Gondwana Research 11 (2007) 504 – 515

www.elsevier.com/locate/gr

Implications of super dense carbonic and hypersaline f luid inclusions in

granites from the Ranchi area, Chottanagpur Gneissic Complex,
Eastern India
B. Mishra a,⁎, C.S. Saravanan a , A. Bhattacharya a , S. Goon a , S. Mahato a , H.J. Bernhardt b
a
Department of Geology and Geophysics, Indian Institute of Technology, Kharagpur 721302, India
b
Institut fur Mineralogie, Ruhr Universitát, D-44801 Bochum, Germany
Received 18 May 2006; received in revised form 20 September 2006; accepted 25 September 2006
Available online 1 November 2006

Abstract

A combined fluid inclusion and mineral thermobarometric study in groups of synchronous inclusions in quartz within weakly foliated granites
from the Chottanagpur Gneissic Complex, India, reveals super dense carbonic (CO2 with minor CH4 and H2O) inclusions and hypersaline (H2O–
NaCl ± NaHCO3) inclusions, with halite- and nahcolite daughter phases. This study documents the highest density (1.115 g cm− 3) CO2 fluids ever
reported in granites. Fluid isochores, constructed from CO2 (± CH4) and halite-bearing inclusions, coupled with two-feldspar thermometry
constrain the minimum P–T at 8 kbar/∼ 750 °C for fluid entrapment in granites. By contrast, the carbonic inclusions in quartz from granite-hosted
metapelite enclaves contain substantial CH4 (up to 30 mol%), and the entrapment pressure (∼4.3 kbar/600 °C) is considerably lower compared to
those in the granites. By implication, the sillimanite-free granites were not derived from the metapelitic enclaves, and instead were formed by
partial melting of fluid-heterogeneous lower crustal protoliths, with fluid entrapment at magmatic conditions.
© 2006 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

Keywords: Super dense CO2; Hypersaline; Granites; Enclaves; Fluid inclusions

1. Introduction
Granulite terrains are dominated by quartzofeldspathic,
mafic and pelitic lithologies that contain biotite and/or
amphiboles as the principal hydroxyl (and halogen) bearing
phases, whereas calcareous rocks with carbonate phases
(calcite, scapolite among others) occur in vastly subordinate
amounts. During prograde granulite facies regional metamor-
phism, the liberated fluids are therefore expected to be
overwhelmingly hydrous on a regional scale, rather being
carbonic in nature, although the latter may locally dominate.
Taking the argument a step further, the regionally expansive
granites produced by middle to lower crustal melting (Fyfe,
1973; Johannes and Holtz, 1996) are expected to be H2O-rich,
rather than carbonic, unless melting occurred under open
⁎ Corresponding author. Tel.: +91 3222 283372; fax: +91 3222 282268.
E-mail address: bmgg@iitkgp.ac.in (B. Mishra).
1342-937X/$ - see front matter © 2006 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.gr.2006.09.002
system condition. A case has been made that CO2 added from
reservoirs external to the crustal sources (cf. Newton et al.,
1980; Touret, 1992) dilutes H2O produced by prograde
dehydration reactions. The feasibility of such a process has
been widely debated (Janardhan et al., 1982; Hansen et al.,
1984; Valley and O'Neill, 1984; Lamb and Valley, 1984). Thus,
fluid inclusions trapped in early fractionating minerals and
incongruently-produced phases (“the early inclusions”) during
closed system crustal melting are likely to be aqueous in nature,
while those trapped by later crystallizing phases are expected to
incorporate modifications effected by subsequent fractionation
and contamination of fluid in the melt (Nabelek and Ternes,
1997). For conditions of open system melting envisaged above,
the “early inclusions” are expected to be aqueous-carbonic and
even carbonic depending upon the magnitude of CO2 fluxing.
Syn-metamorphic fluids in granulites are overwhelmingly CO2-
rich, with typical density values more than 1.0 g cm− 3 (Touret,
1985, 2001; Tsunogae et al., 2002; Fonarev et al., 2003; Santosh
 B. Mishra et al. / Gondwana Research 11 (2007) 504–515 505

Fig. 1. Regional geological map showing the disposition of the CGC, the North Singhbhum Mobile Belt (NSMB) and the Singhbhum Craton. The three granite
samples studied are indicated by arrows (a). Outcrop map at Dasam Falls (sample #SAD34) showing the intrusive relation between the granite and the migmatitic
metapelite enclave (b). Locations for samples #SAD34C, SAD34D and SAD34E are indicated by C, D and E.

