Curtin Sarawak 1st International Symposium on Geology (ISG1-2009)
“Utilizing innovative technologies for sustainable Energy Resources 2009” (5th Sep’ 2009)
Geochemical Proxies and Paleo-
Environmental Conditions of Shahabad
Formation, Bhima Basin, Karnataka, South
India
Ramasamy Nagarajan
Department of Science and Mathematics,
School of Engineering and Science,
Curtin University of Technology,
98009, Miri, Sarawak, Malaysia.
Email:nagarajan@curtin.edu.my
Abstract -The climate during Proterozoic particularly
Neoproterozoic was intimately linked to secular
changes in atmospheric composition and played a
significant role in basin evolution as it controlled the
rate of weathering and denudation. It also strongly
influenced the sea level during global glaciations. Hence
to understand the Neoproterozoic climate changes,
number of geochemical climate proxies were used by
different authors for various successions around the
world. In this study, the following geochemical proxies
such as authigenic uranium, V/Cr and Ni/Co, Cu/Zn,
Ce/Ce* and Mn* were used to understand the paleo-
redox conditions of Shahabad limestone Formation,
Bhima basin which is located in Karnataka, South
India. The above geochemical proxies ratio were
calculated from its elemental concentrations. The
authigenic uranium value range between 0.99 and 4.93,
V/Cr ratio fall below 2, Ni/Co ratio vary from 0.18 to
3.03, positive Mn* values and Ce/Ce* value between
0.51 and 0.68 respectively. Thus, the above geochemical
proxy ratios are clearly indicates that the limestone
succession of Shahabad Formation, Bhima Basin was
deposited under oxygen-rich shallow environmental
condition.
Keywords: Redox condition ; Neoproterozoic ;
limestones ; Bhima Basin ; South India.
I. INTRODUCTION
The chemical signatures, in ancient marine
environments, provide information regarding the
secular changes in detrital influx and oxygenation
conditions at the sediment-water interface (e.g., Jones
and Manning, 1994; Holser, 1997; Kamber and
Webb, 2001; Cullers, 2002). Rare Earth Elements
(REE) and some trace elements are used as an
indicator to understand the depositional
environmental system such as widespread marine
anoxia (Liu et al., 1988; German and Elderfield,
1990; Murray et al., 1991b), oceanic palaeo-redox
conditions (Wang et al., 1986; Elderfield and
Pagett, 1986; Liu et al., 1988; Kato et al., 2002;
Madhavaraju and Lee, 2009). Particularly Ce
anomalies in marine carbonate rocks are used as a
reliable indicator for understanding the paleo-
redox conditions (Liu et al., 1988). Geochemical
elements ratio have been used by various authors
to understand the paleo-oxygenation condition of
ancient sediments (Calvert and Pedersen, 1993;
Jones and Manning, 1994; Nath et al., 1997;
Madhavaraju and Ramasamy, 1999; Cullers, 2002;
Armstrong et al., 2003; Dobrzinski et al., 2004;
Nagarajan et al., 2007). The objective of the
present is to understand the paleo-oxygenation
conditions of Neoproterozoic limestones of
Shahabad Formation, Bhima basin, Southern India
by using geochemical proxy elements
concentrations and geochemical ratios.
II. METHODOLOGY
Limestone samples were collected from
outcrops of Shahabad Formation, Bhima basin.
