FULLERENES IN MID PROTEROZOIC CUDDAPAH BASIN, INDIA
Synopsis
Background:
The ~2.0 Ga intra-cratonic crescent shaped Cuddapah Basin is located in the eastern
part of the Dharwar Craton and occupies an important place in Indian Geology. It extends
over a length of 440 km and trends in NNE-SSW in the north and NNW-SSE in the south
through N-S in the middle. It has a maximum width of 145 km in the middle and
occupies nearly 44,550 sq.km.
The Basin hosts rich deposits of barytes, (vein and
bedded), limestone, dolomite, asbestos, basemetals, clay, slates, uranium etc.,
Diamondiferous, kimberlites, conglomerates, gravels are known from the Basin. Recently
methane gas shows are also reported. The recent discovery of the presence of
“fullerenes” in a few black tuff samples from the Mangampeta area of the Cuddapah
Basin, analysed
at the Stanford University (Sreedhar Murty 2005) added a new
dimension to the mineral wealth, of the Cuddapah Basin and called for immediate
attention.
What are Fullerenes?
Fullerene is a pure carbon molecule composed of at least 60 atoms of carbon and
exhibits a bucky ball structure as shown in Fig.1. The discovery of C60, C70, the carbon
cage molecules popularly known as fullerenes, named after the famous Architect,
Buckminister Fullerene (Kroto et al 1985), opened new and vast vistas in understanding
these curious molecules. The fullerenes, like artificial diamonds, can be synthesized from
carbon.
-1-
Fig.1. An association football is a model of the Buckminster fullerene C60.
Fullerene Applications:
Fullerenes, their derivatives and carbon nano tubes have a number of interesting
properties due to their unusual structures and sizes. The size of the individual fullerene
molecules makes them ideal building blocks for use in designing molecular units that find
application in nanotechnology. The fullerene family of carbon molecules possesses a
range of unique properties. A fullerene nano-tube has tensile strength, about 20 times that
of high-strength steel alloys, and a density half that of aluminum. Carbon nano-tubes
demonstrate superconductive properties, for commercial applications, including computer
memory, electronic wires. Fullerenes can be used in the construction of aerospace
vehicles because of the substantial performance gains. Its molecular nano-technology
improves the existing launch vehicle designs. They are very cost-effective compared to
the present materials being used. Several fullerene derivatives have interesting
pharmacological properties such as anti-Alzheimer’s activity. The fullerene family of
carbon molecules thus belonging to a unique class of strategic minerals, hold a great
promise in a wide spectrum of fields including future micro-electromechanical systems
(MEMS), nanotechnology, solar energy technologies, superconductivity, computer
memory, aerospace vehicle technology, designing and building of atomically precise
programmable machine assemblies that could conceivably adjust to any environmental
conditions.
-2-
Natural Fullerenes:
Synthesis of fullerene from carbon in the laboratories is complex and expensive,
while the reported occurrences of fullerene in nature are rather scanty. The natural
fullerenes when they were detected first during early eighties were originally thought to
be brought from space since these were found to be constituting an important carrier
phase for noble gases in carbonaceous chondrite meteorites. Though the natural
fullerenes were thought to be mainly of extra-terrestrial origin, subsequent studies
showed their existence in the terrestrial rocks as well. Its first reported occurrence in
natural terrestrial rocks was in “shungite”, a ~2.0 Ga. old Proterozoic Formation from
Karelia, Russia, containing highly carbonified carbonaceous matter (Buseck et al 1992).
This paved the way for subsequent studies on natural fullerenes (Buseck 2002, Jan
Jehlicka et al., 2003, etc.). Fullerenes were reported particularly from those lithologies
that experienced high energy events such as lightning (Daly et al 1993), wild fires
associated with K-T boundary (Heyman et al 1994 a, b, 1995, 1996, 1998) or meteoritic
impacts (Becker et al 1994). Occurrence of fullerenes was also reported from the lithounits corresponding to mass extinction boundaries of the Cretaceous-Triassic boundary
event (250m.y) as also from the well-established Cretaceous-Tertiary boundary (65 m.y)
corresponding to the “Dinosaur” extinction period. Similarly, fullerenes were also
reported from Triassic-Jurassic (T-J) boundary, volcano-sedimentary sequences, in
carbonaceous chondrite meteorites and breccia samples from the meteorite impact
craters, in fulgurite in coal samples, and impact craters of NASA’s Long Duration
Exposure Facility (LDEF) space-craft. In India too, occurrence of fullerene is reported
from the Cretaceous rocks at the K-T boundary in Rajasthan and in black tuff samples of
the Pullampet Formation Proterozoic Cuddapah Basin.
Occurrence of Fullerenes in Cuddapah Basin:
Five black tuff samples from
the Mangampeta area of the Cuddapah Basin,
analysed at the Stanford University (Sreedhar Murty 2005) indicated presence of C60,
C70 and C84, suggesting the presence of naturally occurring fullerenes in this part of the
-3-
world. Fig.2 shows the location map of fullerene occurrence in the Mangampeta,
Cuddapah district, Andhra Pradesh.
Mangampeta
(Study area)
Fig.2. Map showing the different sub-basins of the
Cuddapah Basin.
Study area (Mangampeta)
Encouraged by such convincing results and realizing the vast application potential
of this very important and strategic mineral, the Andhra Pradesh Mineral Development
Corporation (APMDC), Government of Andhra Pradesh, has come forward to support
further studies in this area under a research project and entrusted the responsibility of
executing the same to M/s. Geo Resources and Technologies Private Limited (GRTC).
The main objectives of the project are to ascertain the extent of fullerene occurrence,
its nature and distribution, the associated geological and physicochemical conditions, the
subsurface model of the investigated area and to visualize a model for the genesis.
-4-
Summary of The Work done:
Against the above background the present project was implemented by M/s. GRTC
during 2008-2009. Under this programme, integrated geoscientific investigations
including geological, geochemical, geophysical studies in the Mangampeta barytes mine
were conducted.
Representative rock samples collected were subjected to detailed analysis using
different analytical methods like High Performance Liquid Chromotography (HPLC),
Mass Spectrometry, X-Ray Diffraction in different laboratories both in India and U.S.A.
The results clearly brought out presence of “fullerene” in several tuff samples examined,
in significant quantities, much higher than those reported earlier, from different parts of
the world. These results suggest viability of fullerene for exploitation.
Geophysical results have brought out a well defined NW-SE trending linear zone of
high electrical conductivity and polarizability cutting across the mining area This is
interpreted to be representing a deep fracture zone presumably related to the volcanic
activity believed to be responsible for the genesis of the barytes mineralization of this
area.
Based on the studies, a model is proposed for the genesis of Fullerene in this area.
The model postulates that the volcanic activity, supposed to have been associated with
the origin of barytes in the area, played a significant role in creating suitable thermal
conditions and environment conducive to the transformation of the existing hydrocarbon
material into higher order allotropes of carbon representing the family of Fullerenes.
Alternately the magmatic origin model envisaged for barytes may also hold good
for fullerenes as well since the tuff and barytes as also the tuff and fullerenes are
intimately associated and formed in, more or less, identical conditions.
-5-
Future studies:
The study has established the presence of significant amounts of fullerenes C60 as
well as C70 in Mangampeta barytes mine. This valuable nano material with its molecular
closed case structural arrangement of atoms has very special physical applications
including delivering drugs by the Pharmaceutical R&D sector, improving the efficiency
of the solar panels and increasing the output of oil in reservoirs. Considering their high
market value and their immense application potential, the next phase of the activity is
logically related to commercial exploitation of this deposit. Since this is a unique
occurrence it automatically gets focus from various quarters of the world and prompts
search for possible presence of natural fullerenes in similar geological conditions in A.P,
and elsewhere in the country and outside. In order to take advantage of the findings of the
present study, it is indeed necessary that the Mangampeta deposit be exploited
immediately before the strategic importance of this unique find is diluted or lost.
Accordingly, conversion of the present findings of fullerene into a viable deposit
warrants expeditious action and foresight in the form of extensive efforts to extract and
evaluate the resource followed by, viability studies including setting up of a pilot plant
and then finally entering into exploitation. In view of the non availability of the complex
technology and expertise in the country to achieve the above envisaged goals, it becomes
imperative to go in for international collaboration.
-6-
I.
Introduction:
The intracratonic Proterozoic Cuddapah Basin, ~2.0 Ga old, located in the eastern
part of the Dharwar Craton (fig.1), occupies an important place in Indian geology and
tectonics.
The Basin hosts a wide spectrum of rich mineral resources like barytes,
asbestos, basemetals, diamond, uranium, limestone, etc., even “methane gas shows” are
also reported in the south western region of the Basin.
Further, recent studies on analysis of rock samples from the Cuddapah Basin have
added a new dimension to the mineral wealth, that the Cuddapah Basin holds. Five black
tuff samples from the Mangampeta area of the Cuddapah Basin, analysed at the Stanford
University (Sreedhar Murty 2005) indicated presence of naturally occurring fullerenes
C60, C70 and C84 in this part of the world, which is unique. It is not an isolated occurrence,
unlike in the case of several reports from different parts of the world. Encouraged by such
convincing results and realizing the vast application potential of this very important and
strategic mineral, the Andhra Pradesh Mineral Development Corporation (APMDC), a
Government of Andhra Pradesh Enterprise, has come forward to support further studies
under a research project and entrusted the responsibility of executing the same to
M/s. Geo Resources and Technologies Consultants Private Limited (GRTC), Hyderabad.
The main objectives of the project are to examine the nature, distribution and extent
of fullerene occurrence, the associated geological and physicochemical conditions, etc.,
in the Mangampeta Barytes mine. Accordingly the GRTC has undertaken systematic
investigations using integrated geological, geochemical and geophysical studies.
