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

2008, 24-27 November 2008, Miri, Sarawak, Malaysia Geochemistry and Diagenesis of Neo- Proterozoic limestones

Geochemistry and Diagenesis of Neo- Proterozoic limestones of Bhima Basin, Southern India

Ramasamy Nagarajan

Department of Applied Geology, School of Engineering and Science, Curtin University of Technology, 98009, Miri, Sarawak, Malaysia. Email: nagarajan@curtin.edu.my

Abstract: Geochemistry (Major, Trace elements, Stable isotopes (Carbon, Oxygen and 87 Sr/ 86 Sr) are reported for Limestones of Shahabad Formation, Bhima Basin, Karanataka, South India. The limestones show variation in geochemical and petrologic signatures according to the effects of diagenesis in the sedimentary system. Petrographically limestones of Shahabad Formation are micritic (calmicrite) and stylolites and pressure solution structures are present. Some of the pressure solution structures are related to horizontal compressional forces (probably resulting from tectonism). Terrigenous particles like quartz and feldspar occur as aggregates and lenses in the inter-laminar areas. Major and trace elements signatures are varying minimally, according to the lithological variations within the Shahabad Formation. A positive carbon and negative Oxygen isotopic signatures are recorded in the Shahabad limestone, in which most of the samples are similar to the average Precambrian carbonates. However, the more depleted values of oxygen (-5.76 to 12.93PDB ) and high concentration of 87 Sr/ 86 Sr (0.70699 to 0.7117) are clearly indicates that the isotopic signatures are altered due to diagenesis where as the effect of diagenesis on the trace and Rare Elements Elements are less. Two types of diagenetic processes are involved in this formation (early and late diagenesis) which has been confirmed by elements and isotope geochemistry. The terrigenous influx and the signature of REE in Neoproterozoic age is also clearly explained in this paper.

Keywords:

Geochemistry,

Neoproterozoic,

Limestones, Bhima basin, Southern India.

Raghavendra Nagendra

Department of Geology, Anna University, Chennai – 600 025, Tamil Nadu, India geonag@annauniv.edu

I.

INTRODUCTION

Study of bulk chemical composition of sedimentary rocks can be an effective tool to infer the factors that controlled sediment characteristics during and after their deposition. Bulk chemical composition of sedimentary rocks has been widely used to delineate specific units of clastic and carbonate strata (Premmer et al 1990). Chemical studies of ancient carbonate rocks have shown that their composition is facies controlled, and this is particularly for elements and isotopes associated with carbonate lattice (Veizer et al 1978). Such chemical criteria may only be of supplementary importance in Phanerozoic rocks with abundant biota, but they may be

indispensable for interpretation of unfossiliferous, particularly Precambrian carbonates. Furthermore, the knowledge of variations in chemical composition of particular facies will aid in the quantitative reconstruction of diagenetic history. Modification of trace element chemistry during diagenesis serves as an important clue to the lithification process. A carbon isotope variation in seawater is an important tool to understand Neoproterozoic environmental change

because of the anomalously high (and low) δ

values that have been reported from Neoproterozoic carbonate rocks (Knoll et al 1986, Kaufman et al 1997). In recent years, much work has been focused on constraining primary δ 13 C and δ 18 O values of Precambrian carbonate sequences in understanding depositional processes, evolution of the ocean-atmosphere 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

13

C

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

2008, 24-27 November 2008, Miri, Sarawak, Malaysia deposits, Shahabad Formation, Bhima basin,

deposits,

Shahabad

Formation,

Bhima

basin,

India.

II.

METHODOLOGY

Fresh samples were collected from the outcrops and the samples were washed thoroughly in distilled water to remove the contamination. The major, trace, and rare earth elements were analysed using an inductively coupled plasma atomic emission spectrometer (ICP-AES - Jobin- Yvon JY138 Ultrace) at the Department of Geochemistry, Ecole des Mines de Saint-Etienne, France. SiO 2 , Nb, Zr, and Th were analyzed by XRF method on pressed pellets. The analytical precision for trace and REE is better than 5%. For carbon and oxygen isotopic determinations, CO 2 was extracted from powdered carbonates in a high vacuum line after reaction with orthophosphoric acid at 25°C, and cryogenically cleaned, according to the method described by Craig (1957). CO 2 gas released by this method was analyzed for carbon and oxygen

