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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 water) at the time of deposition as well as during


diagenesis (Burke et al., 1982; Faure, 1986; Marshall,
The diagenesis of carbonate sediments encompasses 1992; Banner, 1995; Price and Gröcke, 2002). If the
87
all the processes that affect the sediments after deposi- Sr/86Sr of the present carbonate rocks is significantly
tion up to the realms of metamorphism at elevated different from that of the contemporaneous seawater,
temperatures and pressures (Moore, 2001). When the carbonates should have been altered by waters
carbonate sediments undergo shallow to intermediate containing 87Sr/86Sr derived from outside the carbonate
burial diagenesis, meteoric diagenetic pathways are unit (Burke et al., 1982; Faure, 1986; Gao et al., 1996).
important for major diagenetic changes (Land, 1986). Thus, strontium isotopes can be used to trace the source
Carbon and oxygen isotopes are widely used to waters.
identify the diagenetic environment and processes. In In the southernmost tip of India, upper Miocene
combination with petrographic information, stable shallow marine carbonates and associated siliciclastic
isotope compositions of carbonate rocks may prove to rocks (Kudankulam Formation) are narrowly distrib-
be useful in tracing fluid origin and in reconstructing uted (Fig. 1). The Kudankulam carbonates may provide
large-scale movements and evolution of fluids (e.g., information on the development of coastal aquifer and
Allan and Matthews, 1982; Budd and Land, 1990). paleoecology in the drainage area. The objectives of this
Allan and Matthews (1977, 1982) documented the study are to characterize the stable carbon and oxygen
influence of plant-derived CO2 on the carbon isotope isotope compositions of the Kudankulam carbonates, to
composition of carbonate during sub-aerial diagenesis test the hypothesis of C4 plant expansion in the southern
of both modern and ancient limestones. Furthermore, it Indian subcontinent during the late Miocene as far
has been demonstrated in several studies that the stable south as the southern tip of India, and to examine the
isotope composition of different carbonate components hypothesis on the neotectonic activity in southern India
may reflect the temperature of formation (e.g., Ali, 1995; using Sr isotope compositions.
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, 2. Geologic background
1995; Latorre et al., 1997; Srivastava, 2001; Scott, 2002).
The late Miocene (8–6 Ma) was a critical time for the In the southern part of Peninsular India, the exposed
expansion of C4 plants. In the Indian subcontinent, the rocks are gneisses and charnockites of Archean age
C4 plant expansion has been well documented in (Condie et al., 1986; Jayananda et al., 1995, 2000) as
Pakistan (Quade et al., 1989; Quade and Cerling, well as recent alluvium (Fig. 1). Small limestone deposits
1995), Nepal (Quade et al., 1995), Bengal Fan indicating marine influence during the formation of the
(France-Lanord and Derry, 1994), and as well as in southern part of India have also been discovered
southern India (Rajagopalan et al., 1999). These studies (Bruckner, 1988). These deposits have been called the
indicate the rapid expansion of C4 plants at the end of Kudankulam Formation, which crops out 20 km NE of
the Miocene, starting 8–7 million years ago. Grasses Kanniyakumari, near the Kudankulam village (Fig. 2).
that utilize the C4 photosynthetic pathway are wide- The sediments are exposed in stream sections, well
spread today in tropical and temperate latitudes, cuttings, as well as in quarry sections along the
especially where there is a significant summer rainfall shoreline. Lithology of the Kudankulam Formation is
and a mid-summer temperature minimum of 48 1C dominated by carbonate rocks with subordinate clastic
(Latorre et al., 1997; Rajagopalan et al., 1999; Scott, rocks. The Kudankulam sequence comprises, upwards
2002). The late Miocene expansion of C4 plants has been from the base, algal limestone, sandy shell limestone,
explained by either declining pCO2 levels or climate silty clay, argillaceous limestone, and calcareous sand-
change, such as an increase in summer-dominated stone units (Figs. 2 and 3). The Kudankulam sequence
rainfall regimes (Quade et al., 1989; Ehleringer et al., comprises a transgressive phase from algal limestone to
1991; Cerling et al., 1993; France-Lanord and Derry, silty clay units and a regressive phase from argillaceous
1994; Latorre et al., 1997; Andrews et al., 1998). limestones to calcareous sandstones. Most of the
However, more recent data provide no evidence of sequence is fossiliferous, containing numerous fossils
declining pCO2 in the late Miocene, which suggests that such as bryozoans, mollusks, echinoderms, algae, and
the late Miocene radiation of C4 plants around the globe foraminifera, indicative of a shallow marine deposi-
resulted from increasing seasonality and aridity (Pagani tional environment.
