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Palaeogeography, Palaeoclimatology, Palaeoecology 252 (2007) 347 – 354

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Carbon isotope record of the P/T boundary and the


Lower Triassic in the Southern Alps: Evidence for
rapid changes in storage of organic carbon
Micha Horacek a,⁎,1 , Rainer Brandner b , Rainer Abart a,2
a
Institute of Mineralogy and Petrology, University of Graz, Universitaetsplatz 2, 8010 Graz, Austria
b
Institute of Geology and Paleontology, University of Innsbruck, Innrain 52, 5010 Innsbruck, Austria
Accepted 30 November 2006

Abstract

The carbonate carbon isotope record of Lower Triassic shelf sediments was investigated in the Pufels and L´Om Picol (Uomo)
sections of the western central Dolomites to derive a complete record from the Permian/Triassic transition to the uppermost Lower
Triassic from the western Tethys. The carbon isotope record shows the well-studied decrease at the Permian/Triassic boundary
(PTB), followed by an increase to about 1.5‰. At the Dienerian/Smithian boundary the δ13C values increase to a pronounced
+ 6‰ maximum. A steady rapid drop until the upper Smithian below −2‰ follows this δ13C peak. At the Smithian/Spathian
transition, a steep rise to positive values is documented. The positive carbon isotope peak is interpreted to reflect an interval of
enhanced burial of organic carbon, whereas the isotopic minima provide evidence of periods of oxidation of organic matter and/or
release of isotopically light carbon. This may be ascribed to quickly changing environmental conditions, which have already been
postulated by paleontologists due to the delayed biotic recovery from the Permian–Triassic extinction event. Because of the short-
time interval these positive isotope excursions represent, their generation by burial of organic carbon in periods of high productivity
and/or anoxia appears plausible. Concurrent carbon isotopic excursions are reported from Iran, Pakistan and Oman as well as from
Southern China, which indicate an at least Tethys-wide event. If the excursion proves to be of global significance, dark shale
deposited in the pelagic Panthalassa Ocean may have acted as sink for organic carbon, supporting the hypothesis of a periodically
stratified ocean in the Lower Triassic.
© 2007 Elsevier B.V. All rights reserved.

Keywords: P/T boundary; Triassic; Isotopes; Carbon cycle; Anoxia

1. Introduction

⁎ Corresponding author. The PTB represents the heaviest impact on life


E-mail addresses: micha.horacek@arcs.ac.at (M. Horacek), during Earth's history (Erwin, 1993). More than 90% of
abart@zedat.fu-berlin.de (R. Abart), rainer.brandner@uibk.ac.at all marine skeleton-building species became extinct
(R. Brandner). during this interval (Raup, 1991). What happened after
1
Current address: Austrian Research Centers GmbH - ARC, 2444
Seibersdorf, Austria. the extinction is still unclear and the Lower Triassic
2
Current address: Institute of Geological Sciences, Free University remains so far a “highly anomalous interval of time”
Berlin, Berlin, Germany. (Erwin, 2000). The biotic recovery only started at the
0031-0182/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2006.11.049
348 M. Horacek et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 252 (2007) 347–354

