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Geological Society of America

Special Paper 356

Natural fullerenes from the Cretaceous-Tertiary boundary

layer at Anjar, Kutch, India

G. Parthasarathy
National Geophysical Research Institute, Hyderabad-500 007, India
N. Bhandari*
Physical Research Laboratory, Ahmedabad-380 009, India
M. Vairamani
A.C. Kunwar
B. Narasaiah
Indian Institute of Chemical Technology, Hyderabad-500 007, India


We report here the presence of fullerenes in the iridium-rich Cretaceous-Tertiary

(K-T) boundary layer in the intertrappean beds of Anjar within the Deccan Volcanic
Province. Fullerenes (C60) have been identified in or near the three iridium-rich ho-
rizons from this section by high-resolution electron-impact ionization mass spectrom-
etry, Fourier transform infrared (FT-IR), and 13C-nuclear magnetic resonance spec-
troscopic techniques. Fullerenes are absent in six other iridium-poor horizons of the
same section. The association of high-pressure–high-temperature forms of fullerenes
with high iridium concentrations suggests that fullerenes can be used as geochemical
indicators of an extraterrestrial impact.

INTRODUCTION The first natural occurrence of fullerenes was reported by

Buseck et al. (1992) in ca. 2 Ga Precambrian carbon-rich rocks
Fullerenes have been synthesized in the laboratory by gas- of Shunga (Russia) called shungite. Subsequently, other work-
phase chemistry at high temperatures (⬎1300 K; Kroto et al., ers found fullerenes in rocks that underwent singular geological
1985). However, there are also a few locations on Earth where events such as lightning strikes (Daly et al., 1993), and shock-
natural fullerenes have been found. These include some low- produced impact-generated breccias from the Sudbury mete-
pressure metamorphic rocks such as shungite from Russia orite crater (Becker et al., 1994). Fullerenes presumably pro-
(Buseck et al., 1992; Parthasarathy et al., 1998), clays at the duced in wildfires at the K-T boundary (Heymann et al., 1996)
Cretaceous-Tertiary (K-T) boundary (Heymann et al., 1994a, and from samples of P-T boundary sections (Chijiwa et al.,
1994b, 1996, 1998), claystone from the Permian-Triassic (P-T) 1999) have been reported. The occurrence of fullerenes and an
boundary (Chijiwa et al., 1999), the Sudbury impact structure increase in carbon soot content are considered to be important
(Becker et al., 1994), and in a micrometeorite crater formed on geochemical markers of the K-T boundary (Heymann et al.,
a space platform (Di Brozolo et al., 1994). Here we report the 1998). Mita and Shimoyama (1999) reported ⬃26 polycyclic
first occurrence of fullerenes from the intertrappean sediments aromatic hydrocarbons from naphthalene to coronene from the
of Kutch, on the Indian subcontinent, that are believed to be K-T boundary sediments at Kawaruppu, Hokkaido, Japan, in-
associated with the K-T boundary. dicating a possible combustion origin of these hydrocarbons

*E-mail: bhandari@prl.ernet.in.

Parthasarathy, G., Bhandari, N., Vairamani, M., Kunwar, A.C., and Narasaiah, B., 2002, Natural fullerenes from the Cretaceous-Tertiary boundary layer at Anjar,
Kutch, India, in Koeberl, C., and MacLeod, K.G., eds., Catastrophic Events and Mass Extinctions: Impacts and Beyond: Boulder, Colorado, Geological Society
of America Special Paper 356, p. 345–350.

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346 G. Parthasarathy et al.