et al., 1999) or global cooling (Fox and Koch, 2003). Bruckner (1988) attempted to establish the sea-level
Strontium isotopes can be used to characterize the fluctuations based on a detailed study of coastal
origin of strontium in carbonate rocks because such carbonates of southern India and chose the Kudanku-
rocks will generally record the 87Sr/86Sr of the source lam Formation as one of the markers for reconstruction
waters (seawater as well as groundwater or meteoric 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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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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cement filling intergranualr pores. Both types of sparry were followed. A classification proposed by Gilbert
cements are of meteoric diagenetic origin, suggestive (1954) and the modified classification by Dott (1964)
of coeval precipitation in the freshwater phreatic were followed for the clastic-rich sequence. A brief
environments. description of petrography and diagenetic characters of
Stable isotope compositions of samples were analyzed different litho-units is as follows:
at the US Geological Survey, Federal Center, Denver,
and Institute of Earth Sciences, Academia Sinica, 4.1.1. Calcareous sandstone
Taipei, using reaction with 100% H3PO4 at 25 1C to Fossiliferous calcareous feldspathic quartz arenites
liberate CO2 gas following the standard method of (Fig. 4a) show a framework of well-rounded and sub-
McCrea (1950). The fractionation factor used for rounded quartz grains. Most of the feldspars are
oxygen between liberated CO2 and calcite was 1.01025 plagioclase and less dominantly perthite and alkali type.
(Sharma and Clayton, 1965). The d18O and d13C values Carbonate components are bored by endolithic algae
of NBS-20 were measured at about +26.7% and and fungi, which form micritic envelopes. The cement is
1.0%, respectively. Reproducibility of d13C and d18O peloidal marine type formed in the marine phreatic
determinations was better than 70.2%. The results are environment (Armstrong-Altrin et al., 2003). However,
reported as per mil (%) d18O and d13C values relative to some sparry calcite infillings in dissolved portion of
Pee Dee belemnite (PDB international standard). skeletal particles seem to have developed in fresh water
A total of 15 whole rock samples were analyzed for Sr environment.
isotope compositions at the Korea Basic Science
Institute. Carbonate components were leached from 4.1.2. Argillaceous limestone
whole rock powders using dilute acetic acid and HCl. Bryozoan algal packstone (Fig. 4b) has a number of
Care was taken to avoid contribution from silicate micritised bioclasts of bryozoans. The bryozoan bio-
impurities (Bailey et al., 2000). The 87Sr/86Sr ratios were clasts have been leached and the voids are filled with
measured, following the standard Sr chemistry and mass sparry calcite. Iron oxide accumulation is also notice-
spectrometric procedures using a Micromass VG 54–30 able in the zooecial openings. Sandy algal pelletal
thermal ionization mass spectrometer. The blank con- packstone (Sandy algal pelsparite; Fig. 4c) identified
centrations were below 0.2 ng for Sr. Replicate analyses from the argillaceous limestone litho-unit exhibits a
of standard NBS-SRM 987 for Sr yielded good number of algal pellets along with other bioclasts
87
Sr/86Sr ¼ 0.71024270.000019 (2sE, n ¼ 14). The same such as bryozoa and foraminifers. Some large lumps
15 whole rock samples were also analysed for Sr and Rb enclose rotalid and miliolid foraminifers and algal
concentrations. Sr concentration was determined using a fragments. The cement is sparry calcite. The pellets
Jobin Yvon 138 Ultrace inductively coupled plasma and lumps are rounded, indicative of some movements
atomic emission spectrometer (ICP-AES). Rb concen- from the place of their origin.
