Journal of Asian Earth Sciences 200 (2020) 104432

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Journal of Asian Earth Sciences

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Sediment-derived origin of the putative Munnar carbonatite, South India T

a,⁎ b c a d
Ernst Hegner , Selvaraj Rajesh , Matthias Willbold , Dirk Müller , Michael Joachimski ,
Mandy Hofmanne, Ulf Linnemanne, Johannes Ziegere,
Anakkathil Purushothaman Pradeepkumarb
a
Department of Earth and Environmental Sciences & GeoBioCenter, Ludwig-Maximilians-Universität München (LMU), D-80333 Munich, Germany
b
Department of Geology, University of Kerala, Trivandrum 695581, India
c
Geowissenschaftliches Zentrum, Abteilung für Isotopengeologie und Geochemie, Georg-August-Universität Göttingen, D-37077 Göttingen, Germany
d
Friedrich-Alexander-Universität Erlangen-Nürnberg, GeoZentrum Nordbayern, D-91054 Erlangen, Germany
e
Senckenberg Naturhistorische Sammlungen, Museum für Mineralogie und Geologie, Sektion Geochronologie, D-01109 Dresden, Germany

ARTICLE INFO ABSTRACT

Keywords: Metacarbonate assemblages in high-grade metamorphic terranes often pose challenges when trying to distin-
Metacarbonate guish between mantle-derived carbonatite and sedimentary carbonate protoliths. We present a study of gran-
Carbonatite ulite-facies metacarbonate samples of the putative Munnar carbonatite described as decimeter-thick dikes and
Marble veins, and layers of a meter-thick metacarbonate and calc-silicate assemblage, respectively. Thin sections of the
Geochemistry
metacarbonate dike samples show absence of pyrochlore and ubiquitous scapolite, titanite, wollastonite, and
Nd-Sr-C-O isotopes
Zircon geochronology
detrital zircons are compatible with impure limestone protoliths. Nd and Sr isotope compositions indicate
protoliths with Paleoproterozoic crustal residence times which contrast the mantle sources of Indian and global
carbonatites. Trace-element patterns display the characteristics of upper crust, and Ce- and Y-anomalies in a
number of samples suggest protolith formation under marine conditions. Carbon and oxygen isotope composi-
tions of the metacarbonate samples interlayered with calc-silicate rocks are similar to those in marine limestone.
The metacarbonate dikes, however, show mantle-like compositions which are interpreted as reflecting equili-
bration with mantle-derived CO2 during granulite-facies metamorphism. The dikes yielded a U-Pb zircon crys-
tallization age of 1020 ± 70 Ma and a cross-cutting quartz syenite, thought to be cogenetic, a magmatic age of
620 ± 35 Ma; the hosting gneiss provided a magmatic age of 2452 ± 14 Ma. We conclude that the layered
metacarbonate and calc-silicate rocks represent a former marine limestone and marl sequence and the meta-
carbonate dikes and veins small-volume melts of crust-derived carbonate-rich sediment.

1. Introduction important Nb-LREE deposits. Identification of carbonatites is also of

The granulite terranes of southern India host a number of meta-
carbonate assemblages whose mineralogical and geochemical char-
acteristics have stimulated discussions regarding mantle-derived or
sedimentary protoliths (Subbarao et al., 1995; Schleicher et al., 1998;
Kumar et al., 1992, 2001; Le Bas et al., 2002, 2004; Srivastava et al.,
2005; Ackerman et al., 2017). The reasons for diverging interpretations
of the nature of their protoliths lie in the circumstance that primary
characteristics such as structural relationships, textures, and geo-
chemical signatures were often obscured by rock deformation, fluid-
rock interaction, and granulite-facies metamorphism. Limited data sets
have additionally contributed to ambiguous interpretations. An un-
derstanding of the origin of these metacarbonate assemblages is desir-
able for targeting mineralized carbonatites that may be economically
immense interest for unravelling the geochemical and isotopic evolu-
tion of the Indian subcontinental mantle. This paper examines new
mineralogical, geochemical and isotope data for the putative Munnar
carbonatite and presents new interpretations regarding its source, age,
and origin. The metacarbonates were previously described as sövite and
alvikite carbonatite varieties (Nair et al., 1984; Santosh et al., 1987).
The authors noted similarities in the Th-REE systematics with mantle-
derived (primary) carbonatites as well as low Sr and Ba concentrations,
unlike those in carbonatites. Accordingly, they suggested an origin of
the rocks by CO2 degassing of the mantle, fluid-induced melting of
mantle and lower crust, and immiscibility of an alkali silicate melt. The
rocks were subsequently treated in the literature as mantle-derived
carbonatite (e.g., Veevers, 2007; Woolley and Kjarsgaard, 2008; Catlos
et al., 2008; Krishnamurthy, 2019; Randive and Meshram, 2020; Paul

⁎
Corresponding author.
E-mail address: hegner@lmu.de (E. Hegner).