The collected samples were washed thoroughly in
distilled water to remove the contamination. The
selected samples were grinded and sieved through
a 200 mesh sieve for chemical analysis. The
samples were digested in a solution of HNO3 +
HF. The digested samples were analyzed for major
and trace elements by Inductively Coupled
Plasma–Atomic Emission Spectrometry (ICP-
AES-Jobin-Yvon Jy138 Ultrace). Replicate
analyses of samples indicate that errors for major
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 Curtin Sarawak 1st International Symposium on Geology (ISG1-2009)
“Utilizing innovative technologies for sustainable Energy Resources 2009” (5th Sep’ 2009)
elements are better than 1%, whereas the precision for
trace elements varies between 3 and 5%. 0.2 g of
samples were digested with 4 ml HNO3 and 1 ml of
HClO4 for 24 h in a tightly closed Teflon vessel on a
hot plate at 150°C, heated to dryness, and then
digested with a mixture of 4 ml of HF and 1 ml of
HClO4. Later, the solution was evaporated to dryness,
and extracted with 10 ml of 1% HNO3. Meanwhile,
separate sample aliquots were leached with 2M HCl
plus 0.5M HNO3 for 24 h under 25° C to extract the
leachable fraction. The digested samples were
measured for rare earth elements by ICPMS (Plasma
QUAD 3). The geochemical standard SPL – 29 and
NCS 73303 were used for calibration. The precision
of REE analyses are better than 5%. Representative
proxy elements have been used for this study.
III. GEOLOGY OF THE AREA
The sedimentary rocks of the Mesoproterozoic
sedimentary rocks of Kaladgi supergroup and
Neoproterozoic Bhima Groups were deposited on the
eroded edges of the Dharwar Craton (Senthil Kumar
and Srinivasan, 2002) (Fig.1). The Bhima sediments
are well exposed in the Bijapur and Gulburga
districts of northern Karnataka and Ranga Reddy
district of Andhra Pradesh, India. Bhima exposures
are sandwiched between early Precambrian granite –
greenstone terrain of the East Dharwar Craton in the
south and the late Cretaceous – Paleocene Deccan
Trap volcanic Province in the north. Bhima
sediments extended further towards north, which
concealed under Deccan Traps. King (1872) coined
the term Bhima Series and he has been divided the
sedimentary rocks into Muddebihal Sandstones and
Talikote Limestone. Mahadevan (1947) proposed a
new three fold classification viz. i) Lower Bhima
Series [Basal conglomerate – sandstones and shales],
ii) Middle Bhima Series [dominantly consists of
limestones] and iii) Upper Bhima Series [sandstones,
shales and limestones]. Janardhana Rao et al., (1975)
assigned the Group status to the Neoproterozoic
sedimentary rocks of Bhima basin. They classified
the Bhima Group into five distinct formations i.e. i)
Rabanpalli Formation, ii) Shahabad Formation, iii)
Halkal Shale, iv) Katamadevarhalli Formation and v)
Harwal Shale. The classification proposed by
Janardhana Rao et al. (1975) has been followed in
this study. The sedimentary rocks are trending in the
NE-SW direction, which exhibit total thickness of
about 300m (Misra et al., 1987). These sedimentary
rocks mainly comprise an alternating sequence of
clastic and carbonate rocks (Janardhana Rao et al.
1975; Misra et al., 1987; Kale et al., 1990) and
covering an area of 5,200 km2. In the clastic
rocks, fine-grained sediments dominate over the
coarse clastics. The Rabanpalli Formation has
been considered as the oldest sedimentary rocks in
the Bhima basin, which deposited over the
Archean basement. Harwal shale is the youngest
formation of the Bhima Group, which is
overlained by Deccan Trap with intratrappean
sedimentaries. The Rabanpalli Formation is
placed under the lower series of Bhima Basin.
Quartz arenites, arkoses, siltstones and shale are
the dominant members of this Formation
(Nagarajan et al., 2007a,b). The limestone
member is the dominant lithology of the Bhima
basin and is classified under Shahabad and
Katamadevarahalli Formations.
The Shahabad Formation is exposed in the
central and eastern parts of the Bhima basin (lat.
