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Carbon, oxygen, and strontium isotope geochemistry of carbonate rocks

of the upper Miocene Kudankulam Formation, southern India:
Implications for paleoenvironment and diagenesis
John S. Armstrong-Altrina,1, Yong Il Leeb, Surendra P. Vermaa,, Richard H. Wordenc
a
Departamento de Sistemas Energéticos, Centro de Investigación en Energı´a, Universidad Nacional Autónoma de México (UNAM),
Priv. Xochicalco S/No., Col. Centro, Apartado Postal 34, Temixco, Mor. 62580, Mexico
b
School of Earth and Environmental Sciences, Seoul National University, Seoul 151-747, South Korea
c
Department of Earth and Ocean Sciences, University of Liverpool, Liverpool L69 3GP, UK

Received 6 September 2007; accepted 27 August 2008

Abstract
The carbon, oxygen, and strontium isotope compositions of carbonate rocks from the upper Miocene Kudankulam
Formation, southern India, were measured to understand palaeoenvironment and carbonate diagenesis of this
formation. Both carbon and oxygen isotope ratios of various carbonate phases including whole rocks, ooids,
molluscan mold-fill and sparry pore-fill calcite cements are depleted in 18O and 13C compared to those of
contemporaneous seawater, indicating that the Kudankulam carbonates underwent extensive meteoric diagenesis.
Based on d13C and d18O values for sparry calcite cements (pore-fill and molluscan mold-fill) formed in the meteoric
diagenetic realm (d13C from 7.8% to 6.0% and 9.0% to 7.0%; d18O from 9.2% to 6.5% and 9.4% to
2.6%, respectively), it is interpreted that the diagenetic system was open and was proximal to the vadose water
recharge zone. The negative d18O values of various carbonate components (about 9.4% to 4.1% for whole rocks;
about 8.4% to 2.6% for ooids) suggest that during the late Miocene the paleoclimate of the study area was humid,
unlike today, probably due to the intense Indian monsoon system. The carbon isotope compositions (7.9% to 3.6%
for whole rocks; 4.9% to 1.5% for ooids) are consistent with the interpretation that the paleo-ecosystem comprised
a significant proportion of C4 type plants, supporting a scenario of expansion of C4 plants during the late Miocene in
the Indian subcontinent as far south as the southern tip of India. The 87Sr/86Sr ratios of the Kudankulam carbonates
(0.70920 to 0.72130) are much greater than those of the contemporaneous or modern seawater (between 0.7089 and
0.7091) and show a general decrease up-sequence. Such high Sr isotope ratios indicate significant radiogenic 87Sr influx
to the system from the Archean rocks exposed in the drainage area, implying that the deep-seated Archean rocks were
already exposed in southern India by the late Miocene.
r 2008 Elsevier GmbH. All rights reserved.

Keywords: Stable isotopes; Limestone; Petrography; Palaeovegetation

Corresponding author. Tel.: +52 55 56229745; fax: +52 55 56229766.

E-mail address: spv@cie.unam.mx (S.P. Verma).
1
Present address: Área Académica de Ciencias de la Tierra y Materiales, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria,
Carretera Pachuca-Tulancinco Km. 4.5, Pachuca, Hidalgo 42184, Mexico.

0009-2819/$ - see front matter r 2008 Elsevier GmbH. All rights reserved.
doi:10.1016/j.chemer.2008.09.002
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1. Introduction
The diagenesis of carbonate sediments encompasses
all the processes that affect the sediments after deposi-
tion up to the realms of metamorphism at elevated
temperatures and pressures (Moore, 2001). When
carbonate sediments undergo shallow to intermediate
burial diagenesis, meteoric diagenetic pathways are
important for major diagenetic changes (Land, 1986).
Carbon and oxygen isotopes are widely used to
identify the diagenetic environment and processes. In
combination with petrographic information, stable
isotope compositions of carbonate rocks may prove to
be useful in tracing fluid origin and in reconstructing
large-scale movements and evolution of fluids (e.g.,
Allan and Matthews, 1982; Budd and Land, 1990).
Allan and Matthews (1977, 1982) documented the
influence of plant-derived CO2 on the carbon isotope
composition of carbonate during sub-aerial diagenesis
of both modern and ancient limestones. Furthermore, it
has been demonstrated in several studies that the stable
isotope composition of different carbonate components
may reflect the temperature of formation (e.g., Ali, 1995;
Coniglio et al., 2000), source of carbonate (Hudson,
1977; Gao et al., 1996; Kumar et al., 2002; Poulson and
John, 2003), and/or paleoclimate (Quade and Cerling,
1995; Latorre et al., 1997; Srivastava, 2001; Scott, 2002).
The late Miocene (8–6 Ma) was a critical time for the
expansion of C4 plants. In the Indian subcontinent, the
C4 plant expansion has been well documented in
Pakistan (Quade et al., 1989; Quade and Cerling,
1995), Nepal (Quade et al., 1995), Bengal Fan
(France-Lanord and Derry, 1994), and as well as in
southern India (Rajagopalan et al., 1999). These studies
indicate the rapid expansion of C4 plants at the end of
the Miocene, starting 8–7 million years ago. Grasses
that utilize the C4 photosynthetic pathway are wide-
spread today in tropical and temperate latitudes,
especially where there is a significant summer rainfall
and a mid-summer temperature minimum of 48 1C
(Latorre et al., 1997; Rajagopalan et al., 1999; Scott,
2002). The late Miocene expansion of C4 plants has been
explained by either declining pCO2 levels or climate
change, such as an increase in summer-dominated
rainfall regimes (Quade et al., 1989; Ehleringer et al.,
1991; Cerling et al., 1993; France-Lanord and Derry,
1994; Latorre et al., 1997; Andrews et al., 1998).
However, more recent data provide no evidence of
declining pCO2 in the late Miocene, which suggests that
the late Miocene radiation of C4 plants around the globe
resulted from increasing seasonality and aridity (Pagani
et al., 1999) or global cooling (Fox and Koch, 2003).
Strontium isotopes can be used to characterize the
origin of strontium in carbonate rocks because such
rocks will generally record the 87Sr/86Sr of the source
waters (seawater as well as groundwater or meteoric
water) at the time of deposition as well as during
diagenesis (Burke et al., 1982; Faure, 1986; Marshall,
1992; Banner, 1995; Price and Gröcke, 2002). If the
87
Sr/86Sr of the present carbonate rocks is significantly
different from that of the contemporaneous seawater,
the carbonates should have been altered by waters
containing 87Sr/86Sr derived from outside the carbonate
unit (Burke et al., 1982; Faure, 1986; Gao et al., 1996).
Thus, strontium isotopes can be used to trace the source
waters.
In the southernmost tip of India, upper Miocene
shallow marine carbonates and associated siliciclastic
rocks (Kudankulam Formation) are narrowly distrib-
uted (Fig. 1). The Kudankulam carbonates may provide
information on the development of coastal aquifer and
paleoecology in the drainage area. The objectives of this
study are to characterize the stable carbon and oxygen
isotope compositions of the Kudankulam carbonates, to
test the hypothesis of C4 plant expansion in the southern
Indian subcontinent during the late Miocene as far
south as the southern tip of India, and to examine the
hypothesis on the neotectonic activity in southern India
using Sr isotope compositions.
2. Geologic background
In the southern part of Peninsular India, the exposed
rocks are gneisses and charnockites of Archean age
(Condie et al., 1986; Jayananda et al., 1995, 2000) as
well as recent alluvium (Fig. 1). Small limestone deposits
indicating marine influence during the formation of the
southern part of India have also been discovered
(Bruckner, 1988). These deposits have been called the
Kudankulam Formation, which crops out 20 km NE of
Kanniyakumari, near the Kudankulam village (Fig. 2).
The sediments are exposed in stream sections, well
cuttings, as well as in quarry sections along the
shoreline. Lithology of the Kudankulam Formation is
dominated by carbonate rocks with subordinate clastic
rocks. The Kudankulam sequence comprises, upwards
from the base, algal limestone, sandy shell limestone,
silty clay, argillaceous limestone, and calcareous sand-
stone units (Figs. 2 and 3). The Kudankulam sequence
comprises a transgressive phase from algal limestone to
silty clay units and a regressive phase from argillaceous
limestones to calcareous sandstones. Most of the
sequence is fossiliferous, containing numerous fossils
such as bryozoans, mollusks, echinoderms, algae, and
foraminifera, indicative of a shallow marine deposi-
tional environment.
Bruckner (1988) attempted to establish the sea-level
fluctuations based on a detailed study of coastal
carbonates of southern India and chose the Kudanku-
lam Formation as one of the markers for reconstruction
of former sea-levels. The Kudankulam Formation was
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14°
N