within the K-T boundary clays. However, no fullerenes were The carbonaceous matter was extracted from the powdered
found at these sites. Becker et al. (1996, 2000a, 2000b) reported samples by using a standard acid-digestion method (Wedeking
trapped noble gases in K-T boundary fullerenes, indicating their et al., 1983). All the samples were treated at room temperature
extraterrestrial origin. Although fullerenes have been reported with 12 N HCl for 24 h followed by 60% HF for 18 h. There-
to form by high-temperature benzene flames, they have not after the samples were heated in 60% HF at 70 ⬚C for 1 h. The
been detected in modern-day wildfires (Becker et al., 2000b). resulting solid residue was washed with ⬃1 L of double-
Despite the multiple and poorly understood processes that may distilled water and dried overnight at 80 ⬚C. The carbon-rich
produce fullerenes in nature, there appears to be an association fraction so obtained was analyzed by Fourier transform infrared
of these compounds with the K-T and P-T boundaries. This (FT-IR) spectroscopy. A fraction of the carbon-rich residue was
fact, combined with the otherwise rare occurrence of these car- also treated with toluene or d6-benzene for the extraction of
bonaceous materials in nature, makes fullerenes potential chem- fullerenes, which were then characterized by mass spectroscopy
ical markers for certain geological boundaries. In this chapter and 13C-nuclear magnetic resonance (NMR) spectroscopy. Only
we investigate whether fullerenes are present in the intertrap- four samples, Anjar-J and M (Ir layer, Br-3), L (Ir layer, Br-2),
pean sediment beds at Anjar, India, and whether their presence and 964 (just below Ir layer Br-1) yielded some extractable
can help us confirm that these beds represent a continental fullerenes (Fig. 1). The amounts of the carbonaceous matter
K-T boundary within the Deccan flood basalt area (Bhandari et extracted from these three samples were ⬃1.3%–3.8%. The
al., 1995; Shukla et al., 1997). other samples yielded only neo-formed fluoride residues as
fluorite crystals, and sample 965 had a noticeable amount of
The electron impact ionization mass spectra were obtained
The Anjar volcano-sedimentary sequence is located at the with a VG AUTOSPEC mass spectrometer and an OPUS.
western periphery of the Deccan flood basalt province and con- V3.IX data system. The conditions of measurements were as
sists of nine lava flows and at least four intertrappean beds follows: source temperature, 250 ⬚C; electron energy, 70 eV;
(Ghevariya, 1988; Bhandari et al., 1995). The third intertrap- trap current, 200 mA; resolution, 1000; mass range scanned,
pean bed is well developed (⬃6 m thick) and consists of cherty 300–900 amu; scan time, 5 s per decade of mass; interscan
limestone, shale, and mudstone (Fig. 1). Three thin limonitic delay, 0.5 s. Samples were loaded in a quartz cup, introduced
layers are present in the lower 1.5 m of the intertrappean bed through direct inlet probe, and instantly heated to 250 ⬚C. The
that was exposed in pit BG-1 (Shukla et al., 1997). The limo- mass spectrometer was calibrated to 900 amu with the reference
nitic layers have high concentrations of iridium (650–1333 pg/ sample of high-purity perfluorokerosene. The samples were
g) and osmium (650–2230 pg/g) (Bhandari et al., 1996) com- scanned between 300 and 900 amu to improve the sensitivity
pared to ⬍100 pg/g measured in other horizons of this pit. On of detection of C60 and C70. The spectra, given in Figure 2,
the basis of the geochronological, geochemical, paleomagnetic, clearly show peaks corresponding to C60ⳭⳭ and C60Ⳮ at 360
and paleontological data (Venkatesan et al., 1996; Bhandari, amu (for doubly charged ions) and 720 amu, respectively, and
1998), it is believed that the limonitic layers were deposited ions corresponding to C70Ⳮ are not present. Although a single
during or close to the K-T boundary event. The deposition rate scan gave enough signal to identify C60, an average of 20 scans
of sediments in the intertrappean beds is much higher than in was used for better precision during analysis. C60 was resolved
the contemporaneous marine sections; therefore, they offer a into four peaks at 720, 721, 722, and 723 amu, corresponding
better time resolution. A study of the intertrappean sediments to 12C60Ⳮ, 12C59 13CⳭ, 12C5813C2Ⳮ, and 12C5713C3Ⳮ, respec-
should allow the sequence of events that occurred around the tively, as schematically shown in Figure 3. It is interesting to
K-T boundary and their relation to Deccan volcanism to be note that peaks corresponding to the addition of as many as 3
better defined. oxygen atoms (mass to charge ratio, m/z ⳱ 736, 752 and 768)
are observed in some of the samples. These peaks might be due
EXPERIMENTAL METHODS AND RESULTS to the oxidized fullerenes, because they are very susceptible to
oxidation. T. Bunch (2001, personal commun.) has also ob-
Nine samples from the third intertrappean bed, collected served the presence of oxidized fullerenes in samples that were
from pit BG1 during 1994, were analyzed in this study. Their accidentally exposed to oxidizing conditions during sample
stratigraphic locations with respect to the three iridium-rich lay- preparation. However, we have not observed these peaks in
ers (Br-1, Br-2, Br-3) are shown in Figure 1 (Shukla et al., other samples, which were prepared under similar experimental
1997). Sample 964 was located just below the iridium-rich conditions. Their origin is therefore not yet fully understood.
brown layer (BR-1), sample L is the limonitic layer (BR-2) In order to avoid any contamination, we did not use any syn-
containing the highest concentration of iridium in this section, thetic fullerenes for estimating the concentration of fullerenes
and samples Anjar-J and M represent the third iridium-rich in various samples. Therefore, our estimate of fullerene content
layer (Br-3). Anjar-M was collected from a location laterally in the samples (Fig. 1) is approximate and based only on the
displaced with respect to that of Anjar-J by about 3 m. intensity of the peaks at the mass to charge ratio m/z ⳱ 720.
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Natural fullerenes from the Cretaceous-Tertiary boundary layer at Anjar, Kutch, India 347