tration was determined by a VG Elemental PQII
Plus inductively coupled plasma mass spectrometer 4.1.3. Sandy shell limestone
(ICP-MS) using the method described by Jarvis (1988). Sandy foraminiferal molluscan packstone (Fig. 4d) is made
Before computing the central tendency (mean) and up of a number of molluscan fragments along with larger
dispersion (standard deviation) parameters, the data foraminifera and algal bioclasts. The bioclasts are highly
were tested for possible outliers using univariate fragmented and smaller in size. Sparite is the dominant
discordancy tests (Barnett and Lewis, 1994) for normal cement. Very few argillaceous materials are seen.
samples, along with the new critical values at 99%
confidence level (Verma and Quiroz-Ruiz, 2006a, b). 4.1.4. Algal limestone
When discordant outliers were observed in a given set Sandy bryozoan algal packstone (Fig. 4e) consists of
of data, these parameters were also computed for the bioclasts of bryozoan, mollusks, ostracods, foraminifera
remaining data after excluding the outlying observations including miliolids, echinoderms, and algal elements
as has been recommended by statisticians (Barnett and (Lithothamnium sp. and Amphiroa sp.). Some forami-
Lewis, 1994). 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
4. Results sparry calcite in fresh water phreatic diagenetic environ-
ment. Algal miliolid floatstone (Miliolid biosparite;
4.1. Petrography and diagenesis Fig. 4f) is distinctly dominated by miliolid foraminifers
and algal fragments. Most of the bioclasts show strong
The classification proposed for carbonate rocks by micritic envelopes, most probably by the work of
Dunham (1962), and the extended classification by endolithic algae. Some peloidal materials are also found.
Embry and Klovan (1972) and also by Folk (1959, 1962) They are cemented by sparry calcite.
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Furthermore, the petrographic study of rocks of the 4.2. Carbon and oxygen isotopes
Kudankulam Formation supports several lines of
evidence of meteoric diagenesis such as vadose diage- d13C and d18O values of the Kudankulam carbonates
netic features including precipitation of micrite around are given in Tables 1 and 2 along with their rock types
rootlets in rhizoliths (Fig. 4g), clotted micrite (Fig. 4h), and are plotted in a d13C versus d18O scatter diagram in
horizontal fractures formed due to alternate wet and dry Fig. 5. No general trend between d13C and d18O values is
conditions (Fig. 4i), and circum-granular cracks around observed, except that each carbonate component has its
clastic grains (Fig. 4j). own range in values in this scatter diagram.
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87
The oxygen isotope compositions of whole rock (0.719770.0030, n ¼ 4). The Sr/86Sr ratio decreases
samples range from 4.1% to 9.4% (the mean with up-sequence.
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 5. Discussion
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 5.1. Petrography
the lowest values and a narrow range of d18O values
from 6.5% to 9.2% (8.170.8%, n ¼ 17). Among The petrographic observations suggest that the
the whole rock samples algal limestone have a wide Kudankulam Formation was subjected to shallow to
range of d18O values (4.2% to 9.4%; 6.971.8%, moderate, but not to deep burial diagenesis. The early
n ¼ 10), whereas argillaceous limestone and sandy shell diagenesis on the seafloor resulted in the formation of
limestone have a narrow range of d18O values ranging micritic cements, and large-scale micritization of bio-
from 8.1% to 9.2% (8.870.5%, n ¼ 5) and from clasts including micrite envelopes. Some of the bioclasts
8.2% to 9.3% (8.870.5%, n ¼ 5), respectively. show micritic coatings obviously by the work of
The carbon isotope compositions of whole rock endolithic algae in early diagenetic environment. The
samples range from 3.6% to 7.9% (6.771.1%, association of bioclasts such as bryozoans, mollusks,
n ¼ 28; or better from 6.0% to 7.9%, 7.070.5%, echinoderms, algae, and larger foraminifera suggests
n ¼ 24), of shell fragments from 7.0% to 9.0% that the depositional environment was a shallow
(7.770.7%, n ¼ 8), and of ooids from 1.5% to marginal marine setting. The fragmented and rounded
4.9% (3.771.0%, n ¼ 12). The pore-filling calcites nature of most bioclasts suggests a moderate to highly
have a narrow spread in d13C from 6.0% to 7.8% agitated environment in a bank-like setting.