The present efforts under this project thus aim at examining some representative
rock samples from this Proterozoic Cuddapah Basin and subject them to systematic
analysis for investigation and detection of possible presence of fullerenes. Since some of
the institutions like IICT, M/s. Alkali Metals, ILS at the HCU in India and other
institutions abroad such as the Stanford University, M/s. NANO-C at Boston, USA, have
the required laboratory facilities like the HPLC, Masspectrometry, X-Ray Diffraction,
etc., the cooperation of these institutions was sought to conduct analysis on a few rock
-7-
samples to look for possible presence of fullerene. Besides examining the geological
conditions and collecting representative rock samples and carrying out the analysis for
presence of fullerene, efforts were also made to conduct geophysical studies in order to
understand the subsurface conditions of the study area. Based on such an integrated
approach, the present study brought out several positive signatures to show occurrence of
natural fullerenes, in the Pullampet sediments of Mangampeta area of the Cuddapah
Basin.
Fullerene is a pure carbon molecule composed of at least 60 atoms of carbon and
exhibits a bucky ball structure as shown in Fig.1. The discovery of C60, C70, the carbon
cage molecules popularly known as fullerenes, named after the famous Architect
Buckminister Fullerene (Kroto et al 1985), opened new and vast vistas in understanding
these curious molecules. The fullerene family of carbon molecules belong to a unique
class of strategic minerals that hold a great promise in a wide spectrum of fields including
future micro-electromechanical systems (MEMS), nanotechnology, solar energy
technology, enhanced oil recovery, superconductivity, computer memory, aerospace
vehicle technology, designing and building of atomically precise programmable machine
assemblies that could conceivably adjust to any environmental conditions.
The artificial fullerenes, like artificial diamonds, can be synthesized from carbon
using elaborate, complicated and expensive techniques. But the natural fullerenes when
they were detected during early eighties were originally thought to be brought from space
since these were found to be constituting an important carrier phase for noble gases in
carbonaceous chondrite meteorites.
Though the natural fullerenes were thought to be mainly of extra-terrestrial origin,
subsequent studies showed their existence in the terrestrial rocks as well. Fullerene in
shungite, a ~2.0 Ga. old Proterozoic formation from Karelia, Russia, containing highly
carbonified carbonaceous matter was the first reported occurrence in natural terrestrial
rocks (Buseck et al 1992) which paved the way for subsequent studies on natural
-8-
fullerenes (Buseck 2002, Jan Jehlicka et al., 2003, etc.). Fullerenes were reported
particularly from those lithologies that experienced high energy events such as
lightning (Daly et al 1993), wild fires associated with K-T boundary (Heyman et al
1994 a, b, 1995, 1996, 1998) or meteoritic impacts (Becker et al 1994). Occurrence of
fullerenes was also reported from the litho-units corresponding to mass extinction
boundaries of the Cretaceous-Triassic boundary event (250m.y) as also from the wellestablished Cretaceous-Tertiary boundary (65 m.y) corresponding to the “dinosaur”
extinction period. Similarly, fullerenes were also reported from Triassic-Jurassic (T-J)
boundary section of Queen Charolotte Islands, British Columbia, in solid bitumen
samples from neo Proterozoic (585 Ma) volcano-sedimentary sequence of the
Bohemian Complex in Mitov area of Czech Republic (Jan Jehlicka et al 2003), in
carbonaceous chondrite meteorites and breccia samples from the meteorite impact
craters like Sudbury in Canada, Gardnos in Norway and Ries in Germany (Elsila et al
2005), in fulgurite in coal samples from China and impact craters of NASA’s Long
Duration Exposure Facility (LDEF) space-craft.
In India too, there have been a few reports on the occurrence of fullerene - one in
the Cretaceous rocks at the K-T boundary in Rajasthan and the other, in black tuff
samples of the Proterozoic Cuddapah Basin (Parthasarathy et al 1998, Misra et al 2007,
Sreedhar Murthy 2005). Following is a brief account of the Cuddapah basin and that of
the Mangampeta baryte mine area where from fullerene was reported.
-9-
II. Cuddapah Basin:
The Cuddapah Basin (Fig.1) is a crescent shaped mid-Proterozoic Basin and has
more than six kilometers thick sedimentary pile and rests over a granite gneiss and schist
basement with a profound unconformity. The sedimentary pile is broadly classified into a
lower Cuddapah Supergroup and an upper Kurnool Group.
Studies on the geology and tectonics of the Cuddapah Basin were first carried out
by King (1872) and are continued by several workers even today, though intermittently.
Stratigraphically, the Cuddapah Basin is divided into Papaghni, Chitravathi, Nallamalai
Groups and Srisailam Quartzite. The Basin comprises mainly ortho-quartzite-carbonate
suite and basic to acid volcanics and sills in the lower part and siliceous shales/tuffs with
quartzite interbands in the upper part (Nagaraja Rao et al 1987). Revised strategraphy of
the Cuddapah Basin is given in Table I.
Resting unconformably over the Cuddapah sediments, the Kurnool Group
sediments are exposed in two isolated tracts, in the central (Nandyal depression) and
north-eastern (Palnad depression) parts of the Cuddapah Basin. Both these sub-basins are
separated by the Nallamalai rocks and Srisailam plateau. (Fig .1 & 2).
The Cuddapah sediments were laid under quiet and submergence conditions. The
craton around the Cuddapah Basin (except in the east) was the source for the Cuddapah
(barring the Nallamali Groups) and Kurnool rocks and the Nallamalai Group from the
Eastern Ghats terrain.
The Cuddapah Basin has progressively evolved through the formation of a series of
sub-basins, viz., the Papaghni and Chitravathi Groups in the western sub-basin,
Nallamalai sub-basin in the eastern sub-basin, Srisailam Quartzite in the Srisailam subbasin and the Kurnool and Palnad Groups in the Kurnool/Palnad sub-basins.
- 10 -
Fig.1. Geological map of the Cuddapah Basin (GSI 1981).
- 11 -
TABLE - I
Revised Stratigraphy of the Cuddapah Basin and
Adjoining Crystallines
(After GSI, 1981 )
Kurnool
Palnad
sub-basin
sub-basin
K
U
R
N
O
O
L
Nandyal Shale
50-100m
30- 50m
Koilkuntla Limestone
15-50m
10-30m
Paniam Quartzite
10-35m.
5-40m
G
R
O
U
P
Owk Shale
10-15m
3 – 5m
Narji Limestone
100-200m
300-350m
Banganapalli Quartzite
10-57m
70m
----------Regression or Local Disconformity--------
----------------Unconformity----------------------
Srisailam
Iglapenta Quartzite
200m
Tapasipenta Siltstone
100m
Krishna Quartzite
320 (+) m
Quartzite
C
U
D
D
A
P
A
H
S
U
P
E
R
G
R
O
U
P
----------------Unconformity---------------------Cumbum (Pullampet) FormationNallamalai
shale /phyllite, quartzite/dolomite
2000m
3500m (+)
Group
Bairenkonda / (Nagari) Quartzitequartzite & shale
1500/4000m
--------------Disconformity---------------------Gandikota Quartzite
Chitravati
Group
1200m
Tadipatri Formation-
4600m
shale & tuff, lava flows, sills, etc.,
Pulivendla Quartzite
1200m
Depth to basement at
Muddanuru
--------------Disconformity---------------------Vempalle FormationPapaghni
dolomite and shale with flows
1500m
Group
Gulcheru Quartzite
--------------Non-conformity---------------------Dharwar crystallines
Granite, Gneiss, Schists, etc.,
- 12 -
6000m (+/-)
Six phases of igneous activity were recognized in the Cuddapah Basin. These are
basic volcanism during Vempalle times; basic and acidic volcanism during Tadipatri
deposition; dolerite, gabbro and picrite sills during post Tadipatri period; acid volcanism
during Pullampet/Cumbum Formation; basic intrusive activity during Nagari Quartzite
Formation; and granitic intrusion into the Cumbum Formation along the eastern margin
of the Nallamalai Fold Belt (Nagaraja Rao et al 1987). The acid volcanic activity during
the Pullampet/Cumbum times, represented by tuffs rich in barium, magnetite are by far
the most important from the point of fullerene.
Cuddapah Basin is a north plunging asymmetric synchronism comprising a nonfolded western limb and an intensely folded, overturned and thrusted eastern limb
(Narayanaswami, 1966). Four morphological sub-basins, concomitant with the
depositional sub-basins were recognized. Several linears running for several kilometers in
E–W, ENE–WSW and NW/NNW – SE/SSE were identified. Among these, the ChelimaZangamrajupalle- Mangampeta fracture is considered very significant, as it might have
facilitated movement of exhalatives and /or ejection of tuff material rich in barium, etc.
Based on Rb – Sr, Sm – Nd and Pb – Pb isotopic ages the oldest age given to
Cuddapah Basin is 2170Ma while the youngest is around 1000 m. y. Lampriotes intrusive
into the Cumbum sediments have given an age range between 1090 and 1380Ma. The
fullerene bearing tuffs of Mangampeta are, therefore considered older than 1380Ma.
The Cuddapah Basin abounds in a variety of economic minerals and include
asbestos, barytes (vein and bedded), basemetals, cement – chemical and flux – grade
limestones, dolomite, clay, slates, uranium, fullerene, etc.
More details on the stratigraphy, sedimentation, basin evolution, igneous
activity, structure, geochronology, mineral wealth, etc., of the Cuddapah Basin are given
in Appendix-A for better comprehension and understanding.
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III. Mangampeta Barytes Field (MBF):
Mangampeta (14º 05 ' N : 79º 19 'E ) area, being a part of the Nallamalai sub-basin,
is located in the southern horn of the Cuddapah Basin (see fig.2), and mainly forms the
upper parts of the Pullampet Formation. The world famous barytes deposit of the
Mangampeta Barytes Field (MBF) is located at the Mangampeta village and occurs
confined to the Pullampet Formation. In the following paragraphs, a semi detailed
account of various genetic studies carried out for barytes is given as fullerenes is closely
associated with tuffs associated with the barytes.
Mangampeta
(Study area)
Fig.2. Map showing the different sub-basins of the Cuddapah Basin.