https://doi.org/10.1016/j.jseaes.2020.104432
Received 10 March 2020; Received in revised form 31 May 2020; Accepted 31 May 2020
Available online 30 June 2020
1367-9120/ © 2020 Elsevier Ltd. All rights reserved.
E. Hegner, et al.
Fig. 1. Geological maps of southern India showing the study area in the western
Madurai Domain (map simplified after Brandt et al., 2014). (a) Overview map
of southern India and the Southern Granulite Terrane (SGT) to the south of the
Dharwar Craton. The Madurai Domain encompasses the segment between the
Moyar-Bhavani-Cauvery Shear Zone (MBCSZ) in the north and the Achankovil
Unit (AU) in the south. Solid circles in yellow indicate reported carbonatite
localities. (b) Section of the Western Madurai Domain with the location of the
study area near Munnar. Abbreviations: KKPTSZ = Karur-Kambam-Painavu-
Trissur Shear Zone; SSZ = Suruli Shear Zone.
et al., 2020). We use metacarbonate as a non-genetic description for
granulite-facies carbonate-rich rocks (i.e., limestone, dolomite, impure
limestone, calcio-carbonatite) and marble as genetic description for a
carbonate-rich rock of sedimentary origin. The definition of carbonatite
follows IUGS (Le Maitre et al., 1989) and includes the currently used
trace-element, isotope, and process-oriented criteria, such as an ulti-
mate mantle origin and the exclusion of crustal melts (e.g., Bell, 1989;
Bell et al., 1998; Mitchell, 2005; Jones et al., 2013; and references in
these publications). This more detailed definition is helpful to avoid
misidentification of pegmatitic and sedimentary carbonate material
(e.g., marble) as carbonatite.
2. Geological setting of the study area
The study area is located in the Western Madurai Domain (WMD;
also known as northern Madurai Block, NMB) of the Southern Granulite
Terrain (SGT) in southern India (Fig. 1). For reviews of the tectonic
assemblage of the SGT and its temporal evolution we refer to e.g., Drury
and Holt (1980), Drury et al. (1984), Harris et al. (1994), Chetty
(1996), Ramakrishnan (2003), Rao et al. (2006), Santosh et al. (2012),
Chetty and Santosh (2013), Collins et al. (2014), Clark et al. (2015),
Brandt et al. (2011, 2014), Plavsa et al. (2012, 2014), Tomson et al.
(2013), Kröner et al. (2015), Vijaya Kumar et al. (2017), Chowdhury
and Chakraborty (2019), and Yang et al. (2020). The SGT exposes fault-
bounded crustal blocks exposed at mid- to lower crustal levels with the
WMD comprising predominantly migmatitic hornblende-biotite (hbl-
bt) gneiss, charnockite, and granite gneiss (Fig. 1a).
Zircon geochronology for the WMD revealed four major crust-for-
mation events commencing with emplacement of I-type arc-related
granitoids at ~2.7 Ga to ~2.5 Ga and high-pressure (HP) granulite
metamorphism and crustal melting at ~2.5 to 2.4 Ga (Ghosh et al.,
2004; Braun and Appel, 2006; Plavsa et al., 2012, 2014; Brandt et al.,
2014). Granitoid magmatism and metamorphism at ~0.83 to 0.79 Ga
2
Journal of Asian Earth Sciences 200 (2020) 104432
has been interpreted as related to crustal rifting (Brandt et al., 2014;
Renjith et al., 2016; Santosh et al., 2017). Pan-African crustal assembly
and granulite-facies metamorphism with charnockitization of the SGT
may have commenced along the Karur-Kambam-Painavu-Trissur Shear
Zone (KKPTSZ, Ghosh et al., 2004; Brandt et al., 2011, 2014; Fig. 1).
Widespread high-temperature (HT) to ultra-high temperature (UHT)
metamorphism and crustal melting occurred at ~0.6 to ~0.5 Ma
(Bhadra, 2016; Brandt et al., 2014; Braun et al., 2007; Clark et al.,
2009; Ghosh et al., 2004; Plavsa et al., 2012; Tang et al., 2018). Ac-
cording to Plavsa et al. (2012, 2014), the Madurai Block may be sub-
divided into the NMB and southern Madurai Block (SMB) with distinct
isotopic compositions, geochronology, and lithological units.
The study area near the township of Munnar is situated at the inter-
section of the Kerala (Idamalayar) and Attur lineaments (Katz, 1978;
Santosh et al., 1987) that apparently belong to the KKPTSZ (Fig. 1, Ghosh
et al., 2004). The suture zone has been interpreted by some authors as the
southern margin of the Dharwar craton (Bhaskar Rao et al., 2003; Ghosh
et al., 2004; Brandt et al., 2011). Retrogressed late Archean migmatitic
hornblende-biotite gneiss and granite gneiss dated at ~800 Ma with sub-
ordinate charnockite, alkali granite, calc-silicate and metacarbonate as-
semblages represent the dominant lithologies of the Munnar region (Fig. 2;
Rajesh et al., 2000; Rajesh, 2008; Bhattacharya et al., 2014; Brandt et al.,
2014). Tang et al. (2018) studied a cordierite-bearing gneiss sample col-
lected near Munnar and inferred UHT- metamorphism related to Pan-
African crustal assembly at ~600 to 550 Ma, followed by younger thermal
events at ~530 Ma and 480–490 Ma.
3. Samples and field observations
We sampled metacarbonate material from dikes, veins, and pods at
roadcuts near the village of Kadugumudi (samples M12a, M12b, and
included minerals) and from massive layered metacarbonate and calc-
silicate assemblages at Yellapatti (samples M1 to M7), respectively
(Fig. 2). Metacarbonate at these localities was previously interpreted as
carbonatite (Nair et al., 1984; Santosh et al., 1987). Details of the field
relationships at these roadcuts are presented further below in this
section.
Fig. 2. Geological map of the study area with sample localities. GPS coordinates
of sample localities and brief sample descriptions are given in Appendix A.
Source: District Resource Map of the Geological Survey of India (1995) with
modified outcrop of marble and calc-silicate unit near the village of Top Station.
In the Kurangani Hills, a few kilometers east of Yellapatti (Fig. 2),
we sampled a layered metacarbonate and calc-silicate sequence (sam-
ples M8 to M11) along the trail from Top Station to Kurangani village.
In addition, we collected samples from a major calc-silicate unit in-
folded in basement granitoids near the village of Devikolam (sample
M19, Fig. 2). The samples from Kurangani Hills and Devikolam were
included for data comparison and interpretation of the composition of
E. Hegner, et al.
the Kadugumudi and Yellapatti rock samples that are the focus of this
study. Granitoid samples (M14, M16, M17, M18, M20) were collected
for constraints on sediment provenances and crustal magma sources.
The localities of the samples are shown in Fig. 2 and a list with GPS
coordinates and brief sample descriptions is presented in Appendix A.
In the following paragraphs we describe in more detail the field
relationships at the Kadugumudi and Yellapatti roadcuts. The
Kadugumudi roadcut is located ~15 km north of Munnar township
(Fig. 2). Metacarbonate occur in a foliated migmatitic hornblende-
biotite gneiss as centimeter- to decimeter-thick dikes and dikelets, dif-
fuse veins, and pods (Fig. 3).
The metacarbonate dikes, dikelets, veins and pods occur irregularly
distributed in the gneiss, and at places, parallel to and elsewhere cross-
cutting its foliation (Fig. 3a, c). The dikes and veins show a compositional
zoning with interior portions of mostly coarse calcite interspersed with
anhedral diopside grains. The dike and vein margins consist of diopside-rich
calc-silicate material (Fig. 3e, f) and are often rimmed with pink alkali
feldspar which supports a magmatic origin of the dikes (Fig. 3e). The calc-
silicate margins resemble a mineralogical reaction seam formed by double-
diffusive element transport across the contact between gneiss and marble
(e.g., Hollocher, 2014) but could also represent a primary magmatic zona-
tion within the dikes (see discussion of geochemical-isotopic evidence in
Sections 5.3 and 5.4).
The migmatized hornblende-biotite gneiss and metacarbonate dikes at
3
Journal of Asian Earth Sciences 200 (2020) 104432
Kadugumudi are intruded by a root-like massive pink quartz syenite, which
engulfs blocks of gneiss (Fig. 3a, b, d). The quartz syenite was previously
interpreted as member of a cogenetic alkali granite-syenite-carbonatite suite
(Nair et al., 1984). There is no direct cross-cutting relationship between
metacarbonate dikes and quartz syenite (Fig. 3d) and the latter lacks any
macroscopic metacarbonate inclusions. Near the quartz syenite the meta-
carbonate dikes become stretched and disrupted and metacarbonate and
calc-silicate fragments are aligned subparallel to the syenite contact
(Fig. 3d). Remnants of metacarbonate and calc-silicate material can be seen
as isolated thin streaks parallel to the contact of the gneiss and quartz
syenite (Fig. 3d). We explain these features with ductile deformation and
Fig. 3. Photographs of the Kadugumudi
roadcut. (a) Metacarbonate dikes, veins and
pods (white dotted lines) in foliated mig-
matitic hornblende-biotite gneiss, and in-
trusive quartz syenite on the right of out-
crop. (b) Massive pink quartz syenite with
apophyses intruding gneiss. (c) Irregularly
dispersed metacarbonate dikes, veins, and
pods parallel to and cross-cutting foliation
in hornblende-biotite gneiss. (d) Sharp con-
tact between quartz syenite and gneiss with
deformed and sheared metacarbonate dike-
lets and veins. Single metacarbonate and
diopside streaks (black lines) subparallel to
syenite contact suggest ductile deformation
of gneiss and shearing of metacarbonate
dikes during syenite intrusion. (e)
Metacarbonate vein showing mineralogical
zonation with calcite-rich interior including
mm-size resorbed diopside grains. Vein
margins comprise coarse diopside, sub-
ordinate calcite, and locally pink alkali
feldspar. (f) Hand specimen of sample M12a
(calcite-rich inner portion of dike) which
has previously been interpreted as sövite.
Sample M12b showing part of dike with a
diopside-rich margin (calc-silicate rock, left
portion of hand specimen) and calcite-rich
interior.
shearing of the gneiss-marble assemblage during intrusion of the syenite,
implying dike formation before the intrusion of the quartz syenite (see
Section 5.6 on U-Pb zircon geochronology). The gneiss near the quartz
syenite is pervasively impregnated with calcite, a feature we regard as due
to decarbonation reactions and redistribution of carbonate material by
fluids emanating from the quartz syenite during intrusion and cooling. Thin
sections of the quartz syenite show calcite in the fractures of some of the
feldspar crystals that suggests infiltration of fluids after its emplacement and
possibly during retrograde metamorphism.
We sampled coarse-grained metacarbonate from the interior of the
dikes (Fig. 3c, e, f; sample M12a) and diopside-rich calc-silicate mate-
rial from the margins (Fig. 3e, f; sample M12b). From metacarbonate
sample M12a we separated calcite, apatite, and diopside for additional
E. Hegner, et al.
chemical and isotopic information. For age constraints on dike empla-
cement and protoliths we carried out U-Pb zircon dating of a composite
sample comprising material from the dike margins and interior (sample
M12). The quartz syenite was sampled in the outcrop shown in Fig. 3a
and the hornblende-biotite gneiss in a less migmatized roadcut ~80 m
towards Kudugumudi village. Thin section photomicrographs of the
metacarbonate dikes and veins are described in Section 5.1.
Near the village of Yellapatti, ~24 km east of Munnar on the road to
Top Station, two roadcuts show several square meters of interlayered
metacarbonate and calc-silicate rocks (Fig. 4). Similar rock assemblages
are exposed in the Kurangani Hills east of Top Station and at the northern
shore of Kundala Lake ~4 km due north of Yellapatti (Fig. 2). These in-
dividual occurrences possibly belong to a single metacarbonate and calc-
silicate unit. The Yellapatti roadcuts show ductilely folded alternating
layers of variably pure metacarbonate and calc-silicate rocks that, in the
sampled outcrop, are juxtaposed with a quartzite layer at the top (Fig. 4a,
b). The metacarbonate in contact with calc-silicate material shows mineral
reaction seams of mostly biotite (Fig. 4a, c). The metacarbonate and calc-
silicate layers at Yellapatti, Kurangani Hills, and Kundala Lake are strik-
ingly similar to sequences of folded and metamorphosed impure lime-
stone, marl, and psammite (e.g., Hollocher, 2014).
From the outcrop shown in Fig. 4a, we collected metacarbonate
samples (M3, M5, M6) and calc-silicate samples (M1, M4, M7). For age
Fig. 4. Ductilely folded marble and calc-silicate assemblages at Yellapatti,
Kurangani Hills, and Kundala Lake interpreted as former impure limestone-marl-
psammite sequences. (a) Yellapatti roadcut showing isoclinally folded layered se-
quence of variably pure marble and calc-silicate rocks in contact with quartzite
(open fold at the top). Marble from this locality has previously been interpreted as
alvikite. Light marble layers (samples M5, M6) show dark mineral reaction seams of
mostly biotite next to darker calc-silicate layers (samples M1, M3, M4; description of
sampled material in Appendix A). (b) Tan-colored quartzite in contact with dark
grey calc-silicate layer. (c) Light marble layers with dark silicate reaction seams and
dark grey calc-silicate layer on the left. (d) Folded sequence of marble (low relief)
and thin calc-silicate layers at Kundala Lake. (e) Isoclinally folded layers of variably
pure marble and calc-silicate rocks at Kurangani Hills.
4
Journal of Asian Earth Sciences 200 (2020) 104432
constraints on their protoliths, zircons of metacarbonate sample M3
were dated by the U-Pb method. Thin section photomicrographs of the
samples are shown in Appendix C and described in Section 5.1.
4. Analytical methods
The analytical methods are described in detail in Appendix B and
reported here in brief. The major-element concentrations of whole-rock
samples were determined at Tübingen University, using a Bruker AXS
S4 Pioneer XRF spectrometer. The trace-element analyses were carried
out at Tübingen and Göttingen Universities, using ThermoFisher
Scientific iCAP-Q mass spectrometers. The precision and accuracy of
the trace element data are estimated at <5% and <8%, respectively.
The major- and trace-element concentrations are listed in Table 1, in-
cluding an analysis of the reference material BHVO-2 for data com-
parison.
The electron microprobe analysis of calcite was carried out at the
Department of Earth- and Environmental Sciences at LMU, using a
Cameca SX-100 electron microprobe. The calcite analyses of four
samples from three localities are listed in Appendix D, Table D.1, and
the calcite compositions are shown in Fig. 6.
The U-Th-Pb isotope analyses of zircon were carried out with laser
ICP-MS in the Geochronology Section at Senckenberg Naturhistorische
Sammlungen, Dresden, using a Thermo-Scientific Element 2 XR sector
field ICP-MS coupled with a RESOlution 193 nm Excimer laser system.
The analytical procedures are outlined in Gerdes and Zeh (2006) and
Frei and Gerdes (2009). The analytical spots in zircon cores and over-
growth rims were selected with the help of cathodoluminescence (CL)
images and the Th/U ratio was used as guide for interpretation of
magmatic and metamorphic ages. Data regression analysis and plotting
were carried out with ISOPLOT 4.15 (Ludwig, 2012). The U-Th-Pb
analytical data are listed in Appendix D, Tables D.2 to D.5, and shown
in the concordia diagrams of Figs. 11–13. Probability density distribu-
tion plots according to Reiminck et al. (2016) are shown in Appendix E.
The Sm-Nd and Sr isotope compositions were determined by multi-
collector ICP-MS in the Department of Isotope Geology and
Geochemistry of Göttingen University and by TIMS at LMU Munich.
The procedures of the laboratory at Göttingen University are described
in detail in Appendix B and those at LMU in Hegner et al. (1995, 2010).
The Rb-Sr and Sm-Nd isotope data for the samples and reference ma-
terials are listed in Table 2 and plotted in Fig. 9.
Carbon and oxygen isotope analyses of calcite were carried out at
the University of Erlangen-Nürnberg, Germany. The uncertainty for
δ13C and δ18O analyses is ≤0.07‰ and ≤0.08‰ (1SD), respectively.
Additional samples were analyzed in the Advanced Centre for Material
Science at the Indian Institute of Technology at Kanpur according to
Paul et al. (2007). The uncertainty for these δ18O and δ13C values is
≤0.1‰ and ≤0.2‰ (1SD), respectively. The δ18O and δ13C values are
given in permil relative to Vienna Standard Mean Ocean Water
(VSMOW) and Vienna Pee Dee Belemnite (VPDB), respectively, and are
listed in Table 3 and plotted in Fig. 10.
5. Results and discussion
5.1. Petrography of Kadugumudi and Yellapatti metacarbonate and calc-
silicate samples
Thin section photomicrographs of metacarbonate and calc-silicate
samples of dikes and veins at Kadugumudi are shown in Fig. 5. The thin
sections of two metacarbonate and one calc-silicate sample from Yell-
apatti reveal a similar mineral assemblage and, for brevity, are shown
and described in Appendix C. All thin sections show mineral assem-
blages representative of granulite-facies carbonate and calc-silicate
rocks.
The dikes and veins in gneiss at Kadugumudi show a mineralogical
zonation with inner marble-textured portions comprising up to 90%
E. Hegner, et al. Journal of Asian Earth Sciences 200 (2020) 104432

calcite and margins of mostly diopside (Fig. 5e, f). The dike margins
(sample M12b) consist of 50–90 vol% diopside and smaller proportions
of calcite, scapolite, alkali feldspar, wollastonite (Fig. 5a-d) besides ti-
tanite and zircon (not shown). The inner portions of the dikes and veins
comprise mostly equigranular euhedral and lamellar twinned calcite up
to 1.5 cm with triple junctions and inclusions of resorbed diopside,
apatite, and titanite (sample M12a; Fig. 5e, f). Scapolite, quartz, and
zircon are interspersed or occur as inclusions in calcite (not shown).
metacarbonate samples with mantle-derived carbonatite (e.g., Hogarth,
1989; Viladkar and Subramanian, 1995; Le Bas et al., 2002, 2004). The
high abundance of scapolite, wollastonite, and titanite, absence of
pyrochlore-series minerals, and presence of a multi-age detrital zircon
population (see Section 5.6) in the dike metacarbonate and marble
samples strongly support supracrustal carbonate-rich protoliths (e.g.,
Aitken, 1983; Le Bas et al., 2002, 2004).