and Tsunogae, 2003; Sarkar et al., 2003). Again for closed
system melting in the presence of an H2O–CO2 fluid,
irrespective of the origin of the carbonic component, the
composition of the “early inclusions” is expected to be aqueous-
carbonic. This emphasizes the need to examine the composi-
tions of fluid inclusions in granites as a tool for understanding
crustal anatectic processes.
Phase equilibrium studies suggest that granulites are
depleted in H2O, X(H2O) b 0.2 (Nesbit, 1980; Harris et al.,
1982; Sen and Bhattacharya, 1984; Bhattacharya and Sen,
1986). However, experimental determinations and theoretical
arguments (Tuttle and Bowen, 1958; Burnham and Ohmoto,
1980; Whitney, 1988) seem to suggest H2O to be the most
dominant fluid phase in felsic melts. A review of the available
literature on upper to mid-crustal granites, including the ore-
bearing ones, reveals that the fluid inclusions are dominated by
H2O (± CO2) with dissolved chlorides, sometimes up to
hydrosaline melts (Roedder, 1984; Frezzotti, 1992). However,
the emerging gamut of data mainly from fluid/melt inclusion
studies seems to indicate that CO2 may be a major constituent of
magmatic fluids, especially in the mid-to-lower crustal
granitoids (cf. Frost and Touret, 1989; Frezzotti et al., 1994).
CO2-bearing fluids have been documented in fayalite-bearing
granites as in case of granite–charnockite transformation within
Kleivan granite, South Norway (Konnerup-Madsen, 1977). In
the Gadar Province, southern Greenland, granites and syenites
are characterized by CO2–H2O fluids and the nepheline–
syenites contain reduced CO2–CH4 fluids (Konnerup-Madsen,
1984; Konnerup-Madsen et al., 1985). Low density “comag-
matic” carbonic and rare secondary inclusions with crystalliza-
tion conditions of ∼ 3 kbar and 950°–1000 °C, are reported in
the Sybille monzosyenite, Laramie Anorthosite Complex,
Wyoming (Frost and Touret, 1989). Syn-kinematic leuco-
monzogranite in the Deep Freeze Range, Antarctica, preserves
CO2-rich briny fluid inclusions that imply ‘crystallization
conditions’ of ∼ 3 kbar/750 °C (Frezzotti et al., 1994).
Similarly, fluid inclusion studies in the Harney Peak granite,
Black Hills, South Dakota, USA, indicate a change in magmatic
fluid chemistry from H2O–CO2 to CO2 with increasing
fractional crystallization of the magma at ‘entrapment pressure’
of ∼3.5 kbar (Nabelek and Ternes, 1997). The maximum
reported density value of CO2-rich fluids from non-ore bearing
granites from the Vattamalai granite pluton in the Palaghat-
Cauvery Shear Zone, southern India is 0.912 g cm− 3, consistent
with fluid entrapment at 5 kbar/1000 °C (Santosh et al., 2005).
The emerging data indicate that entrapment pressure of fluid
inclusions in granites proven to be or “suggestive” of magmatic
origin is seldom ≥ 5 kbar, i.e. ∼ 17 km, barely corresponding to
mid-crustal depth. The question remains as to why lower crustal
higher-density fluid inclusions are not reported from granites. Is
it then the investigated fluid inclusions of magmatic origin do
not represent granulite facies anatectic conditions, but corre-
spond to entrapment of magmatic fluids modified by open
system melt crystallization during ascent and emplacement of
the intrusives (cf. Nabelek and Ternes, 1997)? The alternative
explanation would be that the expansive granites do not form at
depths below 5 kbar – the granite–granulite misconnection − in
contradiction to existing models of granite genesis. In the
present study, we demonstrate the existence of super dense
carbonic and hypersaline fluids preserved in weakly foliated
506 B. Mishra et al. / Gondwana Research 11 (2007) 504–515
Fig. 2. Photomicrographs of (a) typical granite showing brittle fracture in K-
feldspar (arrow head) and interstitial nature of quartz and ilmenite grains, and (b)
pelitic enclave showing schistosity defined by biotite–sillimanite, overgrown by
porphyroblastic garnet.
granites from the Chottanagpur Gneissic Complex (CGC) in the
Eastern India. We argue these fluids were neither introduced
during solid state deformation-metamorphism of the granites
nor inherited from the enclaves into which the granites intrude,
but were trapped during crystallization of the magmatic phases
at middle/lower crustal depths.
2. Geological background
The Chottanagpur Gneissic Complex (Fig. 1a) comprises two
major litho-structural units, e.g. multiply deformed amphibo-
lite–granodiorite facies enclaves hosted in blastoporphyritic
granite–granodiorite rocks (Mahadevan, 2002). The intrusive is
characterized by E–W trending monophase fabric variably
developed throughout the CGC. In the Ranchi area (box in
Fig. 1a), the enclave suite comprises of metapelites (muscovite–
sillimanite–K-feldspar–quartz ± biotite, ± garnet), metabasic
gneisses (hornblende–plagioclase–scapolite–clinozoisite), and
calc-silicate gneisses (tremolite–clinopyroxene–clinozoisite).
The map of the Dasam Falls (Fig. 1b) typifies the rela-
tionship between the enclave suite and granite in the Ranchi
area. The metapelites are characterized by alternate leucocratic
layers (quartz N K-feldspar N plagioclase, with minor biotite,
sillimanite) and melanocratic layers (biotite, muscovite, silli-
manite, ilmenite and rutile, with subordinate quartz). The
layering and the strong shape- and lattice preferred orientation
of biotite and muscovite define the earliest fabric (S1) in the
rocks (D1 deformation). Rare garnet porphyroblasts are
restricted to the leucocratic layers or at the leucocratic–
melanocratic layer interface, and typically truncate the S1
schistosity (Fig. 2b). The S1 foliation is affected by tight D2
folds, with development of crenulation schistosity S2, and
refolded (D3) into a set of asymmetric buckle folds with E–W
trending axial planes. The granite and the pegmatites truncate
the D2 structures in metapelites, but are affected by the D3
deformation. The monophase E–W trending fabric in the
foliated granite is axial planar to the D3 folds in metapelites
(Fig. 1b).
The monophase fabric in granites is defined by a weak
shape-preferred alignment of mica minerals (biotite/muscovite)
sub-parallel with weakly amoeboid quartz grains showing strain
wavy extinction and occasional sweeping deformation bands.
The minerals feebly warp around the igneous feldspar clasts
with prominent brittle fractures (Fig. 2a). Occasionally sub-
grains are developed at the margins of the K-feldspar grains that
otherwise show weak strain wavy extinction as the only
evidence for plastic deformation. Chlorite intergrown with
biotite, and rare clinozoisite replacing plagioclase, provide the
only evidence of metamorphic overprinting in the granites.
Garnet, occasionally present in the granites, occurs as inclusions
within weakly deformed magmatic feldspar grains. These garnet
grains are either entrained from the protolith or formed by
incongruent melting that produced the granites. Microtextural
relations involving quartz and especially K-feldspar (brittle-
ductile transition ∼450 °C; Wintsch and Yi, 2002) suggest that
the ambient temperature during the solid state deformation (D3)
did not exceed greenschist facies condition, consistent with the
occurrences of chlorite and clinozoisite in the rocks. On the
contrary, the pre/syn-D1 metamorphic grade recorded by the
enclave suite broadly corresponds to at least upper amphibolite
facies, with anatectic condition barely attained. On the other
hand, the occurrence of post-D3 inter-digital muscovite + quartz
intergrowth at the metapelite–granite interface is in agreement
with the prevailing greenschist facies conditions.
3. Thermobarometry
The chemical data of relevant minerals, along with pertinent
mineral compositions, used for thermobarometry in three
foliated granites (SAD2C, GO56Z, and SAD34D; Fig. 1a)
and the melanosome part of the migmatitic metapelite from the
Dasam Falls (SAD34C; Fig. 1a, b) are furnished in Tables 1 and
2 respectively. The analyses were carried out using a CAMECA
SX-100 microprobe at the Geological Survey of India, Kolkata,
excepting #SAD34C and the feldspars in #SAD34D that were
analyzed with the help of a CAMECA SX-50 probe at the
Zentrale Elektronen Mikrosonde, Ruhr Universitát, Bochum.
In both the equipment, the operating conditions were 15 kV
 B. Mishra et al. / Gondwana Research 11 (2007) 504–515 507