ARABIAN SEA CHENNAI

BANGALORE PALAR RIVER
CAUVERI RIVER

PO
NN
12° AIY
AR BAY OF BENGAL
RIV
ER
RECENT ALLUVIUM
km
0 100
SEDIMENTARY ROCKS CAUVERI RIVER

CLOSEPET GRANITE
10°
CHARNOCKITE VAIGAI RIVER

DHARWAR SCHIST BELT VAIPPAR RIVER

INDIA
CHITTAR RIVER
PENINSULAR GNEISS KE
R
AL Gujarat
A
TIRUCHENDUR Karaikal Jaffna
8° KUDANKULAM Sri Lanka
INDIAN OCEAN Kerala
KANNIYAKUMARI
74° 76° 78° 80° 82° E

Fig. 1. Simplified geological map of southern India (modified after Singh and Rajamani, 2001) showing the location of the study
area near the southern tip of India.

N
PANNAMPARAI

SATTANKULAM
D16 D19 D21 D22
D8 D10 D15 D18
D13 D20
D6 D7 D9 D11 D12 D14 D17 C15 C16
D5 C6 C7
D4 C5 C8 C9 C10 C11 C12 C14
C13
D3 C3 C4 B7 B8 B14
D1 D2 B6 B9 B10 B11
KUDANKULAM C1 C2 B5 A6 B12 B13 A13
B4 A10
B1 B2 B3 A5 NAVALADY A8 A12 TIRUCHENDUR
A4 A9
A1 A2 A7
A3 KUTTAM A11
PERUMANAL OVARI PERIATALAI
KARIKOIL
KANNIYAKUMARI km
GULF OF MANNAR 0 3
MANAPAUD
BAY OF BENGAL

BEACH SEDIMENT SILTY CLAY ARCHEAN

(Quartzo-feldspathic gneiss and
CALCAREOUS SANDSTONE SANDY SHELL LIMESTONE granitic gneiss)

ARGILLACEOUS LIMESTONE ALGAL LIMESTONE N1 SAMPLE LOCATION

Fig. 2. Simplified geological map of Kudankulam Formation, showing sample locations (modified after Armstrong-Altrin et al.,
2003).

correlated with the Karaikal beds of southern India of transgression in southern India occurred in the early
late Miocene to early Pliocene age (Ramanathan, 1979; Miocene and its influence can be traced in Gujarat in the
Paramasivam and Srinivasan, 1980). The last marine western part, and also in Kerala in the southernmost
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48 J.S. Armstrong-Altrin et al. / Chemie der Erde 69 (2009) 45–60

KUTTAM MANAPAUD
NAVALADY OVARI

PERIATALAI
KUDANKULAM PERUMANAL A9
A7
A5 A10 A11
A1 A3 A8 A13
A2 A4 A12
A6
B1 B4 B11 B12 B14
B5 B13
B2 B7 B9
B6 B8 B10
B3
C3
C1 C6 C11
C4 C8 C15
C2 C7 C12
C5 C9 C16
D1 D7 C10 C13 C14
D4 D8
D2 D5 D11 D14 D20
D9 D12 D15 D17
D3 D6 D16
D10 D13
D18
D19

GENERALIZED STRATIGRAPHY (NOT TO SCALE)

SCALE
LITHOLOGY MEMBER AGE Vertical
30m D21
L ATE MIOCENE TO EA RLY PL IOCENE

BEACH SEDIMENT
D22
CALCAREOUS SANDSTONE
(B RUCK NER, 1988)

20
ARGILLACEOUS LIMESTONE
SILTY CLAY 10
SANDY SHELL LIMESTONE
ALGAL LIMESTONE 0
Horizontal
ARCHEAN (Not to scale)

Fig. 3. Columnar sections of the studied sites and sampling horizons. Stratigraphic section names are according to the nearest
village (Fig. 2) and the sample numbers referred to here are the same as in Tables 1–3. Blank crossed space in the Manapaud section
represents the area with no exposures.