end of the Lower Triassic in the Spathian substage or Scholger et al. (2000). The L´Om Picol/Uomo section is
even later during the Middle Triassic (Kozur, 1998; located near Passo San Pellegrino, about 50 km east of
Erwin, 2000). In addition to the extinction at the PTB, at Bozen, at an altitude of about 2300 m (Horacek and
least two minor extinction events are known in the Povoden, 1999). Both sections are regarded as shallow
Lower Triassic, one at the Griesbachian/Dienerian water sections close to a shoreline (Brandner, 1988).
boundary (Kozur, 1998; Mei et al., 1999) and one at In the Late Permian, the marine Bellerophon Forma-
the Smithian/Spathian boundary (review in Hallam and tion carbonates were deposited in the Dolomite basin
Wignall, 1997). (Italy) followed by the Werfen Formation in the Lower
The carbon isotope composition of marine carbonates Triassic, which consists mainly of impure carbonates
mirrors the dynamic equilibrium between the accumu- (Mostler, 1982). The Tesero Oolite represents the
lation of marine carbonate and the burial of organic transition between the Bellerophon Formation and the
carbon (Marshall, 1992). Carbonate reflects δ13C values Werfen Formation, lithostratigraphically it belongs to the
similar to seawater bicarbonate, whereas organic carbon Werfen Formation. An abrupt change in sedimentation
is depleted in 13C with respect to the bicarbonate from a Late Permian fossiliferous wackestone to a
dissolved in ocean water. Changes in the δ13C record can fossiliferous packstone with significantly reduced
mainly be ascribed to changes in the balance between the amounts of organic matter occurs between the Bellero-
carbonate and the organic carbon reservoirs (Marshall, phon Formation and Tesero Oolite. This boundary — the
1992). Many extinction events in Earth's history are so called “Current Event” (Brandner, 1988; Farabegoli
accompanied by carbon isotope changes, which may and Perri, 1998) — can be found throughout the
help to elucidate the kill mechanisms (Walliser, 1996). Dolomites (Brandner, 1988). The Tesero Oolite inter-
For this purpose the sections in Pufels/Bulla and Uomo fingers with and is overlain by the Mazzin Member,
have been studied for their carbon and oxygen isotopic consisting of marine silty clays and carbonate mudstones
compositions. We present the carbon isotope curve of with episodically intercalated bioclastic packstones,
almost the entire Lower Triassic sequences from northern interpreted as tempestites. The sequence was deposited
Italy and its correlation with the bio- and paleomagnetic in a subtidal environment, which was reached by storm
stratigraphy, and make inferences regarding the environ- waves. It is overlain by the supratidal Andraz Horizon, a
mental changes during the Lower Triassic. mainly evaporitic sequence with thin-bedded dolomites
and silty marls. According to Gianolla et al. (1998), this
2. Geological setting horizon is interpreted as a shelf margin wedge (SMW) at
the base of the 3 rd order sequence Sc 2 (Fig. 2). Further
The sampling sites (Fig. 1) are located east of the upwards the submarine Seis/Siusi Member is developed,
Eisack valley (South Tyrol/Alto Adige, Italy). The Pufels/ featuring dm-thick, intraclastic–bioclastic packstones
Bulla section is located approximately 20 km NE of alternating with thin silty marls. The graded packstones
Bozen/Bolzano. It is exposed along the road from St. (tempestites) frequently show fining upwards (FU), and
Ulrich/Ortisei to Pufels/Bulla at approximately 1500 m higher up in the section they show coarsening upwards
altitude. Detailed descriptions of the section can be found (CU) parasequences and are associated with the typical
in Mostler (1982), Farabegoli and Perri (1998) and Werfen lithofacies: flat-pebble conglomerates (so called
“Koken'sches Konglomerat”; e.g., Broglio Loriga et al.,
1990) and the so-called “Gastropodenoolith”, a well
preserved oolite with microgastropodes in the nucleus.
The Gastropod Oolite Member of the Italian authors
(e.g., Gianolla et al., 1998) we included in the Seis/Siusi
Member, as there is locally a strong interfingering of the
two facies types. The succeeding Campil Member, a
dominantly subtidal, terrigenous siliciclastic sedimentary
unit, forms together with the Gastropod Oolite Member at
the top of the Seis Member the sequence Sc 3 (Fig. 2). A
change in sedimentation towards more marine influenced
sediments marks the beginning of the Val Badia Member
Fig. 1. Map of the Central Dolomites (Italy). Investigated Pufels/Bulla
(sequence Sc 4, Fig. 2). The overlying Cencenighe
and L´Om Picol/Uomo sections (underlined) among other boundary Member with a mixed siliciclastic and carbonatic
sections are indicated by stars. Modified after Brandner (1988). lithofacies was deposited in a shallower environment
M. Horacek et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 252 (2007) 347–354 349

Fig. 2. Pufels and Uomo carbon isotope profiles, “Current Event” = 0 m and marks the boundary between the Bellerophon Formation and the Tesero
Oolite. Ages after Young and Laurie (1996), magnetostratigraphy after Scholger et al. (2000), Pufels lithostratigraphy after Mostler (1982) and
Farabegoli and Perri (1998), Uomo stratigraphy after Horacek and Povoden (1999) and unpublished data, conodont biostratigraphy after Farabegoli
and Perri (1998), sequence stratigraphy after Gaetani et al. (1998), Gianolla et al. (1998), modified. A = Andraz Horizon, Aeg. = Aegean, B. =
Bithyian, Bell. Form. = Bellerophon Formation, T = Tesero Oolite, i.Z. = isarcica Zone. Note that at the Pufels section the Val Badia Member is not
present, as the Campil Member is truncated by Middle Triassic sediments. For comparison the δ13C profiles from the Gartnerkofel (Holser et al.,
1989) and China (Payne et al., 2004) are shown. Isotope peaks are labelled (A, B, C) to facilitate identification. For explanation see text.