Table 1
Representative electron probe microanalysis of feldspars in granites
Sample SAD-2C GO-56Z SAD-34D
Mineral Orthoclase Plagioclase Orthoclase Plagioclase Orthoclase Plagioclase
Analysis no. 63 72 85 94 30 39 (5/1) (5/3) 18 (mat) 19 (lam) 31 37
SiO2 64.520 63.880 60.290 61.220 65.630 63.540 61.070 62.250 63.490 64.430 59.340 60.240
TiO2 0.000 0.020 0.000 0.000 0.010 0.020 0.000 0.020 0.000 0.000 0.000 0.000
Al2O3 18.870 18.920 23.910 23.840 19.230 18.560 23.380 23.770 19.220 23.090 25.690 24.560
Cr2O3 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Fe2O3 0.010 0.000 0.000 0.060 0.000 0.010 0.000 0.000 0.020 0.020 0.030 0.020
FeO 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
MnO 0.000 0.010 0.000 0.060 0.040 0.000 0.080 0.000 0.000 0.000 0.000 0.000
MgO 0.000 0.020 0.000 0.040 0.000 0.000 0.000 0.030 0.010 0.000 0.010 0.010
CaO 0.180 0.370 5.750 5.420 0.040 0.010 4.570 4.710 0.570 4.000 6.830 5.750
Na2O 4.930 2.980 8.180 8.420 5.610 0.670 8.490 6.250 1.830 7.870 7.610 8.330
K2O 9.760 12.720 0.350 0.360 9.040 16.090 0.220 0.190 13.240 2.320 0.170 0.170
Total 98.280 98.930 98.480 99.420 99.610 98.920 97.810 97.220 98.400 101.730 99.680 99.080
Si 2.973 2.959 2.722 2.373 2.974 2.975 2.763 2.800 2.956 2.815 2.653 2.703
Ti 0.000 0.001 0.000 0.000 0.000 0.001 0.000 0.001 0.000 0.000 0.000 0.000
Al 1.025 1.033 1.273 1.256 1.027 1.024 1.247 1.261 1.055 1.189 1.354 1.299
Cr 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Fe3+ 0.000 0.000 0.000 0.002 0.000 0.000 0.000 0.000 0.001 0.001 0.001 0.001
Fe2+ 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Mn 0.000 0.000 0.000 0.002 0.002 0.000 0.003 0.000 0.000 0.000 0.000 0.000
Mg 0.000 0.001 0.000 0.003 0.000 0.000 0.000 0.002 0.001 0.000 0.001 0.001
Ca 0.009 0.018 0.278 0.260 0.002 0.001 0.222 0.227 0.028 0.187 0.327 0.276
Na 0.440 0.268 0.716 0.730 0.493 0.061 0.745 0.545 0.165 0.667 0.660 0.725
K 0.574 0.753 0.020 0.021 0.523 0.962 0.013 0.011 0.787 0.129 0.010 0.010
Total 5.022 5.034 5.010 5.010 5.020 5.024 4.992 4.847 4.993 4.988 5.005 5.014
XK 0.561 0.725 0.020 0.021 0.514 0.939 0.013 0.014 0.803 0.131 0.010 0.010
XNa 0.430 0.258 0.706 0.722 0.484 0.060 0.760 0.696 0.168 0.679 0.662 0.717
XCa 0.009 0.017 0.274 0.257 0.002 0.001 0.227 0.290 0.029 0.190 0.328 0.273