- 14 -
III.1. Geology: Pullampeta Formation around Mangampeta Barytes Field:
The Pullampet Formation comprises predominantly tuff with interbands of quartzite
and dolomite. King included Pullampet Shale as a part of the Cheyair Group and
considered it to be older to Bairenkonda Quartzite Formation. But the work by Nagaraja
Rao et al (1987), has shown that Pullampet Formation is a part of the Nallamalai Group
and overlies the Bairenkonda (Nagari) Quartzite. In the Pullampeta hill range, the
Pullampet Formation grades into Cumbum phyllites/slates/shales along the strike and the
dip and hence Cumbum and Pullampet Formation are stratigraphically one and the same
and are referred to as Cumbum Formation in the northern part and Pullampet Formation
in the southern part. Thus, as per the latest classification (GSI 1981), the Pullampet
Formation is shown as time equivalent of the Cumbum Formation belonging to the
Nallamalai Group.
Studies carried out by Karunakaran (1974 & 1976) and Kurien et al (1976) on the
rocks in and around Mangampeta area have brought out volcanogenic nature of the
barytes and the associated rocks (mainly black tuff). Extensive field and petrographic
studies carried out in the adjacent areas in the strike continuity of the MBF for a length of
over 30km has led to the conclusion that a major part of the Pullampet sequence,
lithologically described by the earlier workers as shale, quartzite and dolomite with the
exception of dolomite, is perhaps volcanogenic. A band of magnetite tuff with silica and
carbonate rich flows and bands is recorded from near the base of Pullampet Formation,
near Cheyair river valley along Rajampeta - Rayachoti Road (GSI News, 1977).
Detailed field and petrographic studies in the Mangampeta area have led to
identification of a predominantly volcanogenic sequence of rocks comprising vitric
crystal tuff (tuff) with intercalations of quartz-crystal tuff. In thin sections, the tuffs show
fine grained groundmass made up of chlorite and carbonaceous dust. Here tuff refers to a
combination of altered glass and crystal (quartz) fragments or a mixed one. The tuff and
the associated quartzite beds exhibit excellent sedimentary structures, like graded
bedding, ripple marks, cross-bedding, convolute laminations, etc. On the basis of
- 15 -
petrographic studies, diverse types of tuff have been identified. These include glass tuff,
quartz crystal tuff, quartz pyrite lapilli tuff, barytes lapilli tuff, etc. Interbedded with
these tuffs occur flows extremely rich in barium sulphate. The rocks met within the MBF
are thus comprised of mixed tuff (mixture of vitric and crystal tuff). Crystal tuff and
dolomite with numerous quartz veins cut across all the lithounits. Pyrite is present as thin
stringers and small lenses, knots and disseminations and at places it is associated with
minor amounts of chalcopyrite.
Tuff:
It is earthy white, cream, buff, purple, gray and black in colour and is thinly bedded
and well cleaved. Outcrops are generally weathered and at places they are clayey and
ochreous in nature. Pyrite associated with this rock is limonitised in the weathered
profile. These rocks are weathered to varying depths depending upon the penetration of
the circulating waters. These are weathered to a maximum depth of about 40m. The rock
is fine grained and argillaceous. The black colour of the rock is due to the presence of
carbon. The specific gravity of this rock varies from 2.4 to 2.9, the weathered tuff being
lighter. The rock underwent mild metamorphism of green schist facies and has become
slaty.
In thin sections, the rock is extremely fine grained and contains gray to greenish
gray argillaceous matrix with angular to sub angular, subhedral to anhedral grains of
quartz. Fine acicular grains of sericite are also found admixed with the matrix. At places,
quartz grains
show dark encrustations, which could be carbon. Plagioclase feldspar,
pyrite, tourmaline, zircon are the associated minerals. At places presence of secondary
carbonates is recognized. Plagioclase is fine to medium grained, subhedral in shape and is
at places highly kaolinised and sericitised. Pyrite grains are anhedral and limonitised.
Fibrous rim of quartz is generally present around pyrite grains.
- 16 -
Crystal tuff:
It occurs as interbands within tuff and varies in thickness from less than a
centimeter to 50cm. Thicker bands usually occupy tops of linear edges. There are two
type of crystal tuff. The predominant one is extremely fine grained, compact, massive and
has cherty /flinty appearance and exhibits sub conchoidal fracture. The other type of
crystal tuff, relatively less common, is gritty in appearance and consists of medium sized,
rounded to sub rounded grains of quartz set in siliceous matrix. At places, it is calcareous
and ferruginous. Occasionally it exhibits colour banding suggesting thinly bedded nature.
Outcrops are seen in the area north and east of Mangampeta. The rock is traversed by
thin veins of quartz. Pyrite occurs as lenses, nodules, clots and disseminations.
Under the microscope the rock comprises angular to sub angular grains of quartz,
plagioclase feldspar, sericite, secondary carbonate, pyrite and tourmaline. In general it is
fine to medium grained and shows inclusions of fine dust. At places the rock exhibits
sutured and embayed margins. Undulose extinction of the quartz grains is common.
Occasionally fine grains of barytes and anhedral grains of carbonates are found replacing
quartz grains along their periphery. Pyrite is also found to replace both quartz and
carbonates.
Unidirectional growth of fibrous quartz on secondary pyrite crystals is
observed at places. Frosting of quartz grains is observed occasionally. Sub- rounded to
elliptical grains of tourmaline are present which at places occur as inclusions within in
the quartz grains.
Dolomite:
The rock is gray, extremely fine grained, massive, ramified with irregular veins of
quartz, calcite and occasionally barytes. It is cherty and siliceous at places and occurs as
lenses and intercalations vary in thickness from about a metre to 10m within the tuff.
Outcrops are seen in and around Mangampeta and North West of Rajampeta, etc.
- 17 -
Impure dolomite occurring generally along the fringes of the lenses is flaggy and
exhibits crude banding whereas the pure dolomite occurring in the central parts of the
dolomite bands is massive. At places the rock is tuffaceous. It is more prevalent in the
middle and upper parts of the Pullampet succession. Vein barytes is mostly confined to
this rock and mined at places.
In thin section the rock mainly consists of fine, equigranular grains of carbonates
(mainly dolomite) and presents a mosaic texture. The grains are usually subhedral to
anhedral and at places show sub rhombohedral outline. The associated minerals are
quartz, pyrite (mostly limonitised) and feldspar. The rock is frequently traversed by
veinlets of quartz and carbonates and rarely barytes. At places the rock carries bands of
tuffceous material (fine grained argillaceous material).
III.2. Structure:
The rocks trend in a general NNW-SSE direction with gentle to moderate dips
varying from 10º to 30º towards ENE. Variations in strike and reversal of dip due to
folding and swerving is common.
Primary structures noticed in the tuff and crystal tuff are ripple marks, current
bedding and graded bedding. Stray oscillatory and interference types of ripple marks
suggest a current direction from SSW to NNE. Intraformational conglomerate and breccia
are seen in dolomite and crystal tuff. Chert nodules, geode fillings and stylolites are seen
in crystal tuff and barytes. Penecontemporaneous deformation is not uncommon in tuff
and occasionally in barytes.
The rocks are folded into a series of gently plunging anticlines and synclines over
NNW-SSE axes plunging at 10º -15º towards NNW. Generally the folds are open and
symmetrical type. Another set of folds trending ENE-WSW are represented by gentle
and open warps. These folds are found to be progressively more open from west to east.
The major folding has resulted in the development of NNW-SSE trending axial plane
- 18 -
cleavage in the tuffs. The cleavage plane dips consistently towards ENE at steeper angle
than bedding. The beds are generally right side up except at a few places where
overturning is seen.
Minor faults of dip-slip type with displacement between 2 to 4 metres are observed.
Brecciation, silicification and slicken slide surfaces are the manifestations of the faulting.
In the MBF, the structure of the Northern lens is a cross-folded doubly plunging
asymmetrical syncline (Neelakantam 1987). At places the tuff beds are overturned very
tightly as seen in the mines. These overturned beds are crossed folded subsequently,
lending a cylinder-like appearance at places. Quartz vein/veinlets are found to occupy the
dilation zones in the black tuff as could be seen from the figure3.
Fig.3. Overturned beds of black tuff resembling a cylindrical structure.
- 19 -
III.3. Mangampeta Barytes Deposit:
The Mangampeta barytes deposit occurs in the form of two lensoid bodies within
the tuff sequence of the Pullampet Formation. Fig.4 shows the location of the
Managampeta Barytes mine. The barytes body occurring at Mangampeta village is called
“Northern lens” and is bigger of the two. The other one is located about 700m south of
the Northern lens is called “Southern lens”. From the study of the structural data and
lithological variations it is surmised that the Southern lens is a separate body and occurs
stratigraphically below the Northern lens.
Part of toposheet No 57N/8
Fig.4. Location of the Mangampeta Barytes Mine area.
- 20 -
a) Northern Lens:
The Northern lens occupies an area of about 0.81 sq.km. It is 1220m long and
900m wide. Maximum thickness of barytes is 40m in the central part.
It has an
overburden of black tuff varying in thickness from 0m to 181m. The Northern lens is
estimated to contain a probable reserve of over 74million tonnes of barytes of all grades.
It is the single largest and thickest known deposit containing about a quarter of the known
barytes reserves of the world (Neelakantam, 1987).
The generalized lithological succession of the beds in the Northern lens is as follows:
Quartz veins, stringers & veinlets of barytes
Contains pyrite and chalcopyrites as
pods and stringers
Carbonaceous tuff (partly weathered)
2 to 180m
Carbonaceous tuff with quartz rosettes/ 0 to 6m
lapilli
Tuff with quartz and barytes lapilli/rosettes
0.2 to 3m
Lapilli/rosette barytes
0.23 to 22m
Granular barytes
1.2 to 35m
Carbonaceous tuff
2 to 76m
Dolomite with black tuff bands
>50m
Alternate gray and black tuff with thin >4 to 15m
dolomite bands
Dolomite
> 68m
b) Southern Lens:
It has a strike length of about 300m and maximum width of 70m with steep dips
towards ENE. It has an area extent of 0.0059 sq.km and average thickness of 9.78m
(Neelakantam,1987). Barytes from this lens is completely mined out.