part of India (Fig. 1 inset). On the eastern side of 3. Samples and analytical methods
the Cauvery Basin, based on the fossil assemblages
and facies the Jaffna Formation of Sri Lanka is most A detailed petrographic study covering more than
probably the equivalent of the Kudankulam Formation 75 thin sections was carried out. The thin sections
(Bruckner, 1988). The presence of microfossils like were subjected to Alizarin Red-S stain to confirm
Austrotrillina howchini sp. and Taberiana malabarica the presence or absence of dolomite and calcite, and
sp. places the Jaffna Formation in the upper part of the potassium ferricyanide to ascertain the presence of
upper Miocene (Sahani, 1979; Cooray, 1984). Thus, ferroan/nonferroan calcite. Friedman’s (1959) organic
Bruckner (1988) suggested a late Miocene–Pliocene age stain specific for calcite and Katz and Friedman’s (1965)
for the Kudankulam Formation. combined organic and inorganic stain specific for
Systematic studies have been carried out on this iron-rich calcite have been adopted to identify the
formation by Armstrong Altrin Sam and Ramasamy mineralogical variations.
(1997, 1999); Ramasamy and Armstrong Altrin The carbon and oxygen isotope compositions have
Sam (1998) and Armstrong-Altrin et al. (2003, 2004). been analyzed for 65 samples collected from outcrops
Based on trace and rare-earth element geochemistry, exposed in stream cuts and quarry sections (Fig. 2). The
Armstrong-Altrin et al. (2003, 2004) interpreted that samples were selected as follows: 13 samples from
terrigeneous sediments of the Kudankulam Formation calcareous sandstone, 14 samples from argillaceous
were mainly derived from felsic source rocks. At present, limestone, 16 samples from sandy shell limestone, and
the upper layers of the Kudankulam sequence are 22 samples from algal limestone (Figs. 2 and 3). The
intensely altered and calcrete development is prevalent. samples analyzed in this study are whole rock samples,
Normally this area receives less than 200 mm per year of ooids, molluscan mold-fill cement, and sparry pore-fill
precipitation and can, therefore, be classified as an arid calcites. Molluscan mold-fill cements are calcite filling
type of climate zone (Deshpande et al., 2003). intragranular pores, whereas sparry pore-fill calcites are
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J.S. Armstrong-Altrin et al. / Chemie der Erde 69 (2009) 45–60
cement filling intergranualr pores. Both types of sparry
cements are of meteoric diagenetic origin, suggestive
of coeval precipitation in the freshwater phreatic
environments.
Stable isotope compositions of samples were analyzed
at the US Geological Survey, Federal Center, Denver,
and Institute of Earth Sciences, Academia Sinica,
Taipei, using reaction with 100% H3PO4 at 25 1C to
liberate CO2 gas following the standard method of
McCrea (1950). The fractionation factor used for
oxygen between liberated CO2 and calcite was 1.01025
(Sharma and Clayton, 1965). The d18O and d13C values
of NBS-20 were measured at about +26.7% and
1.0%, respectively. Reproducibility of d13C and d18O
determinations was better than 70.2%. The results are
reported as per mil (%) d18O and d13C values relative to
Pee Dee belemnite (PDB international standard).
A total of 15 whole rock samples were analyzed for Sr
isotope compositions at the Korea Basic Science
Institute. Carbonate components were leached from
whole rock powders using dilute acetic acid and HCl.
Care was taken to avoid contribution from silicate
impurities (Bailey et al., 2000). The 87Sr/86Sr ratios were
measured, following the standard Sr chemistry and mass
spectrometric procedures using a Micromass VG 54–30
thermal ionization mass spectrometer. The blank con-
centrations were below 0.2 ng for Sr. Replicate analyses
of standard NBS-SRM 987 for Sr yielded
87
Sr/86Sr ¼ 0.71024270.000019 (2sE, n ¼ 14). The same
15 whole rock samples were also analysed for Sr and Rb
concentrations. Sr concentration was determined using a
Jobin Yvon 138 Ultrace inductively coupled plasma
atomic emission spectrometer (ICP-AES). Rb concen-
tration was determined by a VG Elemental PQII
Plus inductively coupled plasma mass spectrometer
(ICP-MS) using the method described by Jarvis (1988).
Before computing the central tendency (mean) and
dispersion (standard deviation) parameters, the data
were tested for possible outliers using univariate
discordancy tests (Barnett and Lewis, 1994) for normal
samples, along with the new critical values at 99%
confidence level (Verma and Quiroz-Ruiz, 2006a, b).
When discordant outliers were observed in a given set
of data, these parameters were also computed for the
remaining data after excluding the outlying observations
as has been recommended by statisticians (Barnett and
Lewis, 1994).
4. Results
4.1. Petrography and diagenesis
The classification proposed for carbonate rocks by
Dunham (1962), and the extended classification by
Embry and Klovan (1972) and also by Folk (1959, 1962)
49
were followed. A classification proposed by Gilbert
(1954) and the modified classification by Dott (1964)
were followed for the clastic-rich sequence. A brief
description of petrography and diagenetic characters of
different litho-units is as follows:
4.1.1. Calcareous sandstone
Fossiliferous calcareous feldspathic quartz arenites
(Fig. 4a) show a framework of well-rounded and sub-
rounded quartz grains. Most of the feldspars are
plagioclase and less dominantly perthite and alkali type.
Carbonate components are bored by endolithic algae
and fungi, which form micritic envelopes. The cement is
peloidal marine type formed in the marine phreatic
environment (Armstrong-Altrin et al., 2003). However,
some sparry calcite infillings in dissolved portion of
skeletal particles seem to have developed in fresh water
environment.
4.1.2. Argillaceous limestone
Bryozoan algal packstone (Fig. 4b) has a number of
micritised bioclasts of bryozoans. The bryozoan bio-
clasts have been leached and the voids are filled with
sparry calcite. Iron oxide accumulation is also notice-
able in the zooecial openings. Sandy algal pelletal
packstone (Sandy algal pelsparite; Fig. 4c) identified
from the argillaceous limestone litho-unit exhibits a
good number of algal pellets along with other bioclasts
such as bryozoa and foraminifers. Some large lumps
enclose rotalid and miliolid foraminifers and algal
fragments. The cement is sparry calcite. The pellets
and lumps are rounded, indicative of some movements
from the place of their origin.
4.1.3. Sandy shell limestone
Sandy foraminiferal molluscan packstone (Fig. 4d) is made
up of a number of molluscan fragments along with larger
foraminifera and algal bioclasts. The bioclasts are highly
fragmented and smaller in size. Sparite is the dominant
cement. Very few argillaceous materials are seen.
4.1.4. Algal limestone
Sandy bryozoan algal packstone (Fig. 4e) consists of
bioclasts of bryozoan, mollusks, ostracods, foraminifera
including miliolids, echinoderms, and algal elements
(Lithothamnium sp. and Amphiroa sp.). Some forami-
niferal clasts are reworked materials (those which are
dark and ferrugenised). Many molluscan shell fragments
are completely leached out, and the voids are filled with
sparry calcite in fresh water phreatic diagenetic environ-
ment. Algal miliolid floatstone (Miliolid biosparite;
Fig. 4f) is distinctly dominated by miliolid foraminifers
and algal fragments. Most of the bioclasts show strong
micritic envelopes, most probably by the work of
endolithic algae. Some peloidal materials are also found.
They are cemented by sparry calcite.
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50 J.S. Armstrong-Altrin et al. / Chemie der Erde 69 (2009) 45–60
Furthermore, the petrographic study of rocks of the
Kudankulam Formation supports several lines of
evidence of meteoric diagenesis such as vadose diage-
netic features including precipitation of micrite around
rootlets in rhizoliths (Fig. 4g), clotted micrite (Fig. 4h),
horizontal fractures formed due to alternate wet and dry
conditions (Fig. 4i), and circum-granular cracks around
clastic grains (Fig. 4j).
4.2. Carbon and oxygen isotopes
d13C and d18O values of the Kudankulam carbonates
are given in Tables 1 and 2 along with their rock types
and are plotted in a d13C versus d18O scatter diagram in
Fig. 5. No general trend between d13C and d18O values is
observed, except that each carbonate component has its
own range in values in this scatter diagram.
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The oxygen isotope compositions of whole rock
samples range from 4.1% to 9.4% (the mean with
one standard deviation being 7.771.6%, n ¼ 28),
those of shell fragments from 2.6% to 9.4%
(7.272.2%, n ¼ 8), and of ooids from 2.6% to
8.4% (6.171.5%, n ¼ 12; or from 5.8% to
8.4%, 6.671.0%, n ¼ 10). Pore-filling calcite has
the lowest values and a narrow range of d18O values
from 6.5% to 9.2% (8.170.8%, n ¼ 17). Among
the whole rock samples algal limestone have a wide
range of d18O values (4.2% to 9.4%; 6.971.8%,
n ¼ 10), whereas argillaceous limestone and sandy shell
limestone have a narrow range of d18O values ranging
from 8.1% to 9.2% (8.870.5%, n ¼ 5) and from
8.2% to 9.3% (8.870.5%, n ¼ 5), respectively.
The carbon isotope compositions of whole rock
samples range from 3.6% to 7.9% (6.771.1%,
n ¼ 28; or better from 6.0% to 7.9%, 7.070.5%,
n ¼ 24), of shell fragments from 7.0% to 9.0%
(7.770.7%, n ¼ 8), and of ooids from 1.5% to
4.9% (3.771.0%, n ¼ 12). The pore-filling calcites
have a narrow spread in d13C from 6.0% to 7.8%
(7.270.5%, n ¼ 17). The average carbon isotopic
compositions of whole rock samples of different litho-
units are very similar: 6.171.6% (n ¼ 10) for algal
limestone, 6.970.7% (n ¼ 5) for sandy shell lime-
stone, 6.970.6% (n ¼ 5) for argillaceous limestone
and 7.070.6% (n ¼ 8) for calcareous sandstone.
However, algal limestone and sandy shell limestone
located in the two SW sections (Kudankulam and
Perumanal) have carbon isotope compositions slightly
enriched in 13C compared to those in other sections
(Table 1; Fig. 3).
4.3. Strontium isotopes
The Sr isotope compositions are shown in Table 3.
The 87Sr/86Sr ratio of the Kudankulam Formation vary
from 0.709195 to 0.721304 (0.714270.0043, n ¼ 15);
in order of increasing ratio, calcareous sandstone shows
0.7091950.709818 (0.709670.0003, n ¼ 3), argillaceous
limestone 0.7107920.712923 (0.711770.0010, n ¼ 4),
sandy shell limestone 0.7121880.717142 (0.71457
0.0024, n ¼ 4), and algal limestone 0.7151280.721304
87
(0.719770.0030, n ¼ 4). The Sr/86Sr ratio decreases
up-sequence.
5. Discussion
5.1. Petrography
The petrographic observations suggest that the
Kudankulam Formation was subjected to shallow to
moderate, but not to deep burial diagenesis. The early
diagenesis on the seafloor resulted in the formation of
micritic cements, and large-scale micritization of bio-
clasts including micrite envelopes. Some of the bioclasts
show micritic coatings obviously by the work of
endolithic algae in early diagenetic environment. The
association of bioclasts such as bryozoans, mollusks,
echinoderms, algae, and larger foraminifera suggests
that the depositional environment was a shallow
marginal marine setting. The fragmented and rounded
nature of most bioclasts suggests a moderate to highly
agitated environment in a bank-like setting.
5.2. Oxygen isotope composition
The d18O value of diagenetic carbonates is controlled
by the temperature of precipitation, the 18O/16O ratio of
the water from which they precipitated, the original
d18O values of the carbonate sediments, and the water/
rock ratio, among other factors (Hudson, 1977).
Assuming pore-fill sparry calcites formed during shallow
burial diagenesis (see Fig. 4b, e, f), the d18O values of
pore waters that precipitated these calcites are estimated
to range from 5.6% to 8.3% SMOW (av.
7.270.8%, n ¼ 17) at 20 1C and from 4.5% to
7.2% SMOW (av. 6.170.8%, n ¼ 17) at 25 1C
(Table 2). The molluscan mold-filling calcites also
suggest similar average d18O values of pore waters being
6.372.2% SMOW at 20 1C and 5.272.2% SMOW
at 25 1C (Table 2). During the late Miocene to early
Pliocene, when the Kudankulam carbonates were
deposited, the Antarctic ice-sheet volume fluctuated,
reflecting changes in glacial and interglacial stages
(Ehrmann et al., 1991; Hodell et al., 1994; Larsen

