Early Jurassic carbon and oxygen isotope records and seawater temperature variations: Insights from marine carbonate and belemnite rostra (Pieniny Klippen Belt, Carpathians)

    Early Jurassic carbon and oxygen isotope records and seawater temperature variations: Insights from marine carbonate and belemnite rostra (Pieniny Klippen Belt, Carpathians) Agnieszka Arabas, Jan Schl¨ogl, Christian Meister PII: DOI: Reference:

S0031-0182(16)30921-X doi:10.1016/j.palaeo.2017.06.007 PALAEO 8323

To appear in:

Palaeogeography, Palaeoclimatology, Palaeoecology

Received date: Revised date: Accepted date:

22 December 2016 6 June 2017 11 June 2017

Please cite this article as: Arabas, Agnieszka, Schl¨ogl, Jan, Meister, Christian, Early Jurassic carbon and oxygen isotope records and seawater temperature variations: Insights from marine carbonate and belemnite rostra (Pieniny Klippen Belt, Carpathians), Palaeogeography, Palaeoclimatology, Palaeoecology (2017), doi: 10.1016/j.palaeo.2017.06.007

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ACCEPTED MANUSCRIPT Early Jurassic carbon and oxygen isotope records and seawater temperature variations: Insights from marine carbonate and belemnite rostra (Pieniny Klippen Belt, Carpathians)

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Agnieszka Arabasa , Jan Schl¨oglb , Christian Meisterc a Institute

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of Geological Sciences, Polish Academy of Sciences, Research Centre in Krak´ ow, ul. Senacka 1, 31-002 Krak´ ow, Poland of Geology and Paleontology, Faculty of Natural Sciences, Comenius University in Bratislava, Mlynsk´ a dolina, Ilkoviˇ cova 6, SK-842 15 Bratislava, Slovakia c Department of Geology and Paleontology, Natural History Museum of Geneva, 1 Rte de Malagnou, CP 6434, 1211 Geneva 6, Switzerland

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b Department

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Abstract

New carbon and oxygen isotope records and discussion of the main variations in seawater temperature

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through the Sinemurian–Aalenian of the Pieniny Klippen Basin (northern Tethys Ocean) are presented herein. Comparison of the recorded changes in stable-isotope compositions of bulk carbonate and belemnite rostra from

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an open-marine environment with previously documented, predominantly restricted epicontinental data enables determination of major climatic events that were most likely of worldwide extent. A slight positive δ 13 C shift

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is recorded in the lowermost Upper Pliensbachian. A significant positive excursion in carbonate carbon isotope values is documented in the Lower Toarcian Serpentinum Zone. Furthermore, the δ 13 C values display a falling

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trend in the Lower–Upper Toarcian and relatively constant values in the Aalenian. Temperatures inferred from the δ 18 O values of well-preserved belemnite rostra (10–13 ◦ C) suggest rather cool seawater conditions in the Pieniny Klippen Basin during the Late Sinemurian, warming by 4 ◦ C in the Early Pliensbachian and then cooling by 8 ◦ C in the Late Pliensbachian. The seawater temperature rose once more in the Early Toarcian and began to fall again during the Middle Toarcian. In the Middle–?Late Aalenian, seawater temperatures oscillated between 10 and 13 ◦ C.

Keywords: palaeoclimate, palaeoenvironment, stable isotopes, elemental ratios, Tethys Ocean

1. Introduction Evolution of the Early Jurassic environment is of particular interest to palaeoclimatologists due to cyclic changes from icehouse to greenhouse conditions, striking carbon cycle perturbations, prominent mass extinction, the Central Atlantic and Karoo-Ferrar large igneous provinces activity and progressive disintegration of the 1 E-mail

address: [email protected]

Preprint submitted to Palaeogeography, Palaeoclimatology, Palaeoecology

June 12, 2017

ACCEPTED MANUSCRIPT Pangea supercontinent. The Early Jurassic world witnessed a series of global and regional events which attract attention of researchers. In the Early Toarcian, storage of organic matter in marine sediments led to positive carbon isotope excursion (Jenkyns et al., 2002; Jenkyns, 2010; Izumi et al., 2012) which is interrupted by a

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prominent negative shift and coincides with an extensively studied Toarcian Ocean Anoxic Event (TOAE; e.g., Hesselbo et al., 2000a; McArthur et al., 2000; Bailey et al., 2003; Hesselbo et al., 2007; Suan et al., 2008, 2010; Hesselbo and Pie´ nkowski, 2011; Hermoso et al., 2012; Harazim et al., 2013; Kemp and Izumi, 2014; Suan et al.,

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2015; Korte et al., 2015; Bodin et al., 2016). The TOAE is preceded by three negative carbon isotope excursions (CIE): 1) in the Upper Sinemurian (e.g., van de Schootbrugge et al., 2005a; Riding et al., 2013; Masetti et al.,

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2016), 2) at the Sinemurian–Pliensbachian boundary (e.g., Jenkyns et al., 2002; Suan et al., 2010; Korte and Hesselbo, 2011; G´ omez et al., 2016) and 3) at the Pliensbachian–Toarcian boundary (e.g., Hesselbo et al., 2007;

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Littler et al., 2010; Gr¨ ocke et al., 2011; G´omez et al., 2016; Bodin et al., 2010, 2016; Ait-Itto et al., 2017). Recently published data show positive δ 13 C excursion in the Upper Pliensbachian corresponding to the Late

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Pliensbachian Event (Dera et al., 2009; Suan et al., 2010; Korte and Hesselbo, 2011; Silva and Duarte, 2015; Korte et al., 2015; Ruhl et al., 2016). Palaeotemperature records based on calcite fossil oxygen isotope data

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indicate warm periods in the Late Sinemurian (G´omez et al., 2016), Early Pliensbachian (Suan et al., 2010; G´omez et al., 2016) and in the Early Toarcian (McArthur et al., 2000; Rosales et al., 2004a; Dera et al., 2009),

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while a cooler phase occurred in the Late Pliensbachian (van de Schootbrugge et al., 2005a; Dera et al., 2009; Korte and Hesselbo, 2011; G´ omez et al., 2016). We studied five sections of the Pieniny Klippen Belt (PKBt) in the Slovakian and Ukrainian parts of the Carpathians to document the timing and magnitude of the Early Jurassic environment changes (Figs. 1–6). In contrast to most of previously published data, our results are based on deposits from the open-marine Pieniny Klippen Basin (PKBn) of the northern Tethys. This is a rare and valuable source of information on palaeoenvironment where local factors had limited significance. New, high-resolution δ 13 C data of bulk carbonate from the Sinemurian–Aalenian interval, together with δ 13 C and δ 18 O data from well-preserved belemnite rostra, contribute to regional and global reconstructions of the Early–Middle Jurassic climate. Furthermore, the presented data supplement the previously published studies of carbonates from the Middle–Upper Jurassic of the PKBt (Arabas, 2016).

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ACCEPTED MANUSCRIPT 2. Geological Setting Rock samples and belemnite rostra were collected from three outcrops in the PKBt (Fig.1). Three studied

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sections crop out in an active quarry in the Priborzhavske village in western Ukraine (also known as ”Pri-

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ˇ borzhavskoye”). The other two are located in the Slovakian part of the PKBt – on the slope of the Cerven´ y Kameˇ n Klippe in the Podbiel village and in the abandoned quarry near the Beˇ natina village (Fig.1). The Pri-

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borzhavske succession was deposited in the shallowest environment whereas the Podbiel succession was formed in the deepest one (Figs. 2–6).

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2.1. The Priborzhavske outcrop

The Priborzhavske quarry is located approximately 17 km east of the Irshava, in the western Ukraine

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(48◦ 19’02”N 23◦ 02’15”E; Fig. 1). Deposits cropping out in the quarry consist of two overthrusted tectonic units. The studied sediments of the lower unit are exposed in the south-western part of the quarry and con-

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tain the Lower–Upper Jurassic and the Upper Cretaceous (Wierzbowski et al. 2012; see also Slavin et al. 1967; Kalinichenko and Kruglov 1969, 1971; Kruglov 1971). The second unit consists of deposits of the Mid-

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dle Jurassic–Lower Cretaceous (Wierzbowski et al., 2012). Samples for stable isotope analyses were collected from three sections: Lower Sinemurian (Bucklandi–Turneri zones), Upper Sinemurian–Upper Pliensbachian

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(?Obtusum–Margaritatus zones) and Lower–Upper Pliensbachian (Ibex–Spinatum zones; Figs. 2–4). The deposits consist of the fleckenkalk/fleckenmergel facies of the Perechinska Formation dated the Sinemurian–earliest Late Pliensbachian (Slavin et al., 1967) and highly diversified sediments of the uppermost Pliensbachian– Aalenian Priborzhavska Formation (Slavin et al., 1967; Kruglov, 1971).