Fig. 5. Thin section photomicrographs of Kadugumudi metacarbonate dike samples under cross-polarized light. (a-d) Calc-silicate dike-margin: (a) Dike margin with
resorbed diopside grains and calcite. (b) Scapolite grains with irregular cleavage and resorbed diopside and scapolite inclusions in calcite. (c) Alkali feldspar, calcite,
wollastonite, and scapolite. (d) Alkali feldspar associated with calcite, scapolite, and fibrous grains of wollastonite enclosed in calcite. (e, f) Metacarbonate of the dike
interior with large calcite crystals showing well-developed lamellar twinning and resorbed apatite, diopside, and titanite inclusions (see text for descriptions).

The thin sections of metacarbonate and calc-silicate samples
from Yellapatti show variable proportions of calcite, diopside,
scapolite, titanite, wollastonite, quartz, alkali feldspar, and accessory
apatite, magnetite, rutile, and zircon (Appendix C, Fig. C.1). The mi-
neral assemblage is representative of high-grade limestone and dolo-
mite, impure limestone, and marl (e.g., Bucher and Grapes, 2011;
Hollocher, 2014) and supports the field interpretation of the
assemblage as a former impure limestone, marl, and psammite se-
quence. The metacarbonate samples from Yellapatti and Kurangani
Hills can thus be interpreted as marbles. For the enigmatic material of
the dikes and veins at Kadugumudi we will keep the description as
metacarbonate.
We conclude that the petrographic evidence shows no affinity of the
5.2. Calcite compositions and petrogenetic implications
The SrO-FeO-MnO compositions of calcite in the metacarbonate
dike, marble, and calc-silicate rocks differ mainly with respect to their
SrO abundance (Fig. 6). Calcite of the marble samples M5 and M11
from Yellapatti and Kurangani Hills, respectively, show low Sr con-
centrations (Sr ≤ ~400 ppm, Appendix D, Table D.1) that characterize
carbonate and calc-silicate rocks (e.g., Kretz and Garret, 1980; Moecher
et al., 1997; data compilation in Le Bas et al., 2002; Rosatelli et al.,
2010). Their composition confirms the field, geochemical-isotope, and
zircon evidence (see Sections 5.3, 5.4, 5.6) for impure limestone and
marl protoliths. In contrast, calcite in the metacarbonate dikes and
veins at Kadugumudi for which the mineralogical-geochemical

5
E. Hegner, et al. Journal of Asian Earth Sciences 200 (2020) 104432

evidence (see Sections 5.3 and 5.4) also indicates metasedimentary
protoliths, show much higher Sr concentrations (~800–1000 ppm,
Appendix D, Table D.1) that resemble, to some extent, those for calcite
of mantle-derived carbonatites (e.g., ~2000–20,000 ppm; Viladkar and
Wimmenauer, 1992; Woolley et al., 1995; Moecher et al., 1997; Chen
and Simonetti, 2013; Le Bas et al., 2002; Rosatelli et al., 2010;
Weidendorfer et al., 2016; Chakhmouradian et al., 2016). Calcite in a
typical calc-silicate rock (sample M19) from the basement shows an
intermediate Sr concentrations and higher MnO concentrations.
In summary, the variable Sr concentrations in the calcite samples
Fig. 6. SrO-MnO-FeO composition of calcite crystals in Kudugumudi meta-
carbonate dike samples (red symbols for dike interior sample M12a, light red
symbols for dike margin sample M12b) and Yellapatti and Kurangani Hills
marble samples M5 and M11. Sample M19 represents a calc-silicate rock of the
basement (electron-microprobe data in Appendix D, Table D.1). FeO-rich and
Sr-poor compositions of calcite in samples M5 and M11 are similar to those in
sedimentary carbonate and marble. High SrO abundances in calcite of the
metacarbonate dike sample M12 resemble the compositions of carbonatitic
calcite (data compilations in e.g., Bell, 1989; Le Bas et al., 2002; see text for
discussion).
most likely reflect different petrogenetic processes rather then different
protoliths. The high Sr concentrations in calcite samples from the dikes
and veins are compatible with their crystallization from an anatectic
melt of a carbonate-rich protolith. On the other hand, much lower-Sr
concentrations in other calcite samples can be explained with the re-
crystallization of carbonate-rich protoliths.
5.3. Major- and trace-element data
The major- and trace-element compositions of the samples are listed
in Table 1 and normalized trace-element patterns are shown in Figs. 7
and 8.
The major-element composition of the metacarbonate material from
the dikes and veins at Kadugumudi (sample M12a; previously inter-
preted as sövite) primarily reflects its high abundance of calcite and is
indistinguishable from that of the metacarbonate samples from
Yellapatti and Kurangani Hills (Table 1; since the field and petrographic
evidence indicate a sedimentary origin of these samples, they will be
more precisely described as marbles in the following text). Calc-silicate
sample M12b, representing the dike margin, has much higher SiO2,
MgO, FeO concentrations consistent with the high proportion of diop-
side (Fig. 4a-d). The chemical zonation of the dikes and veins suggest an
origin by melt fractionation with the residual melt represented by the
metacarbonate of the inner dikes and the complementary fractionated
minerals represented by the calc-silicate margin of the dikes.
The REE patterns of the metacarbonate dike, marble, and calc-sili-
cate samples are remarkably similar and differ largely in their overall
REE abundances (Fig. 7a). The salient features are enrichment of the
light rare earth elements (LREE), little fractionated heavy rare earth
element (HREE) patterns and distinct negative Eu-anomalies. These
features (and those of other trace elements; see following paragraphs)
characterize average post-Archean upper continental crust (UCC; e.g.,
Taylor and McLennan, 1985; Rudnick and Gao, 2014). The patterns
clearly are different from those for mantle-derived carbonatite that
show overall much higher REE abundances, no Eu-anomalies, and
highly fractionated LREE and HREE patterns (Fig. 7b; Loubet et al.,
1972; Viladkar and Pawaskar, 1989; Simonetti et al., 1995; Hornig-
Kjarsgaard, 1998; Rosatelli et al., 2010; Mongelli et al., 2013).
The REE abundances of the Yellapatti marble and calc-silicate

Table 1
Chemical composition of marble, metacarbonate dike, calc-silicate, and granitoid samples from the Munnar area, South India.
Sample # M1 M3 M4 M5 M6 M7 M8 M9 M 10 M 11 M 12a M 12a M 12a M 12a M12a M 12b
Yellapatti Kurangani Hills Kadugumudi dikes

Type Casi Mb Casi Mb Mb Casi Casi Casi Casi Mb MC Apatite Diopside Calcite r. Calcite l. Casi

SiO2 35.68 13.00 26.20 0.05 1.59 29.48 29.40 20.20 19.70 5.50 15.30 – – – – 49.35
TiO2 0.26 0.10 0.22 0.01 0.03 0.08 0.31 0.20 0.20 0.13 0.05 – – 0.0015 0.003 0.39
Al2O3 6.10 1.83 4.78 0.00 0.07 1.19 5.13 3.52 3.66 1.01 0.73 – – – – 9.96
Fe2O3 2.83 1.65 2.17 0.87 0.99 1.54 2.68 2.32 2.20 1.38 1.79 – – – – 7.07
MnO 0.09 0.08 0.09 0.10 0.10 0.10 0.11 0.09 0.09 0.09 0.10 – – – – 0.20
MgO 1.44 0.83 1.23 1.51 2.14 11.72 2.02 2.19 2.27 9.17 2.85 – – – – 7.59
CaO 36.52 57.80 41.13 73.08 71.04 35.47 40.25 48.63 49.12 56.89 56.07 – – – – 22.59
Na2O 0.52 0.21 0.52 n.d. n.d. 0.08 0.70 0.80 0.51 n.d. 0.14 – – – – 1.73
K2O 2.61 1.46 2.18 0.03 0.15 0.94 1.14 0.77 0.71 n.d. 0.02 – – – – 0.17
P2O5 0.08 0.07 0.07 0.04 0.06 0.08 0.14 0.06 0.06 0.02 0.22 – – – – 0.30
LOI 13.55 22.06 17.06 24.03 23.18 19.98 18.04 20.32 20.37 23.96 21.85 – – – – 2.47
Sum 99.99 99.39 95.96 99.96 99.65 100.91 100.22 99.39 99.19 98.42 99.48 – – – – 101.82

Sc 5.67 2.77 4.81 0.813 0.916 2.25 5.21 4.68 4.45 2.17 2.23 0.349 24.9 – – 13.3
Cr 40.8 13.5 30.7 1.82 2.64 8.36 38.1 28.3 27.0 9.26 5.44 n.d. n.d. – – 48.1
Co 4.92 2.80 4.66 0.784 0.892 2.75 5.29 5.10 5.04 1.36 3.38 0.030 27.3 – – 31.2
Ni 10.9 8.38 11.2 5.36 5.64 5.13 15.2 14.7 14.7 5.70 11.7 0.096 70.0 – – 34.1
Rb 126 65.6 96.7 2.08 2.24 51.1 25.0 26.4 22.5 0.110 1.28 0.140 0.021 – – 5.98
(continued on next page)

6
E. Hegner, et al. Journal of Asian Earth Sciences 200 (2020) 104432

Table 1 (continued)

Sample # M1 M3 M4 M5 M6 M7 M8 M9 M 10 M 11 M 12a M 12a M 12a M 12a M12a M 12b

Yellapatti Kurangani Hills Kadugumudi dikes

Type Casi Mb Casi Mb Mb Casi Casi Casi Casi Mb MC Apatite Diopside Calcite r. Calcite l. Casi