Fig. 4. Thin-section photomicrographs for carbonate rocks of the Kudankulam Formation. Scale bars ¼ 0.5 mm. (a) Feldspathic
quartz arenite, showing sparry calcite infillings in dissolved portion of skeletal particles developed in fresh water diagenetic
environment and a typical well rounded quartz grain of eolian source (parallel nicols). (b) Bryozoan algal packstone, illustrates the
zooecial openings of a bryozoan filled with sparry calcite and ferruginous materials (parallel nicols). (c) Sandy algal pelletal
packstone, showing coralline algae and peloids made with micrite cemented in sparry calcite (parallel nicols). (d) Sandy
foraminiferal molluscan packstone, exhibits a miliolid foraminifera and molluscan bioclasts (parallel nicols). (e) Sandy bryozoan
algal packstone, exhibits an algal fragment embedded in sparry calcite cement (parallel nicols). (f) Algal miliolid floatstone,
displaying cross-sectional view of the miliolid foraminifera along with other fragmented bioclasts set in a dominantly sparry calcite
cement (parallel nicols). (g) Longitudinal section of rhizolith (plant root) and other minor rootlets (parallel nicols). (h) Clotted
micrite developed in subaerial environment (parallel nicols). (i) Horizontal fractures formed due to alternate wet and dry conditions
subaerially. (j) Circumgranular cracks and precipitation of micrite around clastic grains.
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Table 1. Stable isotopic data for whole rock and ooid samples of the Kudankulam Formation