2.1.1. Priborzhavske section A The section consists of grey to yellowish micritic to fine-grained spotted limestones and yellow, grey and black marls and marlstones (∼ 9 m; Fig. 2). Some beds contain ammonites, oysters (Gryphea), brachiopods, bivalves, pyrite and/or are bioturbated. These sediments are Early Sinemurian in age (Bucklandi–Turneri chrons).

2.1.2. Priborzhavske section B Grey-greenish spotted marly limestones and intercalations of dark marls (∼ 6 m), which are Late Sinemurian in age (?Obtusum–Raricostatum chrons), are exposed at the base of this section (Fig. 3). They are succeeded by the Lower Pliensbachian (Jamesoni Zone, Taylori-Jamesoni subzones and lowermost Ibex Zone, Masseanum Subzone) grey marls and marly limestones with yellowish patina (∼ 3.5 m). These deposits are overlain by 3

ACCEPTED MANUSCRIPT discontinuous grey-greenish biostrome up to 1 m thick with silicisponges, ammonites, belemnites, brachiopods, gastropods and bivalves, dated to the Ibex-lowermost Margaritatus zones of the Lower–Upper Pliensbachian. The highest part of the section contains dark grey, fine-grained limestones and dark marls (sometimes with sandy

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admixtures) and lenses of grey-greenish spotted limestones of the Upper Pliensbachian Margaritatus Zone. 2.1.3. Priborzhavske section C

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The section begins with the Lower Pliensbachian (Ibex Zone) micritic limestone bed. It is overlain by grey-greenish spotted micritic to fine-grained limestones and grey marls of the Lower and Upper Pliensbachian

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(Ibex to Margaritatus zones; Fig. 4). Higher in the sequence occur grey, fine-grained spotted limestones and grey marls (∼ 6 m) with rare pyrite concretions and crinoidal limestone intercalations in the highest part.

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These deposits are Late Pliensbachian in age (Margaritatus–?Spinatum chrons). Trace fossils of ichnogenera Chondrites, Diplocraterion and Scolithos are observed in some beds within the Margaritatus Zone. The highest

Pliensbachian Spinatum Zone.

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2.2. The Podbiel section

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part of the section contains greenish and red marls with crinoidal limestone beds and nodules of the uppermost

ˇ This outcrop is situated on the east side of the Cerven´ y Kameˇ n Klippe (the east part of the Oravsk´a Magura

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Mts.), approximately 0.5 km NE of Podbiel railway station (49◦ 18’15.0”N 19◦ 28’42.9”E). The klippe consists of Upper Sinemurian–Lower Cretaceous deposits in an overturned position (Andrusov, 1931, 1938; Haˇsko, 1978; Borza et al., 1994; Schl¨ ogl et al., 2006). The studied portion of the succession is a part of the Adnet Formation (Fig. 5) and begins with beds of red marls and red marly limestones, some of which are nodular. These sediments (∼ 0.8 m) are Early Pliensbachian in age (Davoei Chron). Higher in the sequence occur red marls and red limestones with greenish spots (∼ 2.3 m) of the Upper Pliensbachian Margaritatus Zone. The lower Spinatum Zone of the uppermost Pliensbachian in Podbiel consists of grey-greenish marls and marly limestones in the lower part (∼ 0.8 m) and grey-greenish cherty limestones in the upper part (∼ 1.8 m). The lowermost part (∼ 0.3 m) of overlying reddish cherty limestones and marls are also Late Pliensbachian in age (Spinatum Chron). Beds of red marls and limestones lying above (some of these are cherty or crinoidal; ∼ 1.8 m) belong to an interval of uncertain stratigraphy where no ammonites were found. A hardground surface with Fe-crusts and concretions is recognised on the top of these deposits. Higher in the sequence there are red marls and red marly limestones (∼ 2.5 m) of the Lower–Middle Toarcian (Serpentinum–Variabilis zones). The red marly limestones lying above are most likely Toarcian, but no particular ammonites have been found in these beds. 4

ACCEPTED MANUSCRIPT 2.3. The Beˇ natina section The Beˇ natina quarry is situated approximately 2 km east of Beˇ natina village (48◦ 48’22.6”N 22◦ 19’14.0”E),

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on the NE margin of the Vihorlat Mts. The studied section is exposed in the NE part of the abandoned

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quarry and comprises ?Upper Pliensbachian–?Upper Aalenian (?Spinatum–?Concavum zones) sediments in an overturned position. The studied part of the section (Fig. 6) begins with grey marly limestones and grey marls of the Allg¨au Formation (∼ 0.4 m) of the Spinatum–?Tenuicostatum zones. The overlying Hˆorka Formation

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(∼ 2.2 m) consists of greenish and dark grey marly crinoidal and sandy limestones with brownish patina and

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intercalations of grey and green marls. The upper part of the formation contains laminated micritic limestones rich in fish bones. The deposits of the Hˆ orka Fm. did not yielded any ammonites, except for its topmost

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bed (Tenuicostatum or Serpentinum Zone). Schl¨ogl et al. (2004) suggest the presence of a condensation or a stratigraphic gap in the uppermost part of the Hˆorka Fm. based on mixed ammonite association of several ammonite zones, ammonites with green-coating signs of condensation, pyrite framboids and the sudden change

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in lithology. Overlying H´rbok Formation (∼ 4.3 m) consists of red marls with thin beds of red marly limestones and sandy marlstones with numerous Fe-Mn concretions, dated to the Lower–Upper Toarcian (Serpentinum–

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Pseudoradiosa zones) with probable stratigraphic gap between Bifrons and Pseudoradiosa zones. Accumulation of the Fe-Mn concretions and corroded ammonite molds on the top of the H´rbok Fm. mark a hardground

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surface. These deposits are separated from the overlying variable marly-crinoidal limestones by a fault. These limestones are yellow and green at the base, becoming grey and yellowish with quartz admixture and with alternations of grey crinoidal marls and marlstones. The crinoidal deposits mark the ?Lower–?Upper Aalenian (?Opalinum–?Concavum zones). Although the entire marly-crinoidal limestone formation, named ”Member A”, attains at least 30 m, only the first ∼4.3 m was studied for bulk rock isotope composition because the high concentration of crinoids in the crinoidal limestones which reveal significant vital offsets from isotope equilibrium and variance in the isotope composition at higher taxonomic levels (e.g., Weber, 1968; Baumiller, 2001; Gorzelak et al., 2012).

3. Biostratigraphy The chronological scale of our study is constrained to the ammonite zone or subzone level and the discussion follows this level of precision. A zone or subzone is defined at its base by a marker, in our case a characteristic ammonite or an ammonite association.

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ACCEPTED MANUSCRIPT 3.1. The Priborzhavske sections The Lower Sinemurian–Upper Pliensbachian fauna of the Priborzhavske sections is of Euroboreal palaeo-

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geographical affinity. The ammonite units, based on the index taxa, are correlated with the standard biostrati-

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graphical zonation (e.g., Dean et al., 1961; Mouterde and Corna, 1997; Corna et al., 1997; Dommergues et al., 1997). The Angulata Zone of the Upper Hettangian is evidenced by Schlotheimia ammonites found ex situ. The presence of Arietites and Coroniceras indicates the upper part of the Lower Sinemurian Bucklandi Zone.

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Furthermore, the Pararnioceras and Arnioceras indicate a greater interval including a part of the Bucklandi

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and Semicostatum zones, except in its upper part. Caenisites is the index genus of the Turneri Zone and the presence of Asteroceras and Eparietites genera found ex situ indicates the middle–upper part of the Upper

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Sinemurian Obtusum Zone. The Oxynotum Zone is documented entirely by Oxynoticeras ssp and the presence of Crucilobiceras, Echioceras, Leptechioceras and Paltechioceras indicates the Upper Sinemurian Raricostatum Zone.