(7.270.5%, n ¼ 17). The average carbon isotopic
compositions of whole rock samples of different litho- 5.2. Oxygen isotope composition
units are very similar: 6.171.6% (n ¼ 10) for algal
limestone, 6.970.7% (n ¼ 5) for sandy shell lime- The d18O value of diagenetic carbonates is controlled
stone, 6.970.6% (n ¼ 5) for argillaceous limestone by the temperature of precipitation, the 18O/16O ratio of
and 7.070.6% (n ¼ 8) for calcareous sandstone. the water from which they precipitated, the original
However, algal limestone and sandy shell limestone d18O values of the carbonate sediments, and the water/
located in the two SW sections (Kudankulam and rock ratio, among other factors (Hudson, 1977).
Perumanal) have carbon isotope compositions slightly Assuming pore-fill sparry calcites formed during shallow
enriched in 13C compared to those in other sections burial diagenesis (see Fig. 4b, e, f), the d18O values of
(Table 1; Fig. 3). pore waters that precipitated these calcites are estimated
to range from 5.6% to 8.3% SMOW (av.
4.3. Strontium isotopes 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
The Sr isotope compositions are shown in Table 3. (Table 2). The molluscan mold-filling calcites also
The 87Sr/86Sr ratio of the Kudankulam Formation vary suggest similar average d18O values of pore waters being
from 0.709195 to 0.721304 (0.714270.0043, n ¼ 15); 6.372.2% SMOW at 20 1C and 5.272.2% SMOW
in order of increasing ratio, calcareous sandstone shows at 25 1C (Table 2). During the late Miocene to early
0.7091950.709818 (0.709670.0003, n ¼ 3), argillaceous Pliocene, when the Kudankulam carbonates were
limestone 0.7107920.712923 (0.711770.0010, n ¼ 4), deposited, the Antarctic ice-sheet volume fluctuated,
sandy shell limestone 0.7121880.717142 (0.71457 reflecting changes in glacial and interglacial stages
0.0024, n ¼ 4), and algal limestone 0.7151280.721304 (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- precipitation, i.e., low d18O is observed in rainy months
nates are interpreted to have undergone only shallow and high d18O in dry months. At low latitudes,
burial diagenesis (Fig. 4g–j). The light oxygen isotope Dansgaard (1964); Yurtsever and Gat (1981) and Yapp
compositions of the pore waters indicate that the (1982) observed a linear relationship between average
diagenetic fluids were meteoric waters. monthly rainfall and its mean monthly d18O value,
In our study, the presence of meteoric diagenetic about 1.5%/100 mm. The 6.8% difference observed in
features (Fig. 4a–f) indicates early sub-aerial influence the Kudankulam molluscan mold-fill calcites would
on the Kudankulam carbonates (Fig. 4g–j). The largest imply a 450 mm difference in precipitation in the study
variation in the oxygen isotopic composition is observed area. Changes of such an amount in precipitation are
in shell fragments (Table 2; molluscan mold-fill calcites realistic and could be partially ascribed to regional
2.6% to 9.4%), which may have been related to a climatic variations, which may suggest the strong
similar variation within the meteoric waters (Muchez seasonality in southern India during the late Miocene.
et al., 1992) and can be explained by seasonal variation The present climatic condition in the study area is arid
in 18O by evaporation (Budd and Land, 1990) and/or and the present groundwater oxygen isotope composi-
by the ‘‘amount’’ effect (i.e., Mack et al., 1991). tion from a site close to the study area was measured to
The ‘‘amount’’ effect relates the d-value and monthly be 2% (Deshpande et al., 2003). The estimated d18O
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values of meteoric waters that precipitated pore-filling may have been under the influence of Northeast trades,
sparry calcites (Table 2) are lower than the present bringing moistures from the Bay of Bengal and South
groundwater value and corresponding precipitation China Sea. Alternatively and more likely, the climatic
value, indicating that the paleoclimate during the change may have been caused by the strong Indian
deposition of the Kudankulam Formation was not arid monsoon system. At present, the eastern coastal plains
like today, but more humid. This suggests that in the of the peninsula, northeast of the study area receive a
late Miocene the paleoclimate was different in southern large amount of NE monsoon precipitation during
India. The present climatic conditions in southern India October–January and groundwater during this period
are controlled by the Indian monsoon system. Probably has d18O values of about 5% (Deshpande et al., 2003).