- 21 -
Granular, lapilli/rosette, vein and replacement are the four genetic types of barytes
found in MBF, the first two being economically significant. Lapilli barytes invariably
overlies the granular barytes beds. The granular barytes is a product of exhalative
volcanic action and the lapilli/rosette barytes represents the pyroclastic phase of the same
volcanism. Vein barytes occurs in the form thin stringers cutting the barytes and tuff
beds and is considered to be hydrothermal. Barytes replacing quartz and pyrite grains is
observed in thin sections only (Neelakantam, 1987).
Generalized geological succession of beds in Southern lens is as follows:
Litho Unit
Thickness range (m)
Soil
0.50 - 2.00
6.Tuff (partly weathered)
2.00 - 51.62
5.Tuff with quartz-pyrite lapilli
1.58
4. Tuff with barytes rosettes
4.55
3.Granular barytes
1.15 - 12.38
2. Tuff with barytes rosettes
0.20
1. Carbonaceous tuff
> 11.30
c) Major Element analysis:
During the course of detailed exploration for barytes by GSI in Mangampeta area,
Neelakantam (1987) analysed several samples of tuff for their major element content.
The major element constituents R2O3, Fe2O3, SiO2 and Loss on Ignition (LOI) are in the
ranges, 2.27-11.7%, 0.85-7.34%, 04.65-50.85% and 0.73-10.59%, respectively. It is
observed that SiO2, R2O3, Fe2O3 and LOI content are higher in tuff than in barytes. It has
also been established that there exists an inverse linear relationship between BaSO4
content and each of the major element constituents, thereby suggesting homogenous
nature of the tuff material associated with the barytes.
- 22 -
Three samples of black tuff (folded sample-6, S-12 OB (bottom) and S-15 OB-3
were analysed for ascertaining their major element chemistry and their results are shown
in Table.2. Results of black and weathered tuffs analysed for the project “geochemistry
of gray and black tuff overburden on the Mangampeta Barytes deposit” are given
alongside for comparison. The range of major element constituents in the tuff by GSI is
also shown.
Table 2
Major element Chemistry of Black tuff and Weathered tuff
Name
of the
element
Concentration (ppm)
1
SiO2
*S-12
OB
(bottom)
2
59.2
Al2O3
16.7
15.10
22.0
15.05
16.07
Fe2O3
4.6
5.1
18.8
5.81
6.83
MgO
6.2
7.4
13.9
3.42
1.55
CaO
6.6
10.1
2.9
2.58
0.15
Na2O
0.6
0.5
0.3
0.78
037
K2O
4.9
4.8
3.2
3.17
3.15
TiO2
0.6
0.6
-
0.45
0.58
P2O5
0.1
0.2
1.5
0.12
0.08
MnO
-
-
-
0.02
0.06
SrO
-
0.01
-
-
-
NiO
0.01
0.08
0.2
-
-
ZrO2
0.05
0.04
-
-
-
S
0.4
0.5
1.5
-
-
*S-15
OB-3
*Folded
sample-6
Black tuff
Weathered
tuff
3
55.7
4
35.0
5
63.71
6
66.5
*Samples. S.No.
2,3 and 4
analysed by
XRF in IICT,
Hyderabad for
GRTC
S.No. 5and 6 by
Dr.V. Sudarshan,
Dept of Applied
Geochemistry,
Osmania
University,
Hyderabad
The above XRF analysis results indicate that the sample Nos. S-12 OB (bottom)
and S-15 OB-3 are alumious sediments rich in MgO (6.2 and 7.4 %) and CaO (6.6 and
10.1 %). This is perhaps due to proximity to dolomite material. In fact, these samples
could be classified as dolomitic tuff. High concentration silica (55.7 and 59.2 %) is
- 23 -
mostly due to presence of quartz. The presence of S (0.4 to 1.5 %) is perhaps due to
presence of sulphides. Neelakantam and Kopresa Rao (1980) have established presence
of elemental sulphur in the barytes beds underlying the black tuffs.
The XRD analytical results more or less compare well with those of XRF. It may be
noted that the analysis of both black tuff and white or weathered tuff compare well,
suggesting derivation from the same source. Minor variations in the Fe2O3, MgO, CaO,
etc., are due to presence of dolomitic material and /or sulphides.
d) Trace Element analysis:
Several black and weathered tuff samples were analysed by GSI and Applied
Geochemistry Dept., Osmania University for their trace element content and the results
are given in Table 3.
Concentration of Cu, Pb, Zn, Co, Ni, Mn, Bi, Sb, Ge are of same order in both
weathered and black tuffs, suggesting derivation from the same source. The concentration
of Mn, Ni, Co, Cu, V, Zr and Ti are significantly higher than normal background values
for similar rocks. Presence of Rb, Ce, La and Li are detected in very low levels. The
trace element analysis suggests that weathered and black tuffs are one and the same and
the former resulted from the surface weathering and alteration of the latter. Higher than
normal background values of Mn, Ni, Co, Cr, V and Ti coupled with the presence of Rb,
Ce, Nb, La
and
Li is suggestive of derivation
from igneous/magmatic source
(Neelakantam, 1987).
These results indicate the trace element contents are of the same order in the black
and weathered (white/cream) tuffs, except for Cu, Pb and Zn in weathered tuffs. The
low content of Cu, Pb and Zn in weathered tuff when compared to the black tuff may be
due to oxidation of chalcopyrite, galena and sphalerite and subsequent removal by the
weathering agents and surface circulating waters. Anomalous concentration of
- 24 -
Pb, Zn,
Table.3
Trace element analysis of Black tuff and Weathered tuff
Concentration (ppm)
Name
of the *Black ** Weathered Black Weathered Black
element
tuff
tuff
tuff
tuff
tuff
1
2
3
4
5
6
Be
0.869
Cr
50-100
100
183
147
-
Co
5
5-10
15
5.7
14.792
Ni
10-100
75
92
39
-
Cu
50-100
5-10
69
36
-
Zn
-
-
82
44
-
Ge
10
100
-
-
1.889
Sr
-
-
59.81
59.66
-
Y
-
-
26.7
28.48
-
Pb
20-100
10-50
89.35
25.41
-
Ga
5-100
10-20
27
28
11.889
Rb
-
-
218
220
-
Sc
-
-
20
21
-
V
10
10
221
220
-
Zr
50-150
50-100
250
301
367.603
Nb
-
-
6
28
12.449
Cs
-
-
17
13
3.148
Hf
-
-
7.5
9.2
9.614
Ta
-
-
0.3
1.1
1.171
Th
-
-
-
-
19.198
U
-
-
-
-
3.072
La
-
-
-
-
37.778
Remarks
7
* average of 14
samples
** average of 4
samples
AAS/Spectrographic
analysis given in
columns 2 & 3 is by
GSI. (Neelakantam,
1987)
ICP-MS analysis in
column 6 by GSI
(Misra, 2007)
XRD analysis given
in column 4 and 5
are by Sudarshan,
(2007)
Rb, Zr, Hf, Ni, V is perhaps attributable to their magmatic origin. ICP-MS analysis of
the black tuff by GSI (Misra 2007) has also shown presence of 37.778 ppm La, 8.894
ppm Pr, 32.183ppm Nd, which is suggestive of igneous origin. Uranium mineralisation is
- 25 -
nown from the granite-gneiss basement of the Cuddapah Basin and hence high Th
(19.198 ppm) and U (3.072 ppm) contents are expected.
Six samples of black tuff with sulphide (pyrite/chalcopyrite) disseminations and
knots and pods of sulphide, were analyzed for their basemetal and noblemetals and the
results are shown in Table 4.
Table.4
Results of analysis of Base and noble metals in Tuffs
Sample
Carbon
Copper Nickel
Gold
Platinum Palladium Rhodium
No.
%
ppm
ppm
ppm
ppb
ppb
ppb
1
4.08
44
72
0.04
<5
<5
<5
2
4.67
33
339
0.04
<5
<5
<5
3
6.40
213
80
0.04
<5
<5
<5
4
4.60
44
88
0.04
<5
<5
<5
5
6.33
129
73
0.04
<5
<5
<5
6
4.52
47
75
0.02
<5
<5
<5
Analysis by Dr. R. Srinivasan, Bangalore
The analyses show that the carbon content varies between 4 and 6 per cent. Average
for six samples is about 5 per cent. The contents of noble metals, copper and nickel are
not significant.
e) Bao:SO3 in Barytes:
Based on study of Bao:SO3 ratio in different types of barytes in the Mangampeta
barytes deposit, Neelakantam and Kopresa Rao (1980) established that SO3 content is
invariably higher than BaO in granular barytes, the ratio varying from 0.94 to 0.99. In
the case of lapilli barytes this ratio is 0.92 to 0.98. Quartz and/or barytes lapilli tuff
contain relatively less SO3, the ratios are of the order of 1.16 to 1.39. The ratio is 1.0 in
the case of vein barytes.
In the granular and lappilli barytes, the water soluble matter (WSM) varies from
0.41 to 1.48% and 0 .40 to 1.17% , respectively. The WSM contains dissolved salts like
- 26 -
HCO3, Cl, SO4, Ca, Mg, Na and K whose total concentration is of the order of 0.3 to
0.50%. The sulphate content in the WSM is insignificant to account for the excess SO3
present in granular and lapilli barytes and the SO4 in WSM together cannot account for
the excess SO3 present in the granular and lapilli barytes. It is, therefore, surmised that
sulphur in the barytes occurs in a form other than sulphide or sulphate. Sulphur extracted
with CS2 together with the sulphur from pyrites and WSM still could not fully account
for the excess SO3 found in the major element analysis. The sulphur extracted by CS2 is
found to be elemental in nature, which could be magmatic.
f) Electron Microprobe studies:
Feldspar microlite from a barytes lapilli tuff sample analysed by electron
microprobe has shown 4.1 mol% albite, 55.9 mol% orthoclase and 40.0 mol% celsian.
Very high percentage of barium in feldspar points to the possibility of separation of
barium rich melt from normal rhyolite magma (R.D. Schuling (1976)-personal
communication).
Composition of feldspar from another sample of barytes lapilli tuff analysed by
ARL-EMX-SM probe is 55.4 mol% orthoclase, 3.1 mol % albite and 41.5 mol% celsian.
