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Palaeogeography, Palaeoclimatology, Palaeoecology 203 (2004) 95^105 www.elsevier.

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Middle Miocene seasonal temperature changes in the Styrian basin, Austria, as recorded by the isotopic composition of pectinid and brachiopod shells
Ana-Voica Bojar a; , Hartmut Hiden a , Alois Fenninger a , Franz Neubauer b
b a Institute of Geology and Paleontology, Karl-Franzens University, Heinrichstrasse 26, A-8010 Graz, Austria Institute of Geology and Paleontology, Paris-Lodron University, Hellbrunnerstrasse 32, A-5020 Salzburg, Austria

Received 28 August 2002; received in revised form 21 August 2003; accepted 22 September 2003

Abstract Using the isotope record on pectinid and brachiopod shells, we reconstructed Middle Miocene palaeotemperatures for a shelf environment in the Styrian basin, Austria. Bivalve shells of Macrochlamys sp., collected from different horizons of the Lower Badenian Leitha limestone, show N18 O values in the range of 33 to 0x (PeeDee Belemnite). The large intrashell variability of 3x indicates significant seawater temperature fluctuation. The results suggest that despite the high geographical latitude (ca. 40N), the climate in southern Austria was warm (subtropical) with a pronounced seasonality at that time. In contrast, the N18 O isotopic composition of a pectinid (Flabellipecten sp.) and an indeterminate terebratulid brachiopod, from the siliciclastic deposits overlying the Leitha limestone, ranges between 0 and 31x. This indicates cooler mean annual temperatures and reduced seasonal variations. A 39 Ar/40 Ar age on fresh volcanic biotites shows a value of 14.2 0.1 Ma. The tuffs containing the biotites are located below the layer containing the terebratulid and the Flabellipecten sp. The stable isotope and radiogenic data suggest that the drop in temperature is in direct relationship with the East Antarctic Ice Sheet expansion, which started at ca. 14 Ma. Due to the variation in temperature, the subtropical fauna in the Retznei quarry disappeared during the Early Miocene and the biogenic limestones were replaced by clastic sediments. The N18 O isotopic profiles from three pectinids collected from the Leitha limestone indicate that these grew within ca. 1.5 years. Growth interruptions occurred during the warm season because during this period the pectinids very likely used their energy for the growth and maturation of gonads. Carbon isotopic compositions vary between 0 and 2x. Statistical tests show that for some of the analyzed shells, the cyclicity of the N13 C profiles may be explained by the temperature-dependent fractionation between air CO2 and dissolved bicarbonate. 2003 Elsevier B.V. All rights reserved.
Keywords: stable isotopes; Styrian basin; Middle Miocene; climate change

1. Introduction
* Corresponding author. Fax: +43-(316)-380-9871. E-mail addresses: ana-voica.bojar@unigraz.at (A.-V. Bojar), alois.fenninger@unigraz.at (A. Fenninger), franz.neubauer@sbg.ac.at (F. Neubauer).

An important interval in the global climatic and cryospheric development of the Cenozoic was the Early to Middle Miocene, from 17 to 12 Ma. The

0031-0182 / 03 / $ ^ see front matter 2003 Elsevier B.V. All rights reserved. doi:10.1016/S0031-0182(03)00662-X

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climatic optimum near the Early/Middle Miocene was followed by global cooling at around 14 Ma, the latter being concomitant with the expansion of the East Antarctica Ice Sheet (Shackleton and Kennett, 1975; Savin et al., 1985; Miller and Katz, 1987; Miller et al., 1991; Woodru and Savin, 1989, 1991; Wright et al., 1992; Flower and Kennett, 1994; Pagani et al., 2000; Billups and Schrag, 2002). Thus, the Middle Miocene is characterized by climatic changes which resulted in a rapid shift from relative high-latitude warmth to high-latitude refrigeration. In this study mollusc and brachiopod shells have been used to evaluate palaeoclimatic parameters for a shelf environment during the Middle Miocene. The studied outcrop, which is stratigraphically well documented, belongs to the Styrian basin. This basin was part of the Paratethys realm, a land-locked remnant sea which formed subsequent to the collision of Europe and Africaderived microplates. When molluscs grow, their shells become biogeochemical recorders of climatic and environmental conditions during their lifetimes. Previous studies have shown that the calcitic shell of pectinids (Arthur et al., 1983; Krantz et al., 1984, 1987; Krantz, 1990; Barrera et al., 1990; Wefer and Berger, 1991; Schein et al., 1991; Jones and Allmon, 1995; Hickson et al., 1999; Hickson et al., 2000) and brachiopods (Lowenstam, 1961; Lepzelter et al., 1983; Mii and Grossman, 1994; Carpenter and Lohmann, 1995; Buening et al., 1998; Picard et al., 1998) are suitable to palaeoclimatic reconstruction, as they secret their skeleton in oxygen isotopic equilibrium with seawater. Because pectinids support little salinity variation (Amler et al., 2000), they are particularly suitable for reconstructing water palaeotemperatures. A radiogenic age of a tu intercalation from the studied outcrop made possible to correlate the evaluated Miocene temperatures and seasonal variations with the interpreted oceanographic changes occurring worldwide at that time. Moreover, the N18 O proles measured on molluscs have been used to evaluate growth rates and to determine the relationship between growth interruption and seasonal variation. The processes that may