Sample nos. Sample description Sample type d13C (% PDB) d18O (% PDB)

A4 Calcareous sandstone Whole rock 7.20 6.90

A5 Calcareous sandstone Whole rock 6.20 4.10
A7 Calcareous sandstone Whole rock 6.50 6.00
A8 Calcareous sandstone Whole rock 7.24 8.34
A10 Calcareous sandstone Whole rock 7.52 8.66
A11 Calcareous sandstone Whole rock 7.94 8.49
A12 Calcareous sandstone Whole rock 6.86 8.76
A13 Calcareous sandstone Whole rock 6.88 6.01
B7 Argillaceous limestone Whole rock 6.27 8.09
B8 Argillaceous limestone Whole rock 6.16 8.38
B9 Argillaceous limestone Whole rock 7.23 9.23
B12 Argillaceous limestone Whole rock 7.35 9.22
B14 Argillaceous limestone Whole rock 7.32 8.98
C1 Sandy shell limestone Whole rock 5.98 8.24
C5 Sandy shell limestone Whole rock 7.20 8.26
C11 Sandy shell limestone Whole rock 7.73 8.98
C14 Sandy shell limestone Whole rock 6.44 9.23
C16 Sandy shell limestone Whole rock 7.15 9.25
D1 Algal limestone Whole rock 5.94 8.41
D2 Algal limestone Whole rock 3.59 7.65
D3 Algal limestone Whole rock 3.73 5.71
D4 Algal limestone Whole rock 6.81 6.02
D5 Algal limestone Whole rock 6.99 8.54
D6 Algal limestone Whole rock 4.77 8.28
D8 Algal limestone Whole rock 6.90 6.60
D9 Algal limestone Whole rock 7.90 4.50
D10 Algal limestone Whole rock 7.60 4.20
D11 Algal limestone Whole rock 7.20 9.37
Mean7one standard deviation (n ¼ 28)a 6.771.1 7.771.6
(n ¼ 24) 7.070.5
D7 Algal limestone Ooid 3.20 8.39
D12 Algal limestone Ooid 4.60 6.02
D13 Algal limestone Ooid 3.30 6.08
D14 Algal limestone Ooid 3.20 6.02
D15 Algal limestone Ooid 4.90 6.30
D16 Algal limestone Ooid 3.40 7.10
D17 Algal limestone Ooid 4.50 4.60
D18 Algal limestone Ooid 2.70 6.10
D19 Algal limestone Ooid 4.10 2.60
D20 Algal limestone Ooid 4.80 8.40
D21 Algal limestone Ooid 4.50 6.30
D22 Algal limestone Ooid 1.48 5.77
Mean7one standard deviation (n ¼ 12)a 3.771.0 6.171.5
(n ¼ 10) 6.671.0
a
n ¼ number of samples; the C and O isotope data were checked for discordant outliers before computing mean and standard deviation values
using discordancy tests for normal samples using new critical values at 99% confidence level (Verma and Quiroz-Ruiz, 2006a, b); in the case of d13C
(% PDB) whole rock data for four algal limestone samples (D1, D2, D3, and D6) were found to be discordant; similarly, for d18O (PDB) ooid data
for two algal limestone samples (D19 and D17) were found to be discordant. Therefore, the mean and standard deviation values are not strictly valid
for these particular cases when all data are considered, and have also been calculated without these four and two samples, respectively.

et al., 1994; Kennett, 1996). Thus, the seawater values for the Kudankulam carbonates are lower than
composition is inferred to have varied between 0.5% the contemporaneous seawater value. The lower values
and +0.5% (SMOW) (Shackleton, 1968; Meyers and of pore water oxygen isotope compositions cannot be
Lohmann, 1985). However, the estimated pore water ascribed to the elevated precipitation temperatures
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Table 2. Stable isotopic data for calcite cement samples of the Kudankulam Formation

Sample Sample descriptiona Sample type d13Ccalcite d18Ocalcite d18Ocalcite d18Owater (SMOW)d
nos. (% PDB) (% PDB) (SMOW)c
20 1C 25 1C

C2 Sandy shell ls Mold-fill calcite 8.18 7.73 22.89 6.80 5.73

C4 Sandy shell ls Mold-fill calcite 8.20 6.68 23.97 5.75 4.68
C6 Sandy shell ls Mold-fill calcite 8.99 7.59 23.04 6.66 5.59
C7 Sandy shell ls Mold-fill calcite 7.25 8.41 22.19 7.48 6.41
C8 Sandy shell ls Mold-fill calcite 7.00 6.03 24.64 5.10 4.03
C10 Sandy shell ls Mold-fill calcite 7.10 2.60 28.18 1.67 0.59
C12 Sandy shell ls Mold-fill calcite 7.20 8.97 21.61 8.04 6.98
C15 Sandy shell ls Mold-fill calcite 7.32 9.40 21.17 8.47 7.41
Mean7one standard deviation (n ¼ 8)b 7.770.7 7.272.2 23.572.2 6.372.2 5.272.2
A1 Calcareous ss Pore-fill calcite 7.80 8.00 22.61 7.07 6.00
A2 Calcareous ss Pore-fill calcite 6.60 8.50 22.10 7.57 6.51
A3 Calcareous ss Pore-fill calcite 7.30 8.70 21.89 7.77 6.71
A6 Calcareous ss Pore-fill calcite 7.60 7.60 23.03 6.67 5.60
A9 Calcareous ss Pore-fill calcite 7.46 8.81 21.78 7.88 6.82
B1 Argillaceous ls Pore-fill calcite 7.59 7.77 22.85 6.84 5.77
B2 Argillaceous ls Pore-fill calcite 7.20 8.70 21.89 7.77 6.71
B3 Argillaceous ls Pore-fill calcite 7.30 7.40 23.23 6.47 5.40
B4 Argillaceous ls Pore-fill calcite 6.96 7.61 23.02 6.68 5.61
B5 Argillaceous ls Pore-fill calcite 6.54 6.51 24.15 5.58 4.51
B6 Argillaceous ls Pore-fill calcite 7.60 7.07 23.57 6.14 5.07
B10 Argillaceous ls Pore-fill calcite 7.29 8.66 21.93 7.73 6.67
B11 Argillaceous ls Pore-fill calcite 7.29 9.08 21.50 8.15 7.09
B13 Argillaceous ls Pore-fill calcite 5.95 9.23 21.35 8.30 7.24
C3 Sandy shell ls Pore-fill calcite 7.82 8.20 22.41 7.27 6.20
C9 Sandy shell ls Pore-fill calcite 7.40 7.07 23.57 6.14 5.07
C13 Sandy shell ls Pore-fill calcite 7.37 9.18 21.40 8.25 7.19
Mean7one standard deviation (n ¼ 17)b 7.270.5 8.170.8 22.570.9 7.270.8 6.170.8
a
ls ¼ limestone; ss ¼ sandstone.
b
n ¼ number of samples; the isotope data were checked for discordant outliers before computing mean and standard deviation values using
discordancy tests for normal samples using new critical values at 99% confidence level (Verma and Quiroz-Ruiz, 2006a, b). No discordant data were
observed.
c 18
d Ocalcite (SMOW) ¼ 1.03086 d18Ocalcite (PDB)+30.86 (Friedman and O’Neil, 1977).
d
These values are calculated by assuming a paleotemperature of precipitation of 20 and 25 1C (e.g., Wright, 1987) and using the calcite
paleothermometer of Friedman and O’Neil (1977).