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The Sinemurian–Pliensbachian boundary in Priborzhavske is defined by the presence of the last Sinemurian representatives of the genus Paltechioceras (P.insigne Trueman and William) and the first index species for

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the base of the Pliensbachian, Tetraspidoceras quadrarmatum (Dumortier). The Lower Pliensbachian Jamesoni Zone is revealed by the presence of Platypleuroceras, Polymorphites, Uptonia and Coeloceras. Several species of

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the Tropidoceras, Acanthopleuroceras and Beaniceras genera are characteristic of the Ibex Zone. Only the lower part of the Davoei Zone (upper Lower Pliensbachian) is apparent in the presence of ammonites from Aegoceras s.s. genus. Several Amaltheus species indicate the presence of the Upper Pliensbachian Margaritatus Zone and Arieticeras determines its upper part. The Spinatum Zone contains some Pleuroceras which mainly indicate its lower-middle part. The Toarcian part of the succession, although rich in ammonites, is extremely condensed and consists of only a few tens of cm of yellowish to reddish limestones, in some places reduced to zero. Thus, the Upper Pliensbachian strata are directly overlain in some places by Bajocian limestones. Due to the strong condensation and mixing of ammonites from different stratigraphical intervals (cf. Wierzbowski et al., 2012), this part of the succession was excluded from geochemical analyses.

3.2. The Podbiel section Ammonite zones and subzones of the Lower Pliensbachian up to the Middle Toarcian are documented in the Podbiel section (biostratigraphy sensu Dommergues et al. 1997 and Elmi et al. 1997). Ibex and Davoei zones of 6

ACCEPTED MANUSCRIPT the Lower Pliensbachian are recognized from the presence of Tropidoceras, Liparoceras and Aegoceras species. Various Amaltheus, Protogrammoceras and Arieticeras species indicate the Upper Pliensbachian Margaritatus Zone and this fauna is followed by Pleuroceras ammonites in the Spinatum Zone. At least the upper part

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of the Lower Toarcian Serpentinum Zone is documented by the various Harpoceras and Hildaites species. In addition, numerous Hildoceras enabled distinction of the Middle Toarcian Bifrons Zone. These ammonites are accompanied by Nodicoeloceras and Frechiella. Finally, the Variabilis Zone is indicated by Pseudopolyplectus

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bicarinatus (Zieten) and Phymatoceratinae (Denckmania and/or Haugia respectively).

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3.3. The Beˇ natina section

Ammonite zones of the Upper Pliensbachian up to the ?Upper Aalenian are documented in the Beˇ natina sec-

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tion (see Schl¨ogl et al. 2004 for an overall view on the entire succession). The association of different Pleuroceras species indicate the Upper Pliensbachian Spinatum Zone. Scarce ammonites from the genus Dactylioceras in the

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overlying beds can occur in both of the Spinatum and the Tenuicostatum zones (e.g. Rak´ us, 1995; Rulleau et al., 2013). The Lower Toarcian Tenuicostatum Zone is indicated only by Dactylioceras (Orthodactylites) semicela-

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tum. The Serpentinum Zone is documented by various Dactylioceras, Harpoceras and mainly Hildaites species. Various Hildoceras species accompanied by Frechiella and some dactylioceratids indicate the Middle Toarcian

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Bifrons Zone. The Upper Toarcian Pseudoradiosa Zone is documented only by rare Dumortieria and the Middle Aalenian Murchisonae Zone is evidenced by juvenile ammonites of Brasilia and Ludwigia genera. Although the Opalinum Zone was not documented by ammonites, Graphoceras prove the Upper Aalenian Concavum Zone in the upper part of Member A crinoidal limestones (see Schl¨ogl et al., 2004).

4. Palaeogeography The earliest stage of PKBn evolution remains unknown. The oldest well-documented PKBt deposits are Hettangian–Sinemurian in age. However, occurrences of exotic pebbles of Triassic pelagic limestones have been reported in the adjacent Cretaceous–Palaeogene flysch by Birkenmajer (1988) and Birkenmajer et al. (1990). This led these authors to suggest Triassic opening of the PKBn. There is also a hypothesis concerning the existence of an embayment of the Vardar—Transylvanian Ocean between the Tisa block and Moesian—Eastern European Platform (S˘ andulescu, 1988) where Triassic limestones could have been deposited (Golonka et al., 2003; Krobicki et al., 2003a).

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ACCEPTED MANUSCRIPT According to Wierzbowski et al. (2012), deposition of the uppermost Pliensbachian–Aalenian sediments in the PKBn may be related to the rifting phase that took place at that time and was distinguished as the Dev´ın phase (Plaˇsienka, 2003). Although this phase is recognised in the Carpathian basins situated south of the PKBn,

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it has not been documented from the Czorsztyn succession in the northernmost PKBn. The lithology of the uppermost Pliensbachian–Aalenian deposits cropping out in Beˇ natina and Priborzhavske is rather similar to that of coeval sediments from the central and western parts of the PKBt in Poland and Slovakia. These two

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facts inspired some authors to conclude that the studied Priborzhavske and Beˇ natina sediments developed in the southern part of the basin (Krobicki et al., 2003b; Schl¨ogl et al., 2004; Wierzbowski et al., 2012). However,

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there remains contrasting opinion that discussed succession is typical for the drowned carbonate platforms and that it developed as a different lithological type of the Czorsztyn succession (see discussion in Schl¨ogl et al.,

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2004; Wierzbowski et al., 2012).

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5. Materials and Methods

Carbon and oxygen isotope composition analyses were performed by cold-cathodoluminescence microscopy

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on 151 belemnite rostra. Identified well-preserved belemnite specimens belong to Acrocoelithes, Hibolithes, Orthobelus, Passaloteuthis, Parapassaloteuthis and Pseudohastites genera. Poorly preserved rostra which revealed

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orange to red luminescence were rejected and the remaining were cleaned with a micro-drill removing sediments, external rims, apical line infillings and even small luminescent fragments. Clean, non-luminescent belemnites fragments were powdered and homogenised to avoid seasonal variations and to obtain average isotope values. Samples were then submitted to trace-element and stable isotope analyses. The Ca, Fe, Mg, Mn and Sr concentrations were determined using the Inductively Coupled Plasma - Optical Emission Spectrometer (ICP-OES) in the Central Chemical Laboratory of the Polish Geological Institute - National Research Institute in Warsaw, Poland. Since diagenetic alteration commonly causes an increase in Mn and Fe as well as a decrease in Sr contents in marine calcite (Veizer, 1974, 1983; Marshall, 1992; Ullmann and Korte, 2015), only samples with low content of iron (Fe < 200 pm) and manganese (Mn < 100 ppm) and high concentration of strontium (Sr > 900 ppm) were used for isotope analyses (cf. Price, 2010; Wierzbowski et al., 2013; Wierzbowski, 2015). Furthermore, carbon isotope composition analyses were performed on 593 bulk carbonate samples. In order to avoid diagenetic overprint, only micritic carbonates with mudstone or wackestone texture were analysed. Recrystallized areas, veins, bioclasts and other allochems were systematically avoided. A state of preservation of bulk carbonate samples was additionally verified by correlation between their δ 18 O and δ 13 C values. A strong 8

ACCEPTED MANUSCRIPT correlation (r > 0.5) may suggest diagenetic changes (cf. Banner and Hanson, 1990; Marshall, 1992). Therefore, bulk samples with r > 0.5 were treated as altered. The bulk carbonate samples from all investigated sections indicate no significant correlation between δ 18 O and δ 13 C (r = 0.01–0.44; see supplementary materials to this

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paper).

Selected bulk and belemnite samples were reacted with 100% H3 PO4 at 70 ◦ C in an online, automated carbonate reaction device (Kiel IV) connected to a Finnigan Mat Delta Plus mass spectrometer at the Institute

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of Geological Sciences, Polish Academy of Sciences in Warsaw, Poland. Isotope ratios were referenced to NBS19 standard (δ 13 C = +1.95 ‰, δ 18 O = –2.20 ‰). Reproducibility for δ 13 C and δ 18 O measurements was <0.1‰.

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Carbon and oxygen isotope ratios are reported in delta (δ) notation in per mil relative to the Vienna Pee Dee Belemnite international standard (VPDB).

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The oxygen isotope composition of belemnite rostra is applied to calculations of seawater palaeotemperature by an equation of Anderson and Arthur (1983):

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T (◦ C) = 16.0 − 4.14(δcalcite − δwater ) + 0.13(δcalcite − δwater )2

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6. Results

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leton and Kennett, 1975).