isotopes in a double inlet, triple collector SIRA II mass spectrometer, using the reference gas BSC (Borborema Skarn Calcite), which calibrated against NBS-18, NBS-19, and NBS-20 has a value of -11.28 ±0.004 ‰PDB for δ 18 O and -8.58 ± 0.02 ‰PDB for δ 13 C. The results are expressed in the notation δ‰ (per mil) in relation to international PDB scale. Two representative samples were selected for Sr isotope analyses. Limestone samples were leached in 1 N ammonium acetate prior to acid digestion. Sr was separated in 2.5 M HCl using Bio-Rad AG50W X8 200-400 mesh cation exchange resin. Total procedure blank for Sr samples prepared with this method was <200 pg. For mass spectrometry, Sr samples were loaded onto single Ta fi laments with 1 N phosphoric acid. Sr samples were analyzed on a VG Sector 54-30 multiple collector

mass spectrometer. A

Sr intensity of 1V (1 ×

10−11A) ± 10% was maintained and the 87 Sr/ 86 Sr ratio was corrected for mass fractionation using 87 Sr/ 86 Sr = 0.1194 and an exponential law. The VG Sector 54-30 mass spectrometer was operated in the peak-jumping mode with data collected as 15 blocks of 10 ratios. For this instrument, NIST SRM987 gave a value of 0.710260 ± 11(1 SD, n

= 17). To facilitate comparison of Sr isotopic data from different laboratories we have adjusted the

Sr values of our limestone samples to NIST

SRM987 87 Sr/ 86 Sr of 0.710230, following the practice of the Max-Planck Institute, Mainz, Germany (see e.g., the data repository in Verma,

87 Sr/ 86

87

2002).

III. GEOLOGY OF THE AREA

The Bhima Basin, southern India is a NE-SW trending S-shaped Neoproterozoic, epicratonic, extensional basin formed due to gravity faulting. The epicratonic Mesoproterozoic Kaladgi sugergroup and Neoproterozoic Bhima Group overlie the Archean granite-greenstone basement in Karnataka, southern India. The Archean granite-greenstone terrain mainly consists of TTG (tonalite-tronjhemite-gneiss) popularly known as Peninsular gneisses (Dharwar greenstone belts). The cratonization of the Archean province occurred ~ 2.5 Ga ago accompanied by the emplacement of K-rich granitoids (Closepet granite; Jayananda et al., 1995). The Mesoproterozoic sedimentary rocks of Kaladgi supergroup and Neoproterozoic Bhima Group were deposited on the eroded edges of the Dharwar Craton (Senthil Kumar and Srinivasan, 2002). The sedimentary rocks of Bhima basin and the granitoids have been affected by intense faulting. Major faults across the basin define the structural boundaries of the different sectors (Kale and Peshwa, 1995). They are (1) East-West trending Tirth, Gogi and Mogalavadikavagu faults, and (2) NW-SE trending Wadi fault. Due to the effect of the E-W trend faults, the limestone of the middle part of the basin directly rests on granites. The sedimentary rocks are trending in the NE-SW direction, and exhibit a total thickness of about 300 m (Misra et al., 1987). These sedimentary rocks mainly comprise an alternating sequence of clastic and carbonate rocks (Janardhana Rao et al. 1975; Misra et al., 1987; Kale, 1990; Kale et al., 1990). In the clastic rocks, fine-grained sediments dominate over the coarse clastics. The sedimentary rocks of Bhima Basin have been divided into five distinct formations i.e. (i) Rabanpalli Formation, (ii) Shahabad Formation, (iii) Halkal Shale, (iv) Katamadevarhalli Formation and (v) Harwal Shale (Janardhana Rao et al. 1975). It comprises an alternating sequence of terrigenous and carbonate sediments. In the terrigenous unit, fine- grained sediments dominate over coarse-grained sediments (Kale et al. 1990). The Rabanpalli Formation has been considered as the oldest sedimentary rocks in the Bhima basin that deposited over the Archean basement which is mainly consists of quartz arenites, arkoses, siltstones, and greenish yellow shale (Nagarajan 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

2008, 24-27 November 2008, Miri, Sarawak, Malaysia Figure 1. Geology map of Bhima basin IV. R
2008, 24-27 November 2008, Miri, Sarawak, Malaysia Figure 1. Geology map of Bhima basin IV. R

Figure 1.

Geology map of Bhima basin

IV. RESULTS AND DISCUSSION

A. Petrography

Petrographically limestones of Shahabad Formation are micritic (calmicrite) and stylolites and pressure solution structures are present. Some of the pressure solution structures are related to horizontal compressional forces (probably resulting from tectonism (fig.2). Terrigenous particles like quartz and feldspar occur as aggregates and lenses in the inter-laminar areas.

occur as aggregates and lenses in the inter-laminar areas. Figure 2. Thin-section microphotograph of Shahabad

Figure 2. Thin-section microphotograph of Shahabad limestone shows the Microstylolites.

B. Geochemistry

The results (minimum, maximum, mean and standard deviation) of major (in wt. %), trace elements (in ppm), strontium isotopes, and

carbon and oxygen isotopes (‰) for the Shahabad limestones are presented in Table 1.