16°15’ to 17°35’N long. 76°15’ to 77°30’E)
(Fig.1). The limestones of Bhima basin are the
nonstromatolitic and nondolomitic nature. These
limestones occupy an area of 2,000 km2 in the
Bhima basin. According to Kale et al (1990)
Shahabad Formation’s vertical thickness is less
than 75m including exposures of the
Katamadevarhalli limestone. These limestones are
micritic in nature, petrographically
cryptocrystalline in texture (Malur and Nagendra,
1994; Nagendra and Nagarajan, 2003) with
number of macro and micro stylolites which are
filled with secondary minerals (Nagarajan et al.,
2008). Representative limestone samples were
collected from various exposures and quarries of
Shahabad Formation (Fig.1) and used for this
geochemical study.
Figure 1. Geology map of Bhima basin showing the
Sahabad Formation (modified after Janardhana Rao et al.,
1975)
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 Curtin Sarawak 1st International Symposium on Geology (ISG1-2009)
“Utilizing innovative technologies for sustainable Energy Resources 2009” (5th Sep’ 2009)
IV. RESULTS AND DISCUSSION
The concentrations of elements (Mn, V, Cr, Ni,
Cu Zn, Co, Th, and U) from limestones of Shahabad
Formation, Bhima basin are listed in Table 1. V and
Cr show the variation between 3.30-17.70ppm and
2.64ppm-18ppm respectively. Co and Cu do not show
much variation ranging between 1-7ppm and 1.19-
10.40ppm respectively. A significant variations
observed in Mn and Th concentration of Shahabad
limestones (108-380ppm and 0-16.6ppm
respectively). The elemental variations among the
limestones of Shahabad formation is shown in fig.2.
The calculated ratios such as U/Th, A/U, V/Cr, Ni/V,
Ni/Co, Mn*, Ce/Ce* are listed in the table. 1 and have
been used in this study to understand the paleo-redox
conditions.
Figure 2. elemental variations in the limestones Shahabad
Formation, Bhima basin.
A. Paleo-oxygenation condition
The oxidation of uranium exerts a strong control
on the marine geochemistry of this element (Barnes
and Cochran, 1990). In oxic condition, uranium is
present in high concentrations as uranyl tricarbonate
species whereas in the reducing condition U(VI) will
be converted into U(IV) species, which can be easily
removed from the seawater and precipitated onto
particle surfaces (Barnes and Cochran, 1990; Nath et
al., 1997). Th is relatively immobile in aqueous
media (Wright et al., 1984). The low content of U is
generally found in the sediments, which deposited in
the oxygenated condition in marine environment
(Somayajulu et al., 1994; Madhavaraju and
Ramasamy, 1999) whereas high content of U is
found in the sediments from low oxygen setting and
oxygen minimum zone (Barnes and Cochran, 1990;
Klinkhammer and Palmer, 1991; Sarkar et al., 1993;
Somayajulu et al., 1994; Nath et al., 1997). The
present study limestones show the U content rages
from 2.58-6.52ppm. The Late Archean granitoids
i.e. the basement rocks of Bhima basin exhibit
high content of U (3-21 ppm with an average of 8
ppm; Senthil Kumar and Srinivasan, 2002). These
granitoids have been altered due to hydrothermal
activity, which leached out uranium from the
accessory minerals and concentrated them along
the fault zones (Senthil Kumar and Srinivasan,
2002). The observed moderate to high content of
U in these limestones are mainly due to
enrichment U in the source rocks which
contributed more U to these limestones.
The authigenic uranium content is also
considered as an index of bottom water condition
in ancient sedimentary sequences (Wignall and
Myers, 1988). The authigenic uranium content can
be calculated as: (authigenic U) = (total U) – Th/3.
The values of authigenic U below 5 thought to
represent oxic depositional conditions while the
values above 5 indicative of suboxic and anoxic
conditions. In this study, authigenic U contents are
less than 5 (~ 0.99-4.93; avg.3.06+0.94). If the
observed high content of U in these limestones
were resulted due to uranium mobilization
(removed from seawater and precipitated on
particles surfaces) then it should be reflected in the
authigenic uranium contents. Thus, the observed
low authigenic U content in these limestones
indicates that these limestones were deposited
under oxic environment.