The results are not conclusive of igneous origin of barium sulphate, which might have
been formed during potash metasomatism of the original barium rich sedimentary rocks
(Jagannadham Akella (1976)- personal communication).
g) Sulphur Isotope Studies:
Based on sulphur isotope studies of six samples of barytes and pyrites, it is
concluded that sulphur in barytes was derived from sea water sulphate enriched in δ34 by
bacteriogenic reduction in an ocean basin whereas sulphur in pyrites associated with
barytes was derived from δ34 depleted- H2S given off during bacteriogenic reduction.
Barium might have been either contributed by submarine exhalative or volcanogenic
source (Karunakaran, 1976). Based on analysis of another four samples analyzed for
sulphur isotopes, it is opined that the source of sulphur could either be an infinite
- 27 -
reservoir of magmatic sulphur or sea-water sulphate or volcanic sulphur or a mixture of
both. (Max Coleman, (1976)-personal communication).
h) Geochronology:
Three sample of black tuff from different levels dated by whole rock K/Ar method
have indicated ages ranging between 461 ± 10 and 542 ± 11 Ma. Age data related to the
intrusives like granite, kimberlite and lamproite into the Nallamalai sediments by Rb/Sr
method have given ages between 1600Ma and 1350 Ma.
Further, the large magnitude of the Mangampeta barytes deposit located only at a
single place and absence of similar deposits in other coeval basins within the Peninsular
Indian shield suggest a localized concentration of the ‘Ba’ element in this area.
Considering very low content of barium in crustal rocks, even the entire sedimentary pile
of the Cuddapah Basin and granites and gneisses in the provenance together cannot
account for such concentration of barium. Also the vein barytes occurrences in the
various rocks of the Cuddapah Supergroup representing a wide range in time and
lithology and the absence of basic intrusives in the vicinity of all the younger vein barytes
occurrences rule out the possibility that the barium-bearing solutions were products of
differentiation of parental basic magma of the intrusive dolerites and basalts. It is
therefore, surmised that barytes, both vein and bedded, are products of extremely barium
rich volcanism (Neelakantam and Roy, 1979). Field and petrographic studies of the
barytes and the associated rocks thus collectively suggest that the Mangampeta barytes
deposit is a product of Ba-rich volcanism (Neelakantam, 1987). The initial volcanism in
the Cuddapah Basin is dominantly basic as testified by the presence of the sub-aerial,
amygdaloidal basalt flows and sub-marine, pillowed spilities in the Papaghni Group of
rocks. In the Nallamalai times basic volcanism gave place to acid volcanism as evidenced
by the presence of quartz-rich acid tuffs, magnetic tuffs, barytes lapilli tuffs and pyrite
tuffs. This observation leads one to think that a single initial, parent magma was
undergoing differentiation from the Papaghni to the Nallamalai times and the magma is
progressively getting enriched in alkalies, silica, iron-oxides, iron sulphides and barium
(sulphate).
- 28 -
IV. Geological Studies For Fullerenes In Mangampeta Barytes Mine:
IV.1. Sample collection:
During the course of studies in the Mangampeta barytes mine area, a total of 1050
samples were collected from156 locations from the barytes mine area and 10 samples
from out side the mining area near Rajampeta and Anantharajupeta. Fig.5 shows the
location map of the sample sites. Of these, white to creamy white tuff samples were
collected from 57 sites, the black tuff samples from 89 locations, barytes from 7 locations
and quartzites from 2 locations. Details of the samples collected along the 12 traverse
lines and those collected from outside the mine area are given in Appendix-B.
14.028
Traverse 12
14.027
Traverse 11
14.026
Traverse 10
100 m
0
14.025
Traverse 9
Traverse 8
14.023
Traverse 7
14.022
Traverse 6
250
230
210
Traverse 5
14.021
Traverse 4
14.020
190
170
150
Traverse 3
130
14.019
Traverse 2
14.018
110
90
Traverse 1
70
14.017
79.325
79.324
79.323
79.322
79.321
79.320
79.319
79.318
79.317
79.316
50
79.315
Latitude (Degrees)
14.024
Longitude (Degrees)
INDEX
INDEX
Sample
locations
Sample
locations
Fig. 5. Map showing sample locations for fullerenes analysis in Mangampeta barytes mine,
Cuddapah Dist., A.P.
- 29 -
IV.2. Physical property measurements:
Laboratory measurements for density and magnetic susceptibility were carried out
on rock samples collected from the field. Fig.6 shows the distribution of density values
for different rock units viz., weathered tuff, black tuff and barytes. The weathered tuff,
with density values ranging from 2.3 to 2.5gm/cc is relatively lighter compared to the
black tuff which shows a density range of 2.5 to 2.8gm/cc. The density of barytes
samples observed varies rather over a wide range from 3.6 to 4.4gm/cc. The
representative density values are adopted for modeling of gravity data along a traverse
across the Mangampeta barytes mining area.
No.of Weathered tuff samples
200
160
(a)
120
80
40
0
1.5-2
2.0-2.1
2.1-2.2
2.2-2.3
2.3-2.4
2.4-2.5
2.5-2.6
2.6-2.7
2.7-2.8
Density (gm /cc)
240
No. of Black tuff samples
200
160
(b)
120
80
40
0
2.0-2.1
2.1-2.2
2.2-2.3
2.3-2.4
2.4-2.5
2.5-2.6
Density (gm /cc)
- 30 -
2.6-2.7
2.7-2.8
2.8-2.9
2.9-3.0
No of barytes samples
16
12
(c)
8
4
0
3.6-3.7
3.7-3.8
3.8-3.9
3.9-4.0
4.0-4.1
4.1-4.2
4.2-4.3
4.3-4.4
Density (gm/cc)
Fig.6. Histograms showing the density values for a) weathered tuff b) black tuffs
c) barytes, Mangampeta area, Cuddapah Basin.
- 31 -
V. Geophysical studies:
V.1. Geophysical field measurements in Mangampeta area:
In the present survey, both resistivity and Induced Polarization measurements were
carried out with the same instrument, the IPRS-1 Resistivity cum I.P instrument
developed by IGIS. Details of the geophysical methods, Resistivity and polarizability
curves are given in Appendix-C. During the present survey, in all, 18 Vertical Electrical
soundings and 13 Induced Polarization Soundings were carried out in the Mangampeta
area using Schlumberger electrode configuration. The maximum current electrode
separation used in the survey varied from about 100m to 1000m. Out of these, 17
soundings fall within the study area while the last one (site no.13) falls 3 km away northwest of the study area. Fig.7 shows the location map of the sounding sites. Fig.8 shows
the photograph of a field measurement at one of the sites.
13
14.040
100 m
0
14.035
6 5
14.030
m
250
230
11
14.025
210
17
15
10
16
190
9
170
14&18
14.020
150
1
130
3
2
110
14.015
90
4
70
50
79.330
79.325
79.320
79.315
79.310
79.305
79.300
7&8
79.295
Latitude (Degrees)
12
Longitude (Degrees)
9
Resistivity/IP sounding point
Elevation Contour
90m.
Boundary of the mining area
Linear Conductive feature delineated from Res/I.P results
Fig.7. Location map of RES/IP sounding sites, Mangampeta area,
- 32 -
Fig.8. Resistivity/IP measurements in Mangampeta area.
The sounding data in general represent either K or A type resistivity curves or their
combination. The sounding curves outside the mine area in general tend to be A-type
while those located in and around the mine exhibit a K-type resistivity distribution.
RES-3 shown in fig.9. represents the sounding curve inside the mining area and RES-6
represents the curve from outside the mining area.
RS-8/IP-3
RES-3
RES-6
Error 1.61%
(a)
RES-6, Error 3.09%
RES-3, Error 1.61%
(b)
Fig.9. (a) Resistivity Sounding Curves, observed (black), model response (red) and subsurface model
(blue) at sites RES 3 and RES 6.
(b) Inversion results showing the layer resistivities (ρ) and thickness (h).
- 33 -
V.2. Modeling and Results:
(a) Resistivity:
To start with, the resistivity sounding data have been analysed using the Inverse
slope technique (Ramanujachary and Sankar Narayan 1967). The analysis provides a
layered geoelectric section which in turn was used as an initial model for inverting the
data. The IPI2WIN programme has been used to invert the VES data to get the
geoelectric layered section at each of the sounding sites. Table.3 shows the results of
Inversion analysis.
In the geoelectric layered structure obtained, the top layer at some places, with
resistivities around a few tens of ohm.m represents the weathered soil cover and the
second layer with resistivities in the range of few tens to a few hundred ohm.m,
corresponds to the gray tuff and this is followed by relatively less resistive layer
10-60 ohm.m that corresponds to black tuff. The bottom high resistive layer present at a
few places either represents barytes horizon inside the mine or a hard compact dolomite
horizon outside the mining area. At some sites, particularly in and around the mining
area, the bottom horizon being conductive is inferred to represent a black tuff horizon.
While the black tuff horizon in the area is generally conductive (10-60 ohm.m).
inversion results suggest that, for the sites located outside the mining area, it tends to be
characterized by slightly higher resistivites (30-60 ohm.m.) and occur at deeper levels as
compared to that inside the mine. On the other hand, this layer (black tuff) becomes more
conductive (<10 ohm.m) and occurs at relatively shallower depths inside the mine. The
conductive bottom horizon (black tuff) as deduced from resistivity sounding results is
confined only to a limited narrow zone (a few tens to a hundred meter width) passing
through the mine and oriented in a NW-SE direction as shown in Fig.10.