Sr 101 119 104 121 110 61.9 233 190 217 268 728 729 31.4 937 844 350
Ba 510 265 364 42.7 48.0 91.8 123 136 165 31.1 111 13.1 1.09 129 69.0 255
Y 7.74 8.76 8.08 5.16 4.56 4.92 14.9 8.05 7.72 11.9 51.9 3578 4.11 45.6 37.2 17.6
Zr 44.6 17.6 68.5 0.428 1.99 6.14 99.7 41.4 36.9 14.7 7.41 39.5 29.7 0.290 0.228 86.6
Nb 4.37 2.41 3.82 0.089 0.228 1.22 4.52 2.75 2.89 0.730 0.607 0.685 0.880 0.059 0.281 15.8
Hf 1.27 0.499 1.59 0.0125 0.0603 0.24 2.43 1.12 1.03 0.410 0.210 2.67 1.01 – – 2.49
Ta 0.332 0.166 0.300 0.010 0.016 0.070 0.323 0.200 0.202 0.084 0.047 0.621 0.067 – – –
Pb 4.89 4.67 5.67 3.86 4.83 2.47 13.6 8.12 6.95 10.3 11.2 76.4 1.68 8.22 8.25 15.8
Th 6.05 2.45 3.91 1.16 0.990 0.380 4.43 2.15 2.93 0.879 6.91 1510 0.172 1.31 0.130 7.42
U 1.11 0.431 0.930 0.110 0.083 0.093 1.26 0.833 0.762 0.475 2.37 515 0.209 0.520 0.084 5.93
La 8.15 10.2 8.92 3.60 3.80 2.65 19.6 9.25 9.62 11.4 234 17,480 2.86 142 125 24.9
Ce 14.1 17.6 15.3 5.05 5.33 4.11 38.1 19.0 19.5 20.8 312 25,892 6.31 175 148 42.2
Pr 1.84 2.28 2.02 0.752 0.805 0.675 4.16 2.20 2.22 2.69 26.7 2534 0.855 14.5 11.4 4.74
Nd 6.87 8.39 7.65 3.02 3.19 2.83 15.0 8.34 8.22 10.5 78.5 7656 3.19 42.8 35.0 17.4
Sm 1.40 1.66 1.54 0.619 0.628 0.602 2.94 1.74 1.66 2.25 10.9 1014 0.637 5.82 5.00 3.59
Eu 0.302 0.363 0.331 0.141 0.137 0.137 0.585 0.353 0.363 0.494 1.72 161 0.129 1.12 0.883 0.700
Gd 1.32 1.54 1.46 0.675 0.637 0.658 2.68 1.57 1.50 2.22 8.60 107 0.091 5.22 4.52 3.02
Tb 0.207 0.236 0.225 0.102 0.0960 0.102 0.426 0.250 0.236 0.339 1.23 812 0.570 0.687 0.612 0.480
Dy 1.25 1.38 1.31 0.603 0.568 0.590 2.53 1.48 1.38 2.00 6.92 564 0.558 4.30 3.85 3.00
Ho 0.263 0.281 0.270 0.128 0.120 0.126 0.525 0.305 0.287 0.408 1.52 108 0.129 0.937 0.856 0.600
Er 0.752 0.781 0.756 0.349 0.324 0.343 1.517 0.867 0.809 1.11 4.53 293 0.488 2.97 2.86 1.82
Tm 0.114 0.116 0.113 0.0480 0.0456 0.0477 0.231 0.129 0.123 0.159 0.700 38.1 0.124 0.490 0.438 0.300
Yb 0.760 0.751 0.731 0.289 0.282 0.288 1.509 0.837 0.786 0.979 4.58 223 1.35 3.07 3.05 2.13
Lu 0.115 0.110 0.109 0.040 0.041 0.043 0.220 0.125 0.116 0.141 0.661 27.0 0.344 0.462 0.462 0.380
Nb/Ta 13.2 14.5 12.9 14.6 14.9 17.4 14.0 13.9 14.3 8.7 13.0 1.10 13.1 – – –
Ce/Ce* 0.883 0.884 0.878 0.746 0.740 0.746 1.02 1.02 1.02 0.913 0.962 0.947 0.981 0.937 0.955 0.944
Y/Ho 29.4 31.2 29.9 40.3 38.0 39.0 28.4 26.4 26.9 29.2 34.1 33.1 31.9 48.7 43.4 29.3
Zr/Hf 35.2 35.2 43.0 35.3 33.0 26.0 41.1 37.0 35.7 35.8 35.3 14.8 29.4 – – 34.8

Sample # M 14 M 16 M 17 M 18 M 19 M 20 BHVO-2
Basement

Type QtzS AGr GrGn GrGn Casi HblBtGn Reference

SiO2 65.34 72.06 70.08 69.40 60.26 65.24 49.35 (49.6)

TiO2 0.04 0.15 0.44 0.49 0.60 0.58 2.75 (2.73)
Al2O3 18.09 14.96 14.43 14.36 14.62 14.41 13.68 (13.44)
Fe2O3 0.51 1.43 3.54 3.96 5.07 5.34 12.13 (12.39)
MnO 0.06 0.07 0.14 0.15 0.18 0.12 0.21 (0.17)
MgO 0.33 0.37 0.52 0.55 3.01 2.39 7.43 (7.26)
CaO 1.59 1.36 1.62 1.71 14.87 3.56 11.49 (11.4)
Na2O 2.58 3.60 3.40 3.45 0.41 3.93 −2.21
K2O 10.62 5.72 5.96 5.76 0.03 3.33 0.51 (0.51)
P2O5 0.22 0.06 0.11 0.13 0.16 0.29 0.27 (0.27)
LOI 0.91 050 0.34 0.16 0.90 0.73 – (–)
Sum 100.9 100.50 100.90 100.50 100.50 100.60 99.05 99.91

Sc 1.39 – 5.91 – 6.99 11.1 32.4 (31.8)

Cr 3.77 – 8.57 – 73.4 80.3 303 (287)
Co – – – – – – 45.3 (44.9)
Ni 1.77 – 3.37 – 31.4 25.3 118 (120)
Rb 329 – 141 – 1.82 115 9.13 (9.26)
Sr 513 – 131 – 219 405 394 (394)
Ba 3440 – 1280 – 105 775 131 (131)
Y 5.96 – 33.9 – 21.7 29.6 24.4 (25.9)
Zr 3.13 – 644 – 183 275 166 (171)
Nb 0.621 – 14.6 – 11.2 17.5 18.3 (18.1)
Hf 0.115 – 14.9 – 5.03 6.65 4.27 (4.47)
Ta – – – – – – 1.14 (1.15)
Pb 62.1 – 24.8 – 6.64 23.7 2.60 (1.65)
Th 2.77 – 17.2 – 13.0 37.1 1.22 (1.22)
U 0.726 – 1.11 – 4.18 1.82 0.430 (0.412)
La 26.0 – 78.3 – 29.0 65.0 15.1 (15.2)
Ce 51.5 – 147 – 59.8 127 37.6 (37.5)
Pr 5.22 – 16.7 – 6.91 13.7 5.36 (5.34)
Nd 17.0 – 60.9 – 25.4 47.7 24.4 24.3)
Sm 2.58 – 10.6 – 5.09 8.63 6.03 (6.02)
Eu 1.06 – 1.97 – 0.983 1.30 2.05 (2.04)
Gd 1.80 – 8.51 – 4.58 6.80 6.25 (6.21)
Tb 0.236 – 1.26 – 0.753 1.01 0.938 (0.939)
Dy 1.17 – 6.87 – 4.48 5.50 5.22 (6.28)
Ho 0.227 – 1.41 – 0.964 1.11 1.00 (0.998)
(continued on next page)

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E. Hegner, et al. Journal of Asian Earth Sciences 200 (2020) 104432

Table 1 (continued)

Sample # M 14 M 16 M 17 M 18 M 19 M 20 BHVO-2
Basement

Type QtzS AGr GrGn GrGn Casi HblBtGn Reference

Er 0.585 – 3.83 – 2.75 3.02 2.52 (2.51)

Tm 0.078 – 0.559 – 0.418 0.446 0.339 (0.335)
Yb 0.448 – 0.610 – 0.730 2.75 2.00 (1.99)
Lu 0.063 – 0.548 – 0.412 0.388 0.272 (0.275)
Nb/Ta – – – – – – 16.1 (15.7)
Ce/Ce* 1.07 – 0.987 – 1.03 1.03 --
Y/Ho 26.2 24.0 22.5 26.7 24.4 (25.9)
Zr/Hf 37.2 – 43.2 – 36.4 41.3 38.9 (38.2)

Major- and trace-element concentrations in wt. % and μg/g, respectively. Casi = Calc-sillicate, Mb = Marble, MC = Metacarbonate, QtzS = Quartz syenite,
AGr = Alkaligranite, GrGn = Granite gneiss, Hb-BtGn = Hornblende-biotite gneiss. Calcite r. = residue, Calcite l. = leachate. Ce/Ce* = CeN/(LaN × PrN)-0.5.
Concentrations in parentheses are GeoReM (georem.mpch-mainz.gwdg.de) “preferred values” (23.02.2020).

samples are intermediate between those in limestone (e.g., Rosatelli

et al., 2010) and UCC (REE pattern similar to that of calc-silicate sample
M19) and consistent with variable proportions of seawater-derived
carbonate and UCC material. The samples also show distinct negative
Ce-anomalies (Ce/Ce* = 0.74 to 0.88; Table 1) and positive Y-
anomalies (Y/Ho = 29–40; Table 1, Fig. 8). Both anomalies are con-
sistent with protolith formation in an oxidizing marine environment
(Elderfield and Greaves, 1982; De Baar et al., 1985; Elderfield et al.,
1990; German et al., 1991; Bau et al., 1997; Tostevin et al., 2016).
Furthermore, high Y/Ho ratios >36 when compared to a ratio of ~25
in UCC (e.g., Rudnick and Gao, 2014) as for samples M5, 6, 7 can also
be interpreted as seawater-derived (e.g., Nozaki and Zhang, 1995; Bau
et al., 1997; Tostevin et al., 2016).
The extended trace-element patterns Fig. 8a show negative Nb and
Ti-anomalies, positive Pb anomalies, and low Ba/Th ratios which are all
consistent with protoliths derived from UCC. The negative Zr anomalies
in Yellapatti samples, which are absent in UCC, apparently reflect the
samples’ high proportions of calcite and apatite which show similar
anomalies (Fig. 8b this study; Belousova et al., 2002; Chen and
Simonetti, 2013; Weidendorfer et al., 2016; Mao et al., 2016). The
average Nb/Ta ratio of ~15 and Zr/Hf ratio of ~35 (Table 1) in the
metacarbonate dike, marble and calc-silicate samples are similar to
those in crustal rocks (e.g., Münker et al. 2004) and much lower than
those in mantle-derived carbonatites with Nb/Ta ratios of ~35 and Zr/
Hf ratios of ~60 (e.g., Chakhmouradian, 2006).
The whole-rock, calcite, apatite, and diopside samples of the me-
tacarbonate dikes at Kudugumudi also share the trace element char-
acteristics of UCC (Figs. 7b, 8b). Metacarbonate sample M12a re-
presenting the calcite-apatite-rich inner dike material has up to a
tenfold higher REE abundance than calc-silicate sample M12b, re-
presenting the dike margin. This relationship is consistent with magma
fractionation as explained earlier. The slightly concave upwards HREE
pattern in calc-silicate sample M12b is due to accumulated diopside as
indicated by a similar HREE pattern for a diopside separate (Fig. 7b). Fig. 7. Chondrite-normalized REE patterns for metacarbonate dike samples and
included minerals, and marble and calc-silicate samples. (a) Whole-rock sam-
The positive Pb anomaly in both samples be explained in a similar way
ples showing subparallel REE patterns with moderate enrichment in LREE, little
(Fig. 8b). Significant contamination of a carbonate-rich siliceous melt
fractionated HREE patterns, and negative Eu-anomalies. These characteristics
by the gneiss and/or diffusive element transfer between dike and gneiss of upper continental crust (Taylor and McLennan, 1985) are distinct from those
resulting in a mineralogical reaction seam (e.g., Hollocher, 2014) is not of mantle-derived carbonatite (see data envelope in 7b; Hornig-Kjarsgaard,
supported by the Sm-Nd isotope relationship between gneiss and 1998; Le Bas, 1999). Negative Ce-anomalies (see Table 1) support protolith
marble dike (see Section 5.4). formation under oxidizing marine conditions (e.g., Elderfield and Greaves,
Although the enrichment of the LREE in whole-rock metacarbonate 1982). Data envelope for limestone from Rosatelli et al. (2010). (b) REE pat-
terns of metacarbonate dike interior sample M12a and included apatite, diop-
side, and calcite. Sample M12b represents the diopside-rich calc-silicate dike
margin. Data normalized to carbonaceous chondrite CI (chondrite Ivuna) of
Palme and O’Neill (2014). See text for discussion.