Figure 1. Stratigraphic locations of sam-

ples analyzed for fullerenes with respect
to iridium-rich layers (Br-1, Br-2, Br-3;
Bhandari et al., 1996). Content of car-
bonaceous matter and approximate con-
centration of fullerenes at various hori-
zons are given. Details of samples L, J,
M and others are given in text.

Because we have not observed any peaks beyond C60, we have ples. In addition, a few vibrational bands at 2920, 2850, and
not attempted to search for higher mass fullerenes. The highest 1380 cmⳮ1, which are characteristic of aliphatic CH, CH2, and
concentration of fullerenes was found in sample L, which con- CH3 groups, have also been observed. Well-resolved peaks at
tains the highest average concentration of iridium (1287 pg/g) ⬃740 and 509 cmⳮ1 in these samples indicate the presence of
(Bhandari et al., 1996). a high-pressure–high-temperature form of fullerenes. The pres-
Because the high-pressure–high-temperature forms of C60 ence of this high-pressure–high-temperature form of fullerenes
fullerenes are insoluble in toluene or benzene (Kozlov and Yak- (probably subjected to 3 GPa and 800 K; Kozlov and Yakashi,
ashi, 1995), we have carried out FT-IR spectroscopic studies 1995) suggests an impact origin, probably during the K-T
directly on the carbon-rich residues of the samples of 964, L, boundary impact.
and Anjar-J to confirm their presence. The standard KBr pellet We also carried out 13C-NMR spectroscopic studies on the
method was employed and the IR-transmission spectra were powdered carbonaceous material to confirm the presence of
collected in the frequency range 400–4000 cmⳮ1 at room tem- fullerenes. The 13C-NMR spectrum was recorded in benzene-
perature, by using a Biorad-FT-IR spectrometer. All the samples d6 at 125 MHz on a Varian INOVA 500 NMR spectrometer.
exhibit identical spectral bands with minor change in intensi- We collected 3200 free induction decays using 30⬚ pulse width
ties. IR bands at 1430, 1180, 575, and 525 cmⳮ1, which are and 15 s relaxation delay. The 13C-NMR spectrum (with an
characteristic of the C60 fullerenes F1U vibrational mode (Koz- acceptable signal to noise ratio) exhibits clearly the presence of
lov and Yakashi, 1995), have been observed in all three sam- a single NMR line at 143.28 ppm for sample L (Fig. 4) and
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348 G. Parthasarathy et al.

Figure 3. High-resolution mass spectra around peak at m/z ⳱ 720 for

samples Anjar-J and Anjar-M, which are resolved into four peaks at
720, 721, 722, and 723 amu. Data are systematically shifted slightly
toward lower values of m/z.

Figure 2. Mass spectrum obtained from sample 964 (A) and L (B)
showing peaks at m/z ⳱ 360 and 720, characteristic of C60 ions.