- 34 -
Table 5
Results of the analysis of Resistivity soundings
layer 1
Rho
layer 2
layer 3
layer 4
layer 5
layer 6
thickness
Rho
thickness
Rho
thickness
Rho
thickness
Rho
thickness
Rho
28
1028
51.7
2978
layer 7
thickness
Rho
8.227
Sounding 1
16.8
6.59
16.7
0.291
1006
9.95
26.9
Sounding 2
15.5
0.768
87.9
23.9
24.3
125
122
Sounding 3
21.22
4.597
39.88
21.94
19.47
88.15
5.476
15.99 3.734 143.7 38.03 163.7
Sounding 4
4.59
1.83
60.8
44.4
40.4
8.53
1.55
32.6
0.58
Sounding 5
130
2.17
3791
2.72
217
10.7
13279
10.7
1333
12.1
92.8
57.5
234
4393
17.6
560
17.6
868
17.3
174
43.1
498
Sounding 6
68.9
8.83
22.9
5.36
21312
27.5
9808
19.3
Sounding 7
19.36
13.63
51.39
12.77
21.35
34.09
72.82
45.94 1.365
Sounding 8
22.97
10.72
58.2
14.39
6.196
21.4
19.05
Sounding 9
316
1.74
7692
4.33
9.76
13.5
13.1
13.7
5.73
Sounding 10
177.5 0.9169
3.591
33.33
1.55
6.393
Sounding 11
98.53
3.875
15.18
5.003
138.7
15.3
0.8267 16.18
92.4
Sounding 12
7.72
0.653
44.7
29
19.1
Sounding 13
10.9
7.1
22.5
9.63
6090
12.2
0.367
498
Sounding 14
222
0.6
42109 0.742
19.2
Sounding 15
68.3
1.57
190
Sounding 16
22.7
0.6604
91.09
3.704 0.7272
Sounding 17
25.4
0.127
78.4
7.07
478
2.15
103
Sounding 18
158
0.6
2952
1.73
3.26
7.48
layer 8
layer 9
thick- Rho thick- Rho thickness
ness
ness
15.3
21.8
47.2
86
610
38.8
22.9
- 35 -
104
32.7
13
14.040
14.035
6
5
0
100 m
14.030
Latitude (Degrees)
12
250
11
230
14.025
17
15
210
10
16
m
190
9
14&18
170
14.020
150
1
3
2
130
110
14.015
90
4
70
7&8
79.330
79.325
79.320
79.315
79.310
79.305
79.300
79.295
50
Longitude (Degrees)
9
Linear conductive feature
Resistivity/IP sounding point
90m.
Boundary of the mining area
Elevation Contour
Fig.10. Map showing the linear conductive feature delineated from resistivity
results, Mangampeta, Barytes mine.
(b) Induced Polarization:
Amongst the different IP parameters
measured and recorded, two parameters in
particular viz., M1-3 and M3-6 have been examined. An impressive feature of the
Induced polarization responses observed is the appearance of anomalous polarizability
values at some of the sites in the Mangampeta area. This pattern may be seen from
Fig.11 which shows the I.P polarizability variation, together with the corresponding
resistivity variation, at two sites -one characterized by normal background values, the site
no.1 and the other, site no.8 showing occurrence of higher values of polarizability.
- 36 -
Results show that higher polarizability values in the range (20-100mv/V.) appear at
sites 7,8,3,9,10 and 12 while relatively smaller magnitudes or normal background values
characterize the remaining sites. It may also be seen that (Fig.11) higher polarizability
values are generally associated with the conductive horizon represented by the
descending branch of the K type apparent resistivity curve. The distribution pattern of the
chargeability parameter in the area of study is shown in fig.12.
1000
rho
RES-1/IP-1
m3,6
RHO (Ohm.m)
100
10
mv/V
1
1
10
100
1000
AB/2
1000
RES-8/IP-8
rho
m3,6
RHO(Ohm-m)
100
mv/V
10
1
1
10
100
1000
AB/2
Fig.11. RES/IP curves at sites IP-1 and IP-8, Mangampeta area.
- 37 -
An interesting feature that could be noticed is that the sites associated with higher
I.P responses tend to fall along a linear zone, which spatially correlates with the NW-SE
trending zone of high conductivity deduced from resistivity modeling results as shown in
fig.12.
13
14.040
14.035
6
5
100
14.030
90
12
m
70
14.025
10
60
9
50
14.020
40
1
30
3
2
20
14.015
10
4
0
79.325
79.320
79.315
79.310
79.305
7&8
79.300
Latitude (Degrees)
80
11
Longitude (Degrees)
9
Resistivity/IP sounding point
Boundary of the mining area
Fig.12. Map showing the spatial correlation of linear conductive and IP
Linear Conductive feature delineated from resistivity results
zones, delineated from RES/IP studies, Mangampeta area.
Anomalous linear IP zone
INDEX
9
Resistivity/IP sounding point
Boundary of the mining area
Linear Conductive feature delineated from resistivity results
Anomalous linear IP zone
- 38 -
Further, the sites showing anomalously higher values of I.P also indicate shallower
depths to the conducting horizon thus indicating a rise or shallowing of the high
conducting zone along this linear feature. The I.P zone, though spatially correlates with
the conductive zone tends to extend more towards southeast. This linear zone
characterized by anomalously high electrical conductivity and polarizability is inferred to
represent a fault/fracture zone cutting across the area in a near NW-SE direction.
(c) Gravity and Magnetic Studies:
The Mangampeta barytes mine area has earlier been covered with gravity
measurements on a detailed scale and the results have been modelled (Bose and
Vaidyanathan 1979). In addition, we have subsurface lithological data from several
boreholes. Fig.13 show the detailed gravity contour map of the mining area together with
its image. The gravity data from a representative traverse (shown in Fig.13) across the
area has been modeled using SAKI Software Package. Average densities measured for
the samples of different lithologies collected from the mining area viz., the white shales
(2.3-2.5gm/cc), the black tuffs (2.5-2.8gm/cc), the barytes (3.6-4.4gm/cc) and quarzites
(2.45-2.57gm/cc) have been used in gravity modeling. Available borehole data are
included in building the initial model. Forward as well as inverse techniques have been
used in arriving at a final subsurface model. Fig.14 shows the model together with the
gravity profile (both observed and computed) along the traverse.
The area was earlier covered by Aeromagnetic surveys. The analog maps were
digitized and images were generated. The magnetic anomaly image of the Cuddapah
Basin is shown in fig.15. The magnetic image brings out a number of cross cutting
linears, Prominent among them lay aligned in NW-SE direction. (Y.Sreedhar Murthy et
al 1998, Babu Rao et al 1998)
- 39 -
Fig.13. Detailed Bouguer gravity anomaly map of Mangampeta Barytes mining
area. (Bose and Vaidyanathan, 1979).
- 40 -
Fig.14 . Subsurface model from Inversion of gravity data along the traverse xx1, Mangampeta area.
Fig.15. The Aeromagnetic shaded relief image of the Cuddapah Basin.
- 41 -
VI. Analysis of rock samples for fullerene:
VI.1. Methods & Problems:
Of the several techniques used for fullerene detection and analysis, High Pressure
Liquid Chromotography (HPLC), Laser Desorption Mass Spectrometer, are need in the
present study. Because of the problems related to possible artifacts and ambiguities
inherent in the experimental approach itself, there has been intense debate on the reported
presence of natural fullerenes, e.g., generation of in-situ fullerenes during analysis of
samples using laser desorption techniques like the one in the case of meteoritic impacts
(Becker et al 1994, Ebbesen et al.,1995, Gu et al 1995) and similarly on the findings of
fullerene in shungite in Karelia (Buseck et al 1992., Heymann 1995, Ebbesen et al 1995,
Pardhasarathy et al 1998). In view this, it is often suggested (see Buseck 2002) that
fullerene measurements including sample preparation, selection of samples from the
point of view of weathering effects, methodologies adopted, etc., that the studies be
carried out by different methods as well as in independent laboratories. The present
measurements were indeed carried out by different methods and at different laboratories
including Nano-C, M/s. Alkali metals, ARC thus facilitating independent evaluation to
confirm the present findings of fullerenes.
While the results of all the measurements are included in Appendix-D, the results
for a few representative samples are presented in the subsequent sections. Fig. 16 shows
the locations of the rock samples analysed.
- 42 -
14.028
14.027
14.026
Folded sample 1
14.025
30
14.024
26 27
0
250
14.023
Latitude (Degrees)
100 m
Folded sample 6
(Cylindrical sample)
33
32
28
29
Folded 31
sample 3
Water body
230
3
14.022
210
1
14.021
190
32
170
150
14.020
4
14.019
Dump
2
FL3/5200/6600/B-10
1
130
110
90
14.018
70
FL1/5000/6400-5
14.017
79.325
79.324
79.323
79.322
79.321
79.320
79.319
79.318
79.317
79.316
79.315
50
Longitude (Degrees)
Fig.16. Map showing the locations of the samples analysed for fullerenes presence
from the Mangampeta area.
INDEX
Alkali metals tested samples:
rock samples 26-33
Rock 12 & 13 (Bulk samples 1,2,3)
Rocks 16 & 17 (Drill Powder 1,2,3,4)
Nano C tested samples
VI.2. Mass Spectrometer analyses at Stanford University, USA:
The results of Laser Desorption /Ionisation Mass Spectrometer (LDIMS) analysis of
five tuff samples carried out at the Stanford University laboratories are presented in
- 43 -
Fig.17 and the corresponding mass spectrometer results at different energy levels for the
same samples are shown in Fig.18.
Samples 1 and 2 (Rock 1 and Rock 2) show clear peaks corresponding to C 60 as
well as C70, while mass spectrometer results show the presence of C60 and C70 in all the
five samples analysed.
750
800
850
Rock 1 extract
200
uA
100
0
Rock 1 procedural blank
200
uA
100
0
750
800
850
750
800
850
3
uA
Rock 2 extract
2
1
0
3
Rock 2 procedural blank
2
uA
1
0
750
750
800
850
800
850
15
Rock 3 extract
10
uA
5
0
15
Rock 3 procedural blank
10
uA
5
0
750
750
800
850
800
850
Rock 4 extract
7.5
5
uA
2.5
0
7.5
Rock 4 procedural blank
5
uA
2.5
0
750
800
850
750
800
850
Rock 5 extract
15
10
uA
5
0
Rock 5 procedural blank
15
uA
10
5
0
750
750
800
800
850
850
2000
uA
C60 and C70 standards
in toluene
1500
1000
500
0
750
800
850
Fig.17. Results of Laser desorption ionisation Mass spectrometer measurements, on rock
samples and their accompanying procedural blanks made at Stanford university, USA. In
all cases the extraction procedure may be seen to have considerably more species present
than the blank. Rocks 1 and 2 have strong fullerene signals not observed in either the
blanks or in other samples.( Dr. Mathew Hammond, personal communication,2006).