and forms the uppermost member of the Werfen 3. Biostratigraphy


Formation at the L´Om Picol/Uomo section. In the
Pufels/Bulla section the upper part of the dominantly The Permian–Triassic boundary is now widely
terrigenous Campil Member featuring a local special accepted to be defined by conodonts with the first
facies with gray limestone layers is discordantly overlain occurrence of Hindeodus parvus, about 1.3 m above the
by Middle Triassic sediments. Current Event in the Pufels section (Farabegoli and
350 M. Horacek et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 252 (2007) 347–354

Perri, 1998). The lower Griesbachian/upper Griesba- were cut and powdered. CO2 was released from the
chian boundary can tentatively be defined by the first sample powder using standard methods. Reproducibility
appearance datum (FAD) of the bivalve Claraia clarai, was better than 0.1‰ for δ13C and δ18O (1σ). All
succeeding Claraia wangi, which approximately corre- isotope values are given in the conventional δ notation
lates with the beginning of the Isarcica Zone (Broglio and are expressed in per mil (‰), for oxygen and for
Loriga et al., 1990). The Griesbachian/Dienerian carbon with respect to the V-PDB standard. Dolomitic
boundary cannot be defined, as no relevant marker is samples have not been corrected for the different acid
present. The approximate position can be estimated by fractionation factor.
correlating the magnetostratigraphy (Scholger et al.,
2000) with the data from the Abadeh profile (Gallet 5. Results
et al., 2000), or tentatively correlated with the FAD of
Claraia aurita succeeding C. clarai about 25 m above 5.1. Carbon isotope data
the onset of the Seism member in the Uomo section
(Broglio Loriga et al., 1986, 1990). The Dienerian/ The Pufels carbon isotope profile starts in the
Smithian boundary cannot exactly be defined due to the uppermost Bellerophon Formation in the Late Permian
lack of appropriate fossils. The onset of the Spathian can (Fig. 2), 1.5 m below the Current Event. High values for
be defined by the FAD of the ammonite Tirolites the Bellerophon Formation between 2.5‰ and N4‰ are
cassianus (Broglio Loriga et al., 1990), just above the followed by a drop to 1‰ into the Tesero Oolite. This
evaporitic transition between the Campil and the Val drop continues in the Mazzin Member to a minimum
Badia members. value below − 2‰. The values then rise to values be-
tween − 1.0 and − 1.5‰ and fall to a second minimum
4. Analytical techniques around − 2‰. In the upper Mazzin Member values
increase uninterruptedly to around +1‰ at the Mazzin
The samples from the Pufels/Bulla section are exactly Member/Andraz Horizon boundary. The Andraz Hori-
correlated to samples used for paleomagnetic analysis by zon is almost completely covered, due to its low weath-
Scholger et al. (2000). Hand specimens from the Pufels/ ering resistance. In the upper Seis Member, a moderate
Bulla and Uomo sections were critically investigated for and constant rise to +3‰ (Fig. 2: peak A) succeeded by
stylolites, cracks, veins, weathering and strong recrys- a decrease to 0‰ at the Seis/Campil Member boundary
tallisation. These parts were removed before samples occurs. The δ13C values rise again and remain at this

Fig. 3. Oxygen and carbon isotopes diagram of Pufels and L´Om Picol/Uomo samples. No overall trend is visible, making less likely a major
diagenetic event. 18O isotope enriched samples above approximately − 4‰ V-PDB are dominantly dolomitic.
M. Horacek et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 252 (2007) 347–354 351

decreasing tendency towards negative δ13C ratios in the


Val Badia and Cencenighe Members.

5.2. Oxygen isotope data

Oxygen isotope ratios in carbonates are very suscep-


tible to alteration during diagenesis (Marshall, 1992). For
the two sections investigated in this study the C and O
isotope values are uncorrelated (Fig. 3), suggesting that
the 13C values remained unchanged during diagenetic
alteration (Buggisch et al., 1994). Carbonates with higher
dolomite content can be detected by their higher oxygen
isotope signals. However, these samples do not show any
deviation in their carbon isotope ratio with respect to
neighboring dolomite-poor samples (Fig. 4).