have produced the variations in the N13 C proles were also discussed. In this study we have investigated the potential of the oxygen isotope proles along pectinid and brachiopod shells in order to: (1) reconstruct the Middle Miocene climatic changes for a shelf environment situated within the Paratethys realm, and (2) study the link between seasonal temperature variation and life history. 2. Geological situation The Styrian basin, formed during the eastward tectonic extrusion and orogen-parallel extension, is related to the last collisional phase between the Adriatic and the European continental plates (Neubauer and Genser, 1990). There are several published studies concerning the stratigraphy, lithology and palaeogeography of the basin deposits (Ebner and Sachsenhofer, 1991; Rogl, 1998; Gross, 2000; Rogl, 2001). The sedimentation started in Ottnangian times (Early Miocene); the preserved thickness of the deposits reaches ca. 4 km. The Retznei Zementwerk quarry is situated not far away from the border to Slovenia (Fig. 1). The lithology and faunal assemblage have been described by Friebe (1990, 1991) and Fritz and Hiden (2001) and are of Badenian age (for the Paratethys timescale, see Rogl, 1996). From bottom to top, the following lithofacies were found (Fig. 2): (1) sands and silts with marl boulders of Karpathian and/or Badenian age with Gastrochaena and Lithophaga. For this facies Friebe (1991) assumed deposition in a sub- to intertidal environment. (2,3) coral carpets (with Porites, Tarbellastraea, Acanthastraea, Montastraea, Sparidae, Balistidae and shark teeth) with intercalations of sand with crustaceans. (4) algal debris. According to Friebe (1991), lithofacies (2^4) were deposited at a depth above the fair weather-wave base. (5) bioclastic rhodolith limestones with various fossils, e.g. pectinids, oysters, red algae. (6) marly limestone.

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Fig. 1. Geological map of the Styrian basin (after Flu gel and Neubauer, 1984).

(7) sands and silts with molluscs and crabs. At the base of lithofacies (7), a discontinuous tu intercalation was described (Hauser, 1951). The tu contains unaltered phenocrysts of feldspars and fresh biotites, and was deposited during an eruption of one of the volcanic centers situated farther to the east (e.g. Ebner and Sachsenhofer, 1995). The lithofacies levels (5^7) were deposited

at depths less than the storm waves base. For lithofacies (7), an ichnofauna (Ophiomorpha, Scolithos and Planolites) was described by Hiden (1995). This fauna is characteristic of the transition from nearshore to shoreface, and indicates depths around 10 m (Dodd and Stanton, 1990). Facies (1^6) are characterized by the occurrence of various coral fauna. In contrast, this coral fau-

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Fig. 2. Simplied lithostratigraphic section of the Retznei quarry (after Friebe, 1990). M1, M2, M3, F1 and B1 indicate the locations of the analyzed shells.

na is not found in facies (7), but echinoids (Schizaster), crustaceans (Calianassa, Portunus) were found. This change is interpreted as indicating a transition from a subtropical to a temperate faunal assemblage. 3. Materials and methods In this study we analyzed three large calcitic shells of Macrochlamys sp., one shell of Flabellipecten sp. and one of an indeterminate terebratulid collected from dierent horizons of the outcrop (Fig. 2). Macrochlamys, Flabellipecten and the terebratulid were benthic organisms. The pectinid shells consist of an external foliated layer, an in-

Fig. 3. Internal structure of the Macrochlamys shell. All the samples were taken from the outer foliated layer, along the dorso-ventral axis.