The V/Cr ratio has been used as an index of
paleo-oxygenation in many studies (Ernst, 1970;
Bjorlykke, 1974; Dill, 1986; Dill et al., 1988). Cr
is mainly incorporated in the detrital fraction of
sediments and it may substitute for Al in the clay
structure (Bjorlykke, 1974). Vanadium may be
bound to organic matter by the incorporation of
V4+ into porphyrins, and is generally found in the
sediments, which deposited under reducing
environments (Shaw et al., 1990). The solubility
of vanadium in natural waters, its extraction from
seawater and absorption onto sediments are mainly
influenced by redox conditions (Bellanca et al.,
1996). Dissolved vanadium is readily bound to
high molecular metallo-organic complexes (Lewan
and Maynard, 1982) or absorbed onto biogenic
materials (Prange and Kremling, 1985). During the
early diagenetic alteration of sediments, vanadium
tends to mobilize from the biogenic materials
under oxic environments, whereas the mobilization
of vanadium is very restricted in anoxic conditions
(Shaw et al., 1990). If the values are above 2, it
indicates anoxic conditions whereas values below
2 suggest more oxidizing conditions (Jones and
Manning, 1994). In the present study, the V/Cr for
all samples varies between 0.71 and 1.84, which
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 Curtin Sarawak 1st International Symposium on Geology (ISG1-2009)
“Utilizing innovative technologies for sustainable Energy Resources 2009” (5th Sep’ 2009)
imply that these limestones were deposited under oxic
depositional environment.
Dypvik (1984) and Dill (1986) used the Ni/Co
ratio as a redox indicator. Jones and Manning (1994)
suggested that the Ni/Co ratio below 5 indicates the
oxic environment whereas the ratio above 5 suggests
the suboxic and anoxic environment. In addition,
nickel, along with Cu and Cr, is mainly enriched in
organic-rich sediments where these metals are trapped
with organic matter (Leventhal and Hosterman, 1982;
Gilkson et al., 1985). Nevertheless, vanadium
accumulates relative to nickel in reducing
environments, where sulphate reduction (production
of H2S) is more efficient and Ni2+ may be partially
delayed by NiS complexes (Lewan and Maynard,
1982; Lewan, 1984; Odermatt and Curiale, 1991;
Huerta-Diaz and Morse, 1992). In sediments both Ni
and Co are found in Pyrite (e.g., Raiswell and Plant,
1980; Patterson et al., 1986) and diagenetic pyrite
usually has Ni/Co > 1. Ni/Co ratio is always less than
5 in sediments deposited oxic water column, 5 to 7
indicate dysoxic water column and values above 7
indicate anoxic water column (Jones and Manning,
1994).The Limestones of Shahabad formation show
low Ni/Co ratio (~ 0.18-3.03 with an average
1.85+0.77), which suggest that these sediments were
deposited under well oxygenated environment and the
higher concentration of this ratio should be due to
presence of pyrite in some of the samples of the study
area. In addition, the Cu/Zn ratio also have been used
as a redox parameter (Hallberg, 1976). According to
him the increasing Cu/Zn ratio indicates a reducing
depositional condition, while decreasing Cu/Zn ratio
suggest oxidizing conditions. However, the low
Cu/Zn ratios for this study samples are 0.09 to 0.63
(avg.0.66+0.04) which indicates that these limestones
were deposited in a well oxidizing condition.
In oxic conditions, Ce is less readily dissolved in
seawater, so that oxic seawater is more depleted with
respect to Ce, whereas oxic sediments are more
enhanced with respect to Ce. Accordingly, organisms
extracting phosphate from oxic seawater show a
negative Ce anomaly (Wright et al 1987) and may
result from the presence of Calcareous and siliceous
organisms, phillipsites and smectite (Goldberg et al.,
1963; Piper, 1974a,b; Courtois and Jaffrezic-Renault,
1977; Desprairies and Courtois, 1980; Tlig and
Steinberg, 1982), whereas Fe oxide-rich oxic
sediments, such as red clay, have a positive Ce
anomaly (Piper, 1974b; Thomson et al 1984).