during burial diagenesis, since the Kudankulam carbo-
nates are interpreted to have undergone only shallow
burial diagenesis (Fig. 4g–j). The light oxygen isotope
compositions of the pore waters indicate that the
diagenetic fluids were meteoric waters.
In our study, the presence of meteoric diagenetic
features (Fig. 4a–f) indicates early sub-aerial influence
on the Kudankulam carbonates (Fig. 4g–j). The largest
variation in the oxygen isotopic composition is observed
in shell fragments (Table 2; molluscan mold-fill calcites
2.6% to 9.4%), which may have been related to a
similar variation within the meteoric waters (Muchez
et al., 1992) and can be explained by seasonal variation
in 18O by evaporation (Budd and Land, 1990) and/or
by the ‘‘amount’’ effect (i.e., Mack et al., 1991).
The ‘‘amount’’ effect relates the d-value and monthly
precipitation, i.e., low d18O is observed in rainy months
and high d18O in dry months. At low latitudes,
Dansgaard (1964); Yurtsever and Gat (1981) and Yapp
(1982) observed a linear relationship between average
monthly rainfall and its mean monthly d18O value,
about 1.5%/100 mm. The 6.8% difference observed in
the Kudankulam molluscan mold-fill calcites would
imply a 450 mm difference in precipitation in the study
area. Changes of such an amount in precipitation are
realistic and could be partially ascribed to regional
climatic variations, which may suggest the strong
seasonality in southern India during the late Miocene.
The present climatic condition in the study area is arid
and the present groundwater oxygen isotope composi-
tion from a site close to the study area was measured to
be 2% (Deshpande et al., 2003). The estimated d18O
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54 J.S. Armstrong-Altrin et al. / Chemie der Erde 69 (2009) 45–60

values of meteoric waters that precipitated pore-filling
sparry calcites (Table 2) are lower than the present
groundwater value and corresponding precipitation
value, indicating that the paleoclimate during the
deposition of the Kudankulam Formation was not arid
like today, but more humid. This suggests that in the
late Miocene the paleoclimate was different in southern
India. The present climatic conditions in southern India
are controlled by the Indian monsoon system. Probably
in the late Miocene, the Indian monsoon system was
weak or not well established, and thus the study area
may have been under the influence of Northeast trades,
bringing moistures from the Bay of Bengal and South
China Sea. Alternatively and more likely, the climatic
change may have been caused by the strong Indian
monsoon system. At present, the eastern coastal plains
of the peninsula, northeast of the study area receive a
large amount of NE monsoon precipitation during
October–January and groundwater during this period
has d18O values of about 5% (Deshpande et al., 2003).
If this interpretation is accepted, the study area was
probably under the intense monsoon influence in the late
Miocene.

5.3. Carbon isotope composition

Modern marine carbonate sediments generally have

Fig. 5. A scatter plot of d13C and d18O values of the upper
Miocene Kudankulam carbonates. Note that each carbonate
component has its own range in values, and that there is a wide
scatter and a lack of a general trend between d13C and d18O
values.
d13C values ranging from 0% to 4% (Hudson, 1977;
Moore, 2001). The variation in d13C values of carbonate
rocks are related to degrees of alteration, and the
amount and source of CO2 derived from the oxidation
of organic carbon added to the pore waters during
limestone recrystallization and cementation (Marshall,
1992; Maliva et al., 1995; Maliva and Dickson, 1997).
Since carbon isotope compositions are less sensitive to
changes in temperature, the lower d13C values of the
Kudankulam carbonates compared to the modern
carbonate sediments may be related to the influence
soil-gas CO2 (Cerling and Hay, 1986), and may suggest
incorporation of 13C-depleted carbon. The wide varia-
tion in d13C values (1.5% to 9.0%; Tables 1 and 2)
of the Kudankulam carbonates thus indicate exposure