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termediate ne crystalline layer and an internal foliated layer (Watabe, 1988). Study of thin sections under polarized light shows preservation of the internal structure of the pectinid shells (Fig. 3). Microbeam analyses indicate that all measured shells consist entirely of low-magnesium calcite, implying that the primary mineralogical composition has been preserved. Cathodoluminescence may also serve as an indicator of eventual alteration because the manganese content, the common activator of luminescence in calcite, increases as skeletal carbonates are diagenetically altered (Brand and Veizer, 1980). Thin sections of the studied shells show no luminescence. For these reasons, we consider that the eect of diagenesis was minimal and that the data can be used for palaeoclimatic reconstruction. Samples of powdered shell of Macrochlamys sp. (M1, M2, M3), Flabellipecten sp. (F1) and the terebratulid (B1) were analyzed for N18 O and

N13 C. The shells were sequentially sampled along the dorso-ventral axis (average sample separation 1.5^2 mm) using a 0.5-mm drill bit. Isotopic analyses were performed using an automatic Kiel II preparation line and a Finnigan MAT Delta Plus Mass Spectrometer. NBS-19 and an internal laboratory standard were analyzed continuously for accuracy control. Standard deviation was 0.1x for both N18 O and N13 C. All isotopic results are reported in per mil, relative to the PeeDee Belemnite (PDB) standard. The 40 Ar/39 Ar laser-ablation technique was applied to several fresh grains of biotite phenocrysts from the tu level (sample AVB-2). The technique is described in detail by Liu et al. (2001). The biotite concentrate of sample AVB-2 records a plateau age of 14.2 0.1 Ma. Neither extraneous argon nor disturbances of the age pattern were detected. The age is therefore considered to be geologically signicant, recording the age of the volcanic eruption.

Fig. 4. Oxygen and carbon isotopic proles from the Macrochlamys (M1, M2 and M3) external shell surface. The calculated temperatures are displayed for each measured prole. For M1, two parallel proles were measured.

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4. Results The resulting N18 O and N13 C values are plotted on the y-axis against shell length from the origin of growth (Figs. 4 and 5). The N18 O values of M1, M2 and M3 show cyclical patterns ranging between approximately 33.5 to 0x. The N13 C values in the shells range between 0 to 2.2x. To test the reliability of the data, two dierent proles for M1 were measured along the dorso-ventral axis. Except for the umbo region, the results for the two proles are very similar. For F1 and B1, the N18 O values range from 31 to 0%, and the N13 C values from 0.5 to 2.2x.

5. Discussion and conclusions 5.1. Oxygen isotope proles Previous studies have shown that pectinids grown in various climatic settings, such as tropical and subtropical (Jones and Allmon, 1995; Hickson et al., 2000), temperate (Krantz et al., 1987; Hickson et al., 1999) and Antarctic (Barrera et al., 1994) climates, precipitating their shells in equilibrium with the seawater. Moreover, pectinids as well as brachiopods populate only environments with little salinity variation. Consequently, when their shells are not diagenetically altered, the N18 O

Fig. 5. Oxygen and carbon isotopic proles from the indeterminate terebratulid (B1) and Flabellipecten (F1) external shell surface. The calculated temperatures are displayed for the measured prole.

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values of calcite can be interpreted in terms of seasonal changes in water temperatures, with lower values of calcite representing summer and higher values winter conditions. For M1, M2 and M3 abrupt variations of N18 O values can be observed in the umbo region. These may be related to vital eects and disequilibrium during the early, fast growth period of the shells (Wefer and Berger, 1991). Palaeotemperatures were calculated using the equation of ONeil et al. (1969) for the water^calcite system. Taking into account that at that time Paratethys was related to the oceanic domain, and that within the Styrian realm there was no massive freshwater input, we assume an interglacial value of 30.7x for the N18 O value of water (Lear et al., 2000). Excluding the umbo region, the calculated temperatures range between approximately 13 and 26C and indicate a subtropical environment and strong seasonal variations. Previous studies have shown that for temperate regions, growth cessations, marked by prominent rings on the shell surface, occur during the cold season (Tan et al., 1988; Dare and Deith, 1991; Hickson et al., 2000). The studied Macrochlamys shells show that growth began during the warm season, and that growth interruptions on the external surface were associated with the next warm season (Fig. 4). The growth interruptions are likely related to the warm season because during this period the pectinids used their energy for the growth and maturation of gonads (Amler et al., 2000 ; Mandic, pers. commun.). Ansell (1968) has shown that temperature is the major factor controlling metabolism and hence growth rate of pectinids. If the cycle in oxygen isotopes reects growth rate, then the pectinid shells analyzed in this study reached their preserved length within approximately 1^2 years. This is faster than the growth rate determined for modern sea pectinids from temperate regions (Krantz et al., 1984; Schein et al., 1991), but ts with growth rates determined by Jones and Allmon (1995) for a ca. 3-Ma-old Carolinapecten arboreus from a subtropical environment. At about 14 Ma, a signicant change in the N18 O value of the ocean occurred due to a major widespread of the Antarctic Ice Sheet. Following Lear et al., 2000, for calculating the temperature