in the late Miocene, the Indian monsoon system was If this interpretation is accepted, the study area was
weak or not well established, and thus the study area probably under the intense monsoon influence in the late
Miocene.

5.3. Carbon isotope composition

Modern marine carbonate sediments generally have


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
Fig. 5. A scatter plot of d13C and d18O values of the upper carbonate sediments may be related to the influence
Miocene Kudankulam carbonates. Note that each carbonate soil-gas CO2 (Cerling and Hay, 1986), and may suggest
component has its own range in values, and that there is a wide incorporation of 13C-depleted carbon. The wide varia-
scatter and a lack of a general trend between d13C and d18O tion in d13C values (1.5% to 9.0%; Tables 1 and 2)
values. 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 respectively; Table 2) isotopic compositions. This
content (Hudson, 1977; Allan and Matthews, 1977, indicates that pore waters that precipitated these calcite
1982). cements were proximal to the vadose water recharge
Ooids in algal limestone show the least altered d13C zone. Most of the whole rock samples except algal
values (3.771.0%, n ¼ 12) compared to those of limestones show similar carbon and oxygen isotope
whole rock (6.771.1%, n ¼ 28, or 7.070.5%, compositions to these calcite cements (Table 1), which
n ¼ 24; Table 1) and sparry calcite cements (pore-fill suggests that the pore waters were also in close
7.270.5% and molluscan mold-fill 7.770.7%; proximity to the vadose recharge zone. The algal
Table 2). This may be due to relatively early stabiliza- limestones have slightly variable oxygen isotope com-
tion of ooid-forming minerals during diagenesis by the positions that range from 4.2% to 9.4% (Table 1).
pore waters having lesser contribution of organically This suggests that rock–water interactions were variable.
derived light carbon. Whole rock samples in the SW sections (Kudanklam
It is likely that ooid sediments would have been and Perumanal) are slightly enriched in 13C compared to
affected by meteoric waters in the deeper part of the associated calcite cements, indicating that water/rock
phreatic zone. In contrast to the ooids, the whole rock ratio was relatively low with respect to carbon. Due to
samples of the ooid-bearing algal limestone, are depleted the narrow coastal belt in these areas (Fig. 2) resulting in
in 13C, indicating that algal limestone contains signifi- smaller meteoric recharge zone, carbon isotope compo-
cant amount of meteoric cement. Similar influence of sitions of allochems seem to have been less influenced
meteoric water conditions as in ooids might have by meteoric waters during their early stabilization. Vari-
contributed to the algal limestone distributed in the ation in the carbon and oxygen isotope compositions
southwestern sections where shoreline zone is narrower may indicate variable degrees of rock–water interactions
in width than the northeastern sections (Fig. 2). during the meteoric water flow.

5.4. Water–rock interaction 5.5. Paleovegetation

The d18O value is a sensitive parameter for evaluating The role of plants is also indicated by the negative
water–rock ratios, during multiple interactions of d13C values obtained for the Kudankulam carbonates.
meteoric water with the limestones in a diagenetic The isotopic composition of plant-CO2 is dependent
system. The oxygen isotope composition of the rock can on the proportion of different types of vegetation since
achieve isotopic equilibrium with the water at a the d13C values of the plants are determined by the
relatively low water/rock ratio because water (H2O) photosynthetic pathways (Cerling, 1991; Mack et al.,
forms a very large reservoir of oxygen. The reservoir for 1991). C3 plants (Calvin Cycle) have a mean d13C value
carbon in water is much smaller than for oxygen and of about 26%, but display a range from 20% to
much higher water/rock ratios are needed to lower the 35% (Ehleringer, 1989). C4 plants (Hatch–Slack
d13C values of the limestones significantly (Hudson, Cycle) range between 7% and 15%, having an
1977). This water/rock ratio-dependent change is average of 13% (Cerling and Quade, 1993; Smith and
reflected in the wide spread of the d13C values of the Epstein, 1971).