143.24 ppm for sample 964, corresponding to the sp2 carbons

of the C60 fullerenes (Ajie et al., 1990). The peaks expected for
C70 at 130.9, 145.4, 147.4, 148.1, and 150.7 ppm are not ob-
served in any of the samples, corroborating the results obtained
by mass spectroscopic studies. The concentration of C60 fuller-
Figure 4. 13C-NMR (nuclear magnetic resonance) spectrum showing
ene is approximate, but appears to be higher than the values single NMR line at 143.278 ppm for sample L, corresponding to sp2
found in K-T boundary samples at other locations (Heymann carbons. Peaks at ⬃128, which can be resolved into six peaks (shown
et al., 1996), and lower than some natural samples such as Ka- in inset) are due to d6-benzene solvent.
relian shungite, which was estimated to be ⬃0.01–0.1 wt%. The
C70 abundance is found to be between one-third and one-fifth
relative to C60 in a few K-T boundary clays, whereas it is absent periments of Heymann et al. (1996) disagree with this expla-
at many other locations, e.g., at Woodside Creek (Heymann et nation. Becker et al. (1994) suggested that the survival of
al., 1996, 1998). Shungites of Karelia (Parthasarathy et al., fullerenes in the Sudbury crater is due to the presence of dia-
1998) and the P-T boundary (Chijiwa et al., 1999) also show genetic sulfides, indicating low oxygen and high sulfur concen-
an absence of C70. It has been suggested that the absence of C70 trations. In such an environment, fullerenes were protected from
may be due to weathering and differential oxidation, as indi- oxidation by their surrounding sulfide-silicate matrix. However,
cated by the results of Chibante et al. (1993), although the ex- in the Anjar samples, despite the noticeable sulfur content in
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Natural fullerenes from the Cretaceous-Tertiary boundary layer at Anjar, Kutch, India 349