GEOCHEMICAL ELEMENTS

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

TABLE I.

THE

 

Min

Max

Mean

StD

SiO 2

9.12

33.90

17.60

5.85

TiO 2

0.03

0.18

0.10

0.04

Al 2 O 3

0.69

4.42

2.33

1.08

Fe 2 O 3

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

Na

2 O

0.03

0.19

0.11

0.05

K

2 O

0.18

1.03

0.54

0.26

P

2 O 5

0.07

0.73

0.17

0.15

Mn

14.50

488.00

283.61

105.60

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

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

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

Cu

1.19

10.40

5.05

2.64

Zn

9.26

32.90

18.71

7.33

Ga

1.10

15.50

4.39

2.79

Pb

0.00

26.10

4.33

6.81

Co

0.00

8.50

2.97

1.94

Y

6.57

19.70

11.13

3.43

1)

Major Oxides and trace elements

All the samples show high concentration of CaO than other elements followed by SiO 2 . High concentration of SiO 2 is encountered in the peripheral areas of the basin and the SiO 2 content decreases approximately towards the central portion of the basin. The high SiO 2 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 TiO 2 , Al 2 O 3 and K 2 O. The terrigenous influx into system is indicated by factor 1 on the principal component analysis. Factor 1 is highly loaded with the variance of 41.28% followed by factor 2 (21.48%) and factor 3 (11.07%) table 2. Al 2 O 3 shows positive correlation with TiO 2 , Fe 2 O 3 , K 2 O, Mn, Sc, V, Cr, Ni, and Cu which are loaded in factor 1. This perfect correlation of these elements suggests the terrigenous influx in to 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

2008, 24-27 November 2008, Miri, Sarawak, Malaysia factor 2. SiO 2 , P 2 O 5

factor 2. SiO 2 , P 2 O 5 , Cu, Zn, Co, and Y are loaded in Factor 3 and show good correlation within them which indicates the influence of diagenesis in the system.

TABLE II. RESULTS OF PRINCIPAL COMPONENT ANALYSIS (VARIMAX AND KAISER NORMALISATION) FOR SHAHABAD LIMESTONES OF BHIMA BASIN (N=25).

 

Factor 1

Factor 2

Factor 3

SiO 2

0.03

-0.08

0.91

TiO 2

0.96

-0.01

0.21

Al 2 O 3

0.97

0.02

0.19

Fe 2 O 3

0.93

-0.04

0.17

CaO

-0.38

0.25

-0.84

MgO

0.75

-0.16

0.08

Na 2 O

0.69

-0.21

0.02

K

2 O

0.95

0.04

0.24

P

2 O 5

-0.38

-0.22

0.79

Mn

0.61

0.00

-0.20

Sr

0.09

-0.23

0.00

Rb

-0.01

0.62

-0.10

Ba

0.28

-0.33

-0.24

Zr

-0.04

0.94

-0.11

Nb

-0.02

0.94

-0.07

Th

0.00

0.95

-0.16

U

-0.12

0.74

-0.16

Sc

0.94

0.03

0.19

V

0.97

0.01

0.15

Cr

0.96

-0.02

0.06

Ni

0.95

0.06

0.15

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

Co

0.46

0.17

0.56

Y

0.36

-0.27

0.70

2)

Rare Earth Elements

Shahabad limestones have consistent seawater like shale normalized REE+Y pattern (Fig.) 3. LREE depletion (average Nd SN /Yb SN = 0.64+0.08 (Present study); Nd SN /Yb SN of modern shallow seawater = 0.205 to 0.497 for 50m water depth samples; Zhang and Nozaki, 1996; de Baar et al., 1985 respectively); 2. Consistent negative Ce SN and positive La SN anomalies; 3. consistent positive Gd SN anomalies (average 1.05+0.16 (Present study); Gd SN /Gd* of modern shallow seawater 1.30 to 1.05 from the data of de Baar et al., 1985 and Zhang and Nozaki, 1998 respectively); 4. Super chondritic Y/Ho ratio (average Y/Ho = 38.13+21.35; Y/Ho of seawater 44-74 Bau 1996). Negative Ce anomalies on shale normalised, REE variation diagrams in two samples with very low REE contents suggest a marine influence on the REE distribution. Differences in ΣREE content among individual samples are mainly related to variations in the amount of terrigenous sediment included in these limestone samples. In Shale normalized REE

plots (Fig.3), the limestone samples from Shahabad Formation show LREE depletion and slight enrichment in HREE with negative Ce anomaly and positive Eu anomaly. Positive correlation of ∑REE with Al (R = 0.912) and negative correlation of ∑REE with Ca (R= - 0.642) implies that the presence of terrigenous fraction is also the possible source for REE in these limestones. The terrigenous source of REE is further confirmed by the strong positive correlation of ∑REE with Fe Ni, Cr, Sc, Y and Zr. Among the REE group, the LREE show a stronger positive correlation with terrigenous elements like Al, Fe, Ti, Mg and Zr compared to middle REE (MREE) and heavy REE (HREE). The negative Ce anomaly reflects the incorporation of REE directly from seawater or pore water under oxic condition. This also implies the mixing of two-component systems with terrigenous clay (detrital) in the marine sediments.