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The accepted δwater value is –1 ‰ SMOW (Standard Mean Ocean Water) as specific for ice-free Earth (Shack-

6.1. δ 13 C values

The measured values of carbon isotope composition of the bulk carbonate (δ 13 Ccarb ) range from –8.7 to +4.1 ‰ VPDB in the entire investigated interval (Figs. 2–6). While the lowest δ 13 Ccarb values are recorded in the uppermost Lower Sinemurian (Turneri Zone; Fig. 2) and the Upper Sinemurian (?Obtusum–Raricostatum zones) of the Priborzhavske section B (Fig. 3), the highest values are recorded in the Lower Toarcian of the Beˇ natina section (Serpentinum Zone; Fig. 6). The δ 13 Ccarb values increase from approximately –7 ‰ up to 0 ‰ in the Bucklandi Zone and show a decreasing trend in the upper part of the Lower Sinemurian reaching -8.5 ‰ in the Turneri Zone (Fig. 2). There is a subsequent increase to -0.3 ‰ in the Upper Sinemurian Raricostatum Zone and then a rapid decrease to –8.7 ‰ (Fig. 3). The δ 13 Ccarb values systematically increase in the remainder of the Upper Sinemurian to approximately +1 ‰ at the Sinemurian–Pliensbachian boundary (Fig. 3). In the Pliensbachian, carbon isotope values continue to rise to +2 ‰ in the lower Margaritatus Zone of the Priborzhavske section B (Fig. 3); to 9

ACCEPTED MANUSCRIPT +1.8 ‰ in the Margaritatus Zone of the Priborzhavske section C (Fig. 4), and to +2.6 ‰ in the Podbiel section’s Margaritatus Zone (Fig. 5). The δ 13 Ccarb values oscillate between +1 and +2.5 ‰ for the reminder of the Margaritatus Zone and a lower part of the Spinatum Zone (Figs. 4, 5) and increase to +2.3 ‰ in the upper

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Spinatum Zone of the Priborzhavske section C (Fig. 4). Further increase is observed in the Lower Toarcian Serpentinum Zone of the Podbiel and Beˇ natina sections (Figs. 5, 6), where the δ 13 Ccarb values reach +3.9 and +4.1 ‰, respectively. After this positive carbon isotope excursion, the δ 13 Ccarb values decrease throughout the

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rest of the Lower and the Middle Toarcian to approximately +2 ‰. This fall is noted in the Podbiel and the Beˇ natina sections (Fig. 5, 6). In the Lower–Middle Aalenian (?Opalinum–Murchinsonae zones), the δ 13 Ccarb

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values remain relatively constant, between +1 and +2 ‰ (Fig. 6) and show a weak positive trend at the Middle and Upper Aalenian boundary (Fig. 6).

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The measured carbon isotope values of belemnite rostra (δ 13 Cbel ) range from –0.8 to +3.2 ‰ VPDB in the entire investigated interval (Figs. 3, 4, 6). The δ 13 Cbel values are scattered. In the Priborzhavske section

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B (Fig. 3), the carbon isotope values of well-preserved belemnite rostra range between –0.8 and +1.6 ‰ in the uppermost Sinemurian Raricostatum Zone. In the same section, the δ 13 Cbel values vary between 0 and

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+0.8 ‰ in the Jamesoni Zone and between +0.1 and +2.8 ‰ in the Pliensbachian Ibex–Margaritatus zones. In the Upper Pliensbachian Margaritatus Zone of the Priborzhavske section C, the δ 13 Cbel increase from +0.4 to

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+3.2 ‰ and then decrease to +0.7 ‰(Fig. 4). Higher in the sequence (Margaritatus or Spinatum zones), the δ 13 Cbel values range between +0.3 and +1.9 ‰. In the Beˇ natina section (Fig. 6), the δ 13 Cbel values decrease from +2.7 ‰ in the Serpentinum Zone of the Lower Toarcian to +0.3 ‰ in the ?Bifrons or ?Pseudoradiosa zones of the Middle–Upper Toarcian. In the Murchinsonae and Concavum zones of the Middle–Upper Aalenian, the δ 13 Cbel range between –0.4 and +1.3 ‰.

6.2. δ 18 O values The measured values of the oxygen isotope composition of belemnite rostra (δ 18 Obel ) range between –1.5 and +0.9 ‰ VPDB (Figs. 3, 4, 6). While the lowest δ 18 Obel values are observed in the Lower Toarcian Serpentinum Zone (Fig. 6), the highest are recorded in the Upper Pleinsbachian Margaritaus or Spinatum Zone (Fig. 4). In the uppermost Sinemurian (Raricostatum Zone) the δ 18 Obel values vary between –0.2 and +0.4 ‰ (Fig. 3). Through the Pliensbachian (Jamesoni–Spinatum zones) the δ 18 Obel values are scattered (Figs. 3, 4). In the Priborzhavske section B (Fig. 3), the δ 18 Obel values range between –1 and +0.6 ‰ in the Ibex–Margaritaus zones of the Lower–Upper Pliensbachian. In the Priborzhavske section C (Fig. 4), the δ 18 Obel values range between –0.5

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ACCEPTED MANUSCRIPT and +0.9 ‰ through the Upper Pliensbachian Margaritatus–Spinatum zones. In the Beˇ natina section (Fig. 6), the δ 18 Obel values increase from –1.5 ‰ in the Lower Toarcian Serpentinum Zone to –0.2 ‰ in the Middle Toarcian ?Bifrons Zone or the Upper Toarcian ?Pseudoradiosa Zone. In the Middle–?Upper Aalenian (Murchin-

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sonae and/or Concavum zones) the δ 18 Obel values remain relatively constant, between –0.2 and +0.3 ‰, with one outlier value of –1‰ (Fig. 6).

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6.3. Mg/Ca and Sr/Ca ratios of belemnite rostra from the Beˇ natina section

While Mg/Ca ratios of well-preserved belemnite rostra in all studied sections vary between 2.6 and 6.2

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mmol/mol, Sr/Ca ratios ranged between 5.4 and 9.7 mmol/mol (see supplementary materials to this paper). However, only Mg/Ca and Sr/Ca ratios of belemnite rostra from the Beˇ natina section correlate with δ 18 Obel

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values and vary between 2.9 and 5.8 mmol/mol, and between 5.7 and 7.5 mmol/mol, respectively (see supplementary materials to this paper).

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7. Discussion

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7.1. Chemical composition of belemnite rostra as palaeoenvironmental proxies Carbon and oxygen isotope composition of belemnite rostra are commonly used proxies for Jurassic palaeo-

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climatic studies as belemnites are considered to have secreted their calcite rostra close to the isotopic equilibrium with ambient seawater (e.g. Wefer and Berger, 1991; Sælen et al., 1996; Wierzbowski, 2004; L´ecuyer et al., 2004; Rosales et al., 2004b; Rexfort and Mutterlose, 2006). While the belemnite rostra oxygen isotope composition is assumed to reflect changes in seawater temperature, changes in the δ 13 Cbel values are considered to reflect global variations in the isotopic composition of dissolved inorganic carbon (DIC), despite the vital effect of metabolic 12

C incorporation in the rostrum (e.g., Wierzbowski, 2002; Wierzbowski and Joachimski, 2007). However, the utility of belemnite rostra in palaeoclimatic studies, especially in regard to their life habits, has

been questioned by some authors. Although belemnites have traditionally been regarded as nectonic organisms which may have migrated in the water column (e.g., Stevens and Clayton, 1971; Doyle and Bennett, 1995; Price and Sellwood, 1997; Mutterlose et al., 2010), many authors suggest they were nectobenthic animals because temperatures calculated on the basis of their δ 18 O composition are comparable to those obtained from benthic bivalves and brachiopods (Anderson et al., 1994; Wierzbowski, 2002; Wierzbowski and Joachimski, 2007; Dera et al., 2009; Price and Teece, 2010; Wierzbowski and Rogov, 2011; Wierzbowski et al., 2013). To explain why temperatures calculated from belemnites are sometimes even lower than those from benthic organisms, F¨ ursich 11

ACCEPTED MANUSCRIPT et al. (2005) suggested that belemnites could have migrated to spawning grounds in cooler areas (see also Alberti et al., 2012). Most recent studies infer that different belemnite taxa might have inhabited different depths (Price and Page, 2008; Mutterlose et al., 2010; Price et al., 2011; Wierzbowski et al., 2013). Others

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consider that belemnites may have changed their nectobenthic lifestyle after the TOAE, and adapted to life at diverse depths as a result of bottom water anoxia (Ullmann et al., 2014).