6. Discussion

The carbon isotope record of most of the bulk car-


bonate samples with high carbonate content most likely
does not change significantly due to diagenesis (Scholle
Fig. 4. Oxygen and carbon isotope curves of the lower Pufels section. and Arthur, 1980; Marshall, 1992), because the carbon
“Current Event” = 0 m. Dolomitic samples can be detected by their reservoir of the rock far outmatches the amount of carbon
significantly enriched δ18O signal. Shaded bar represents the dissolved in a diagenetic fluid. Carbon isotope alteration
evaporitic–dolomitic Andraz Horizon. in carbonates most likely leads to depleted values
(Marshall, 1992). Only bacterial methanogenesis in
higher level in the lower Campil Member. Upsection the organic rich rocks can alter carbon isotope values of
carbon isotopes can only vaguely be traced due to carbonate to higher δ13C values (for a review see Magaritz
insufficient exposure of the rocks. Further upwards in et al., 1983). Because the sampled lithologies are poor in
the Campil Member follows a steep positive excursion organic carbon and rich in carbonate, we suggest that the
to above 5‰ (Fig. 2: peak B), followed by a decrease to carbon isotope pattern is a primary feature with no
negative values and encountering values around 0‰ at detectable modification during diagenesis.
the top of the sampled interval. The Pufels and L´Om Picol sections can be correlated
The L´Om Picol/Uomo section (Horacek et al., 2000) very well to each other (Fig. 2) and demonstrate
starts a few meters below the Current Event in the comparable, quickly changing carbon isotope trends in
Bellerophon Formation (Fig. 2), which yields high iso- the Lower Triassic of the Dolomite Basin. The Permian/
topic values around +4‰, followed by a sudden decrease Triassic transition is marked by a pronounced depletion
to values between 1 and 1.5‰ around the PTB. This step in 13C isotopes, followed by a moderate increase in the
probably indicates a hiatus. The drop apparently con- upper Griesbachian, as has been found at numerous
tinues over some unexposed metres to a minimum below other sections (e.g., Baud et al., 1989; Holser et al.,
−2‰ in the lower Mazzin Member and rises moderately 1989). In the Dienerian, an excursion up to +3‰
to ca. 1‰ in the upper Mazzin Member. The Andraz succeeded by a decrease to almost 0‰ can be found in
Horizon is not exposed. The δ13C values of the Seis both sections. Further upwards a prominent carbon
Member continue at +1.5‰ until the upper Seis Member, isotope excursion to + 6‰, immediately followed by a
where the profile succeeds into a constant rise above +2‰ steep drop to negative values, gives a total change of
(Fig. 2: peak A) followed by a drop to values below 0‰. almost 8‰ in δ13C. A short and steep positive carbon
The base of the Campil Member can be placed at this isotope excursion close to the Dienerian–Smithian
level. In the Campil Member the curve rises to a maxi- boundary has already been reported from Pakistan by
mum near +6‰ (Fig. 2: peak B) and decreases steadily to Baud et al. (1996). Although it is of smaller magnitude
−2‰ in the uppermost Campil Member. The Campil–Val we suggest that this is the same excursion. Investiga-
Badia transition shows a steep rise to above +1‰ (Fig. 2: tions of sections in South China (Payne et al., 2004) and
peak C), succeeded by heterogeneous values of overall Iran (Horacek et al., 2007) have revealed δ13C curves
352 M. Horacek et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 252 (2007) 347–354