E81 S-26 S56C S-38 S-17 S57 10 1 0.1 0.01 Element/PASS La Pr Sm Gd
E81
S-26
S56C
S-38
S-17
S57
10
1
0.1
0.01
Element/PASS
La
Pr
Sm
Gd
Dy
Ho
Tm
Lu

Figure 3. Post-Archean Average Shale (PASS) normalized REE pattern of the limestone of Shahabad Formation.

Positive Eu anomalies are uncommon in seawater, which are generally results of input from hydrothermal discharges along mid-ocean ridges (Klinkhammer et al., 1983, 1994). Significant negative or positive Eu anomalies

may occur in crustal rocks, which are mainly as an effect of intracrustal fractionation separating granitic melts from residues containing feldspar,

which is the major host of Eu

by Elderfield and Sholkovitz (1987), and MacRac et al. (1992) have shown that sediments can attain the positive Eu anomaly within a time span of 10,000 – 12,000 yr of diagenetic history using the porewater REE data of Buzzards Bay sediments. These sediments show positive Eu anomaly ranges of 1.24 to 1.26 in the samples taken closest to the shore, which owing to dominantly terrestrial source (Nath et al., 1997). The Shahabad limestone samples display a range of

2+

in rocks. Studies

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

2008, 24-27 November 2008, Miri, Sarawak, Malaysia Eu (Eu/Eu*) anomaly mostly with low to moderate positive

Eu (Eu/Eu*) anomaly mostly with low to moderate positive values, (normalized by PAAS values) which indicates that this positive anomaly is due to presence of detrital feldspar in the carbonates.

3)

Stable and Radiogenic isotopes

δ 13 C excursions studied worldwide imply that the oceanic environment has affected the carbon reservoir in a basin or on a global scale. Variations in the carbon isotopes of limestones and co-occurring organic matter record secular changes in the burial rate of the carbon phases with increasing δ 13 C values (Hayes, 1993). Post- depositional thermal alteration of organic matter often preserves primary carbon isotopic signatures in carbonate phases (Kah et al., 1999). Therefore, ancient carbonates commonly retain their primary carbon isotopic compositions (Knoll et al., 1995; Nagarajan et al., 2008). The variations of δ 13 C (+3.5 to – 1.38PDB ), in limestones of Shahabad formation is related to the environmental oscillations during late Neoproterozoic age.

The range of moderately depleted δ 18 O values

in most limestones is supportive of cementation under mainly burial and/or meteoric conditions rather than by syn-sedimentary marine cements as in many tropical carbonate deposits. The

depletion in

carbonates, commonly ascribed to post- depositional isotope exchange with meteoric waters (Clayton and Degens, 1959), also holds in

the case of many Proterozoic carbonate formations (Nagarajan et al., 2008). The 18 O signature shows a significant variation in their concentration ranging between -5.76 to 12.93PDB. However a cluster of the samples resembles the concentration of the average

Precambrian carbonates. The 87 Sr/

composition of seawater has been considered as a powerful tool for making correlations and indirect

age assignment, reconstruction of global

tectonics, and tracing diagenetic processes

(Banner, 2004; Halverson et al., 2007).

of the modern ocean (0.7092) generally indicates a combination of hydrothermal alteration of the oceanic crust (~0.7035) and input from continental weathering (0.7120; Edmond, 1992). However, the more depleted values of oxygen (- 5.76 to 12.93PDB ) and high concentration of 87 Sr/ 86 Sr (0.70699 to 0.7117) are clearly indicates that the isotopic signatures are altered due to diagenesis.

18

O observed in geologically older

86

Sr

87

Sr/ 86 Sr

V.

CONCLUSIONS

The overall studies have clearly indicated the effect of terrigenous influx and diagenesis in the Neoproterozoic sedimentary basin of Southern India. The limestones of Shahabad formation is affected diagenesis (post and late). The limestones are retaining the original geochemical signatures which are comparable with global Neoproterzoic basins.

ACKNOWLEDGEMENT

The authors thank Dr. Moutte, Dr. A.N. Sial, Dr. Rob Ellam for their assistance in chemical analyses. This study was greatly improved by Prof. R.L. Cullers, Prof. S.P. Verma, Dr. J. Madhavaraju and Dr. J. S. Armstrong-Altrin from critical reviews.

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