Although the belemnite rostra Mg/Ca ratio is commonly used as a complementary, salinity-independent

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palaeotemperature proxy (e.g., McArthur et al., 2000; Bailey et al., 2003; Rosales et al., 2004a,b; McArthur et al., 2007a,b; Nunn and Price, 2010; Armend´ ariz et al., 2012; Wierzbowski et al., 2013; Arabas, 2016), some authors

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question the relationship between this ratio and their calcification temperature (e.g., McArthur et al., 2004; Li et al., 2013; Wierzbowski, 2015). Recent studies indicate that mesohibolitid Mg/Ca ratios are temperature

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independent, or have weak dependency from high skeletal partitioning of Mg (McArthur et al., 2004, 2007b; Bodin et al., 2009; Wierzbowski and Joachimski, 2009; Wierzbowski and Rogov, 2011; Armend´ariz et al., 2012).

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Furthermore, the Mg/Ca ratios and δ 18 O values of the Acroceolites and Passaloteuthis belemnite genera common in the Lower Jurassic deposits do not correlate (McArthur et al., 2007a; Ullmann et al., 2015). Therefore, factors

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other than temperature, such as biofractionation, may affect Mg/Ca ratios of some belemnite genera. Some authors suggest that Sr/Ca ratio of certain Jurassic belemnites could be a better palaeotemperature

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proxy than Mg/Ca ratio (e.g., McArthur et al., 2007a; Nunn and Price, 2010; Li et al., 2012; Wierzbowski et al., 2013). However, other studies (e.g., Rosales et al., 2004a; Wierzbowski, 2015) show lack of correlation between Sr/Ca ratio and δ 18 O in other Jurassic belemnite groups. While Mg/Ca and Sr/Ca ratios of belemnites from the Beˇ natina section reveal good correlation with their δ 18 O values (see supplementary materials to this paper), the ratios of those collected in all Priborzhavske sections do not correlate with their δ 18 O values, and this casts doubts on these parameters as palaeotemperature proxies. In addition, identification of belemnite taxonomy appears essential for palaeoenvironmental studies based on belemnite rostra and it should be kept in mind that fragmentation in collected material has enabled recognition of only a few belemnite specimens (see supplementary materials to this paper). Furthermore, scattered δ 13 Cbel and δ 18 Obel values in the uppermost Sinemurian (Raricostatum Zone), in the Pliensbachian and in the Middle Aalenian (Murchinsonae Zone) may result from condensations and/or the presence of a variety of belemnites species with different habitats in the one bed.

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ACCEPTED MANUSCRIPT 7.2. Carbon isotopes Three prominent negative shifts in δ 13 Ccarb values are recorded in the Sinemurian of the Priborzhavske

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sections A and B (Figs. 2, 3, 7). The first is documented at the Lower–Upper Sinemurian boundary, the second

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in the Oxynotum Zone and the third in the Raricostatum Zone of the Upper Sinemurian. Similarly low δ 13 Ccarb values were recorded in the Lusitanian Basin of Portugal by Duarte et al. (2014) in the Upper Sinemurian Raricostatum Zone. Although petrological study and our statistical analysis (see section 5) have provided no

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direct evidences for diagenesis, the strongly negative (up to approximately -8.5 ‰) and scattered δ 13 Ccarb values

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most likely result from post-depositional rock alteration, perhaps via early cementation associated with bacterial processes during organic matter decay, as discussed in Silva et al. (2011). Furthermore, these exceptionally low

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δ 13 Ccarb values in studied sections have been recorded in limestone-marl alternations which appear particularly prone to alteration during lithification and/or burial diagenesis (Frank et al., 1999). It is worth noting that the negative CIE reported by various authors in the Raricostatum–Jamesoni zones of

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the Sinemurian–Pliensbachian boundary (e.g., Podlaha et al., 1998; Jenkyns et al., 2002; Woodfine et al., 2008; Suan et al., 2010; Korte and Hesselbo, 2011; Franceschi et al., 2014; G´omez et al., 2016; Bougeault et al., 2017)

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is not observed in carbonates of the PKBt (Fig. 3, 7). Although this negative excursion is suggested to be a global event, no source of the isotopically light carbon has been documented yet (cf. Korte and Hesselbo, 2011;

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G´omez et al., 2016). Recent studies by Ruhl et al. (2016) suggest a relative increase in radiogenic

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Sr/86 Sr

flux into the global oceans in the Early Pliensbachian in response to a late phase of enhanced global continental weathering induced by CO2 input from CAMP volcanism. Since the Sinemurian–Pliensbachian boundary is well documented in Priborzhavske section B (Fig. 3), other factors must have had a greater impact on the carbon isotope composition of carbonates precipitated in the PKBn. Many authors reported a positive CIE in the Upper Pliensbachian (Margaritatus Zone) of the northern Tethyan sections: southern Switzerland, northern Italy, United Kingdom and Portugal based on bulk carbonate samples (Jenkyns and Clayton, 1986; van de Schootbrugge et al., 2005a; Silva et al., 2011), northern Spain based on belemnites (Rosales et al., 2001, 2004a,b, 2006; G´omez et al., 2016) and United Kingdom based on calcite fossils and fossil wood (Korte and Hesselbo, 2011). This Late Pliensbachian event (Fig. 8) is linked to global enhancement of the carbon burial under favourable marine redox conditions (e.g., Suan et al., 2010; Korte and Hesselbo, 2011; Silva et al., 2011; Silva and Duarte, 2015). This excursion is recorded in the Priborzhavske section C (Fig. 4) where the δ 13 Ccarb and δ 13 Cbel values increase by approximately 0.7 ‰ and 2.8 ‰, respectively.

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ACCEPTED MANUSCRIPT In the Podbiel section (Fig. 5), the δ 13 Ccarb values increase by only 0.4 ‰ in the Margaritatus Zone. In the Priborzhavske section B, the δ 13 Cbel values are significantly scattered and any trend is indistinguishable (Fig. 3). However, the Margaritatus Zone may be incomplete in this section.

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The following two prominent carbon isotope events occurr at the Pliensbachian–Toarcian boundary and in the Tenuicostatum–Falciferum zones of the Lower Toarcian. The first of these is documented by carbonates from multiple sections including: Peniche, Portugal (Hesselbo et al., 2007; Suan et al., 2008, 2010), Yorkshire,

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England (Littler et al., 2010; Korte and Hesselbo, 2011), Rodiles in Spain (G´omez et al., 2016), Central High Atlas Basin in Morocco (Bodin et al., 2010, 2016; Ait-Itto et al., 2017), from Katsuyama, Japan deep ocean

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sediments (Gr¨ocke et al., 2011) and from terrestrial material from the Polish Basin (Hesselbo and Pie´ nkowski, 2011). The simultaneous isotope variations recorded worldwide suggest global character of this excursion.

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The second, named Toarcian Ocean Anoxic Event (TOAE), was marked by worldwide deposition of organicrich shales in marine settings and an abrupt negative carbon isotope excursion. This perturbation in the carbon

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cycle is recorded in terrestrial and marine facies in both shallow and deep ocean sediments (e.g., Jenkyns and Clayton, 1986, 1997; Hesselbo et al., 2000a; Jenkyns et al., 2002; Bailey et al., 2003; Hesselbo et al., 2007; G´omez

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et al., 2008; Suan et al., 2010; Al-Suwaidi et al., 2010; Caruthers et al., 2011; Gr¨ocke et al., 2011; Hesselbo and

2016).

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Pie´ nkowski, 2011; Kemp et al., 2011; Hermoso et al., 2012; Metodiev et al., 2014; Suan et al., 2015; Fu et al.,

There is an interval of uncertain stratigraphy at the Pliensbachian–Toarcian boundary in the Podbiel and the Beˇ natina sections (Figs. 5, 6) as no specific ammonites have been found between the uppermost Spinatum Zone of the Upper Pliensbachian and the Lower Toarcian Serpentinum Zone. The δ 13 Ccarb record of the Podbiel and Beˇ natina sections shows a gradual increase in this interval (Figs. 5, 6). Above, in both sections, is a hardground surface corresponding to a period of non-deposition or condensation. Other features such as Fe-crusts and Fe-concretions in the Podbiel section and the phosphatised fish bones, Fe-oncoids and pyrite framboids in the Beˇ natina section, support the hiatus hypothesis (cf. Schl¨ogl et al., 2004, 2006). However, it is worth noting that the Pliensbachian–Toarcian boundary beds are commonly highly condensed or absent (Morard et al., 2003), and that the negative CIE of the Lower Toarcian is missing from records of δ 13 Ccarb and δ 13 Cbel throughout some European carbonate sequences (McArthur et al., 2000; van de Schootbrugge et al., 2005b; G´omez et al., 2008). Furthermore, the negative CIE of the Lower Toarcian has been documented only in the organic carbon isotope record in the Zazriva section of the PKBt in northwestern Slovakia (Suan et al., 2015).