Conversely, in suboxic seawater, Ce containing
sediments are mobilized so that Ce is released into the
water column resulting in a less negative to positive
anomaly in seawater (De Baar 1991). Therefore, in
anoxic sediments, Ce is depleted and the sediments
show a negative anomaly. The values of Ce/Ce* >1
and <1 indicate the positive and negative
anomalies, respectively (Toyoda et al., 1990). The
negative Ce anomaly reflects the incorporation of
REE directly from seawater or pore water under
oxic condition. The presence or absence of Ce
anomalies in ancient marine authigenic sediments
has the potential for establishing paleoredox
variations in ancient oceans (Wright et al 1984,
Liu et al 1988, Armstrong-Altrin et al., 2003). In
the present study limestones show negative Ce
anomaly and Ce/Ce* ranges between 0.51 to 0.68,
which supports for the oxic condition.
The limestones of Shahabad Formation show
little variations in Mn concentration (108ppm to
380 ppm). The fluctuation in Mn values in these
limestones may be due to the variations in the
environmental conditions. Variation in the
solubility of Fe and Mn may lead to significant
fractionation of these metals across the redox
boundaries with the most Fe being fixed in
sulphide under low Eh conditions, while Mn tends
to incorporated under more oxygenated conditions
above the redox boundary (Krauskopf, 1979;
Bellanca et al., 1996). Based on this, Machhour et
al. (1994) and Bellanca et al. (1996) have proposed
the relationship Mn* = log
[(MnSample/MnShale)/(FeSample/Feshale)] to find out the
redox conditions of the depositional environment
and Mn* values have been used by various authors
(i.e. Machhour et al., 1994; Bellanca et al., 1996;
Cullers, 2002; Nagarajan et al., 2007a;
Madhavaraju and Lee, 2009) to find out the redox
potential of the depositional environment. The
mean shale value used for Mn and Fe is 600ppm
and 46,150ppm respectively (Wedepohl, 1978).
These limestones show significant positive Mn*
values (0.41 to 0.98 table.1) which suggesting that
these limestones have been deposited under oxic
conditions. The inverse correlation of the Ce/ Ce*
values and Mn* values suggests that the redox
distribution of Ce was linked with that of Mn and
Fe. The oxidizing conditions that produced the
positive Mn* values also could have produced the
most negative Ce/Ce* anomalies; the more
reducing conditions that produced the negative
Mn* values could have produced the most positive
Ce/Ce* values. The Ce/Ce* ratios are lower and
the Mn* values are more positive in the limestones
of Shahabad Formation, suggesting that they
formed in an oxidizing environment.
V. CONCLUSIONS
Geochemical proxies such as authigenic
uranium, V/Cr and Ni/Co, Cu/Zn, Ce/Ce* and
Mn* are clearly indicates that the limestone
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 Curtin Sarawak 1st International Symposium on Geology (ISG1-2009)
“Utilizing innovative technologies for sustainable Energy Resources 2009” (5th Sep’ 2009)
succession of Shahabad Formation, Bhima Basin was
deposited oxygen-rich environmental shallow marine
condition.
ACKNOWLEDGEMENT
The author thanks Dr. Moutte, for his assistance in
chemical analyses. This study was greatly improved
by Dr.Nagendra, Dr. Srinivasalu, Dr. J. Madhavaraju
and Dr. J. S. Armstrong-Altrin from their decisive
suggestions.
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 Curtin Sarawak 1st International Symposium on Geology (ISG1-2009)
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TABLE I. ELEMENTS CONCENTRATION AND PROXY RATIOS OF SHAHABAD LIMESTONES OF BHIMA BASIN.