samples 965, just above Br-2 (Fig. 1), C70 is not found. We ACKNOWLEDGMENTS
therefore believe that C70 is absent at Anjar because it was not
deposited, rather than having been later lost by oxidation. The We are grateful to Govardhan Mehta, K.V. Raghavan, and H.K.
occasional presence of C70 at the K-T boundary, therefore, still Gupta for providing facilities and support for this work. We
remains to be fully understood in terms of its production and thank A.D. Shukla for his help in preparation of the samples.
preservation. This chapter was improved substantially by the constructive
comments of Ted Bunch, Mark Sephton, and C. Koeberl.
Several mechanisms for origin of fullerenes at the K-T
Ajie, H., Alvaris, M.M., Anz, S.J., Beck, R.D., Diederich, F., Fost, K., Poulous,
boundary have been proposed. These include (1) survival of I.R.O., Huffman, D.R., Krafschmer, W., Rubin, Y., Shriber, K.E., Sen-
fullerenes that were already present in the K-T impactor. sharma, U., and Whepten, R.L., 1990, Characterization of the soluble all
Trapped 3He in fullerenes, reported by Becker et al. (2000a), carbon molecules C60 and C70: Journal of Physical Chemistry, v. 94, p.
support this mechanism. Pentagonal-shaped fullerenes-like 8630–8633.
nanoparticles 2–10 nm in diameter were found in the Allende Becker, L., Bada, J.L., Winans, R.E., Hunt, J.E., Bunch, T.E., and French, B.M.,
1994, Fullerenes in the 1.85 billion year old Sudbury impact structure:
meteorite by Harris et al. (2000), suggesting that these nano- Science v. 265, p. 642–645.
particles could be carriers of planetary gases. (2) Another mech- Becker, L., Poreda, R.J., and Bunch, T.E., 2000a, Fullerenes: An extraterrestrial
anism is the formation of fullerenes during combustion of car- carbon carrier phase for noble gases: Proceedings of the National Acad-
bonaceous material in wildfires created by the K-T impact emy of Sciences, v. 97, p. 2979–2983.
(Heymann et al., 1994a, 1994b, 1996, 1998). However, the ab- Becker, L., Poreda, R.J., and Bunch, T.E., 2000b, The origin of fullerenes in
the 65 Myr old Cretaceous/Tertiary ‘K/T’ boundary [abs.]: Lunar and
sence of fullerenes in modern wildfires reported by Becker et Planetary Sciences, v. 31, p. 1832.
al. (2000a) makes this mechanism improbable (3) Heymann et Becker, L., Poreda, R.J., and Bada, J.L., 1996, Extraterrestrial helium trapped
al. (1998) suggested that fullerenes may have formed in the hot in fullerenes in the Sudbury Impact Structure: Science, v. 272, p. 249–
atmospheric plume of the Chicxulub crater (Smit, 1999). Hey- 252.
mann et al. (1996) estimated that the mean global C60 concen- Bhandari, N., 1998, Astronomical and terrestrial causes of physical, chemical
and biological changes at geological boundaries: Proceedings of the In-
tration at the K-T boundary is 14 ng/cm2, which corresponds dian Academy of Sciences: Earth and Planetary Sciences, v. 107, p. 251–
to a mean C60 content of 0.41 ppm in the soot. They suggested 263.
that these values are consistent with the formation of fullerenes Bhandari, N., Shukla, P.N., Ghevariya, Z.G., and Sundaram, S.M., 1995, Impact
by wildfires than by carbon chemistry in the hot atmospheric did not trigger Deccan volcanism: Evidence from Anjar K/T boundary
intertrappean sediments: Geophysical Research Letters, v. 22, p. 433–436.
plume of the Chicxulub impact (Heymann et al., 1996).
Bhandari, N., Shukla, P.N., Ghevariya, Z.G., and Sundaram, S.M., 1996, K/T
Whether these wildfires were impact related or were caused by boundary layer in Deccan Intertrappeans at Anjar, Kutch, in Ryder, G.,
volcanism remains to be established. It is difficult to get further Fastovsky, D., and Gartner, S., eds., The Cretaceous-Tertiary event and
insight into the mechanism of formation of fullerenes, but we other catastrophes in Earth history: Geological Society of America Spe-
make use of the association of fullerenes with K-T boundary to cial Paper 307, p. 417–424.
understand the peculiar stratigraphic distribution of iridium at Buseck, P.R., Tsipursky, S.J., and Hettich, R., 1992, Fullerenes from the geo-
logical environment: Science, v. 257, p. 215–217.
Anjar, where there are three iridium-rich horizons (Bhandari et Chibante, L.P.F., Pan, C., Pierson, M.L., Haufler, R.E., and Heymann R., 1993,
al, 1996). The question has arisen whether these represent three Rate of decomposition of C60 and C70 heated in air and the attempted
independent events of deposition or whether the three layers characterization of the products: Carbon, v. 31, p.185–193.
have been enriched in iridium due to secondary processes such Chijiwa, T., Arai, T., Sugai, T., Shinohara, H., Kumazawa, M., Takano, M., and
as downward fluid mobilization during the emplacement of the Kawakami, S., 1999, Fullerenes found in the Permo-Triassic Mass ex-
tinction period: Geophysical Research Letters, v. 26, p. 767–770.
upper basaltic flow F4 (Courtillot et al., 2000). Because fuller- Courtillot, V., Gallet, Y., Rocchia, R., Feraud, G., Robin, E., Hofmann, C.,
enes and iridium are both insoluble in water, it is unlikely that Bhandari, N., and Ghevariya, Z.G., 2000, Cosmic markers, 40Ar/ 39Ar
their coexistence in three different layers (Fig. 1) is due to fluid dating and paleomagnetism of the KT sections in the Anjar area of the
mobilization. The presence of any other impact markers, e.g., Deccan large igneous province: Earth and Planetary Science Letters, v.
planar deformation features in quartz or the existence of Ni- 182, p. 137–156.
Daly, T.K., Buseck, P.R., Williams, P., and Lewis, C.F., 1993, Fullerenes from
rich spinels, could have been useful in understanding the de- the fulgurite: Science, v. 259, p. 1599–1601.
positional history of the Anjar K-T boundary section, but their Di Brozolo, F.R., Bunch, Th.E., Fleming, R.H., and Macmillan, J., 1994, Fuller-
search has not yielded any positive results (Courtillot et al., enes in an impact crater on the LDEF spacecraft: Nature, v. 369, p. 37–
2000). The present experimental studies reveal the presence of 40.
trace amounts of the high-pressure form of fullerenes C60, in- Ghevariya, Z.G., 1988, Intertrappean dinosaurian fossils from Anjar area,
Kachchh District, Gujarat: Current Science, v. 57, p. 248–251.
dicating that they are formed by impact, and their association Harris, P.J.F., Vis, R.D., and Heymann, D., 2000, Fullerene-like nanostructures
with iridium-rich horizons supports their association with the in the Allende meteorite: Earth and Planetary Science Letters, v. 183, p.
K-T boundary event. 355–359.
Downloaded from specialpapers.gsapubs.org on April 7, 2015