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ACCEPTED MANUSCRIPT The δ 13 Ccarb values show a positive excursion in the Lower Toarcian Serpentinum Zone (Figs. 5, 6, 7). According to the previous studies (Jenkyns and Clayton, 1997; Hesselbo et al., 2000a; Jenkyns et al., 2001; Hermoso et al., 2012; Sabatino et al., 2013), the Lower Toarcian δ 13 C curve shows two positive excursions

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interrupted by a prominent negative shift characteristic for TOAE. The post-TOAE increase in δ 13 C values is remarkable, and interpreted as a result of accelerated sequestration of marine organic matter with relative enrichment in

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C (Jenkyns et al., 2002; Sabatino et al., 2013). The positive δ 13 Ccarb excursion in the Podbiel

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and Beˇ natina sections records the post-TOAE positive shift (Fig. 8).

Despite hiatuses in the Beˇ natina section (Fig. 6), its Upper Toarcian–Upper Aalenian δ 13 Ccarb pattern

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is consistent with the stable carbon-isotope trend in the western Tethys region (e.g., Duarte, 1998; Sandoval et al., 2008; G´omez et al., 2008, 2009; Price, 2010; Sandoval et al., 2012). The δ 13 C falling trend recorded in

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Beˇ natina section in the uppermost Lower–Upper Toarcian (upper Serpentinum–Pseudoradiosa zones, Fig. 6) is also observed in other Tethyan sections, e.g., in the United Kingdom (Jenkyns and Clayton, 1997), northern

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Spain (G´omez et al., 2008), Portugal (Suan et al., 2010), SE France (Harazim et al., 2013) and Morocco (Krencker et al., 2014).

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The presence of another hardground surface and the stratigraphical gap in the Beˇ natina section (Fig. 6) preclude documentation of the entire Aalenian isotope record; including a probable positive carbon isotope shift

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from the Lower Aalenian Scissum (Comptum) Zone reported by Price (2010). However, the increasing δ 13 Ccarb values derived from the ?Concavum Zone of the ?Upper Aalenian (Fig. 6) appear consistent with the previously reported δ 13 C pattern (e.g., Bartolini et al., 1999; Sandoval et al., 2008). Sandoval et al. (2008) suggest that the rise in δ 13 C is related to high biological productivity of surface waters. The scattered δ 13 Cbel values in the Middle–Upper Aalenian present difficulties in distinguishing actual trends (Fig. 6).

7.3. Oxygen isotopes and palaeotemperatures The recorded δ 18 Obel values of the uppermost Sinemurian Raricostatum Zone and the Lower Pliensbachian Jamesoni Zone indicate seawater temperatures between 10 and 13◦ C and between 12 and 13◦ C, respectively (Fig. 3). These results are lower than the previously recorded temperatures (over 15◦ C) for the Sinemurian– Pliensbachian transition (e.g., Hesselbo et al., 2000b; Suan et al., 2010; Korte and Hesselbo, 2011; G´omez et al., 2016). The decreasing δ 18 Obel values in the uppermost Lower Pliensbachian of Priborzhavske section B (Fig. 3) indicate seawater temperature warming by approximately 4◦ C. The calculated temperatures reached around

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ACCEPTED MANUSCRIPT 16◦ C in the early Margaritatus Chron of the Late Pliensbachian (Figs. 3, 7). The Early Pliensbachian warming event (Fig. 9) is also documented in northern Spain (e.g., Rosales et al., 2004b; G´omez et al., 2016), France (e.g., van de Schootbrugge et al., 2010), United Kingdom (e.g., Korte and Hesselbo, 2011) and Portugal (e.g.,

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Suan et al., 2010). The positive εN d excursion led Dera et al. (2009) to suggest a temporary northward incursion of Tethyan or Panthalassan seawater to the Euro-boreal region, and this could have favoured the Early Pliensbachian warming; at least in the NW Tethys.

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After the Early Pliensbachian warming event, the δ 18 Obel values increase in the Upper Pliensbachian Margaritaus–Lower Spinatum zones in the Priborzhavske sections B and C (Figs. 3, 4). This indicates sea-

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water cooling of approximately 8◦ C (Figs. 3, 4). The Late Pliensbachian cooling event is recognised from other Tethyan sections (Fig. 9); e.g., in northern Spain (e.g., Rosales et al., 2004a; van de Schootbrugge et al., 2005a;

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G´omez et al., 2016), in United Kingdom (e.g., Bailey et al., 2003; Korte and Hesselbo, 2011), in Portugal (e.g., Suan et al., 2008, 2010) or France (e.g., Dera et al., 2009; van de Schootbrugge et al., 2010; Harazim et al.,

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2013; Bougeault et al., 2017). The occurrence of glendonites in northern Siberia observed by some authors (e.g., Kaplan, 1978; Price, 1999; Rogov and Zakharov, 2010) corroborates the presence of cool high-latitude

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climatic conditions during the Late Pliensbachian. This temperature decrease coincides with the regressive trend documented in several European locations (e.g., Haq et al., 1988; Quesada et al., 2005; Suan et al., 2010).

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The observed trace fossils of ichnogenera Chondrites, Diplocraterion and Scolithos of the Margaritatus Zone in the Priborzhavske sections corroborate a shallower environment during the Late Pliensbachian. Furthermore, authors reported enhanced worldwide preservation of organic matter and resultant lowered atmospheric pCO2 level in this period (e.g., Suan et al., 2010; Dera et al., 2011; Silva and Duarte, 2015; Steinthorsdottir and Vajda, 2015), with important implications for the following TOAE. The major Early Toarcian warming event is recorded in the oxygen isotope composition of belemnite rostra from the PKBt. Temperatures calculated on the basis of the δ 18 Obel values of the Lower Toarcian Serpentinum Zone in the Beˇ natina section average 18.5◦ C (Fig. 6). The rapid change from the cool climate conditions in the Late Pliensbachian to the greenhouse in the Early Toarcian has been documented in many studies (e.g., McArthur et al., 2000; Bailey et al., 2003; Rosales et al., 2004b; Dera et al., 2009; van de Schootbrugge et al., 2010; Suan et al., 2010; Dera et al., 2011; G´ omez et al., 2016). This warming event coincides with high atmospheric CO2 concentration (e.g., Steinthorsdottir and Vajda, 2015), transgression (e.g., Hallam, 2001), strong negative carbon-isotope perturbation (see section 7.2) and prominent extinction (e.g., Wignall et al., 2006; Arias, 2009;

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ACCEPTED MANUSCRIPT Dera et al., 2010; G´ omez and Goy, 2011; Fraguas et al., 2012; Guex et al., 2016). The seawater temperature in the PKBn began to fall in the Middle Toarcian Bifrons Chron, decreasing gradually by approximately 5 ◦ C (Fig. 6). This drop occurred earlier than in the NW Europe basins where

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the seawater temperature began to fall at the Toarcian–Aalenian transition (cf. Price, 2010; Korte et al., 2015). However, Krencker et al. (2014) also reported the beginning of a pronounced seawater cooling in the Bifrons Chron based on well-preserved brachiopods shells from Morocco.

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Concomitant changes in δ 18 O values and Mg/Ca and Sr/Ca ratios of belemnites from the Beˇ natina section substantiate the presence of a cool period at the Early–Middle Jurassic transition. Although the only

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known temperature equation for belemnite Mg/Ca ratios has a speculative character (cf. Nunn and Price, 2010; Wierzbowski et al., 2013; Wierzbowski, 2015), the decrease in Mg/Ca ratio of belemnite rostra from the Beˇ natina

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section throughout the Middle Toarcian–Middle Aalenian may be linked to a temperature drop of approximately 5 ◦ C (see supplementary materials to this paper).

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Scattered δ 18 Obel values in the Middle–?Upper Aalenian (Murchinsonae and/or Concavum zones) may have resulted from condensation or the presence of varied belemnite species of different life habits (see section 7.1). A

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range of seawater temperatures between 10.5 and 13 ◦ C, with one outlier at 16 ◦ C, is calculated for this interval (Fig. 6). Although G´ omez et al. (2009) reported increased seawater temperature during the Murchinsonae Chron

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in the Basque–Cantabrian Basin, Price (2010) documented a decrease in temperature in the Murchinsonae Chron of Scotland. While our results show rather stable conditions at that time, the PKBn temperatures range is more similar to that recorded in Scotland (approximately 9–12 ◦ C). It may be related to the presence of a long-term cooler period or the inflow of cooler bottom waters during PKBn deepening.

