded indispensable for interpretation of unfossiliferous,
in the Shahabad limestone, in which most of the particularly Precambrian carbonates.
samples are similar to the average Precambrian Furthermore, the knowledge of variations in
carbonates. However, the more depleted values of chemical composition of particular facies will aid
oxygen (-5.76 to 12.93‰PDB) and high in the quantitative reconstruction of diagenetic
concentration of 87Sr/86Sr (0.70699 to 0.7117) are
history. Modification of trace element chemistry
clearly indicates that the isotopic signatures are
during diagenesis serves as an important clue to
altered due to diagenesis where as the effect of
diagenesis on the trace and Rare Elements the lithification process. A carbon isotope
Elements are less. Two types of diagenetic variation in seawater is an important tool to
processes are involved in this formation (early and understand Neoproterozoic environmental change
late diagenesis) which has been confirmed by because of the anomalously high (and low) δ 13C
elements and isotope geochemistry. The values that have been reported from
terrigenous influx and the signature of REE in Neoproterozoic carbonate rocks (Knoll et al
Neoproterozoic age is also clearly explained in this 1986, Kaufman et al 1997). In recent years, much
paper. work has been focused on constraining primary
δ13C and δ18O values of Precambrian carbonate
sequences in understanding depositional
Keywords: Geochemistry, Neoproterozoic, processes, evolution of the ocean-atmosphere
Limestones, Bhima basin, Southern India. system and interactions of biotic and abiotic
processes during the earth’s history (Burdett et al
1990, Knoll et al 1995). This paper is focused on
the geochemistry and diagenesis of limestone
CUTSE International Conference 2008, 24-27 November 2008, Miri, Sarawak, Malaysia