- 44 -
(a)
(b)
(c)
(d)
(e)
Fig.18. Results of Laser desorption ionisation Mass spectrometer measurements, at four energy
levels(a,b,c and d) on sample 1 at Stanford University, USA. The higher amplitude signal over the
sample compared to standard (e) is clearly seen.
VI.3. Analysis at Nano-C laboratories, Boston, U.S.A:
Five samples of black tuff from Mangampeta area, OS-1, OB-2, OB-4, OB-5, OB-8
were subjected to detailed analysis for fullerene, using both High Pressure Liquid
Chromatography (HPLC) and Mass Spectrometer measurements at the laboratories of
Nano-C, Boston, USA. For the purpose of the analysis, rock samples were first crushed to
powder. The rock powder was placed in toluene solvent and stirred thoroughly for 48hrs
at room temperature. The suspension was filtered and concentrated to a 5ml using a
- 45 -
rotovap. The solution thus obtained was analysed using HPLC. The HPLC results, for the
sample S10-OB-4, are shown in fig.19. The HPLC results for fullerenes standards C 60,
C70 as also those for toluene blank are included in fig.19. The HPLC results for all the
samples showed the presence of materials that elute at the same time as C60, C70, and C84.
For the purpose of an independent evaluation of the HPLC results, the samples were
run through mass spectrometer measurements using MALDI, a type of laser ionization.
Fig.20. shows the results of mass spectrometer measurements for the same sample S10OB-4. The mass spectrometer results have clearly detected C60 in the sample while these
did not confirm the presence of C70 and C84. The combination of fullerene detection in
mass spectrometer and the presence of coincidental peaks at the elution times of C60, C70
and C84 in the HPLC results indicate the presence of fullerenes in the sample. Results of
analysis of all the remaining four OS-1, OB-2, OB-5, OB-8 and presented in Fig.19 also
showed presence of fullerene. Table.6 provides the quantitative analysis of the results
obtained for all the five samples.
Subsequent analysis of additional samples at Nano-C, using HPLC clearly brought
out the presence of fullerenes in all the samples. An example of these results are also
shown in Fig. 21. As may be seen, the results at Nano-C also indicated, interestingly,
presence of C70 with concentrations comparable to C60 in some of the samples. Based on
these results which show fullerenes in all the samples analysed the Nano-C has surmised
that the entire overburden at the mine area has fullerenes in varying concentrations.
- 46 -
Fig.19 (a-f). Results of HPLC measurements carried out at Nano-C, USA, for
the rock samples OS-1, OB-5, OB-8, OB-2 and for Toluene blank.
OS-1
Fig.19 (a)
S7-OB-5
Fig.19.(b)
- 47 -
S10-OB-8
Fig.19.(c)
S14-OB-2
Fig.19.(d)
- 48 -
S16-OB-4
Fig.19.(e)
Toluene blank
Fig.19.(f)
- 49 -
S10-OB-8
Fig.20.(a).
Fig.20.(b).
Fig. 20. Results of Mass Spectrometer measurements (MALDI) for fullerenes on the rock
sample OB-8, at Nano-C, USA.
- 50 -
Table 6 (a)
Summary of the results of analysis of the five rock samples for fullerenes, at Nano-C, USA
Table 6(b)
Projected quantitative estimates of fullerenes based on the results of analysis
S7-0B-5 OS1
Sample size, gms
C60 in mg
%yield
Yield in gms/ton
C70 in mg
%yield
Yield in gms/ton
C84 in mg
%yield
Yield in gms/ton
0.128
S10-OB-8
2.42
S14-0B-2
3.45
S16-0B-4
5.09
12.54
0.101
0.086
0.084
0.07
0.103
0.07890625 0.00355372 0.00243478 0.00137525 0.00082137
789.0625
35.5372
24.3478
13.7525
8.2137
0.055
0.024
0.052
0.014
0.033
0.04296875 0.00099174 0.00150725 0.00027505 0.00026316
429.6875
9.9174
15.0725
2.7505
2.6316
0.002
0.002
0.002
0.001
0.002
0.0015625
8.26E-05
5.76E-05
1.96E-05
1.59E-05
15.625
0.82645
0.575971
0.19646
0.15949
Table-6(c)
Summary of HPLC Results of analysis of the four rock samples for fullerenes, at Nano-C, USA
Sample Name
FL1
Folded Sample 1
FL3
Folded Sample (Cylindrical Sample)
% C60
% C70
C60 Peak Area
after
after
after
subtracting subtracting
subtracting
blank
blank
blank
37.0
19.1
55.1
80.6
15.8
6.5
44.9
8.6
285.71661
116.42463
82.56399
845.55798
- 51 -
C70 Peak Area
after
subtracting
blank
122.50496
39.40548
67.12904
90.30352
mg C60
mg C70
calculated calculated
0.0065
0.0026
0.0019
0.0191
0.0055
0.0018
0.0030
0.0041
Initial
Rock
Sample
Weight (g)
%
C60
By
Weight
%
C70
By
Weight
10.57926 6.11251E-05 5.22296E-05
10.58032 2.49049E-05 1.67987E-05
10.72131 1.74294E-05 2.8241E-05
10.61302 0.00018032 3.83781E-05
Fig. 21. Results of HPLC measurements carried out at Nano-C, USA, for
the folded sample-6 (Cylindrical sample).
- 52 -
In addition to the HPLC and Mass Spectrometer measurements, X-ray diffraction
analysis have also been carried out on a few samples at Nano-C, USA and at ARC,
Hyderabad.
VI.4. X-Ray Diffraction studies at Nano-C, USA:
Four samples viz., two samples with a highly folded banding of Carbonacous
material and quartz, folded samples 1 & cylindrical sample (corresponding to folded
sample 1 and folded sample 6 as in Appendix-B) and two other tuff samples FL1, FL3
(corresponding to FL1/5 and FL3/B-10 in Appendix-B) from the southern part of the
mine area were subjected to XRD analysis. All the four samples exhibited spectral peaks
at points corresponding to those observed in the XRD results of fullerene standards C60 &
C70. Fig.22. shows these results for the samples as well as for the standards. These
results are consistent with those from HPLC and Mass Spectrometry analysis of these
rock samples.
- 53 -
22 (a). C60, C70 and C60/C70 mixture as references
22.(b). Cuddapah samples, overview
Fig.22.Results of X-Ray Diffraction measurements for the four rock samples (folded
sample 1, & cylindrical sample, FL1, FL3, at Nano-C, USA..
- 54 -
VI.5. X-Ray diffraction analysis at ARC laboratories, Hyderabad:
In addition to the above, two more samples were analysed using powder X-ray
diffraction method at ARC, Hyderabad. The rock sample, from which the powder is
taken, is a part of a tightly folded black tuff with quartz vein. The results clearly brought
the presence of fullerene C60 in both the samples as shown in fig.23.
Fig.23. (a)
Fig.23.(b)
Fig.23. Results of X-Ray Diffraction measurements for two samples from a folded
black tuff, at ARC, Hyderabad.
- 55 -
VI.6. HPLC measurements at M/S Alkali metals, Hyderabad:
Thirteen more samples were subjected to detailed analysis at M/s.Alkali Metals,
following the same procedure adopted at Nano-C. All the samples analysed showed
positive signatures of fullerenes. Some samples are seen to exhibit larger amplitude peaks
in HPLC results indicating higher concentration fullerenes.
However, the results
obtained at Alkali metals and those at Nano-C will become more comparable when
identical columns in HPLC measurements are employed. Results for a few of the samples
ananlysed at Alkalimetals are presented in Fig.24 (a) to Fig.24 (e). It is interesting to
note that in some of the samples, the peaks corresponding to C70 also appear clearly.
Similar phenomena is observed in the results of Nano-C. These observations on C70 need
further experimentation.
Fig.24. (a-e). Results of HPLC measurements carried out at Alkalimetals, Hyderabad,
for the fullereneC60 standard and the rock samples 16,17,26,31.
Fullerenes C60 standard
Fig.24 (a)
- 56 -
Rock-16
Fig.24(b)
- 57 -
Rock-17
Fig.24(c)
- 58 -
Rock-26
Fig.24(d)
- 59 -
Rock-31
Fig.24(e)
- 60 -
VII. Discussion:
Results of the present study have clearly brought out significant occurrence of
fullerenes in the mid-Proterozoic black tuff of the Cuddapah Basin, in the Mangampeta
barytes mine area. C60 and C70 are the two prominent natural members of the fullerene
family that have been identified from this group of rocks.
The black tuffs from the Cuddapah Basin show about 5% non carbonate carbon and
are different from the shungites from Karelia, which are characterized by more than 90%
carbon (Buseck et al 1994) and also differ from those examined from Mitov area in
Czech Republic (Jan Jehlicka et al 2003. Results from the present analysis suggest
significantly higher amounts of fullerene in the samples analysed. It may be pointed out
in this context, that, samples analysed, were obtained from inside a mine, at depth levels
of as much as 70-80m. This might partly account for the occurrence of fullerene in
Cuddapah Basin at relatively higher quantitative levels as compared to those from other
localities. This is because fullerenes are known to be readily destroyed by ultraviolet
(UV) light, as well as ozone (O3) and the failure or scarcity of naturally occurring
fullerene C60 is because of such unfavorable conditions on the surface of the earth or in its
atmosphere (Taylor et al. 1991, Chibante et al 1993, Chibante and Heymann 1993,
Becker et al. 1994). Since the samples collected from the Mangampeta area are from
deeper levels and hence protected from such losses.
A model:
It is widely recognized that
natural fullerenes are known to be mainly associated
with those lithological units that experienced high-energy geological events such as
lightning, wild fires, or meteoritic impacts. Lithologies associated with volcanic events
also showed presence of fullerenes, as in Mitov area, where from fullerene C60 were
detected in solid bitumen samples collected from pillow lavas of the Bohemian Complex
of Czech Republic (Jan Jehlicka et al 2003).