Kudankulam carbonates (Fig. 5). The present carbon isotopic composition of the
The depletion in 13C in the Kudankulam carbonates is atmosphere is 7.8%, but it varies locally and
probably due to the fact that the diagenetic system was seasonally and being depleted relative to the pre-
relatively open, water residence time was short, and soil- industrial atmosphere, which was about 6.5% (Friedli
gas CO2 could mix far down the groundwater flow et al., 1986). In pre-industrial conditions the average
paths. In regions proximal to vadose water recharge, isotopic composition of C3 and C4 plants should have
precipitate and replaced carbonates should have lower been about 25.0% and 11.0%, respectively. Assum-
d13C and 18O values due to the meteoric diagenetic ing an enrichment factor of 1.0% (calciteHCO3 ) at 25 1C
influence (Allan and Matthews, 1982). As the meteoric (Romanek et al., 1992), meteoric water carbon reservoir
water flow becomes more distal, the d13C of the host with which the Kudankulam calcite cements (pore-fill
carbonate becomes less 13C-depleted as a consequence and molluscan mold-fill) precipitated in equilibrium
of a decreasing influence of soil-gas CO2, whereas the would have d13C values of about 8.5%. The carbon
d18O tends to be similar to that of the proximal area reservoirs in the vadose zone of the recharge area have
because meteoric water is a ubiquitous source of oxygen three sources: CO2 from organic respiration (d13C values
during the meteoric diagenesis process. would be variable depending on the vegetation types in
The pore-fill and molluscan mold-fill calcite cements the terrestrial biomass), atmospheric CO2, and dissolved
have similar light carbon (7.270.5% and 7.770.7%, carbonate minerals. A varied mixture of carbon from all
respectively) and oxygen (8.170.8% and 7.272.2%, these sources is also possible. However, considering that
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groundwater bicarbonate ions in recharge areas form Archean rocks such as gneiss and charnockite in
from approximately equal amounts of soil-gas CO2 and southern India could have been uplifted and exposed
limestone carbonate (Garrels and Christ, 1965; Mook, anytime from the Cenozoic to as late as the Quaternary,
1972), meteoric water d13C values of 8.5% would probably due to the stress buildup by the Himalayan
indicate that carbon reservoir was sourced from organic Orogeny. Our study of the Kudankulam carbonates
respiration of the biomass with significant fraction provides additional constraints on this timing. The
(60%) of C4 plants. Since the age of the Kudankulam exposed Archean charnockite and gneiss contain aver-
limestone inferred to be late Miocene to early Pliocene age Sr content of 330 and 319 ppm, respectively
(Bruckner, 1988) when plants utilizing C4 photosyn- (summary in Singh and Rajamani, 2001), and the gneiss
thetic pathways may have already evolved (Quade and has a very high 87Sr/86Sr ratio of about 0.74269
Cerling, 1995), the result of this study supports the (Jayananda et al., 2000). Thus, radiogenic strontium
expansion of C4 plants in the Indian subcontinent by responsible for high 87Sr/86Sr ratios in the Kudankulam
the late Miocene. Strong seasonality due to intense carbonates was probably derived from such Archean
monsoon system is suggested to have contributed the rocks. The production of 87Sr from in-situ Rb-bearing
expansion of C4 plants in southern India. The presence minerals in the Kudankulam carbonates (low Rb
of the C4 plants in southern India paleo-ecosystem as concentrations ranging from 6.5 to 2.8 mg/g and high
suggested by the carbon isotope data is in good Sr concentrations from 81 to 467 mg/g; Table 3) during
agreement with the result of the oxygen isotope data diagenesis is not likely due to the negligibly small
that the paleoclimate was seasonally humid and production of radiogenic 87Sr by decay of 87Rb in
influenced by high rainfall. 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-
5.6. Strontium isotopes an rocks in southern India were already exposed in
late Miocene and supplied sediments to the study
Because of the long residence time of strontium in the area, thus leading to the conclusion that the exposure
ocean the 87Sr/86Sr ratio of seawater is nearly constant of gneisses and deep-seated charnockites in southern
at one specific period in geologic time throughout the India occurred prior to the late Miocene. This inter-
oceans (Burke et al., 1982; Hodell et al., 1989). The ratio pretation is supported also by the results of rare-earth
of 87Sr/86Sr of seawater during the late Miocene to early element geochemistry on the Kudankulam sandstones
Pliocene lies between 0.7089 and 0.7091 (estimated by (Armstrong-Altrin et al., 2004).