acceleration voltage, 15 nA beam current, 20–30 s counting
time. The beam diameter was set 1 μm for all phases excepting
mica and feldspars, which were analyzed by larger beams.
Appropriate natural and synthetic minerals were used as
standards and the raw data were corrected by using the PAP
program (Pouchou and Pichoir, 1984).
Feldspars in granites contain micron to sub-micron scale
perthites and anti-perthites. Hence, analysis of individual fine
lamellae and the matrix was not possible. On the other hand,
integrated analyses were performed at many places using a
20 μm beam and average compositions were used for ternary
feldspar thermometry. For thermometric purpose the SOLV-
CALC program (Wen and Nekvasil, 1994) was used. The
results of SOLVCALC program, considering six available
formulations therein, yielded a temperature range of 660°–
740 °C. The temperature range represents a minimum estimate
at which Na–Ca exchange between the feldspars was locked in
on cooling from the magmatic values. The depth of formation/
emplacement of the granites is difficult to estimate. However,
based on the occurrence of rare garnet and absence of cordierite
in the granites, a minimum melting pressure of ∼ 4 kbar may be
inferred from the results of melting experiments (c.f. Vielzeuf
and Montel, 1994).
Biotite–garnet Fe–Mg exchange thermometry was used for
temperature estimation in the melanosome part of the
migmatitic metapelite enclave from Dasam Falls using the
compositions of the matrix biotite and garnet core. In all, eight
calibrations (Thomson, 1976; Holdaway and Lee, 1977; Ferry
and Spear, 1978; Hodges and Spear, 1982; Perchuk and
Lavrent'eva, 1983; Dasgupta et al., 1991; Bhattacharya et al.,
1992) were tried and the results were found to be more or less
consistent. The biotite–garnet thermometer of Bhattacharya
et al. (1992) yielded the lowest temperature (520°–585 °C),
whereas the Hodges and Spear's formulation (1982) recorded
the highest temperature (660°–690 °C).
Pressure estimate for the metapelite (biotite–garnet–musco-
vite–sillimanite–plagioclase–quartz) was carried out using the
THERMOCALC program (Holland and Powell, 1998). The
following end member reactions (Eqs. (1)–(4)) were used.
grossular þ 2 sillimanite þ quartz ¼ 3 anorthite ð1Þ
pyrope þ grossular þ muscovite
¼ phlogopite þ 3 anorthite ð2Þ
almandine þ grossular þ muscovite
¼ annite þ 3 anorthite ð3Þ
annite þ 2 sillimanite þ quartz
¼ almandine þ muscovite ð4Þ
The P–T locations for the reactions (Eqs. (1)–(4)) were
computed using the analytical data in Table 2. The pressure
508 B. Mishra et al. / Gondwana Research 11 (2007) 504–515

Table 2
Representative electron probe microanalysis of minerals in melanosome of migmatitic metapelite enclave
Sample SAD-34C
Mineral Garnet Biotite Muscovite Plagioclase
No g c34 g 32 g 31 g 33 g 34 bi c33 bi 24 bi 23 bi 25 mu 41 fsp c29 fsp c30
SiO2 36.490 35.280 35.930 35.800 35.790 34.150 33.860 34.080 33.120 45.280 62.090 62.040
TiO2 0.000 0.000 0.000 0.040 0.000 3.470 3.250 3.370 2.980 1.120 0.000 0.070
Al2O3 21.020 20.620 20.840 20.790 20.610 18.070 18.200 18.460 17.720 35.310 23.970 23.420
Cr2O3 0.020 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Fe2O3 0.570 2.800 1.480 2.050 2.520 0.000 0.000 0.000 0.000 0.000 0.000 0.000
FeO 31.660 29.900 31.010 30.100 29.860 24.190 23.990 23.830 24.570 0.990 0.000 0.000
MnO 7.320 7.720 7.670 8.710 8.730 0.220 0.210 0.230 0.190 0.040 0.020 0.030
MgO 1.800 1.690 1.650 1.430 1.420 6.190 5.980 5.880 5.720 0.520 0.000 0.010
CaO 0.980 0.990 0.970 0.990 1.030 0.010 0.030 0.000 0.020 0.020 4.930 4.570
Na2O 0.020 0.040 0.000 0.010 0.040 0.160 0.220 0.200 0.210 0.710 8.950 9.190
K2O 0.000 0.000 0.000 0.020 0.020 8.580 9.340 9.480 9.590 10.640 0.100 0.100
Total 99.880 99.040 99.550 99.940 100.010 95.050 95.090 95.540 94.130 94.640 100.060 99.430
Si 2.974 2.913 2.947 2.932 2.932 2.669 2.657 2.659 2.647 3.040 2.750 2.765
Ti 0.000 0.000 0.000 0.002 0.000 0.204 0.192 0.198 0.179 0.057 0.000 0.002
Al 2.020 2.007 2.015 2.008 1.990 1.665 1.684 1.698 1.670 2.795 1.252 1.230
Cr 0.001 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Fe3+ 0.0-35 0.174 0.091 0.126 0.155 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Fe2+ 2.158 2.065 2.127 2.062 2.045 1.581 1.575 1.555 1.642 0.056 0.000 0.000
Mn 0.505 0.540 0.533 0.604 0.606 0.015 0.014 0.015 0.013 0.002 0.001 0.001
Mg 0.219 0.208 0.202 0.175 0.173 0.721 0.699 0.684 0.681 0.052 0.000 0.001
Ca 0.086 0.088 0.085 0.087 0.090 0.001 0.003 0.000 0.002 0.001 0.234 0.218
Na 0.003 0.006 0.000 0.002 0.006 0.024 0.033 0.030 0.033 0.092 0.769 0.794
K 0.000 0.000 0.000 0.002 0.002 0.856 0.936 0.944 0.979 0.912 0.006 0.006
Total 8.000 8.000 8.000 8.000 8.000 7.735 7.794 7.782 7.845 7.008 5.011 5.017
XFe 0.727 0.712 0.722 0.704 0.702 0.682 0.687 0.690 0.702 – – –
XMn 0.170 0.186 0.181 0.206 0.208 0.006 0.006 0.007 0.006 – – –
XMg 0.074 0.072 0.069 0.060 0.059 0.311 0.305 0.303 0.291 – – –
XCa 0.029 0.030 0.029 0.030 0.031 0.000 0.001 0.000 0.001 0.001 0.232 0.214
XNa – – – – – – – – – 0.092 0.762 0.780
XK – – – – – – – – – 0.907 0.006 0.006