8
E. Hegner, et al.
Fig. 8. Bulk-Silicate-Earth (BSE)-normalized trace-element patterns for meta-
carbonate dike and included minerals, marble, and calc-silicate samples. (a)
Whole-rock patterns with negative Eu, Nb, Ti, Zr, and positive Pb anomalies
(except for Pb in dike sample M12a, see explanation in Section 5.3) and low Ba
and Sr concentrations relative to Th and Nd, respectively, support sedimentary
protoliths. Positive Y- and negative Ce anomalies suggest marine deposition of
protoliths. (b) Patterns for Kadugumudi metacarbonate dike sample M12a and
included calcite, diopside, and apatite, and calc-silicate dike margin sample
M12b. See text for discussion. Normalizing concentrations from Palme and
O’Neill (2014).
sample M12a overlaps the lower data envelope of mantle-derived car-
bonatites (Fig. 7b), its little fractionated HREE pattern, as well as the
negative Eu anomaly, seawater-derived small Ce- and Y-anomalies
(Table 1), all preclude a similarity with mantle-derived carbonatite
(e.g., Simonetti et al., 1995; Hornig-Kjarsgaard, 1998; Rosatelli et al.,
2010; Mongelli et al., 2013; Weidendorfer et al., 2016). The negative Pb
anomaly, as opposed to a positive one in UCC, apparently reflects the
abundant calcite and apatite in this sample (see mineral patterns in
Fig. 8b this study; e.g., Belousova et al., 2002; Chen and Simonetti,
2013; Weidendorfer et al., 2016). Both minerals apparently control the
incompatible trace element budget in sample M12a. Lastly, the apatite
separate shows a relatively low Sr concentration of ~700 ppm when
compared to typical 5 to 10 times higher concentrations in apatite from
carbonatites (Table 1 this study; e.g., Nelson et al., 1988; Bell, 1989;
Zaitsev and Bell, 1995; Belousova et al., 2002; Chen and Simonetti,
2013; Mao et al., 2016) further emphasizing the sedimentary
9
Journal of Asian Earth Sciences 200 (2020) 104432
characteristics of the metacarbonate dike protolith.
The calc-silicate samples from Kurangani Hills and the basement
inlier at Devikolam (sample M19) show the expected trace-element
patterns akin to UCC. Seawater-derived Ce- and Y-anomalies and ne-
gative Zr anomalies, well-developed in the marble and calc-silicate
samples from Yellapatti, are subtle or absent which is in agreement with
the subordinate limestone component in these rocks.
We conclude that the trace-element data of the marble and calc-
silicate samples from Yellapatti support limestone and marl protoliths
which is in agreement with the field and petrographic observations.
Negative Ce-anomalies and positive Y-anomalies in a number of these
samples corroborate deposition under marine oxidizing conditions. We
explain the mineralogical/chemical zonation of the metacarbonate
dikes at Kadugumudi with fractionation of a crust-derived carbonate-
rich siliceous melt. The little fractionated HREE patterns (as opposed to
highly fractionated ones in carbonatites) indicate source melting at
crustal levels and outside the garnet stability field. This important
finding precludes a classification of the metacarbonate dikes and veins
as carbonatite. Furthermore, the negative Eu anomaly, seawater-de-
rived Ce- and Y anomalies, low Nb/Ta-, Zr/Hf-and Ba/Th ratios, and the
low Sr concentration in apatite, clearly oppose the characteristics of a
carbonatite derived from metasomatized lithospheric mantle or plume-
related sources (e.g., Woolley et al., 1995; Bell, 1989, Le Bas,
19992005; Simonetti et al., 1995; Mitchell, 2005; Chakhmouradian,
2006; Jones et al., 2013).
5.4. Sr and Nd isotope systematics
The Rb-Sr and Sm-Nd isotope data for metacarbonate dike, marble,
calc-silicate, and basement samples are listed in Table 2 and plotted in
Fig. 9. Table 2 lists Nd model ages and initial εNd values and 87Sr/86Sr
ratios for 1.0 Ga, the inferred crystallization age of the metacarbonate
dikes and veins at Kadugumudi. Data for the yonger quartz syenite
sample M14 (~620 Ma, this study; M18 ~ 800 Ma, Brandt et al., 2014;
and the possibly similarly old samples M16, M17) were not recalculated
to 1.0 Ga. In addition, the measured isotope ratios were corrected for
in-situ decay over 570 Ma, the peak of granulite metamorphism in the
study area, as we have inferred from the age of metamorphic zircons in
hornblende-biotite gneiss sample M20 (see Section 5.6). During this
high-T metamorphic event the Sm-Nd isotope system (and Rb-Sr isotope
system) were reset as suggested by an internal Sm-Nd isochron age of
~600 Ma (see end of section).
The metacarbonate dike, marble, and calc-silicate samples show a
wide range of negative initial εNd(0.57 Ga) values of −7 to −18 corre-
sponding to early Paleoproterozoic average crustal residence times of
their protoliths; i.e., depleted mantle Nd model ages (NdTDM) of
1.7–2.5 Ga (Table 2). The range of εNd values is consistent with mixed
protoliths comprising Archean and more juvenile material. The Kadu-
gumudi whole-rock dike samples (metacarbonate dike sample M12a,
calc-silicate sample M12b) have NdTDM of ~2.0 to ~2.4 Ga and for a
magmatic age of ~1.0 Ga (see Section 5.6, U-Pb Geochronology) highly
radiogenic 87Sr/86Sr ratios of ~0.723 at εNd −11.6 (Fig. 9). The whole-
rock sample M12a and included nominally Rb-free apatite, calcite, and
diopside (the latter alteration-resistant and fresh), all yield consistent
and highly radiogenic 87Sr/86Sr isotope ratios (Fig. 9; Table 2) so that
we accept the radiogenic Sr in the dike samples as reliable source in-
formation. In Fig. 9, the dike samples plot near the data of the sur-
rounding basement and are clearly distinct from global and Indian
carbonatites.
The Yellapatti marble and calc-silicate rocks shows a large range of
 E. Hegner, et al.

Table 2
Rb-Sr and Sm-Nd isotope data for marble, metacarbonate dike, calc-silicate, and granitoid samples from the Munnar area, South India.
87 87 87 87 147 143
Sample type Rb [μg/g] Sr [μg/g] Rb/86Sr Sr/86Sr md. Sr/86Sr 0.57 Ga Sr/86Sr 1.0 Ga Nd [μg/g] Sm [μg/g] Sm/144Nd Nd/144Nd md. εNd 0.57 Ga εNd 1.0.Ga TDM

M 1 CaSi 146 101 4.20 0.754192 ± 5 0.7200 0.6941 6.61 1.31 0.1198 0.511524 ± 5 −16.0 −11.8 2.47
M 3 Mb 84.9 119 2.07 0.735644 ± 6 0.7188 0.7060 8.27 1.59 0.1162 0.511568 ± 5 −14.9 −10.5 2.30
M 4 CaSi 123 104 3.43 0.744591 ± 5 0.7167 0.6955 7.41 1.46 0.1182 0.511542 ± 5 −15.6 −11.3 2.39
M 5 Mb 2.74 121 0.0656 0.722153 ± 7 0.7216 0.7212 2.93 0.587 0.1213 0.511906 ± 5 −8.7 −4.6 1.86
M 6 Mb 2.92 110 0.0769 0.718399 ± 5 0.7178 0.7173 3.09 0.596 0.1166 0.511865 ± 5 −9.1 −4.8 1.84
M 7 CaSi 63.1 61.9 2.96 0.736648 ± 5 0.7126 0.6943 2.59 0.540 0.1270 0.511858 ± 5 −10.0 −6.2 2.07
M 8 CaSi 30.5 233 0.379 0.713255 ± 6 0.7102 0.7078 14.8 2.81 0.1148 0.511905 ± 5 −8.2 −3.8 1.74
M 9 CaSi 33.4 190 0.509 0.711708 ± 5 0.7076 0.7044 8.08 1.63 0.1221 0.511992 ± 5 −7.1 −3.0 1.74
M 10 CaSi 28.5 217 0.380 0.711288 ± 5 0.7082 0.7058 7.89 1.56 0.1194 0.511958 ± 4 −7.5 −3.3 1.74
M 11 Mb 0.148 268 0.00160 0.719692 ± 5 0.7197 0.7197 9.80 2.06 0.1270 0.512071 ± 5 −5.9 −2.1 1.70
M 12a wr MC 1.65 728 0.00657 0.722654 ± 7 0.7226 0.7226 94.4 12.8 0.08200 0.511289 ± 2 −17.9 −11.6 2.02
M 12a cpx* Diopside 0.056 34.8 0.00454 0.722203 ± 6 0.7222 0.7221 9.54 1.59 0.1008 0.511362 ± 5 −17.8 −12.6 –

10
M 12a cal* Calcite 0.027 276 0.000281 0.722320 ± 12 0.7223 0.7223 37.7 5.12 0.08201 0.511288 ± 5 −17.9 −11.6 –
M 12a ap* Apatite 0.017 743 0.00007 0.722323 ± 8 0.7223 0.7223 6807 953 0.08464 0.511297 ± 5 −17.9 −11.8 –
M 12b wr CaSi 6.15 341 0.0523 0.724196 ± 5 0.7238 0.7234 18.9 3.84 0.1227 0.511594 ± 4 −14.9 −10.8 2.43