deposits, Shahabad Formation, Bhima basin,


India.
III. GEOLOGY OF THE AREA
II. METHODOLOGY
Fresh samples were collected from the The Bhima Basin, southern India is a NE-SW
outcrops and the samples were washed trending S-shaped Neoproterozoic, epicratonic,
thoroughly in distilled water to remove the extensional basin formed due to gravity faulting.
contamination. The major, trace, and rare earth The epicratonic Mesoproterozoic Kaladgi
elements were analysed using an inductively sugergroup and Neoproterozoic Bhima Group
coupled plasma atomic emission spectrometer overlie the Archean granite-greenstone basement
(ICP-AES - Jobin- Yvon JY138 Ultrace) at the in Karnataka, southern India. The Archean
Department of Geochemistry, Ecole des Mines de granite-greenstone terrain mainly consists of TTG
Saint-Etienne, France. SiO2, Nb, Zr, and Th were (tonalite-tronjhemite-gneiss) popularly known as
analyzed by XRF method on pressed pellets. The Peninsular gneisses (Dharwar greenstone belts).
analytical precision for trace and REE is better The cratonization of the Archean province
than 5%. For carbon and oxygen isotopic occurred ~ 2.5 Ga ago accompanied by the
determinations, CO2 was extracted from emplacement of K-rich granitoids (Closepet
powdered carbonates in a high vacuum line after granite; Jayananda et al., 1995). The
reaction with orthophosphoric acid at 25°C, and Mesoproterozoic sedimentary rocks of Kaladgi
cryogenically cleaned, according to the method supergroup and Neoproterozoic Bhima Group
described by Craig (1957). CO2 gas released by were deposited on the eroded edges of the
this method was analyzed for carbon and oxygen Dharwar Craton (Senthil Kumar and Srinivasan,
isotopes in a double inlet, triple collector SIRA II 2002). The sedimentary rocks of Bhima basin and
mass spectrometer, using the reference gas BSC the granitoids have been affected by intense
(Borborema Skarn Calcite), which calibrated faulting. Major faults across the basin define the
against NBS-18, NBS-19, and NBS-20 has a structural boundaries of the different sectors
value of -11.28 ±0.004 ‰PDB for δ18O and -8.58 (Kale and Peshwa, 1995). They are (1) East-West
± 0.02 ‰PDB for δ13C. The results are expressed trending Tirth, Gogi and Mogalavadikavagu
in the notation δ‰ (per mil) in relation to faults, and (2) NW-SE trending Wadi fault. Due
international PDB scale. Two representative to the effect of the E-W trend faults, the
samples were selected for Sr isotope analyses. limestone of the middle part of the basin directly
Limestone samples were leached in 1 N rests on granites. The sedimentary rocks are
ammonium acetate prior to acid digestion. Sr was trending in the NE-SW direction, and exhibit a
separated in 2.5 M HCl using Bio-Rad AG50W total thickness of about 300 m (Misra et al.,
X8 200-400 mesh cation exchange resin. Total 1987). These sedimentary rocks mainly comprise
procedure blank for Sr samples prepared with this an alternating sequence of clastic and carbonate
method was <200 pg. For mass spectrometry, Sr rocks (Janardhana Rao et al. 1975; Misra et al.,
samples were loaded onto single Ta fi laments 1987; Kale, 1990; Kale et al., 1990). In the clastic
with 1 N phosphoric acid. Sr samples were rocks, fine-grained sediments dominate over the
analyzed on a VG Sector 54-30 multiple collector coarse clastics. The sedimentary rocks of Bhima
mass spectrometer. A 87Sr intensity of 1V (1 × Basin have been divided into five distinct
10−11A) ± 10% was maintained and the 87Sr/86Sr formations i.e. (i) Rabanpalli Formation, (ii)
ratio was corrected for mass fractionation using Shahabad Formation, (iii) Halkal Shale, (iv)
87
Sr/86Sr = 0.1194 and an exponential law. The Katamadevarhalli Formation and (v) Harwal
VG Sector 54-30 mass spectrometer was operated Shale (Janardhana Rao et al. 1975). It comprises
in the peak-jumping mode with data collected as an alternating sequence of terrigenous and
15 blocks of 10 ratios. For this instrument, NIST carbonate sediments. In the terrigenous unit, fine-
SRM987 gave a value of 0.710260 ± 11(1 SD, n grained sediments dominate over coarse-grained
= 17). To facilitate comparison of Sr isotopic data sediments (Kale et al. 1990). The Rabanpalli
from different laboratories we have adjusted the Formation has been considered as the oldest
87
Sr/86Sr values of our limestone samples to NIST sedimentary rocks in the Bhima basin that
SRM987 87Sr/86Sr of 0.710230, following the deposited over the Archean basement which is
practice of the Max-Planck Institute, Mainz, mainly consists of quartz arenites, arkoses,
Germany (see e.g., the data repository in Verma, siltstones, and greenish yellow shale (Nagarajan
2002). et al., 2007a,b). Harwal shale is the youngest
formation of the Bhima Group, which is overlain
by Deccan Trap with intratrappean sediments.
CUTSE International Conference 2008, 24-27 November 2008, Miri, Sarawak, Malaysia

carbon and oxygen isotopes (‰) for the


Shahabad limestones are presented in Table 1.

TABLE I. THE GEOCHEMICAL ELEMENTS


CONCENTRATIONS (MINIMUM, MAXIMUM, MEAN AND
STANDARD DEVIATION) OF SHAHABAD LIMESTONES (N=25)

Min Max Mean StD


SiO2 9.12 33.90 17.60 5.85
TiO2 0.03 0.18 0.10 0.04
Al2O3 0.69 4.42 2.33 1.08
Fe2O3 0.27 1.95 0.82 0.41
CaO 28.40 49.00 40.93 4.35
MgO 0.23 0.85 0.47 0.17
Na2O 0.03 0.19 0.11 0.05
K2O 0.18 1.03 0.54 0.26
P2O5 0.07 0.73 0.17 0.15
Mn 14.50 488.00 283.61 105.60
Figure 1. Geology map of Bhima basin Sr 102.00 349.00 157.50 51.94
Rb 4.00 173.00 33.75 40.52
Ba 56.70 3565.00 565.17 912.48
Zr 5.45 180.00 27.92 35.21
Nb 0.51 13.10 1.99 2.60
IV. RESULTS AND DISCUSSION
Th 0.00 16.60 2.96 3.28
U 2.15 6.52 3.78 0.98
Sc 0.85 4.41 2.53 0.98
A. Petrography V 3.30 19.80 10.64 4.74
Cr 2.64 21.20 10.09 5.31
Ni 1.80 10.60 5.77 2.88
Petrographically limestones of Shahabad Cu 1.19 10.40 5.05 2.64
Formation are micritic (calmicrite) and stylolites Zn 9.26 32.90 18.71 7.33
and pressure solution structures are present. Some Ga 1.10 15.50 4.39 2.79
of the pressure solution structures are related to Pb 0.00 26.10 4.33 6.81
horizontal compressional forces (probably Co 0.00 8.50 2.97 1.94
resulting from tectonism (fig.2). Terrigenous Y 6.57 19.70 11.13 3.43
particles like quartz and feldspar occur as
aggregates and lenses in the inter-laminar areas.
1) Major Oxides and trace elements