8. Conclusions This study presents new carbon and oxygen isotope data of bulk carbonate and belemnite rostra from the rarely studied, open-marine PKBn and provide valuable information on environmental variations in the northern region of the Tethys Ocean during the Sinemurian–Aalenian. Two previously described positive carbon isotope excursions, one in the Margaritaus Zone of the Upper Pliensbachian and the other in the Serpentinum Zone of the Lower Toarcian, have been recorded in the PKBt. The δ 13 C values display a decreasing trend throughout the Lower–Upper Toarcian and relatively constant values in the Aalenian. Moreover, the Sinemurian–Pliensbachian negative δ 13 C boundary event, which is assumed to have been global, has not been recorded in PKBt carbonates. The presented δ 18 Obel data corroborate previously documented oscillations of the Early Jurassic climate. Present 17

ACCEPTED MANUSCRIPT data point to warming of seawater temperature of about 4 ◦ C in the latest Early Pliensbachian and a major cooling of around 8 ◦ C in the Late Pliensbachian. A further prominent warming of around 10 ◦ C occurred in the Early Toarcian. The temperature decreased again by 5.5 ◦ C during the Middle Toarcian. During

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the Middle–?Late Aalenian, PKBn seawater temperature was rather low and stable, between 10 and 13 ◦ C. Temperatures calculated on the basis of the δ 18 Obel from the PKBt are lower then those reported previously from epicontinental basins and can be related with a considerable depth of the PKBn and a minor impact of

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Supplementary data to this article can be found online.

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freshwater inflow. However, other open-marine sections need to be studied to test this hypothesis.

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Acknowledgments

This research work was financed by Polish National Science Centre - grant no. 2011/03/N/ST10/05518. Jan Schl¨ogl acknowledges support of the Scientific Grants Agency by Ministry of Education, Science, Research

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and Sport of the Slovak Republic (project no. VEGA 2/0136/15) and Slovak Research and Development Agency (project no. APVV-14-0118). Hubert Wierzbowski is thanked for valuable discussions and suggested

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corrections. We are indebted to Zbigniew Remin and Alexei Ippolitov for valuable assistance in the determination ˇ of belemnite specimens and to Vladimir Simo for the interpretation of ichnofacies in the Priborzhavske sections.

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ˇ We are grateful to Adam Tomaˇsov´ ych, Mari´an Golej, Stefan J´ozsa and Tam´asz Muller for their help during the fieldwork and to Raymond Marshall for improving English of this manuscript. The authors thank the editor, Thomas Algeo and the reviewers, Stephane Bodin and the anonymous reviewer for their comments and suggested improvements.

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Wierzbowski, A., Krobicki, M., Matyja, B. A., 2012. The stratigraphy and palaeogrographic position of the

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Wierzbowski, H., 2002. Detailed oxygen and carbon isotope stratigraphy of the Oxfordian in Central Poland. International Journal of Earth Sciences (Geologische Rundschau) 91, 304–314.

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cology 203, 153–168.

Wierzbowski, H., 2015. Seawater temperatures and carbon isotope variations in central European basins at the

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Palaeoecology 440, 506–523.

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ACCEPTED MANUSCRIPT Woodfine, R. G., Jenkyns, H. C., Sarti, M., Baroncini, F., Violante, C., 2008. The response of two Tethyan carbonate platforms to the early Toarcian (Jurassic) oceanic anoxic event: environmental change and differential

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subsidence. Sedimentology 55, 1011–1028.

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ACCEPTED MANUSCRIPT Fig. 1: Location map of the Pieniny Klippen Belt and the studied sections.

23oE

OUTER

PODBIEL N CARPATHIAN WESTER S

CA R

PAT H IA

NS

¡

AUSTRIA

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BENATINA

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PRIBORZHAVSKE

Bratislava

100 km

Budapest

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48oN

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PT

ED

Fig. 1

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POLAND

SLOVAKIA

EP

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FORE DE

Kraków 50oN

H EC LIC CZ UB P E R

UKR AINE

o o 2121 E

19oE

17oE

HUNGARY

Tertiary Molasse Zone Flysch Belt Pieniny Klippen Belt Alpine-Carpathian-Dinaride and Pannonian internides Neogene volcanics Neogene basins

ACCEPTED MANUSCRIPT

Fig. 2: Priborzhavske section A. Lithology, stratigraphy and δ 13 C values of bulk carbonates. Green circles - bulk carbonate, grey

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circles - diagenetically altered bulk carbonate. The thick grey trend line represents the 5-point running average. The grey colour

Bucklandi

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marls

red gray limestone gray marly limestone gray marly limestone with yellowish patina crinoidal limestone

5

biostrome highly bioturbated marls and marly limestone

4

Fe-Mn concretions pyrite concretions nodular intervals

2

?Bucklandi

gray

greenish

3

?SINEM.

black

yellowish

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6

Legend (Figs. 2-4)

Altered interval

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Perechinska Formation

7

Ccarb (‰) VPDB

-9 -8 -7 -6 -5 -4 -3 -2 -1 0

9

8

SINEMURIAN

13

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Turneri

hy m) ap igr ess ( rat t n s e k o g ic ne Sta Zo Lith Th

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in the stratigraphical column corresponds to uncertainties in the biostratigraphic framework. Sinem. - Sinemurian.

1

-9 -8 -7 -6 -5 -4 -3 -2 -1 0 13

Ccarb (‰) VPDB

Fig.2

35

SC

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ACCEPTED MANUSCRIPT

Fig. 3: Priborzhavske section B. Lithology, stratigraphy, δ 13 C and δ 18 O values of bulk carbonates and belemnite rostra, and

hy ) rap (m e tratig ess n n e ne bzo os k g c i h Th Sta Zo Su Lit

13

13

Ccarb (‰ VPDB)

-9

-7

-5

-3

-1

3

0 1 2 3 Cbel (‰ VPDB)

-2

2

15

10

ED

7

2

1

PT

8

3

20

0

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Perechinska Formation

9

4

3

-1

MA

Margaritatus

Subnodosus Jame- Massesoni naum Taylori

Ibex Raricostatum

Jamesoni

PLIENSBACHIAN

11

10

Oxynotum

SINEMURIAN

12

5

T (oC)

Cbel (‰ VPDB)

1

13

6

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estimated palaeotemperatures. The legend is the same as on Fig. 2, green diamonds - belemnite data.

Altered interval

1

-9

-7

-5 -3 -1 1 Ccarb (‰ VPDB)

13

3

-1

13

36

-1 18

0

Obel (‰ VPDB)

1

Fig.3

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ACCEPTED MANUSCRIPT

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Fig. 4: Priborzhavske section C. Lithology, stratigraphy, δ 13 C and δ 18 O values of bulk carbonates and belemnite rostra, and estimated palaeotemperatures. The legend is the same as on Fig. 2, green diamonds - belemnite data, Mass. - Massenaum

13

1.5

8

0

1

2

3

4

3

4

15

10

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Perechinska Formation

Margaritatus

PLIENSBACHIAN

5

T (oC)

Cbel (‰ VPDB)

2.5

PT

7

Subnodosus

2

MA

1

9

6

13

Ccarb (‰ VPDB)

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Apyren.

Priborzhavska Formation

Spinatum

hy ) rap s (m tig s e on ostra ckne e z e g b i n h Zo Su Sta Th Lit

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Subzone, Apyren. - Apyrenum Subzone.

4

3

2

1 Stokesi

Ibex

Mass.

1 13

1.5 2 2.5 Ccarb (‰ VPDB)

0

1

2

13

Cbel (‰ VPDB)

37

-1

0 18

Obel (‰ VPDB)

1

Fig. 4

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Fig. 5: Podbiel section. Lithology, stratigraphy and δ 13 C values of bulk carbonates. Yellow squares - bulk carbonate data. The thick grey trend line represents the 5-point running average. The grey colour in the stratigraphical column corresponds to uncertainties

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in the biostratigraphic framework. Dav. - Davoei Zone, Serp. - Serpentinum Zone, Var. - Variabilis Zone, Copri. - Copricornus

?TOARCIAN

1.5

SC Legend gray marls red marls gray limestone red limestone

10

ED

gray cherty limestone reddish cherty limestone red crinoidal limestone reddish crinoidal limestone

hardground surface

Fe-Mn concretions nodular intervals

Margaritatus

6

5

Apyrenum

ADNET

7

4

Gibbo.