Basement
M 14 QSyn 329 513 1.86 0.739495 ± 5 0.7244 – 19.6 2.78 0.08573 0.511105 ± 4 −21.7 – 2.30
M 16 AGr 134 556 0.698 0.723248 ± 6 0.7176 – 27.5 2.65 0.0582 0.511044 ± 6 −20.9 – 1.95
M 17 GrGn 140 131 3.10 0.753010 ± 5 0.7278 – 64.6 10.9 0.1024 0.511390 ± 3 −17.4 – 2.26
M 18 GrGn 137 131 3.04 0.754043 ± 5 0.7293 – 68.8 11.9 0.1049 0.511403 ± 5 −17.3 – 2.29
M 19 CaSi 1.83 219 0.0242 0.715869 ± 5 0.7157 0.7155 25.4 5.07 0.1205 0.511953 ± 5 −7.7 −3.5 1.77
M 20 HblBtGn 115 405 0.824 0.740831 ± 6 0.7341 49.9 8.65 0.1048 0.511094 ± 5 −23.3 −18.3 2.73

md. = measured ratio. 143Nd/144Nd normalized to 146Nd/144Nd = 0.7219 and 87Sr/86Sr to 86Sr/88Sr = 0.1194. MC-ICPMS analyses are relative to 0.710247 ± 11 (2SD, N = 13) in NIST SRM 987 and 0.512092 ± 7
(2SD, N = 16) in JNdi-1. For the samples indicated by asterisk, TIMS analyses of JNdi–1 yielded 143Nd/144Nd = 0.512102 ± 4 (N = 3) and 87Sr/86Sr = 0.710245 ± 9 (N = 2) for NIST 987. εNd calculated with CHUR
values (143Nd/144Nd = 0.512630; 147Sm/144Nd = 0.1960) of Bouvier et al. (2008). Rb and Sr concentrations determined by ICP-MS and Sm-Nd by isotope dilution in μg/g. TDM (depleted mantle model age) calculated
according to De Paolo (1981). Abbreviations: Wr = whole rock, Mb = Marble, MC = metacarbonate, QSyn = Quartz-syenite, AGr = Alkali granite, GrGn = Granite gneiss, CaSi = Calc-silicate rock,
HblBtGn = Hornblende-biotite gneiss.
Journal of Asian Earth Sciences 200 (2020) 104432
E. Hegner, et al.
εNd(0.57 Ga) values of ~-9 to −16 which correspond to average crustal
residence times of their protoliths of 1.8 to 2.5 Ga. The 87Sr/86Sr ratios
for some samples show large variations at similar εNd values that may
partly be due to Rb and Sr mobility and arbitrary in-situ decay-cor-
rected 87Sr/86Sr ratios. In any case, the overall radiogenic Sr isotope
compositions of the samples are in agreement with the Nd isotope
evidence for protoliths comprising large proportions of Archean mate-
rial. This conclusion is supported by the detrital zircon age spectrum
which we have studied for marble sample M3 (see Section 5.6). The
marble and calc-silicate samples from Kurangani Hills and Devikolam
(sample M19) yielded Paleoproterozoic average crustal residence times
of ~1.7 Ga.
In conclusion, the Nd-Sr isotope data for the metacarbonate dike,
Fig. 9. 87Sr/86Sr vs.143Nd/144Nd isotope systematics for metacarbonate dike
and included minerals, marble, calc-silicate, and basement samples (ratios
correspond to the time of isotope resetting during high-grade metamorphism at
0.57 Ga; see text for details). Data for Kadugumudi metacarbonate dike samples
are also shown for the crystallization age of ~1.0 Ga; note the stark difference
from Indian mantle lithosphere (e.g., HG, SI, N, AD). The data for metacarbo-
nate and calc-silicate samples indicate protoliths comprising variable propor-
tions of Archean and more juvenile material, with a very high proportion of old
crust in the putative Kadugumudi carbonatite material. Data for comparison:
present-day MORB-OIB and carbonatites of various ages: HG = ~2.4 Ga
Hogenakal carbonatites, southern India (Kumar et al., 1998; Pandit et al., 2002,
2002), SIC = Neoproterozoic South Indian carbonatites (Schleicher et al., 1998;
Kumar et al., 1998; Pandit et al., 2002; Ackerman et al., 2017; data field from
Paul et al., 2020), N = ~1.5 Ga Newania carbonatites (Ray et al., 2013),
AD = ~65 Ma Amba Dongar carbonatites, North India (Simonetti et al., 1995);
LZ = ~122 Ma Laiwu-Zibo carbonatites from ancient mantle lithosphere, East
China (Ying et al., 2004); data envelope for <200 Ma global carbonatites from
Ying et al. (2004); black bar = East African Carbonatite Line (<40 Ma car-
bonatites; Bell and Blenkinsop, 1987).
marble, and calc-silicate samples indicate mixed protoliths with
Paleoproterozoic average crustal residence times and probably high
proportions of Archean material. The metacarbonate dike samples
thought to represent carbonatite show no similarity with global
11
Journal of Asian Earth Sciences 200 (2020) 104432
carbonatite including Indian carbonatites from metasomatized mantle
(e.g., Bell and Blenkinsop, 1987; Bell 1989; Bell et al., 1998; Jones
et al., 2013; Paul et al., 2020; Ray et al., 2013, and references in Fig. 9,
this study).
The Sm-Nd isotope data for the Kadugumudi dike samples provide
some constraints on their magmatic age and metamorphic history. A
Sm-Nd internal isochron for metacarbonate dike sample M12a and in-
cluded apatite, diopside, and calcite yielded an isochron age of
600 ± 49 Ma (isochron not shown; MSWD = 0.22; 2SD input errors:
0.15% and 0.0018% for 147Sm/144Nd and 143Nd/144Nd, respectively).
We interpret the date as the time of isotope resetting (also resetting of
the Rb-Sr system which yielded no age information probably due to Rb
and Sr mobility) during UHT metamorphism reported to have lasted
from 600 to 550 Ma in the Munnar region (Tang et al., 2018), a finding
which is corroborated by the metamorphic U-Pb zircon ages of this
study (see Section 5.6). The resetting of the 147Sm-143Nd isotope system
apparently was not achieved on the whole-rock scale as suggested by
the different εNd values of −17.9 and −14.9 (at 0.57 Ga) for samples
M12a and M12b, respectively. An explanation of the different εNd va-
lues invoking magma contamination with gneiss is not plausible be-
cause dike margin sample M12b (εNd −14.9) would be expected to
show an intermediate εNd value between the endmember values of
−17.9 (dike interior, sample M12a) and −23.3 (gneiss). The Nd iso-
tope evidence thus supports the trace-element evidence for an origin of
the dike zonation by fractionation of a carbonate-rich siliceous magma.
Under the premise that the whole-rock samples behaved as closed-
systems during high-grade metamorphism (e.g., Faure, 1986), we ac-
cept a two-point whole-rock isochron age of 1142 ± 48 Ma (isochron
not shown; 2SD input errors, 0.15% and 0.0018% for 147Sm/144Nd and
143
Nd/144Nd, respectively) as the approximate time for crystallization
of the dike melt. The 147Sm-143Nd age is supported by the predominant
~1.0 to 1.1 Ga zircon population in the dike material (see Section 5.6,
U-Pb zircon geochronology), our field observation that the meta-
carbonate dikes are cut by quartz syenite of ~620 Ma (Section 5.6, U-Pb
Geochronology), and the apparent lack of magmatic zircons of inter-
mediate age in the dike sample.
5.5. Carbon and oxygen isotope systematics
The δ18O and δ13C values for calcite samples from metacarbonate
dike, marble, and calc-silicate rocks are listed in Table 3. In Fig. 10, the
data show two groups with the Kurangani Hills and Yellapatti samples
being isotopically similar to Precambrian marine limestone and the
calcite samples from the metacarbonate dikes similar to granulite-facies
metacarbonate samples with more depleted C and O isotope composi-
tions due to sample equilibration with mantle-derived carbonic fluids
(e.g., Baker and Fallick, 1988; Buick et al., 1994; Satish-Kumar et al.,
2001; Morteani et al., 2013; Martin et al., 2014; Zhang and Santosh,
2019). The massive and ductilely deformed marble and calc-silicate
sequences at Kadugumudi and Kurangani Hills have preserved their
primary limestone isotope characteristics whereas the thin and dis-
rupted metacarbonate dikes, veins and pods in gneiss at Kadugumudi
have undergone secondary depletion in both 13C and 18O isotopes.
The difference between the δ18O and δ13C values of the two sample
E. Hegner, et al. Journal of Asian Earth Sciences 200 (2020) 104432

Table 3
δ18O and δ13C values for calcite separates of marble, metacarbonate dike, and
calc-silicate samples.
Sample δ18OSMOW δ13CPDB

Kadugumudi
M12a-1 7.31 −4.73
M12a-2 7.60 −4.57
M12a-3 7.41 −4.56
M12a-4 7.40 −4.94
M12b-1 7.43 −4.39
M12b-2 7.47 −4.54
M12b-3* 8.45 −4.66
M12b-4* 9.60 −5.31