All the samples show high concentration of


CaO than other elements followed by SiO2. High
concentration of SiO2 is encountered in the
peripheral areas of the basin and the SiO2 content
decreases approximately towards the central
portion of the basin. The high SiO2 content in the
peripheral areas may be due to terrigenous influx
and silicification processes in these limestones.
The major and trace elements show their total
contribution about 73.84% in the principal
component analysis. CaO exhibits negative
correlation with negative correlation with TiO2,
Al2O3 and K2O. The terrigenous influx into
system is indicated by factor 1 on the principal
Figure 2. Thin-section microphotograph of Shahabad component analysis. Factor 1 is highly loaded
limestone shows the Microstylolites. with the variance of 41.28% followed by factor 2
(21.48%) and factor 3 (11.07%) table 2. Al2O3
B. Geochemistry shows positive correlation with TiO2, Fe2O3,
K2O, Mn, Sc, V, Cr, Ni, and Cu which are loaded
The results (minimum, maximum, mean and in factor 1. This perfect correlation of these
standard deviation) of major (in wt. %), trace elements suggests the terrigenous influx in to
elements (in ppm), strontium isotopes, and system Rb, Zr, Nb, Th, U, Ga and Pb show
positive correlation between them and loaded in
CUTSE International Conference 2008, 24-27 November 2008, Miri, Sarawak, Malaysia

factor 2. SiO2, P2O5, Cu, Zn, Co, and Y are plots (Fig.3), the limestone samples from
loaded in Factor 3 and show good correlation Shahabad Formation show LREE depletion and
within them which indicates the influence of slight enrichment in HREE with negative Ce
diagenesis in the system. anomaly and positive Eu anomaly. Positive
correlation of ∑REE with Al (R = 0.912) and
TABLE II. RESULTS OF PRINCIPAL COMPONENT
negative correlation of ∑REE with Ca (R= -
ANALYSIS (VARIMAX AND KAISER NORMALISATION) FOR 0.642) implies that the presence of terrigenous
SHAHABAD LIMESTONES OF BHIMA BASIN (N=25). fraction is also the possible source for REE in
Factor 1 Factor 2 Factor 3
these limestones. The terrigenous source of REE
SiO2 0.03 -0.08 0.91 is further confirmed by the strong positive
TiO2 0.96 -0.01 0.21 correlation of ∑REE with Fe Ni, Cr, Sc, Y and
Al2O3 0.97 0.02 0.19 Zr. Among the REE group, the LREE show a
Fe2O3 0.93 -0.04 0.17 stronger positive correlation with terrigenous
CaO -0.38 0.25 -0.84 elements like Al, Fe, Ti, Mg and Zr compared to
MgO 0.75 -0.16 0.08 middle REE (MREE) and heavy REE (HREE).
Na2O 0.69 -0.21 0.02 The negative Ce anomaly reflects the
K2O 0.95 0.04 0.24
P2O5 -0.38 -0.22 0.79
incorporation of REE directly from seawater or
Mn 0.61 0.00 -0.20 pore water under oxic condition. This also
Sr 0.09 -0.23 0.00 implies the mixing of two-component systems
Rb -0.01 0.62 -0.10 with terrigenous clay (detrital) in the marine
Ba 0.28 -0.33 -0.24 sediments.
Zr -0.04 0.94 -0.11
Nb -0.02 0.94 -0.07 E81 S-26 S56C
Th 0.00 0.95 -0.16
U -0.12 0.74 -0.16 S-38 S-17 S57
Sc 0.94 0.03 0.19 10
V 0.97 0.01 0.15
Cr 0.96 -0.02 0.06
Element/PASS