Table 3. Elemental and strontium isotopic data of the Kudankulam Formation

87
Sample nos. Sample description Rb (mg/g) Sr (mg/g) Sr/86Sr72sEa (87Sr/86Sr)ib

A1 Calcareous sandstone 17.4 92.2 0.709195711 0.709118

A8 Calcareous sandstone 15.6 110.5 0.709679711 0.709621
A13 Calcareous sandstone 20.8 80.9 0.709818713 0.709713
B1 Argillaceous limestone 10.2 108.2 0.712923713 0.712884
B7 Argillaceous limestone 12.5 90.5 0.710792710 0.710735
B11 Argillaceous limestone 11.7 139.4 0.712028711 0.711993
B14 Argillaceous limestone 10.5 120.5 0.711169710 0.711133
C2 Sandy shell limestone 9.2 231.0 0.715866710 0.715849
C8 Sandy shell limestone 13.8 206.4 0.717143715 0.717115
C12 Sandy shell limestone 12.2 205.1 0.712843711 0.712819
C16 Sandy shell limestone 15.3 189.7 0.712188711 0.712155
D2 Algal limestone 11.2 321.6 0.721192711 0.721177
D9 Algal limestone 10.7 274.1 0.715129714 0.715112
D15 Algal limestone 6.5 466.7 0.721185711 0.721179
D21 Algal limestone 7.3 311.3 0.721304714 0.721294
a
The Sr-isotope data are reported after adjusting them to NBS-SRM 987 87Sr/86Sr ¼ 0.710230, following the practice of the Max-Planck Institute
of chemistry, Mainz, Germany (see e.g., Verma and Hasenaka, 2004). The errors quoted for individual measurements are two times the standard
error of the mean (2sE).
b
Initial 87Sr/86Sr ratios were estimated for a maximum age of 10 Ma. Further, no discordant outliers were observed (Verma and Quiroz-Ruiz,
2006a, b).
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to meteoric waters with high, but variable light carbon
content (Hudson, 1977; Allan and Matthews, 1977,
1982).
Ooids in algal limestone show the least altered d13C
values (3.771.0%, n ¼ 12) compared to those of
whole rock (6.771.1%, n ¼ 28, or 7.070.5%,
n ¼ 24; Table 1) and sparry calcite cements (pore-fill
7.270.5% and molluscan mold-fill 7.770.7%;
Table 2). This may be due to relatively early stabiliza-
tion of ooid-forming minerals during diagenesis by the
pore waters having lesser contribution of organically
derived light carbon.
It is likely that ooid sediments would have been
affected by meteoric waters in the deeper part of the
phreatic zone. In contrast to the ooids, the whole rock
samples of the ooid-bearing algal limestone, are depleted
in 13C, indicating that algal limestone contains signifi-
cant amount of meteoric cement. Similar influence of
meteoric water conditions as in ooids might have
contributed to the algal limestone distributed in the
southwestern sections where shoreline zone is narrower
in width than the northeastern sections (Fig. 2).
5.4. Water–rock interaction
The d18O value is a sensitive parameter for evaluating
water–rock ratios, during multiple interactions of
meteoric water with the limestones in a diagenetic
system. The oxygen isotope composition of the rock can
achieve isotopic equilibrium with the water at a
relatively low water/rock ratio because water (H2O)
forms a very large reservoir of oxygen. The reservoir for
carbon in water is much smaller than for oxygen and
much higher water/rock ratios are needed to lower the
d13C values of the limestones significantly (Hudson,
1977). This water/rock ratio-dependent change is
reflected in the wide spread of the d13C values of the
Kudankulam carbonates (Fig. 5).
The depletion in 13C in the Kudankulam carbonates is
probably due to the fact that the diagenetic system was
relatively open, water residence time was short, and soil-
gas CO2 could mix far down the groundwater flow
paths. In regions proximal to vadose water recharge,
precipitate and replaced carbonates should have lower
d13C and 18O values due to the meteoric diagenetic
influence (Allan and Matthews, 1982). As the meteoric
water flow becomes more distal, the d13C of the host
carbonate becomes less 13C-depleted as a consequence
of a decreasing influence of soil-gas CO2, whereas the
d18O tends to be similar to that of the proximal area
because meteoric water is a ubiquitous source of oxygen
during the meteoric diagenesis process.
The pore-fill and molluscan mold-fill calcite cements
have similar light carbon (7.270.5% and 7.770.7%,
respectively) and oxygen (8.170.8% and 7.272.2%,
55
respectively; Table 2) isotopic compositions. This
indicates that pore waters that precipitated these calcite
cements were proximal to the vadose water recharge
zone. Most of the whole rock samples except algal
limestones show similar carbon and oxygen isotope
compositions to these calcite cements (Table 1), which
suggests that the pore waters were also in close
proximity to the vadose recharge zone. The algal
limestones have slightly variable oxygen isotope com-
positions that range from 4.2% to 9.4% (Table 1).
This suggests that rock–water interactions were variable.
Whole rock samples in the SW sections (Kudanklam
and Perumanal) are slightly enriched in 13C compared to
associated calcite cements, indicating that water/rock
ratio was relatively low with respect to carbon. Due to
the narrow coastal belt in these areas (Fig. 2) resulting in
smaller meteoric recharge zone, carbon isotope compo-
sitions of allochems seem to have been less influenced
by meteoric waters during their early stabilization. Vari-
ation in the carbon and oxygen isotope compositions
may indicate variable degrees of rock–water interactions
during the meteoric water flow.
5.5. Paleovegetation
The role of plants is also indicated by the negative
d13C values obtained for the Kudankulam carbonates.
The isotopic composition of plant-CO2 is dependent
on the proportion of different types of vegetation since
the d13C values of the plants are determined by the
photosynthetic pathways (Cerling, 1991; Mack et al.,
1991). C3 plants (Calvin Cycle) have a mean d13C value
of about 26%, but display a range from 20% to
35% (Ehleringer, 1989). C4 plants (Hatch–Slack
Cycle) range between 7% and 15%, having an
average of 13% (Cerling and Quade, 1993; Smith and
Epstein, 1971).
The present carbon isotopic composition of the
atmosphere is 7.8%, but it varies locally and
seasonally and being depleted relative to the pre-
industrial atmosphere, which was about 6.5% (Friedli
et al., 1986). In pre-industrial conditions the average
isotopic composition of C3 and C4 plants should have
been about 25.0% and 11.0%, respectively. Assum-
ing an enrichment factor of 1.0% (calciteHCO3 ) at 25 1C
(Romanek et al., 1992), meteoric water carbon reservoir
with which the Kudankulam calcite cements (pore-fill
and molluscan mold-fill) precipitated in equilibrium
would have d13C values of about 8.5%. The carbon
reservoirs in the vadose zone of the recharge area have
three sources: CO2 from organic respiration (d13C values
would be variable depending on the vegetation types in
the terrestrial biomass), atmospheric CO2, and dissolved
carbonate minerals. A varied mixture of carbon from all
these sources is also possible. However, considering that
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groundwater bicarbonate ions in recharge areas form
from approximately equal amounts of soil-gas CO2 and
limestone carbonate (Garrels and Christ, 1965; Mook,
1972), meteoric water d13C values of 8.5% would
indicate that carbon reservoir was sourced from organic
respiration of the biomass with significant fraction
(60%) of C4 plants. Since the age of the Kudankulam
limestone inferred to be late Miocene to early Pliocene
(Bruckner, 1988) when plants utilizing C4 photosyn-
thetic pathways may have already evolved (Quade and
Cerling, 1995), the result of this study supports the
expansion of C4 plants in the Indian subcontinent by
the late Miocene. Strong seasonality due to intense
monsoon system is suggested to have contributed the
expansion of C4 plants in southern India. The presence