350 G. Parthasarathy et al.

Heymann, D., Chibante, L.P.F., Brooks, P.R., Wolbach, W.S., and Smalley, Mita, H., and Shimoyama, A., 1999, Characterization of n-alkanes, pristane
R.E., 1994a, Fullerenes in the K/T boundary layer: Science, v. 265, p. and phytane in the K/T boundary sediments at Kawaruppu, Hokkaido,
645–647. Japan: Geochemical Journal, v. 33, p. 285–294.
Heymann, D., Wolbach, W.S., Chibante, L.P.F., Brooks, R.R., and Smalley, Parthasarathy, G., Srinivasan, R., Vairamani, M., Ravikumar, K., and Kunwar,
R.E., 1994b. Search for extractable fullerenes in clays from the Creta- A.C., 1998, Occurrence of natural fullerenes in low grade metamorphosed
ceous/Tertiary boundary of the Woodside Creek and Flaxbourne river Proterozoic shungite from Karelia: Geochimica et Cosmochimica Acta,
sites, New Zealand: Geochimica et Cosmochimica Acta, v. 58, p. 3531– v. 62, p. 3541–3544.
3534. Shukla, P.N., Shukla, A.D., and Bhandari, N., 1997, Geochemical character-
Heymann, D., Chibante, L.P.F., Brooks, R.R., Wolbach, W.S., Smit, J., Koro- isation of the Cretaceous-Tertiary Boundary sediments at Anjar, India:
chantsev, A., Nazarov, M.A., and Smalley, R.E., 1996, Fullerenes of pos- Palaeobotanist, v. 46, p. 127–132.
sible wildfire origin in Cretaceous-Tertiary boundary sediments, in Ryder, Smit, J., 1999, The global stratigraphy of the Cretaceous-Tertiary boundary
G., Fastovsky, D., and Gartner, S., eds., The Cretaceous-Tertiary event impact ejecta: Annual Reviews of Earth and Planetary Sciences, v. 27,
and other catastrophes in Earth history: Geological Society of America p. 75–113.
Special Paper 307, p. 453–464. Venkatesan, T.R., Pande, K., and Ghevariya, Z.G., 1996, 40Ar/ 39Ar ages of
Heymann, D., Yancey, T.E., Wolbach, W.S., Thiemens, M.H., Johnson, E.A., Anjar Traps, western Deccan Province (India) and its relation to the
Roach, D., and Moecker, S., 1998, Geochemical markers of the Creta- Cretaceous-Tertiary boundary events: Current Science, v. 70, p. 990–996.
ceous-Tertiary Boundary event at Brazos River, Texas, U.S.A.: Geochim- Wedeking, K.W., Hayes, J.M., and Matzigkeit, U., 1983, Procedures of organic
ica et Cosmochimica Acta, v. 62, p. 173–181. geochemical analysis, in Schopf, J.W., ed., Earth’s earliest biosphere:
Kozlov, M.E., and Yakushi, K., 1995, Optical properties of high-pressure phase Its origin and evolution: New Jersey, Princeton University Press, p. 428–
of C60 fullerene: Journal of Physics (Condensed Matter), v. 7, p. L209– 441.
Kroto, H.W., Heath, J.R., O’Brien, S.C., Curl, R.F., and Smalley, R.E., 1985, MANUSCRIPT SUBMITTED OCTOBER 5, 2000; ACCEPTED BY THE SOCIETY
C60: Buckministerfullerene: Nature, v. 318, p. 162–163. MARCH 22, 2001

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Geological Society of America Special Papers

Natural fullerenes from the Cretaceous-Tertiary boundary layer at Anjar, Kutch,
G. Parthasarathy, N. Bhandari, M. Vairamani, et al.

Geological Society of America Special Papers 2002;356; 345-350


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