Sample
No. Mn Th U. V. Cr Ni Cu Zn Co A/U V/Cr Ni/Co Cu/Zn Ce/Ce* Mn*
S62 263 1.66 5.48 4.81 2.7 1.27 2.15 7.6 7 4.93 1.78 0.18 0.28 0.68 0.81
S26 232 1.9 2.58 3.3 2.64 1.8 6.43 10.2 1 1.95 1.25 1.80 0.63 0.61 0.98
E28 232 16.6 6.52 5.53 4.23 2.99 1.19 12.7 2 0.99 1.31 1.50 0.09 NA 0.78
E85 266 1.48 3.81 6.2 3.37 3.21 1.3 13.4 3 3.32 1.84 1.07 0.10 NA 0.72
S65 318 3.2 4.75 8.05 11.3 3.6 2.2 13.3 2 3.68 0.71 1.80 0.17 NA 0.82
S56AG 310 2.34 3.45 7.89 6.41 3.25 3.5 11.6 6 2.67 1.23 0.54 0.30 NA 0.78
S38A 310 2.49 4.11 7.64 5.76 3.73 3.59 10.2 2 3.28 1.33 1.87 0.35 0.52 0.87
C46 263 BDL 3.5 8.37 8.74 4.27 5.67 13.7 3 3.50 0.96 1.42 0.41 NA 0.71
S56B 349 1.57 3.28 7.14 6.07 3 4.23 10.8 2 2.76 1.18 1.50 0.39 0.54 0.84
E167 232 3.15 4.35 12.8 13.1 8.32 5.14 25.6 5 3.30 0.98 1.66 0.20 NA 0.53
E81 108 BDL 2.85 4.79 3.87 2.74 3.36 9.26 1 2.85 1.24 2.74 0.36 NA 0.42
S50 349 2.21 4.65 8.88 7.95 6.15 4.18 14.3 3 3.91 1.12 2.05 0.29 NA 0.68
S38C 379 3.52 4.15 10.8 8.34 5.89 2.75 19.8 4 2.98 1.29 1.47 0.14 0.59 0.71
S60 271 2.92 3.95 10.2 11.4 5.65 4.19 22.4 2 2.98 0.89 2.83 0.19 NA 0.60
E143 186 BDL 3.68 4.78 4.74 2.46 4.33 28.5 2 3.68 1.01 1.23 0.15 NA 0.60
S17 364 2.65 2.66 12.9 14.3 6.64 3.26 15.5 3 1.78 0.90 2.21 0.21 0.62 0.41
S56 380 1.76 4.36 16.2 15 9 4.5 25.8 3 3.77 1.08 3.00 0.17 0.58 0.49
S56AB 364 2.08 4.54 17.2 17.4 10.5 9.08 29.7 4 3.85 0.99 2.63 0.31 0.51 0.84
S38B 318 3.38 2.99 14.9 13.3 7.67 5.53 21.8 3 1.86 1.12 2.56 0.25 0.60 0.55
S38D 341 4.61 4.77 15.7 15.3 10.3 10.4 22.6 6 3.23 1.03 1.72 0.46 0.55 0.56
S24 379 3.73 3.17 17.7 18 9.1 7.42 20.3 3 1.93 0.98 3.03 0.37 NA 0.44
Min 108.00 0.00 2.58 3.30 2.64 1.27 1.19 7.60 1.00 0.99 0.71 0.18 0.09 0.51 0.41
Max 380.00 16.60 6.52 17.70 18.00 10.50 10.40 29.70 7.00 4.93 1.84 3.03 0.63 0.68 0.98
Avg 295.90 2.92 3.98 9.80 9.23 5.31 4.50 17.10 3.19 3.01 1.15 1.85 0.28 0.58 0.67
StdDev 71.60 3.37 0.97 4.52 5.03 2.89 2.35 6.79 1.63 0.91 0.27 0.77 0.13 0.05 0.16

*BDL-Below Detection Limit; NA-Not Analysed

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