of the C4 plants in southern India paleo-ecosystem as
suggested by the carbon isotope data is in good
agreement with the result of the oxygen isotope data
that the paleoclimate was seasonally humid and
influenced by high rainfall.
5.6. Strontium isotopes
Because of the long residence time of strontium in the
ocean the 87Sr/86Sr ratio of seawater is nearly constant
at one specific period in geologic time throughout the
oceans (Burke et al., 1982; Hodell et al., 1989). The ratio
of 87Sr/86Sr of seawater during the late Miocene to early
Pliocene lies between 0.7089 and 0.7091 (estimated by
Hodell et al., 1989, 1991). The isotopes of Sr are not
fractionated in nature (Faure, 1986), such as during
precipitation of carbonate minerals from aqueous
solutions. Thus, at the time of deposition the Kudanku-
lam limestones should have recorded the isotope
compositions of Sr in late Miocene seawater. However,
all the Kudankulam samples have higher 87Sr/86Sr
ratios than the contemporary seawater, indicating
significant input of radiogenic 87Sr to the system
after deposition. Such high 87Sr/86Sr ratio is indicative
of radiogenic strontium flux and its 87Sr/86Sr ratio
derived from tectonoclimatic processes such as the
exposure and chemical weathering of the ancient
crystalline rocks with high 87Sr/86Sr ratios (Armstrong,
1971; Moore et al., 1988; Hodell et al., 1989). Since the
Kudankulam Formation underwent shallow burial
diagenesis (Fig. 4a–j), the radiogenic strontium may
have been supplied during diagenesis by meteoric
waters draining the area composed of old crystalline
rocks (Moore et al., 1988; Hodell et al., 1989) such as
those present in southern India (Fig. 1). High rainfall
during that period would have been helpful for this
process.
Based on the geochemistry of immature flood plain
sediments of the Cauvery (also written as Kaveri) river,
Singh and Rajamani (2001) interpreted that the exposed
Archean rocks such as gneiss and charnockite in
southern India could have been uplifted and exposed
anytime from the Cenozoic to as late as the Quaternary,
probably due to the stress buildup by the Himalayan
Orogeny. Our study of the Kudankulam carbonates
provides additional constraints on this timing. The
exposed Archean charnockite and gneiss contain aver-
age Sr content of 330 and 319 ppm, respectively
(summary in Singh and Rajamani, 2001), and the gneiss
has a very high 87Sr/86Sr ratio of about 0.74269
(Jayananda et al., 2000). Thus, radiogenic strontium
responsible for high 87Sr/86Sr ratios in the Kudankulam
carbonates was probably derived from such Archean
rocks. The production of 87Sr from in-situ Rb-bearing
minerals in the Kudankulam carbonates (low Rb
concentrations ranging from 6.5 to 2.8 mg/g and high
Sr concentrations from 81 to 467 mg/g; Table 3) during
diagenesis is not likely due to the negligibly small
production of radiogenic 87Sr by decay of 87Rb in
carbonate rocks (in-situ growth corrected 87Sr/86Sr
values are similar to the measured ratios; Table 3).
Accordingly, the present study suggests that the Arche-
an rocks in southern India were already exposed in
late Miocene and supplied sediments to the study
area, thus leading to the conclusion that the exposure
of gneisses and deep-seated charnockites in southern
India occurred prior to the late Miocene. This inter-
pretation is supported also by the results of rare-earth
element geochemistry on the Kudankulam sandstones
(Armstrong-Altrin et al., 2004).
The decrease in 87Sr/86Sr ratio stratigraphically up-
sequence from algal limestone to calcareous sandstone
(Table 3; Fig. 3) indicates the influx of lesser amount
of radiogenic Sr to the Kudankulam Formation with
time during diagenesis. This suggests the reduction of
influence of the chemical weathering of Archean
rocks on the diagenesis of the Kudankulam carbonates
through time. This was probably caused by the existence
of carbonate sediments of the lower-lying litho-units
between the Archean rocks and the upper litho-units,
thus reducing direct influence of meteoric waters
draining the Archean rocks. Carbonate rocks onshore
must have reacted with meteoric waters draining
the Archean rocks, and this might have progressively
buffered the 87Sr/86Sr ratio for the younger Kudanku-
lam litho-units. Alternatively, the decrease in Sr isotopic
ratio up-sequence could have been caused by an increase
in more pristine carbonate as inferred from slight
difference in 87Sr/86Sr ratio between calcareous sand-
stone and late Miocene seawater. However, this
interpretation is not supported by the stable isotope
data and petrographic observations. The result of
this study show that 87Sr/86Sr ratios of sediments
during diagenesis could vary significantly stratigraphi-
cally although sediments underwent similar meteoric
alteration.
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6. Conclusions
(1) Both d18O and d13C values of the Kudankulam
carbonates are depleted in 18O and 13C, respectively,
compared to those of carbonates in equilibrium with
contemporaneous seawater. Based on the depleted
oxygen and carbon isotope compositions of the
sparry calcite cements, it is interpreted that the
Kudankulam carbonates underwent meteoric diag-
enesis in an open diagenetic system that was
proximal to vadose water recharge zone.
(2) Petrographic data from Upper Miocene Kudankulam
carbonates, southern India indicate extensive meteoric
diagenesis in shallow burial setting. Stable isotope
compositions of whole rocks, ooids, shell fragments,
and pore-fill calcite samples are consistent with the
petrographic characteristics.
(3) In contrast to the present-day arid climatic condi-
tion, the paleoclimate of the study area was humid,
probably caused by the intense Indian monsoon
system. The less negative carbon isotope composi-
tions suggest that C4-type vegetation formed
a significant fraction of the terrestrial paleo-
ecosystem. The latter interpretation supports the
expansion of C4 plants in the Indian subcontinent by
the late Miocene up to as far south as the study area
(Kudankuam Formation).
(4) The in-situ growth-corrected 87Sr/86Sr ratio of the
Kudankulam carbonates ranges from 0.70920 to
0.72130, which is much higher than that of the
contemporaneous seawater (between 0.7089 and
0.7091). Such high Sr isotope ratios indicate signifi-
cant radiogenic Sr influx to the Kudankulam diage-
netic system from the Archean rocks exposed in the
drainage area. This implies that the deep-seated
Archean rocks in southern India were already uplifted
and exposed in late Miocene, probably due to the
neotectonic activity. This interpretation is consistent
with our rare-earth element study of the Kudankulam
Formation (Armstrong-Altrin et al., 2004).
Acknowledgments
We are thankful to Prof. Mohan, Head, for providing
certain facilities through University Grants Commission
– Special Assistance Programme (Phase II), COSIST
and DST-FIST awarded to the Department of Geology,
University of Madras. The first author expresses his
gratefulness to Ramasamy, Banerjee, Walter E. Dean,
and Tzen-Fu-Yui for their continuous encouragement
and help during the course of this study. We are grateful
to Lim for drafting figures. This research was partly
supported by the Korea Science and Engineering
Foundation (KOSEF) grant (R01-2000-00056-0 to
YIL). The first author also thanks SEP-PROMEP
57
(Programa de Mejoramiento del Profesorado; Grant
No: UAEHGO-PTC-280) – CONACYT (Consejo
Nacional de Ciencia y Tecnologı́a; 52574), and PAI
(Programa Anual de Investigación; Grant no: 69B),
Mexico, for financial assistance. We are very much
grateful to Dr. Joachimski and Prof. Dr. Tobschall for
their comments and suggestions, which greatly im-
proved our final manuscript.
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