3

2 Stokesi

Spinatum

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FORMATION

8

reddish limestone

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9

Falciferum

Bifrons

SublevisoniBifro.

4.5

MA

11

Serp.

TOARCIAN

2

12

Var.

PLIENSBACHIAN

Ccarb (‰) VPDB 2.5 3 3.5 4

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13 hy ) rap (m e tratig ess n n o ge ne bz hos hick T Sta Zo Su Lit

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Subzone, Gibbo. - Gibbosus Subzone, Bifro. - Bifrons Subzone.

1

Dav.Copri.

1.5

2 13

2.5 3 3.5 4 Ccarb (‰) VPDB

38

4.5

Fig. 5

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ACCEPTED MANUSCRIPT

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Fig. 6: Beˇ natina section. Lithology, stratigraphy, δ 13 C and δ 18 O values of bulk carbonates and belemnite rostra, and estimated palaeotemperatures. Blue triangles - bulk carbonate data, blue pentagons - belemnite data. The thick grey trend line represents the 5-point running average. The grey colour in the stratigraphical column corresponds to uncertainties in the biostratigraphic

13

13

Ccarb (‰ VPDB)

0

1

2

3

4

5

10

9

15

10 Legend gray marls dark gray marls red marls marly limestones gray marly limestone greenish crinoidal limestone

hardground surface

Pse

6

5

4

dark gray crinoidal limestone with intercalations of marls light gray crinoidal limestone green and yellow crinoidal limestone Fe-Mn concretions pyrite nodular intervals

hardground surface

2

1

Allgäu Fm.

Hôrka Fm.

3

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Serp.

H bok Formation

7

Bifrons

20

PT

8

TOARCIAN

T (oC)

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Member A

AALENIAN

Murchisonae

11

-1

Cbel (‰ VPDB) 0 1 2 3

MA

y ph (m) gra ati ness r t ge ne hos hick T Sta Zo Lit

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framework. Serp. - Serpentinum Zone, Pse. - Pseudoradiosa Zone.

0

1

2

13

3

4

Ccarb (‰ VPDB)

5

-1

0

1

13

2

Cbel (‰ VPDB)

39

3

-2 18

-1 0 1 Obel (‰ VPDB)

Fig. 6

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ACCEPTED MANUSCRIPT

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Fig. 7: Simplified stratigraphy, δ 13 Ccarb , δ 13 Cbel and δ 18 Obel values from all studied sections of the Pieniny Klippen Belt. Green circles – bulk carbonate data from the Priborzhavske sections A, B and C; yellow squares – bulk carbonate data from the Podbiel section; blue triangles – bulk carbonate data from the Beˇ natina section; green diamonds - belemnite data from the Priborzhavske

Upper

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ED

?Opalinum

?Pseudoradiosa

Variabilis

Bifrons

Serpentinum

Spinatum

Margaritatus

Ibex Jamesoni

Raricostatum

Sinemurian

MA

Murchinsonae

Oxynotum

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Stage

Aalenian

?Concavum

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Middle Upper

Ammonite Zone

Davoei

Lower

Pliensbachian

Lower

Toarcian

Upper Lower Middle Upper Substage

sections B and C; blue pentagons - belemnite data from the Beˇ natina section; black circles - altered samples.

Altered interval

?Obtusum

Lower

Turneri

?Semicostatum

Bucklandi

Fig.7

40

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Fig. 8: Comparison of the δ 13 C records obtained from bulk carbonate and calcareous shells of the Pieniny Klippen Belt and other European basins. Data from A) Korte and Hesselbo 2011, black circle - oyster, open circle - Pinna, triangle - belemnite, cross -

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brachiopod, star - pecten; B) Katz et al., 2005 (stratigraphy after Schootbrugge et al., 2005a); C) this study and D) Sabatino et

5

Tenuicostatum

Ammonite Zone

-8

-4

-6

-2

Spinatum

Thouarsense

Margaritatus

2

4

Aalenian

Lavesquei

0

Variabilis

Bifrons

Falciferum

Early Toarcian positive CIE TOAE

PT

Davoei

Ammonite Zone

-5

-1

-3

1

3

5

Substage

4

D

Pieniny Klippen Basin

Jamesoni

S-P event

Raricostatum

Jamesoni

3

4

5

4

5

?Pseudoradiosa

Variabilis

Bifrons

Serpentinum

Lower Toarcian

Lower

Ibex

2

?Opalinum

Spinatum

Upper

Pliensbachian

Davoei

1

Murchinsonae

Margaritatus Davoei

Lower

Pliensbachian

Ibex

Late Pliensbachian event

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Lower Pliensbachian

Spinatum

Margaritatus

Adriatic Basin 0

?Concavum

Tenuicostatum

P-T event

Ammonite Zone

3

Stage

2

Upper Lower Middle Upper Substage

1

Middle

0

Toarcian

-1

MA

Cleveland Basin -2

C

Cardigan Bay Basin

ED

Ammonite Zone

Substage

B

Toarcian

Upper Pliensbachian L. Toar. Substage

A

Falciferum

al., 2013.

Ibex Jamesoni

Raricostatum

Upper

Obtusum

Bucklandi

Obtusum

Semicostatum

Angulata

Turneri

Lower

Hettangian

Oxynotum

?Obtusum

?Semicostatum

Liasicus

Bucklandi

Planorbis

-2

-1 0 13

1

2

3

4

Cshell (‰ VPDB)

5

-8

-4

-6

-2

0

2

4

-5

13

-1

-3 13

Ccarb (‰ VPDB)

1

Ccarb (‰ VPDB)

Fig. 8

41

3

5

Spinatum Tenuicostatum

Semicostatum

TOAE

Oxynotum

Upper Pliensbach.

Turneri

Sinemurian

Turneri

Sinemurian

Upper Sinemurian

Raricostatum

L. Sin.

Oxynotum

0

1 13

2

3

Ccarb (‰ VPDB)

SC

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ACCEPTED MANUSCRIPT

Fig. 9: Comparison of the δ 18 O records obtained from belemnite rostra and various calcareous shells of the Pieniny Klippen Belt

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Stokesi

Raricostatum -4

Stage

Aalenian

Margaritatus

-3 18

-2

-1

0

Ammonite Zone

Pieniny Klippen Basin T (oC) 20

10

15

?Concavum

Murchinsonae

?Opalinum

?Pseudoradiosa

Variabilis

Bifrons

Early Toarcian warming

Serpentinum

Spinatum

Ibex

Late Pliensbachian cooling

Margaritatus

Early Pliensbachian warming

Davoei Ibex Jamesoni

Raricostatum

Late

Ibex

E. Sin.

L. Sin.

Obrach (‰) VPDB

0

Spinatum

bottom water cooling

Oxynotum

Sinemurian

Raricostatum

Oxynotum

?Obtusum

Turneri

Early

Late Sinemurian

Early Pliensbachian

Da. Ibex Jamesoni

18

-1

Tenuicostatum

Jamesoni

Jamesoni

-2

10

Davoei

Davoei

-3

15

Late Early Middle Late Substage

ED

Margaritatus

20

Toarcian

Tenuicostatum

25

Early

Serpentinum

30

Late

10

Pliensbachian

15

PT

Late Pliensbachian

Poly. Spinatum ?

20

D

Cleveland Basin T (oC)

Ammonite Zone

MA

T ( C) 25

Spinatum

Margar.

Late

Pliensbachian Early Sinemurian

o

Late Pliensbachian E. Toar. Substage

Bifrons

Early Toarcian

15

C Basque-Cantabrian Basin Ammonite Zone

Early Pliensbachian

Substage

Zone

20

Levisoni

Stage

Substage

Middle Toarcian Early

Lusitanian Basin T (oC)

Early

B

A

Middle

Fig. 8A and D) this study.

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and other European basins. Data from A) Suan et al., 2010; B) Rosales et al., 2004a; C) Korte and Hesselbo, 2011, symbols as in

Obtusum

?Semicostatum

Turneri Bucklandi

Semicostatum

-5

1

Obel (‰) VPDB

Fig.9

42

-3 0 -4 -2 -1 18 Oshell (‰) VPDB

1

-2

-1 18

0

Obel (‰) VPDB

1

ACCEPTED MANUSCRIPT Highlights

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• Our data corroborate cyclic changes in the Early Jurassic climate

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• New stable isotope data of open marine carbonates and belemnite rostra

• δ13C values record the Late Pliensbachian and the Early Toarcian positive excursions

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MA

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• The SinemurianPliensbachian boundary event is not recorded

43