Yellapatti
M1-1 17.1 0.90
M1-2* 16.1 1.44
M3 16.6 1.23
M4 16.8 1.10
M5-1 17.3 2.14
M5-2* 16.1 1.60
M6-1 17.0 2.17
M6-2* 16.5 1.53
M7 17.2 1.78
Fig. 10. δ18O and δ13C values for calcite of metacarbonate dike, marble, and Kurangani Hills
calc-silicate samples compared to the compositions of primary igneous carbo- M8 16.1 1.33
natite (PIC; Taylor et al., 1967; Hoefs, 1997; Keller and Hoefs, 1995); mantle M9 17.5 2.33
(M; Kyser, 1986; Deines, 1989), and marine limestone (Schidlowski et al., 1975; M 10 18.5 2.85
Nelson et al., 1988; compilations in Shields and Veizer; 2002; Bell, 2005). Data M 11 16.4 2.11
fields for granulite-facies metacarbonate samples interpreted as equilibrated
with mantle-derived CO2: KKB = Kerala Khondalite Belt, Southern Granulite Precision (1SD) of δ18O values is ± 0.07‰ and for δ13C values ± 0.08‰
Terrane, India (Satish-Kumar et al., 2001; Zhang and Santosh, 2019); (Erlangen data). *Data IIT Kanpur (1SD): δ18O ≤ 0.1‰, δ13C values ≤ 0.2‰.
SM = South Madagascar (Morteani et al., 2013; Martin et al., 2014); EA = East
Antarctica (Buick and Cartwright, 1994); solid circle, Norway (Baker and limestone (Ray et al., 1999; Wang et al., 2014; Liu et al., 2015; Tappert
Fallick, 1988). p. = data field extending beyond figure boundary. See Section et al., 2009; see review of Gao et al., 2017) owing to the very low
5.5 for discussion. diffusion rates of these isotopes even at high temperatures (Cole and
Ohmoto, 1986). Furthermore, experimental melting studies on carbo-
groups is too large to be compatible with closed-system and internally nated pelites have shown that subduction of carbonate-rich sediment
buffered Rayleigh decarbonation reactions alone, so that additional (e.g., Johnson and Plank, 1999; Grassi and Schmidt, 2011; Grassi et al.,
open system fluid-rock interactions need to be invoked (e.g., Valley, 2012) leads to chemical and physical fractionation of the subducted
1986; Baumgartner and Valley, 2001). The details of this process are material, with a hydrous melt portion metasomatizing the lithospheric
beyond the scope of this study but we note that coupled depletions of mantle, and residual material being deeply subducted. These results
13
C and 18O isotopes are a ubiquitous feature of many marble and calc- imply that plate subduction obliterates the trace-element features of
silicate rocks that underwent granulite-facies metamorphism and con- subducted material in line with the evidence that melting of metaso-
comitant equilibration with mantle-derived CO2-rich fluids (e.g., Pili matized lithospheric mantle can generate carbonatitic/kimberlitic ra-
et al., 1997). This process has also been proposed as the underlying ther than typical upper crustal geochemical signatures. This inference
cause for the formation of the abundant charnockites in the Southern substantiates our hypothesis that the chemical and isotopic features of
Granulite Terrane which was associated with mantle degassing during the dikes and veins resulted from crustal processes rather than were
the Pan-African event (e.g., Newton, 1987; Jackson and Santosh, 1992; inherited from the mantle.
Santosh, 1991; Satish-Kumar et al., 2001). The absence of graphite- As explanation for the mantle-like O-C isotope compositions of the
bearing lithologies as source for isotopically light carbon in the Munnar metacarbonate dikes and veins at Kadugumudi, we propose the well-
basement further reinforces our view of involvement of mantle-derived studied process of overprinting of crustal rocks by mantle-derived CO2
CO2 although we cannot preclude contribution of fluids from the in- during granulite-facies metamorphism. Mantle-like O-C isotope com-
truded quartz syenite at Kadugumudi. positions in granulite-facies carbonates of southern India, have been
A model invoking the derivation of the dike melt from metasoma- interpreted by Satish-Kumar et al. (2001) to represent a two-stage
tized lithospheric mantle, as has been assumed for many carbonatites process with decarbonation and isotopic resetting during prograde Pan-
including those from the Indian subcontinent, seems not viable in view African metamorphism and infiltration of mantle-derived carbonic fluid
of the crustal trace-element characteristics of the dike samples (e.g., during retrograde metamorphism. Pili et al. (1997) reported a corre-
little fractionated HREE patterns preclude lithospheric mantle sources lation between the magnitude of mantle-derived CO2-flux and the scale
in the garnet-stability field and negative Eu-anomalies, low Ba/Th, Nb/ of shear zones in the Pan-African granulite terranes of Madagascar.
Ta and Zr/Hf ratios are all different from those in carbonatite of pre- Metacarbonate pegmatites from southern Madagascar with significant
sumably lithospheric mantle origin). Furthermore, the Nd-Sr isotopes in depletions in 13C and 18O (Fig. 10), as seen in the Munnar dikes, were
the dike samples are typical of old continental crust and clearly dif- related to melting of carbonate-rich material in deep crustal shear zones
ferent from the mantle sources of Indian and global carbonatites (see acting as pathways for mantle-derived CO2 during Pan-African post-
data comparison in Fig. 9). collisional crustal extension (Morteani et al., 2013; Martin et al., 2014).
Similarly, subduction of marine carbonate material and isotope In this context, we suggest that the mantle-like isotope composition of
equilibration with mantle CO2 before melting and dike formation is an the thin and disrupted metacarbonate dikes and veins at Kadugumudi
equally implausible origin of the carbonate melt since subducted car- may have resulted from overprinting by mantle-derived CO2 degassing
bonate is likely to preserve the primary O and C isotope compositions of along the Kerala and Attur lineaments (Katz, 1978) and KKPTZ and SSZ