distribution for F1 and B1, we assumed a 30.1x value of water. In this case, the temperatures calculated from the N18 O isotopic proles across both F1 and B1 show lower values, between 15 and 19C and reduced seasonal temperature variation (Fig. 5). The data indicate change in the annual temperature distributions across, below and above the tu level. Radiogenic dating of the tu layer situated in the uppermost part of the marly limestone layer makes it possible to correlate this climatic shift with the worldwide palaeoceanographic events of that time. 39 Ar/40 Ar dating of the fresh biotites gives a plateau age of 14.2 0.1 Ma. The position of this sample is within the clastic deposits, just below the sand layers where the Flabellipecten sp. and the terebratulid come from. The radiogenic data t well with the beginning of the spread of the Antarctic Ice Sheet, for which an age of ca. 14 Ma has been assumed (Shackleton and Kennett, 1975; Savin et al., 1985; Billups and Schrag, 2002). Thus, we consider that the shift from a subtropical climate to much cooler annual temperatures, as well as the shift from biogenic carbonates to the dominantly clastic deposits, are related to the widespread of the East Antarctica Ice Sheet. This event constituted one of the major palaeoceanographic events of Miocene times. 5.2. Carbon isotope proles The N13 C values of brachiopods and molluscs are usually similar to those of ambient dissolved inorganic carbon (DIC), but cases of N13 C depletion also occur (Epstein et al., 1952; Craig, 1953; Mook, 1971). These depletions, due to skeletal incorporation of respired CO2 into the shell skeleton, are related to metabolic activities (Aharon, 1991; Wefer and Berger, 1991; Tanaka et al., 1986; Krantz et al., 1987). More recent studies (McConnaughey et al., 1997; Hickson et al., 1999) have shown that aquatic invertebrates using respiration incorporate little respired CO2 into their shells. However, this issue is still under discussion (Owen et al., 2002). Thus, for this group of organisms, the N13 C values of the shells are primarily controlled by the N13 C of DIC, and secondary by the metabolic rates.

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Fig. 6. Calculated vHCO3 ^CO2 values and the N13 C values measured along shells. 3

For marine waters, the main inorganic dissolved carbon species is HCO3 , the occurrence 3 of dissolved CO2 being subordinate. Thus, the N13 C values of shells will reect the N13 C composition of dissolved HCO3 . The calcite^bicarbon3 ate fractionation is not temperature-dependent for

carbon (Romanek et al., 1992), but the isotope fractionation between dissolved HCO3 and air 3 CO2 is temperature-dependent (Mook, 1974). For the analyzed shells, the amplitude of temperature-dependent vHCO3 -CO2 values t the am3 plitude of N13 C values measured in calcite (Fig. 6).

Table 1 Statistical tests of the correlation between the vHCO3 ^CO2 variation and the N13 C values measured along shells 3 Sample M1 M2 M3 B1 F1 Number of measurements 52 70 55 15 16 Pearson correlation P 6 0.001 Cor = 0.81 P = 0.06 Cor = 0.22 P = 0.01 Cor = 0.37 P = 0.05 Cor = 0.52 P = 0.33 Cor = 0.27 Spearman correlation P 6 0.001 Cor = 0.82 P = 0.83 Cor = 0.02 P = 0.06 Cor = 0.25 P = 0.06 Cor = 0.5 P = 0.34 Cor = 0.26

P = P-value; Cor = correlation coecient

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Moreover, some of the N13 C proles show cyclicity, in phase with the N18 O values. Therefore, for temperatures calculated using the calcite thermometer, we have statistically tested the presence of the correlation between the calculated vHCO3 ^CO2 and the measured N13 C values 3 along the shells, using both the Pearson and Spearman tests (Table 1). The data indicate that for M1, M3 and B1 there is a correlation between the two data sets. In this case the cyclical uctuation of the N13 C values of calcite may be explained considering the temperature-dependent fractionation between dissolved HCO3 and air CO2 . Rel3 atively low water depths and a favorable mixing of waters may have favored the seasonal equilibration between CO2 and HCO3 as well. For M2 3 and F1 the correlation between the two data sets is poor, most probably due to local, seasonal events which can be poorly documented. Acknowledgements Financial support for this study was provided by FWF Project 13029-Geo. V. Atudorei, Z.D. Sharp (Albuquerque) and F. Vaida (Harvard) are thanked for interesting discussions and comments. The authors wish to acknowledge O. Mandic (Wien) and W. Piller (Graz) for useful advice into the biology of molluscs. We thank also J. Hickson and A. Longinelli for constructive comments that greatly improved the manuscript. Angela Poly is thanked for general text revisions. References
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