Hodell et al., 1989, 1991). The isotopes of Sr are not The decrease in 87Sr/86Sr ratio stratigraphically up-
fractionated in nature (Faure, 1986), such as during sequence from algal limestone to calcareous sandstone
precipitation of carbonate minerals from aqueous (Table 3; Fig. 3) indicates the influx of lesser amount
solutions. Thus, at the time of deposition the Kudanku- of radiogenic Sr to the Kudankulam Formation with
lam limestones should have recorded the isotope time during diagenesis. This suggests the reduction of
compositions of Sr in late Miocene seawater. However, influence of the chemical weathering of Archean
all the Kudankulam samples have higher 87Sr/86Sr rocks on the diagenesis of the Kudankulam carbonates
ratios than the contemporary seawater, indicating through time. This was probably caused by the existence
significant input of radiogenic 87Sr to the system of carbonate sediments of the lower-lying litho-units
after deposition. Such high 87Sr/86Sr ratio is indicative between the Archean rocks and the upper litho-units,
of radiogenic strontium flux and its 87Sr/86Sr ratio thus reducing direct influence of meteoric waters
derived from tectonoclimatic processes such as the draining the Archean rocks. Carbonate rocks onshore
exposure and chemical weathering of the ancient must have reacted with meteoric waters draining
crystalline rocks with high 87Sr/86Sr ratios (Armstrong, the Archean rocks, and this might have progressively
1971; Moore et al., 1988; Hodell et al., 1989). Since the buffered the 87Sr/86Sr ratio for the younger Kudanku-
Kudankulam Formation underwent shallow burial lam litho-units. Alternatively, the decrease in Sr isotopic
diagenesis (Fig. 4a–j), the radiogenic strontium may ratio up-sequence could have been caused by an increase
have been supplied during diagenesis by meteoric in more pristine carbonate as inferred from slight
waters draining the area composed of old crystalline difference in 87Sr/86Sr ratio between calcareous sand-
rocks (Moore et al., 1988; Hodell et al., 1989) such as stone and late Miocene seawater. However, this
those present in southern India (Fig. 1). High rainfall interpretation is not supported by the stable isotope
during that period would have been helpful for this data and petrographic observations. The result of
process. this study show that 87Sr/86Sr ratios of sediments
Based on the geochemistry of immature flood plain during diagenesis could vary significantly stratigraphi-
sediments of the Cauvery (also written as Kaveri) river, cally although sediments underwent similar meteoric
Singh and Rajamani (2001) interpreted that the exposed alteration.
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6. Conclusions (Programa de Mejoramiento del Profesorado; Grant


No: UAEHGO-PTC-280) – CONACYT (Consejo
(1) Both d18O and d13C values of the Kudankulam Nacional de Ciencia y Tecnologı́a; 52574), and PAI
carbonates are depleted in 18O and 13C, respectively, (Programa Anual de Investigación; Grant no: 69B),
compared to those of carbonates in equilibrium with Mexico, for financial assistance. We are very much
contemporaneous seawater. Based on the depleted grateful to Dr. Joachimski and Prof. Dr. Tobschall for
oxygen and carbon isotope compositions of the their comments and suggestions, which greatly im-
sparry calcite cements, it is interpreted that the proved our final manuscript.
Kudankulam carbonates underwent meteoric diag-
enesis in an open diagenetic system that was
proximal to vadose water recharge zone. References
(2) Petrographic data from Upper Miocene Kudankulam
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