estimates, along with results of biotite–garnet thermometry
yielded the P–T box for metamorphic equilibration in Fig. 7.
4. Fluid inclusion studies
Fluid inclusion studies were undertaken in quartz from wafers
of three granites, e.g. SAD2C, SAD34D, GO56Z, and one
garnet-bearing metatexite leucosome in the Dasam Falls
metapelite enclave (#SAD34E, Fig. 1b). Although inclusions
were also observed in garnet and feldspar, these are extremely
small in size (≤2 μm). Therefore, no further study could be
pursued on them. Inclusions are classified on the basis of their
disposition and phase contents. Suitable chips of wafer and
groups of synchronous inclusions (GSI; Touret, 2001) are
selected for microthermometry in each sample. Microthermo-
metric runs were conducted on a LINKAM THMS 600 heating-
freezing unit, calibrated at − 56.6 °C, 0 °C and 327.5 °C by
melting of synthetic CO2, H2O inclusions and spec pure metallic
Pb respectively. The precision during freezing was ± 0.1 °C, and
± 1.0 °C on heating. Representative inclusions were analyzed by
a RENISHAW RM1000B laser Raman Microspectrometer,
routinely calibrated by the first order Raman band of silicon (at
520 cm− 1). The Raman system is equipped with edge filters to
block the Rayleigh lines, confocal configuration, thermoelec-
trically cooled CCD detector, air-cooled laser and powerful
software to acquire and evaluate the spectral data. Irradiation
was by the 514.5-nm line of a continuous wave Ar-ion laser,
which delivered about 8 mW laser power at the sample surface.
The acquisition time was 60 s. With several scans on the same
inclusion, the reproducibility of the Raman shift was found to be
± 1 cm− 1. For calculation of fluid density/salinity and construc-
tion of isochores the AQSO, BULK and ISOC programs,
available in the package, FLUIDS (Bakker, 2003) was used. For
this purpose, the equations of state (EOS) of Thiéry et al. (1994a)
and Duan et al. (1992) for CO2 ± CH4 system and those of Archer
(1992) and Zhang and Frantz (1987) for H2O–NaCl system were
used.
4.1. The granite suite
Two types of primary inclusions were observed in granite
quartz. They are as follows: Type-I: At ambient laboratory
temperature, these are monophase carbonic inclusions. At
times, they contain small amount of CH4 and invariably
homogenize in liquid state (i.e., Lco2 + Vco2 → Lco2). Further, a
thin rim of H2O occurs in these inclusions that surrounds the
gaseous part. These occur as clusters or isolated inclusions
(Fig. 3a). Type-II: These are aqueous polyphase high saline
 B. Mishra et al. / Gondwana Research 11 (2007) 504–515 509

Fig. 3. Photomicrographs of fluid inclusions in granite (a) type-I, (b-c) type-II inclusions with a prismatic unidentified phase in (b), (d) type-I inclusion with planar
fracture patterns, (e) hook-shaped type-II inclusions. H, V and N respectively stand for halite, aqueous vapor and nahcolite, (f) coexistence of type-I and type-II
inclusions, and (g) a sketch showing one representative GSI of type-I inclusions. Semi-schematic iso-Th,CO2 contours show density decrease (arrows) from high-
density islands. Bar length in (a) through (g) is 10 μm.

inclusions with a cubic crystal (halite) and with or without
(Figs. 3b, c; 4d) a small second prismatic and birefringent
daughter phase (nahcolite). These inclusions occur as isolated,
clustered and intragranular trails (Touret, 2001). They appear as
negative crystals, oval and of irregular shapes. Inclusions are in
general very small (3–10 μm: type-I) and (3–15 μm: type-II).
While the isolated and clustered inclusions are interpreted to be
primary, those confined to intragranular trails are pseudo-
secondary in nature (Roedder, 1984). Often medium sized type-
I inclusions produce crystallographically oriented fracture
patterns (Fig. 3d). Furthermore, type-II inclusions occasionally
show explosion texture in the form of annular or hook-shaped
inclusions (Fig. 3e). These petrographic features, termed as
explosion texture, are characteristic of post-entrapment reequi-
libration resulting from plastic deformation of inclusions under
conditions of high internal overpressure during isothermal
decompression (cf. Vityk and Bodnar, 1995). Inclusions are
subjected to high internal overpressure, for example during
post-entrapment uplift of the rocks at nearly isothermal
conditions, accompanied by decrease in density of the original
510 B. Mishra et al. / Gondwana Research 11 (2007) 504–515

Fig. 4. Photomicrographs of fluid inclusions in the migmatitic metapelite enclave. Synoptic disposition of the quartz grains within and outside of the garnet
porphyroblast in the studied wafer (a), type-I inclusions in included quartz (b), matrix quartz (c), type-II inclusions in included quartz (d). The dashed lines in (b) and
(d) stand for the orientation of the intragranular trails along which the inclusions occur. Bar length in (b) through (d) is 10 μm.