- 61 -
The Mangampeta barytes deposit with which the fullerene occurrence is associated,
is considered to be of volcanogenic origin (Neelakantam1987). The initial volcanism in
the Cuddapah Basin is dominantly basic in the Papaghni Group of rocks. In the Nallamali
times, basic volcanism gave place to acid volcanism. This observation suggests that a
single initial parent magma was undergoing differentiation from the Papaghni to the
Nallamalai times. It was established that precipitation of vapours under submarine
conditions resulted in the formation of granular barytes whereas subaerial showering of
ash and molten barytes lapilli represent explosive phase of the same volcanism.
In view of the region witnessing such a volcanotectonic activity, it is possible to
look for a model linking the occurrence of fullerene, with the physico-chemical
conditions obtained during the course of such a high energy event of volcanic
activity involved in the formation of the barytes. The anomalous thermal conditions
characterized by high temperatures associated with such a volcanic event and the event
itself occurring in a host lithology dominated by carbonaceous Pullampet tuff possibly
appears to create a suitable scenario for initiation of subsequent reactions leading to
formation of higher order isotopes of carbon. Alternately the magmatic origin model
envisaged for barytes may also hold good for fullerenes as well, since the tuff and barytes
as also the tuff and fullerenes are intimately associated.
Geophysical modeling results particularly from the resistivity and I.P sounding
responses clearly brought out a NW-SE trending linear feature that cuts across the area.
Considering the high conductive nature of the bottom horizon as deduced from resistivity
sounding results and this being confined only to a limited narrow zone (a few tens to a
hundred meter width) passing through the mining area, it is interpreted to be fracture
zone of a few hundred meters width cutting across the area in the NW-SE direction. This
linear structural feature in turn falls in a NW-SE oriented tectonically active mega linear
zone identified earlier from an integration of different geophysical signatures. The
volcano tectonic disturbance that the area witnessed and the associated minerals may be
linked to this subsurface structural fabric as deduced from geophysical studies. Also the
deep seated rocks in the Nallamalai sub-basin, viz., alkaline rocks (riebeckite syenite)
- 62 -
from Giddalur and micaceous kimberlite dykes from Chelima and Zangamrajupalle are
known to be emplaced along the NNW–SSE Chelim- Zangamrajupalle deep fracture.
Mangampeta barytes deposit falls on the southern extension of this deep fracture along
which fluids rich in barium poured out (GSI 2001 Symposium (by post) on Cuddapah
Basin).
The fracture zone must have served as a conduit for the outpouring of
magma/volcanic fluids from below onto the Cuddapah ocean floor. As the fluids
accumulate at the top of the fracture zone on the ocean floor they get more and more
thickened at the centre and the fluids tend to spread laterally on either side and along the
fracture zone which is about a kilometer long. This pattern of deposition of barium rich
volcanic material on the tuff horizon results in the formation of a lensoid shaped body
consistent with the known geometry of the deposit. The highly folded nature of the
geological formations as seen in the mining area also indicates intense tectonic activity
and is consistent with the development of NW-SE oriented fracture zone inferred from
geophysical studies. The differences in the electrical character of the tuff between the
mining area particularly along the fracture zone (being relatively more conductive and
polarizable) and its surroundings may be attributed to the anomalous local thermal
conditions obtained during the postulated volcanic activity.
The suggested mechanism of fullerene generation in Bohemian complex of Mitov
area involves a primary algal phase, generation of a hydro carbonaceous mixture in the
course of thermal evolution of sedimentary sequence and their high-temperature
transformation related to the extrusion of andesitic basalts in the area (Jan Jehlicka et al
2003). A similar geological environment also exists in the Cuddapah Basin. In the
Cuddapah sediments extensive presence of microbial mats, their eroded fragments, etc.,
were recorded. Cherts from the Cumbum/Pullampet Formation are packed with microbial
muddy chips in the shallow marine facies. The chips are usually fine grained. Reduction
of atmospheric carbon dioxide might have contributed additional amounts of organic
carbon (Dasgupta and Biswas, 2006). In Cuddapah sediments, particularly in the
Pullampet Formation, carbon occurs in the pelitic sediments in finely comminuted form,
- 63 -
which could be organic, as testified by the presence of extensive microbial mats. It is also
observed that quartz veins cutting across black tuff carry pockets of carbon at places,
which was scavenged from the host rocks during their ascent (GSI 2001). Transformation
of microbial mats derived organic carbon from Cuddapah sediments may be converted
into an assemblage of hydrocarbons during the process of sedimentation. Evidence on
such a possibility for generation of hydrocarbons in the Proterozoic Cuddapah sediments
may also be seen from the recent reports on the occurrence of ‘Gas shows” in the
southwestern region of Cuddapah Basin (Dayal.2007, Sreedhar Murthy et al 2007). These
might have served as precursors to fullerene formation. This precursory material must
have been transformed into fullerenes under favourable P-T conditions provided by the
volcanic event believed to be responsible for the barytes deposition in the region.
Alternately the magmatic origin model envisaged for barytes may also hold good
for fullerene as well, since the tuff and barytes as also the tuff and fullerene are observed
to be intimately associated.
- 64 -
VIII. Summary and Conclusions:
1.
Under this integrated geoscientific programme, systematic rock sampling has been
carried out in the Mangampeta barytes mine. A total of 1050 rock samples were collected
from the mine sections at different depth levels and also from the mine dumps. A few
samples were also collected in the northern and southern strike continuity of the mine.
2.
Some of the representative rock samples were subjected to analysis using different
analytical methods like High Pressure Liquid Chromotography (HPLC), Mass
Spectrometry, X-Ray diffraction. The results of analysis clearly pointed out to the
presence of fullerene in all the rock samples indicating a prolific occurrence of fullerene
in tuffs of Mangampeta barytes mine.
3.
The results of analysis also indicated that fullerenes are present in significant
quantities much higher than those reported earlier, from different parts of the world, thus
suggesting the feasibility of its exploitation.
4.
Geophysical measurements using electrical and induced polarization methods were
carried out for the purpose of subsurface imaging of the area. Modeling of the data has
brought out a well defined NW-SE trending linear zone of high electrical conductivity
and polarizability cutting across the Mine. This is interpreted to be representing a deep
fracture zone presumably related to the volcanic activity believed to be responsible for
the localization of barytes.
5. Based on the studies, a model is proposed for the genesis of fullerene. The model
postulates that the volcanic activity, supposed to have been responsible for the origin of
barytes, played a significant role in creating suitable thermal conditions and environment
conducive to
transformation of the existing hydrocarbon material into higher order
allotropes of carbon representing the family of fullerenes. The higher quantities of
fullerene is attributed to the sampling of host rock from relatively deeper levels.
Alternately the magmatic origin model envisaged for barytes may also hold good for
fullerene as well, since the tuff and barytes as also the tuff and fullerene are observed to
be intimately associated.
- 65 -
IX. Recommendations:
1. The study has established the presence of Fullerene (C60) in Mangampeta barytes
mine and pointed out to its occurrence at significant amounts and these results call for
initiation of efforts towards exploitation of this strategic natural resource.
2. It is imperative to launch extensive efforts including the R & D, to evaluate, process
and extract fullerenes from the Mangampeta Barytes Mine area. In view of the non
availability of such complex technology and expertise needed within the country, it
becomes imperative to go in for international collaboration to strengthen indigenous
efforts and expedite the studies to realize the goals over a reasonable time frame.
3. In order to take advantage of the discovery of a unique deposit of natural fullerenes in
the world as a result of the present study, it is indeed necessary to exploit the deposit
expeditiously before the strategic importance of these efforts are lost or diluted. It may
be noted that the possible presence of natural fullerenes in similar geological conditions
in A.P, elsewhere in the country or outside, can not be ruled out.
4. It is of immediate interest to examine and extend these integrated geoscientific studies
to other areas of similar geological conditions in the Cumbum/Pullampet Formation and
subsequently to other coeval basins in India. Further scientific studies are also needed
to ascertain the extent of the presence of higher order allotropic forms of carbon
including the C70,C84 etc., which are known to be highly valuable are necessary.
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ACKNOWLEDGEMENTS
The project for carrying out Integrated Geoscientific investigations in the
Mangampeta Barytes mine area for Fullerenes is sponsored by the Andhra Pradesh
Mineral Development Corporation (APMDC), Govt. of Andhra Pradesh and we
gratefully acknowledge the award of the project.
Mr. V.D. Rajagopal, Vice-Chairman and Managing Director, APMDC is
thanked for his initiative and the keen interest shown in the progress of the scientific
work and his support in bringing the project to fruition.
Mr. H. D. Nagaraja, General Manager and his staff at Mangampeta Barytes
mines and Mr. G. Srinivasa Chowdary are thanked for their unstinted cooperation.
Many scientific organizations and individuals have helped in the present studies
for which we are grateful. We are extremely thankful to

Dr. Viktor Vejins, President and CEO, Nano-C, USA for many useful
discussions and his colleagues for analytical measurements for analysis
of rock samples at their laboratories.

Dr. Mathew Hammond, Stanford University for many useful
discussions, Mass spectrometric measurements and the first report on
presence of Fullerene.

Mr. Y.S.R. Venkata Rao, Managing Director, M/S Alkali Metals,
Hyderabad for his inspiration and cooperation and his staff for HPLC
measurements.

Dr.K.R.R. Ramanujachary, MD, Integrated Geo-Instruments and
Services Pvt. Ltd. (IGIS), Hyderabad and his staff for their support in
the geophysical field data acquisition.

Prof. Nehru E. Cherukupalli, Professor of Geology, Brooklyn
College, CUNY, New York for his initiatives and support.
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
Dr. Caroline A. Masiello, Assistant Professor, Dept of Earth Sciences,
Rice University, Houston for enabling scientific discussions.

Dr. Y. Srinivasa Rao, Scientist, ARC, Hyderabad for scientific
discussions and the XRD measurements.

Dr. R Srinivasan and Prof. S. Murali for useful discussions and
support.

Dr. Aravind and Dr. Anil Kumar of the institute of the life sciences,
University of Hyderabad Campus, for many useful discussions.

Mr. V. Anand Rao, Director, GRTC for his support.

Mr. Raghu Yabaluri, Houston and Ms. Sowmya Yabaluri , Seattle,
USA for their support.
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