with an almost identical pattern as described in the δ13C values, which he ascribed to increasing bioproduc-
Pufels and L´Om Picol sections. Another positive δ13C tivity (process (II) described above). Apparent deteriora-
excursion with similar shape and a magnitude of + 7‰ tion of the environmental conditions in the Campil
has been documented in Oman by Hauser et al. (2001); Member (Twitchett and Wignall, 1996; Twitchett, 1999)
however, it has been ascribed to the Smithian/Spathian is explained by salinity changes due to increased runoff
boundary. from the hinterland, and therefore ascribed to a probably
Comparison of the Pufels and L´Om Picol profiles regional effect. Shao et al. (2000) demonstrated that a
with the Gartnerkofel δ13C profile (Holser et al., 1989; reduction of salinity coincides with reduced carbon
Fig. 2) yields a good correlation. The almost identical isotope values, thus the positive excursion in the Campil
pattern in the Chinese sections (Payne et al., 2004) and Member cannot be explained by this mechanism.
the localities in northern Italy indicates that the observed Furthermore, this excursion has also been documented
excursions represent an at least Tethys-wide carbon in Pakistan and Oman, which provides additional evi-
isotope signal. dence against a local variation. We suggest that the large
Generally, global variations in carbon isotope ratios isotopic excursion is a result of at least Tethys-wide
of marine sediments can evolve from two processes changes in the carbon cycle, which lead to an extensive
(Magaritz et al., 1992): (1) Changes in the sedimentary removal of organic carbon due to increased bioproductiv-
reservoirs of the carbon cycle and (2) Rate of uptake of ity, probably caused by an increase in phosphate delivery,
13
C-depleted carbon in shallow ocean, and transport and as modelled in Kump and Arthur (1999) and combined
remineralization in the deep ocean. The first mechanism with ocean stratification/anoxia (Woods et al., 1999). If
involves a net flux of carbon from the total organic the isotopic pattern proves to be global, the pelagic
reservoir to the carbonate reservoir, to produce lower Panthalassa Ocean with its frequent black shales
δ13C values and vice-versa. This can be accomplished deposited in the Lower Triassic would be the plausible
by changes in burial or erosion/oxidation rates of or- sink for organic carbon (e.g., Suzuki et al., 1998). Each of
ganic matter relative to the accumulation of Ccarb. The the excursions we found in the Lower Triassic was
second mechanism is based on vertical isotopic frac- produced within one conodont biozone (Baud et al., 1996;
tionation in the ocean, which may occur due to: (I) ocean Farabegoli and Perri, 1998), hinting at quick changes
stratification and the associated decoupling of the shallow similar to the processes that have resulted in the sharp
and deep ocean δ13C trends, or due to: (II) variations in carbon isotope rise of the Late Permian (Magaritz et al.,
bioproductivity in the ocean with depth. Decreasing or 1983) or the Early Carboniferous (Saltzman, 2002).
increasing productivity reduces or raises, respectively, Climatic changes or tectonic events can occur almost
the fractionation of 13 C-enriched surface water and instantaneous on a geological timescale, thus the reported
13
C-depleted deep ocean water (Kump, 1991). Changing isotopic pattern indicates such events may be the causes
burial rates of organic carbon can result from (Baud for paleoenvironmental changes.
et al., 1989): (A) sea level changes, (B) decreased
thermohaline circulation of the ocean and anoxia, and 7. Conclusions
(C) changes in terrestrial and marine productivity of
organic material. A Tethys-wide +6‰ positive δ13C excursion around
For the PTB, currently a combination of anoxia, the Dienerian/Smithian boundary suggests that at this
which already existed in the Late Permian (e.g., Kajiwara time substantial amounts of biomass have again been
et al., 1994; Isozaki, 1997), eruption of the Siberian trap produced after the “faunal collapse” at the PTB. This
basalts (e.g., Renne et al., 1995) and erosion of coal indicates that there was a recovering of the biota already
deposits on the continents and release of methane (e.g., at this time. Given that a recovery has been identified for
Retallack, 1999), in combination with the release of H2S the latest Early Triassic or the beginning of the Middle
(Kump et al., 2005) are proposed to explain the decrease Triassic, one may also hypothesize that the increase of
in δ13C. bioproductivity was independent of faunal recovery and
Through analyses of Th/U ratios in sediments of the mainly resulted from the flourishing of the survivors.
Uomo section, Twitchett and Wignall (1996) had Concurrent ocean stratification led to an uncoupling of
demonstrated low oxygen levels during the Griesbachian the Tethys surface water from deep water during the
and oxic conditions since the lower Seis Member, which Dienerian/Smithian and Smithian/Spathian boundary
they interpreted as indicative of amelioration in the periods causing the positive δ13C peaks, followed by
environment. Holser (1997) had suggested amelioration periods of circulation in the Smithian and Spathian
already for the upper Mazzin Member due to the rising evidenced by low carbon isotope values.
M. Horacek et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 252 (2007) 347–354 353

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