fluid. While both the types of inclusions coexist in #SAD2C and
#GO56Z, #SAD34D contains exclusively type-II inclusions.
Furthermore, both the types of inclusions occur as isolated ones
in the same GSI plane, implying their possible synchronous
entrapment (Fig. 3f).
Type-I inclusions mostly contain CO2, as seen from the
prominent clusters in their temperatures of CO2 melting (Tm,CO2)
around − 56.7 °C (Fig. 5a). However, the maximum depression
in Tm,CO2 is − 58 °C (Fig. 5a), which along with the relevant CO2
homogenization temperature (Th,CO2) correspond to about
XCH4 = 0.05, as estimated by the graphical method of Thiéry
et al. (1994b). Raman studies confirmed the presence of little
CH4 (Fig. 5e), responsible for depression in Tm,CO2. The peak
for N2 (at ca. 2331 cm− 1) was looked for but was not obtained.
Semi-quantitative calculation of the carbonic phases using the
formulation and Raman scattering cross-sections listed in Burke
(2001) and assuming the instrumental efficiency factors (for
CO2 and CH4) as unity, we arrived at XCH4 values that are
remarkably similar to those obtained by the graphical method.
Many type-I inclusions contained thin rims of H2O (Fig. 3a).
However, no clathrate melting could be observed. Nevertheless,
the presence of H2O was confirmed from its characteristic
Raman hump at ca. 3475 cm− 1 (Fig. 5f). Occurrence of some
carbonic inclusions with narrow rims of H2O indicates the
possible existence of an early CO2–H2O fluid, the aqueous part
is considerably diminished as a consequence of preferential
leakage of H2O (Bakker and Jansen, 1991, 1994). These
inclusions homogenize in liquid state over a wide temperature
(Th,CO2) range of − 42.6 to + 29.3 °C (Fig. 5b), implying
extensive variation in fluid density. This study records the
maximum CO2 density (1.115 g cm− 3) ever reported in relation
to granitic fluids. Interestingly, comparable high-density
(1.172–1.155 g cm− 3) pure CO2 fluid inclusions have been
reported in lower crustal garnet granulites at Kondalpattimedu,
Southern India that formed at 9–11 kbar/740–800 °C (Santosh
and Tsunogae, 2003). Halite-bearing inclusions finally homog-
enized both by liquid–vapor homogenization (Th N Ts,NaCl) and
by halite dissolution (Ts,NaCl N Th). Variations in Th and Ts,NaCl
are respectively in the ranges of 225°–495 °C (Fig. 5c) and
205°–525 °C (Fig. 5d). The maximum salinity value, recorded
in this study is 63.20 wt.% NaCl equivalents and the density
varies between 1.08 and 1.36 g cm− 3.
 B. Mishra et al. / Gondwana Research 11 (2007) 504–515 511

Fig. 5. Histograms of temperatures of melting (a), homogenization of the carbonic phase (b), aqueous liquid–vapor homogenization (c), and halite dissolution (d) of
type-I and II inclusions in granite and leucosome. Number (n) of fluid inclusions studied (a–d) are indicated in each histogram. Raman spectra of CO2 (1282 and
1386 cm −1) and CH4 (2912 cm −1) (e, h), H2O (f: ∼3475 cm −1) in type-I inclusions and nahcolite (g) in type-II inclusions. Raman peaks of quartz appeared at ∼ 1081,
1162 cm −1 and at 1157 cm −1.