Ni 0.95 0.06 0.15 1


Cu 0.62 -0.10 0.53
Zn 0.56 0.03 0.73
Ga 0.11 0.95 -0.12
Tb 0.21 0.76 0.09 0.1
Co 0.46 0.17 0.56
Y 0.36 -0.27 0.70
0.01

Tm
Sm

Gd

Ho
Pr

Dy
La

Lu
2) Rare Earth Elements
Figure 3. Post-Archean Average Shale (PASS) normalized
Shahabad limestones have consistent seawater REE pattern of the limestone of Shahabad Formation.
like shale normalized REE+Y pattern (Fig.) 3.
LREE depletion (average NdSN/YbSN = 0.64+0.08
(Present study); NdSN/YbSN of modern shallow Positive Eu anomalies are uncommon in
seawater = 0.205 to 0.497 for 50m water depth seawater, which are generally results of input
samples; Zhang and Nozaki, 1996; de Baar et al., from hydrothermal discharges along mid-ocean
1985 respectively); 2. Consistent negative CeSN ridges (Klinkhammer et al., 1983, 1994).
and positive LaSN anomalies; 3. consistent Significant negative or positive Eu anomalies
positive GdSN anomalies (average 1.05+0.16 may occur in crustal rocks, which are mainly as
(Present study); GdSN/Gd* of modern shallow an effect of intracrustal fractionation separating
seawater 1.30 to 1.05 from the data of de Baar et granitic melts from residues containing feldspar,
al., 1985 and Zhang and Nozaki, 1998 which is the major host of Eu2+ in rocks. Studies
respectively); 4. Super chondritic Y/Ho ratio by Elderfield and Sholkovitz (1987), and MacRac
(average Y/Ho = 38.13+21.35; Y/Ho of seawater et al. (1992) have shown that sediments can attain
44-74 Bau 1996). Negative Ce anomalies on the positive Eu anomaly within a time span of
shale normalised, REE variation diagrams in two 10,000 – 12,000 yr of diagenetic history using the
samples with very low REE contents suggest a porewater REE data of Buzzards Bay sediments.
marine influence on the REE distribution. These sediments show positive Eu anomaly
Differences in ΣREE content among individual ranges of 1.24 to 1.26 in the samples taken
samples are mainly related to variations in the closest to the shore, which owing to dominantly
amount of terrigenous sediment included in these terrestrial source (Nath et al., 1997). The
limestone samples. In Shale normalized REE Shahabad limestone samples display a range of
CUTSE International Conference 2008, 24-27 November 2008, Miri, Sarawak, Malaysia

Eu (Eu/Eu*) anomaly mostly with low to V. CONCLUSIONS


moderate positive values, (normalized by PAAS
values) which indicates that this positive anomaly
The overall studies have clearly indicated the
is due to presence of detrital feldspar in the
carbonates. effect of terrigenous influx and diagenesis in the
Neoproterozoic sedimentary basin of Southern
India. The limestones of Shahabad formation is
3) Stable and Radiogenic isotopes affected diagenesis (post and late). The
limestones are retaining the original geochemical
δ13C excursions studied worldwide imply that signatures which are comparable with global
the oceanic environment has affected the carbon Neoproterzoic basins.
reservoir in a basin or on a global scale.
Variations in the carbon isotopes of limestones ACKNOWLEDGEMENT
and co-occurring organic matter record secular The authors thank Dr. Moutte, Dr. A.N. Sial,
changes in the burial rate of the carbon phases Dr. Rob Ellam for their assistance in chemical
with increasing δ13C values (Hayes, 1993). Post- analyses. This study was greatly improved by
depositional thermal alteration of organic matter Prof. R.L. Cullers, Prof. S.P. Verma, Dr. J.
often preserves primary carbon isotopic Madhavaraju and Dr. J. S. Armstrong-Altrin from
signatures in carbonate phases (Kah et al., 1999). critical reviews.
Therefore, ancient carbonates commonly retain
their primary carbon isotopic compositions
(Knoll et al., 1995; Nagarajan et al., 2008). The
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