12
E. Hegner, et al.
shear zones (Fig. 1). In the SGT a major mantle degassing event has
been documented for the late stage of the Pan-African orogeny. We
therefore assume that this event also caused the modification of the O
and C isotope systematics in the dikes and veins at Kadugumudi rather
than one related to the Grenvillian orogeny when the dikes and veins
were formed.
In summary, the O- and C-isotope compositions of the Yellapatti
13
Journal of Asian Earth Sciences 200 (2020) 104432
Fig. 11. Wetherill diagrams showing LA-ICPMS zircon data for marble sample
M3 from Yellapatti and metacarbonate dike sample M12 from Kadugumudi. (a)
Marble sample M3 showing a single late Archean zircon population with vari-
able degrees of isotope resetting at ~550 Ma (Pan-African metamorphism). A
statistical analysis of the zircon data according to Reiminck et al. (2016) in-
dicates a zircon upper intercept age of ~2.5 and a thermal event at ~430 Ma
(Appendix E, Fig. E.1). (b) Dike sample M12 (composite sample of rim and
interior material) from Kudugumudi showing a spectrum of late Archean to
Neoproterozoic zircon cores with isotope resetting at ~520 Ma. The ~1.1 Ga
upper intercept age for 20 zircon cores is interpreted as the approximate
magmatic age of the marble dike as supported by a ~1.1 Ga Sm-Nd whole-rock
date (see Section 5.4). (c) Diagram showing the data of oldest concordant zircon
data of sample M12 (grains B05, B09, B14, B21) which suggest dike emplace-
ment at 1.02 ± 0.07 Ga (see text for discussion). A statistical analysis of the
zircon data after Reiminck et al. (2016) suggests multiple sources with upper
intercept ages of ~2.7 Ga, ~2.2 Ga, ~2.1 Ga, and ~1.1 Ga, and a common
thermal event at ~500 Ma (Appendix E, Fig. E.2).
marble and calc-silicate samples agree with the geochemical evidence
for carbonate-rich protoliths. The rocks escaped pervasive isotope
equilibration with mantle-derived CO2, probably due to their massive
occurrence and non-brittle behavior during rock deformation. The
mantle-like compositions of the metacarbonate dikes and veins at
Kadugumudi are interpreted as secondary characteristics caused by
isotope exchange with mantle-derived carbonic fluids during the late
Pan-African orogeny as has been extensively documented for the SGT.
5.6. U-Pb zircon geochronology of marble, metacarbonate dike, and
granitoid samples
We determined U-Pb zircon ages for marble sample M3 from
Yellapatti, the composite dike sample M12 from Kadugumudi, the
hosting migmatitic hornblende-biotite gneiss (sample M20), and in-
truding quartz syenite (sample M14). The latter was previously thought
to be genetically related to the formation of the metacarbonate dikes
and veins.
The data for twenty-five zircon cores of marble sample M3 plot
along a discordia with intercepts at 2.53 ± 0.05 Ga and 0.55 ± 0.04 Ga
(MSWD = 18, Fig. 11a, Appendix D, Table D.2). The alignment of data
points suggests a single late Archean source for the sample and a zircon
population which underwent variable degrees of isotope resetting
during a metamorphic event at ~0.55 Ga. The time of isotope resetting
agrees with the timing of the Pan-African thermal event in the Madurai
Domain (e.g., Ghosh et al., 2004; Brandt et al., 2014; Tang et al., 2016).
The data for twenty-eight zircon rim analyses with <10% discordance
at the ~0.55 Ga discordia intercept (at this degree of discordancy ty-
pical data uncertainties overlap the concordia and therefore the ages
can be considered as concordant, and least ambiguous for interpreta-
tions, e.g., Mezger and Krogstad, 1997; Spencer et al., 2016) yielded a
weighted average 238U/206Pb age of 530 ± 9 Ma (not shown) which
overlaps within uncertainty with the discordia intercept age.
The results of statistical modeling of the U-Pb data of the detrital
zircons in this sample according to Reiminck et al., 2016 are shown in
Appendix E, Fig. E.1. The likelihood of binned upper and lower inter-
cept ages reproduces the evidence for a ~2.5 Ga magmatic zircon age
population and the likelihood curve of lower intercept ages suggest
thermal events as young as ~430 Ma.
The zircon core analyses for metacarbonate dike sample M12 are
shown in Fig. 11b and listed in Appendix D, Table D.3. Twenty of al-
together twenty-five data points plot along a discordia with intercepts
at ~1.1 Ga and ~0.5 Ga. Four of the least discordant (<10%) zircon
core data (grains B05, B09, B14, B21) yielded a 207Pb/206Pb upper in-
tercept age of 1020 ± 70 Ma (MSWD = 1.3; Fig. 11c). A marginally
older age, indistinguishable within uncertainties, of 1038 ± 50 Ma (not
shown) is provided by the oldest two zircon cores (grains B14, B21).
The CL-images of some of these zircons show CL-dark grey planar-
E. Hegner, et al.
Fig. 12. Wetherill and Tera-Wasserburg diagrams showing zircon data for
Kadugumudi hornblende-biotite gneiss sample M20. (a) Oldest least discordant
core data suggest a magmatic protolith age of 2452 ± 14 Ma. (b) Near-con-
cordant zircon core data at the lower discordia intercept suggest resetting of the
U-Pb system at 570 ± 14 Ma. This age is interpreted as reflecting the peak of
Pan-African metamorphism in the Munnar region (see text for discussion).
banded to structurally uniform and resorbed cores mantled by bright
luminescent metamorphic rims of ~900 Ma (data A14; Table E.2; CL-
images not shown). The cores have intermediate Th/U ratios of 0.46 to
0.55 which support a magmatic origin (Rubatto, 2017, Yakymchuk
et al., 2018) and the combination of little structured CL-images and
resorbed core rims may be explained with crystallization in a deep-
seated slowly cooling magma undergoing episodic Zr undersaturation
(e.g., Corfu et al., 2003). Our interpretation of the ~1.02 Ga zircon age
as magma crystallization age rather than a detrital zircon age is cor-
roborated by the Sm-Nd age of 1142 ± 48 Ma for the whole-rock
samples of dike interior and dike margin (see Section 5.4 for details).
Including the ~20 Ma uncertainty resulting from the decay constant
error for 147Sm at ~1.1 Ga (Begemann et al., 2001), the Sm-Nd date is
indistinguishable from the U-Pb zircon age. We regard the agreement of
the two chronometers as significant and suggest magma crystallization
and formation of the metacarbonate dikes and veins at 1020 ± 70 Ma.
This age would place the origin of the dikes in the framework of Ro-
dinia, possibly during its break-up history.
The evidence for late Mesoproterozoic magmatism in the Western
14
Journal of Asian Earth Sciences 200 (2020) 104432
Fig. 13. Tera-Wasserburg diagrams showing zircon data for quartz syenite
sample M14 thought to be cogenetic with the marble dike. Only zircon data
with ≤10% discordance are shown (Appendix D, Table D.4, includes the data
for older zircon xenocrysts). (a) Data for zircon cores (red) and rims (green)
overlap with the core data yielding an upper magmatic intercept age of
630 ± 40 Ma. Rim data suggest zircon overgrowth and recrystallization from
~600 to ~510 Ma. (b) Data only of large zircon cores, considered to be least
affected by isotope resetting, suggest a magmatic age of 620 ± 35 Ma (see text
for discussion). (For interpretation of the references to color in this figure le-
gend, the reader is referred to the web version of this article.)
Madurai Domain (WMD) is sparse to date (Brandt et al., 2014) and
apparently more widespread in the Eastern Madurai Domain (EMD) (or
Southern Madurai Block, SMB) where Plavsa et al. (2012) obtained
crystallization ages of 1007 ± 23 Ma for a charnockite protolith col-
lected about 100 km to the SE of Munnar, and protolith ages of
1031 ± 25 Ma for detrital zircons. The authors interpreted the igneous
activity at ~1.02 Ga as evidence for a different geodynamic develop-
ment of the WMD and EMD.
The zircon population of the dike samples includes five detrital
grains with highly discordant data points and 207Pb/206Pb minimum
ages of ~2.2 to ~2.7 Ga assuming isotope resetting during the Pan-
African thermal event for these grains as well (Fig. 11b). The NdTDM for
the whole-rock samples of ~2.0 to 2.4 Ga indicate that the source
material of the dike was derived predominantly from similarly old
sources.
The likelihood diagram of binned upper intercept ages shown in
E. Hegner, et al.
Appendix E (Fig. E.2) suggests a wide age spectrum of sediment pro-
venances of ~2.7 Ga, ~2.2 Ga, and ~2.1 Ga. A similar age spectrum as
in the dike sample has been previously reported for detrital zircons
from the Madurai Domain (Plavsa et al., 2014). The binned lower in-
tercept ages for sample M12 confirm isotope resetting at ~0.6 to
~0.5 Ga (i.e., the Pan-African thermal event).
The zircon data for hornblende-biotite gneiss sample M20 are
shown in Wetherill and Tera-Wasserburg diagrams in Fig. 12 (data in
Appendix D, Table D.5). Regression analysis of twenty-five core data
with ≤10% discordance yields discordia intercepts at 2450 ± 27 and
562 ± 10 Ma (MSWD = 16, not shown). Eleven data points defining
the upper intercept provide an indistinguishable yet more precise date
of 2452 ± 14 Ma (MSWD = 2.3, Fig. 8a) which we interpret as best
estimate for the crystallization of the gneiss protolith. The gneiss ap-
parently belongs to the suite of ~2.5 Ga tonalites that constitute a
major episode of crustal growth in the Madurai Domain (see data
compilation in Brandt et al., 2014; Plavsa et al., 2014).
Data of fourteen zircon cores defining the lower discordia intercept
are shown in a Tera-Wasserburg diagram in Fig. 12b. We interpret the
age of 570 ± 14 Ma (MSWD = 1.2) as best estimate of the peak of the
Pan-African thermal event in the study area. It coincides with the
~40 Ma duration of UHT metamorphism in the Madurai Domain with
peak conditions at ~550 to ~530 Ma (Clark et al., 2009, 2015), and
agrees with the timing of major deformation and shearing in the
northern Nilgiri Block (Fig. 1b; Raith et al., 1999). Apparently, UHT
metamorphism in the northern Madurai Block preceded peak granulite-
metamorphism at ~530 Ma for parts of the Kerala Khondalite Belt in
the southernmost SGT (Shabeer et al., 2005).
Eighty-five zircon core and rim analyses for quartz syenite sample
M14 are listed in Appendix D, Table D.4. The overwhelming number of
zircon data (sixty-five core and rim analyses, ≤10% discordant) plot
about the concordia between ~660 and ~500 Ma (Fig. 13a). The
spread of data points suggests a protracted history of zircon crystal-
lization and resetting of the U-Pb isotope system. An extended Pan-
African thermal event from ~600 to ~540 Ma has also been docu-
mented for a cordierite granulite sample from the Munnar region (Tang
et al., 2018). Regression of twenty core analyses suggests a magmatic
age of 630 ± 40 Ma (MSWD = 0.4; not shown). Limiting the data set to
eleven of the largest zircon grains, whose interior we consider to be
least affected by post-magmatic zircon modification, provides a similar
intercept age of 620 ± 35 Ma (MSWD = 0.3; Fig. 13b). We accept this
date as best estimate of the crystallization age of the quartz syenite
which clearly postdates the age of dike emplacement and disagrees with
the earlier notion of a cogenetic origin (Nair et al., 1984).
A small number of zircons interpreted as xenocrysts derived from
the crustal protolith of the syenite yielded concordant and near con-
cordant 207Pb/206Pb ages of 2.34 and 2.46 Ga (2 grains), and
207
Pb/206Pb minimum ages of 2.36 Ga and 2.49 Ga (2 grains). These
data agree with the age spectrum of detrital zircons from the WMD (the
NMB of Plavsa et al., 2014). A single zircon grain yielded a concordant
rim 207Pb/206Pb age of ~803 Ma (a14 rim, Appendix D, Table D.4)
which is indistinguishable from the 804 ± 6 Ma magmatic age of the
Munnar alkali granite (Brandt et al., 2014), and a distinct thermal event
in the WMD (e.g., Teale et al., 2011), and also reflected in the detrital
zircon record for the EMD (SMB; Plavsa et al., 2014).
In conclusion, we suggest that the zircons and related detritus in
marble sample M3 were derived from a ~2.5 Ga late Archean prove-
nance. Absence of post-Archean zircons including Grenville-age com-
ponents, suggest deposition of the Yellapatti marble and calc-silicate
rocks earlier than the Neoproterozoic. This result is in overall agree-
ment with a slightly younger Nd model age of 2.3 Ga suggesting an
additional yet small component of zircon-deficient mafic juvenile ma-
terial in the sample.
Metacarbonate dike sample M12 shows detrital zircons from
Paleoproterozoic and Archean sources and a dominance of ~1.0 Ga
zircons. In conjunction with a similar whole-rock Sm-Nd age we suggest
15
Journal of Asian Earth Sciences 200 (2020) 104432
dike emplacement during the late evolution (break-up?) of Rodinia. The
evidence for Grenville-age crustal melting in the WMD is of interest as it
has only been recognized in detrital zircons and metamorphic zircon
overgrowth dated at ~1.0 Ga (Brandt et al., 2014; Tang et al., 2018). In
the EMD, evidence for ~1.0 Ga igneous activity is widespread (e.g.
Plavsa et al., 2012, 2014; Kooijman et al., 2011; Sekaran et al., 2016)
and has been proposed as feature distinguishing the EMD from the
WMD (Plavsa et al., 2014). The new evidence for ~1.0 Ga crustal
melting in the WMD may require some modification of the suggested
boundary between the WMD and EMD.
The quartz syenite sample M14 yields a magmatic age of
620 ± 35 Ma and detrital zircon ages point to crustal sources com-
prising material up to ~2.5 Ga old. In combination with a ~2.3 Ga Nd
model age, the data indicate melting of predominantly Paleoproterozoic
crust. The hosting hornblende-biotite gneiss yielded a magmatic pro-
tolith age of 2.45 ± 14 Ma and the slightly older Nd model age of
~2.7 Ga suggests contributions of subordinate amounts of older crust,
not found in the zircon population analyzed by us. All of the zircons
show a protracted interval of isotope resetting during Pan-African
metamorphism from ~580 Ma to 530 Ma with peak conditions in the
study area at ~570 Ma.
6. Conclusions
Magmatic zircons from the enigmatic metacarbonate dikes and
veins near Munnar township yielded an intrusion age of 1020 ± 70 Ma
compatible with the late Grenvillian orogeny and development of
Rodinia. A cross-cutting quartz syenite, previously thought to be co-
genetic yielded a magmatic age of 620 ± 35 Ma.
Field relations, petrographic and geochemical-isotope assessment of
the marble and metacarbonate dike samples indicate old crustal char-
acteristics and absence of carbonatite. Little fractionated HREE patterns
support protolith evolution at crustal levels and outside the garnet-
stability field of the mantle. Negative Eu-anomalies and low crustal Ba/
Th-, Nb/Ta-, and Zr/Hf ratios, and a low Sr concentration in apatite are
consistent with sedimentary protoliths and contradict mantle-derived
carbonatite characteristics. Ce- and Y-anomalies suggest deposition of
the protoliths in an oxidizing marine environment.
Sr and Nd isotope compositions of marble and metacarbonate dike
samples are similar to those of the surrounding late Archean basement
which rules out any affinity with global and Indian carbonatites. The
massive layered marble and calc-silicate assemblages show primary
limestone oxygen and carbon isotope compositions whereas mantle-like
composition in thin metacarbonate dikes and veins most likely were
inherited during Pan-African granulite-facies metamorphism of the
basement.
CRediT authorship contribution statement
Ernst Hegner: Conceptualization, Writing - original draft, Writing -
review & editing, Visualization, Methodology, Investigation. Selvaraj
Rajesh: Writing - review & editing, Visualization, Investigation.
Matthias Willbold: Writing - review & editing, Methodology,
Investigation. Dirk Müller: Writing - review & editing, Investigation.
Michael Joachimski: Writing - review & editing, Investigation. Mandy
Hofmann: Writing - review & editing, Visualization, Methodology,
Investigation. Ulf Linnemann: Investigation. Johannes Zieger:
Writing - review & editing, Visualization, Methodology, Investigation.
Anakkathil Purushothaman Pradeepkumar: Conceptualization,
Writing - review & editing, Investigation.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to
E. Hegner, et al.
influence the work reported in this paper.
Acknowledgements
We thank the staff at the Universities of Tübingen, Göttingen,
Erlangen-Nürnberg and Senckenberg Museum, Dresden, for analytical
support and D. Weidendorfer for discussions. We are indebted to
Debjyothi Paul at the Advanced Centre for Material Science of the
Indian Institute of Technology at Kanpur for C-O isotope analyses for a
pilot study. Tomson J. Kallukalam at the National Centre for Earth
Science Studies, Trivandrum, provided access to mineral separation
facilities. Thanks go to Jean Wong, University of Hong Kong, for testing
calcite dating by the U-Pb method. O. Bartos helped with field work and
sample preparation and presented some of the data in his M.Sc. thesis.
S.R. was supported by a doctoral Rajiv Gandhi National Fellowship,
India. The project was funded by the University Grants Commission
(India) through the SAP DRS II grants to the Department of Geology,
University of Kerala (A.P.P.). E.H. acknowledges financing of field work
and laboratory expenses by the Department of Earth & Environmental
Sciences at LMU. Zircon analyses were financed by Senckenberg
Museum. Thanks go to M. K. Pandit for editorial handling and the re-
viewers for their time and helpful comments.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.jseaes.2020.104432.
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Further reading
Yellappa, T., Mallikharjuna Rao, J., 2018. Geochemical characteristics of Proterozoic
granite magmatism from Southern Granulite Terrain, India: Implications for
Gondwana. J. Earth Syst. Sci. 127, 1–31.