4.2. The enclave suite
Inclusions were studied in garnet-hosted (included) quartz
grains and matrix quartz grains in the leucosome (#SAD34E)
within the migmatitic metapelite enclave (Fig. 4a). While both
type-I and type-II inclusions were observed in included quartz
(Fig. 4b, d), the matrix quartz mostly contain type-I inclusions
(Fig. 4c). Thin rims of H2O occur in type-I inclusions in both
garnet-hosted and matrix quartz grains (Fig. 4b, d). Although
the size and shape of the inclusions are comparable to those in
granites, significant differences are evident in the disposition
and composition of inclusions in the granite and the enclave
suites. Inclusions in the latter mostly occur along intra-granular
trails. And further, unlike in granite quartz, the type-I inclusions
in both included and matrix quartz are never pure CO2, as seen
from substantial lowering in their Tm,CO2 (maximum up to
− 61 °C). Variation in Th,CO2 falls in the range of − 31.8 to
20.8 °C (garnet-hosted quartz) and 6.1 to 26.5 °C (matrix
512 B. Mishra et al. / Gondwana Research 11 (2007) 504–515
quartz). The maximum estimated CH4 value, both by graphical
method (Thiéry et al., 1994b) and Raman analysis (Burke,
2001) is 15 mol% in garnet hosted quartz and 30 mol% in
matrix quartz (Fig. 5h). Variations in Th and Ts,NaCl of type-II
inclusions in the included quartz are respectively in the ranges
of 185°–445 °C (Fig. 5c) and 170°–325 °C (Fig. 5d).
5. Discussion
5.1. P–T conditions of fluid entrapment
Representative isochores of type-I inclusions in granites are
plotted in Fig. 6. Those marked with 1.115 and 1.065 (density
values in g cm− 3) respectively correspond to Th,CO2 values
−39.5° (pure CO2) and −42.6 °C (CO2 + 5 mol% CH4). The other
two isochores in Fig. 6 relate to the other modal Th,CO2 values
(−15° and +10 °C) in Fig. 5b. Likewise, two isochores of halite-
bearing inclusions, one for the maximum Ts,NaCl value (525 °C,
density = 1.279 g cm− 3) and the other pertaining to the clustered
Ts,NaCl value in Fig. 5d (301 °C, density = 0.858 g cm− 3) are
shown in Fig. 6. Results of ternary feldspar thermometry, in all the
three granites samples (#SAD2C, #SAD34D, #GO56Z: lines A
and B) intersect the isochores of type-I inclusions, thus yielding
the upper-shaded P–T box in Fig. 6. The P–T estimate (∼8 kbar/
660°–740 °C) is however, a minimum because of the perthitic
nature of K-feldspar and the unaccounted amount of H2O in the
type-I inclusions. Two isochores of halite-bearing inclusions pass
within and close to the P–T condition of the granites (Fig. 6),
implying simultaneous entrapment of carbonic and hypersaline
fluids, further substantiating the textural evidence pertaining to
their coevality (Fig. 3f). Coexistence of dense carbonic fluids and
brines has been reported from Bamble granulites (Touret, 1985
amongst others) and interpreted as a consequence of phase
separation from a mixed fluid system during magmatic evolution
(Frost and Touret, 1989; Johnson, 1991).
The results of thermobarometric analysis for the metapelite
enclave (the melanosome part of the metapelite, sample
Fig. 6. P–T diagram showing isochores of type-I and type-II inclusions in
granite. Numbers are density values (g cm −3) of isochores. The high-P box is the
magmatic P–T conditions of granites and the low-P one is for the metamorphic
condition of the migmatitic metapelite enclave, shown in detail in Fig. 7. The
Al2SiO5 triple point (Holdaway, 1971) and H2O-saturated granite solidus G
(Brown and Fyfe, 1970) are shown for visual aid.
Fig. 7. P–T diagram showing the metamorphic equilibration condition for the
metapelite enclave (sample #SAD34C). The P–T box was constructed from the
intersection of (i) the temperature range (lines A and B) retrieved from biotite–
garnet thermometry, and (ii) the four barometers (Eqs. (1)–(4)) in the
assemblage Bt + Grt + Pl + Sil + Ms + Qtz for the maximum variation in mineral
composition (Table 2). Isochores of type-I and type-II inclusions in included
(within garnet) and matrix quartz in the leucosome (sample #SAD34E) are also
shown.
#SAD34C, Fig. 1b), using biotite–garnet thermometry (520°–
680 °C; several formulations) and the four barometers (Eqs.
(1)–(4)) are shown in Fig. 6, with details amplified in Fig. 7.
Representative isochores of type-I and type-II inclusions in
quartz grains hosted within garnet pass over, within and below
the mineral P–T box (Fig. 7), entailing their syn-metamorphic
nature. The isochores of type-I inclusions in the matrix quartz
are located at lower pressure, compared to the mineral P–T box,
which is effectively due to their relatively larger CH4 contents.
Such difference in fluid chemistry is possibly an indication of
later entrapment of type-I inclusions in matrix quartz compared
to that in included quartz and at comparatively shallower levels.
5.2. Magmatic origin for fluid inclusions in granites
Several lines of evidence considered together suggest that
the P–T conditions for fluid entrapment in granites represent
magmatic conditions. First, the spatial variation of Th,CO2
values in type-I carbonic inclusions shown in one representative
GSI plane (Fig. 3g) indicate high-density ‘islands’ bounded by
progressively lower density fluid inclusions towards the grain
margin. Although no correlation exists between inclusion size
and Th,CO2 (density), the inclusions that yielded lower Th,CO2
values (higher density) are in general smaller. In spite of the fact
that the number of inclusions are inadequate for drawing
statistically constrained Th,CO2 contours, the textural relations
may suggest that the smaller inclusions escaped post-entrap-
ment re-equilibration (Vityk and Bodnar, 1998; Van den
Kerkhof and Hein, 2001; Touret, 2001), and in turn represent
reasonably original trapping conditions. Consistent with the
above arguments, the higher-density smaller inclusions in
Fig. 3g, may represent magmatic trapping conditions. Further-
more, nahcolite has been interpreted to be a daughter phase in
fluid inclusions in rocks of mostly magmatic origin (see Bakker
and Mamtani, 2000 and the references therein). The presence of
 B. Mishra et al. / Gondwana Research 11 (2007) 504–515
nahcolite in type-II inclusions provides indirect evidence
favoring a magmatic origin for the hypersaline fluids in the
Anidih granite. Small nahcolite crystals possibly formed by
speciation reaction from an aqueous-carbonic fluid, in the
process completely consuming relatively smaller amount of
CO2. On this premise, these rare nahcolite containing halite-
bearing inclusions perhaps represent chronologically an earlier
fluid that had a composition of H2O–NaCl–CO2.
Second, the maximum pressure obtained from the pre-D2
Grt–Sil–Kfs–Ms–Qtz–Pl assemblage and the corresponding
syn-metamorphic leucosome fluid isochores in the metapelitic
enclave is lower compared to the highest density isochores of
carbonic fluids in granites. Such pressure difference coupled
with the fact that the granites were emplaced post-dating D2
deformation in the metapelites indicates that the fluids in
granites could not have derived from the partial melting of
metapelites. However, fluid mixing during ascent and emplace-
ment of the granite into the crust represented by the enclave
suite cannot be discounted. Third, melting experiments on
muscovite-bearing pelitic assemblages demonstrate that silli-
manite is a product of incongruent melting at P–T conditions
higher than the second sillimanite isograd (Huang and Wyllie,
1974; Le Breton and Thompson, 1988). But in the Ranchi area,
sillimanite is ubiquitous by its absence. The absence of
sillimanite in the granites can be explained by either of the
two possibilities, i.e., (a) the granites were not produced by the
melting of the muscovite-bearing metapelites, or (b) the granites
were indeed produced by the melting of muscovite-bearing
metapelites, but the incongruently produced sillimanite grains
were selectively segregated from the crystallizing melt during
ascent/emplacement. The second possibility appears untenable
because of the frequent presence of restitic garnet grains in the
granites around the Ranchi area. It was unlikely that the
crystallizing granitic melts somehow were able shed the
sillimanite grains, but retain the restitic garnet grains. It is
suggested, therefore, that the granites were not produced by
anatectic melting of metapelites, and instead, muscovite-absent
protoliths (Clemens and Wall, 1981; Miller, 1985; Johannes and
Holtz, 1996; Clemens and Watkins, 2001) were better
candidates as the source for the granitic rocks at Ranchi.
Finally, the P–T conditions of entrapment of highest density
fluids in granites (Fig. 6) are significantly higher compared to the
syn/post-D3 greenschist facies metamorphic P–T conditions in
granites. On the other hand, the P–T disposition of the lower
density isochores (Fig. 6) in granites may suggest post-
entrapment fluid re-equilibration in the granites. Such modifica-
tions in the inclusions may have been achieved via decompression
induced during accent of the intrusives to the middle/upper crustal
domains represented by the enclave suite. Petrographic manifes-
tation of such decompression is shown in Fig. 3d and e. Further,
the presence of minor amount of CH4 in type-I inclusions in
granites can possibly be explained by fluid mixing, i.e., mixing of
original pure CO2 fluid in the granite with more reduced CH4-
bearing fluid in the migmatitic metapelite.
Based on the above arguments, it appears reasonable to
assume that the super dense carbonic and hypersaline fluid
inclusions in the granites were trapped during the crystallization
513
of magmatic phases. The protoliths that produced the granites
by lower crustal anatexis of muscovite-absent lithologies are not
exposed at Ranchi presumably because the granites were
detached from their root zones following ascent and emplace-
ment at the upper crustal section presently exposed in and
around Ranchi. The studied inclusions may not represent the
pristine fluids generated during melting because of modifica-
tions during magma accent, crystallization and to a lesser extent,
interaction with externally derived fluids. Even then, the
entrapment of the highest density fluid inclusions cannot be
explained by post-entrapment modifications. Super dense CO2
fluid inclusions in quartz showing metastable homogenization
at temperature less than − 56.6 °C have been reported in
migmatites from the Colorado Front Range, USA (Van den
Kerkhof and Olsen, 1990). The authors explain the high density
as a consequence of near-isobaric cooling. But in the present
case, the inclusion textures (Fig. 3d, e), the representative GSI,
indicating progressive density decrease during grain growth
(Fig. 3g) and absence of implosion textures (Vityk and Bodnar,
1995) do not support such a phenomenon.
6. Conclusions
Fluid inclusion microthermometric results in granites
suggest magmatic fluid entrapment at depths in excess of
26 km. At such lower crustal depth, the granites formed by
partial melting of muscovite-absent protoliths under conditions
of high a(CO2) manifested by the abundance of carbonic
inclusions and the paucity of aqueous-carbonic inclusions. In
spite of the extreme rarity of aqueous-carbonic fluid, with
substantial aqueous part, the contribution from closed system
melting in presence of an H2O–CO2 fluid cannot be ruled out.
This is because it is not possible to estimate the amount of H2O
leakage from some of the type-I inclusions in granite quartz.
Besides, as mentioned before, the likelihood of an early H2O–
NaCl–CO2 fluid does exist. The studied inclusions preserve
magmatic trapping P–T conditions that are considerably lower
than the ambient melting conditions, given largely a carbonic
fluid composition according to the fluid inclusion data.
However, assuming the P–T conditions of melting were higher
than those inferred in this study, the evolution of the pristine
magmatic fluid could have followed either an isobaric cooling
or a coupled decompression-cooling path.
Two isochores of halite-bearing inclusions pass within and
close to the magmatic P–T condition of the granites (Fig. 6),
entailing that the brines and the carbonic fluids were present in
the lower crustal protoliths from which the granites were
derived by anatexis. This study corroborates the proposition of
Newton et al. (1998) that both type of fluids may be responsible
for reducing a(H2O) and promoting anhydrous melting in the
lower crust. Furthermore, as mentioned before, barring some
type-I inclusions with thin rims of H2O, sans any observed
clathrate melting, and the saline inclusions containing nahcolite,
the absence of any mixed fluid (H2O–CO2–NaCl) inclusions in
granites in about 200 fluid inclusions examined in this study is
significant. Such absence may be explained by complete phase
separation of the pristine magmatic aqueous-carbonic fluid
514 B. Mishra et al. / Gondwana Research 11 (2007) 504–515
during granite ascent. In such a case, the P–T conditions for
entrapment of the unmixed magmatic fluid will be higher than
those suggested in this study (Fig. 6). Synchronized operation
of two paired processes, i.e., dehydration-melting and fluid-
assisted metamorphism may also produce two mutually ex-
clusive fluids, which may occur in diverse domains at varying
magnitudes. Additionally, dehydration melting can produce the
above two contrasting fluid types, characteristically both low a
(H2O) fluids that could neither partitioned into the granitic melt
nor get fixed in any stable mineral structure in the crystallizing
granite (cf. Touret and Huizenga, 1999). In summary, our study
records both granulite-like super dense CO2 as well as briny
fluid inclusions in granites that are interpreted to represent
magmatic trapping conditions. Thus we believe our results help
in bridging the missing link between high-density granulite
fluid domains and those of granites, thus restoring the granite–
granulite connection (Clemens, 1990).
Acknowledgements
This study was funded by a research grant (ESS/23/VES/125/
2001) from the Department of Science and Technology (DST),
India. The Laser Raman unit was procured through DST funding
(SR/FST/ESII-020/2000) to this department. We sincerely
acknowledge the thoughtful reviews by J Touret, M. Santosh,
J.D. Clemens and S. Dasgupta on an earlier manuscript.
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