Integrated stratigraphy of Lower Cretaceous sediments (Ryazanian–Hauterivian) from North-East Greenland

    Integrated stratigraphy of Lower Cretaceous sediments (Ryazanian - Hauterivian) from North-East Greenland Carla M¨oller, Joerg Mutterlose, Peter Alsen PII: DOI: Reference:

S0031-0182(15)00374-0 doi: 10.1016/j.palaeo.2015.07.014 PALAEO 7362

To appear in:

Palaeogeography, Palaeoclimatology, Palaeoecology

Received date: Revised date: Accepted date:

9 January 2015 3 July 2015 8 July 2015

Please cite this article as: M¨oller, Carla, Mutterlose, Joerg, Alsen, Peter, Integrated stratigraphy of Lower Cretaceous sediments (Ryazanian - Hauterivian) from North-East Greenland, Palaeogeography, Palaeoclimatology, Palaeoecology (2015), doi: 10.1016/j.palaeo.2015.07.014

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ACCEPTED MANUSCRIPT Integrated stratigraphy of Lower Cretaceous sediments (Ryazanian - Hauterivian) from North-East Greenland

Institut für Gelogie, Mineralogie und Geophysik, Ruhr-Universität Bochum Universitätsstraße 150,

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Carla Möllera, Joerg Mutterlosea, Peter Alsenb

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D-44801 Bochum, Germany, E-Mails: [email protected], [email protected] Geological Survey of Denmark and Greenland (GEUS), Øster Voldgade 10, DK-130 Copenhagen

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K, Denmark, E-Mail: [email protected]

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Abstract

The reconstruction of past climates and oceanography requires a solid stratigraphic

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framework ideally applicable on a global scale. The earliest Cretaceous, however, was a time of

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strong faunal provincialism, making supra-regional correlation of biostratigraphical zonations difficult. The step-by-step correlations between neighbouring provinces/subprovinces that are

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commonly utilized bear the risk of loosing accuracy in every step. Here we present 87Sr/86Sr- and stable isotope-data (δ13C, δ18O) from belemnite rostra of the Rødryggen section in North-East Greenland. The integrated stratigraphy based on Sr-isotope ratios, ammonite and calcareous nannofossil biostratigraphy offers the opportunity for a direct comparison of the different stratigraphic zonations. These are complemented by δ13Cbel-data recording the positive carbon isotope excursion of the Valanginian Weissert Event, which is a reliable stratigraphic event. The geochemical data furthermore allow a reliable correlation of Tethyan and Boreal strata. The stratigraphic range of the Rødryggen section resulting from Sr-isotope stratigraphy (Ryazanian – Barremian) is in agreement with the biostratigraphic findings. Mismatches regarding stage/ substage boundaries demand a reconsideration of the nannofossil biostratigraphy of the Boreal Lower Cretaceous. Our findings suggest stratigraphic ranges for two nannofossil index species (Sollasites arcuatus, Micrantholithus speetonensis) different from published ranges. The

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ACCEPTED MANUSCRIPT new observations imply changes in the Boreal Ryazanian-Valanginian nannofossil zonation scheme. Specifically the base of calcareous nannofossil zone BC3, originally defined as uppermost Ryazanian, is shifted to the lower Valanginian.

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Based on these new stratigraphic interpretations a decrease in the abundance of nannoconids observed in the Rødryggen section can now be identified as the Valanginian

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nannoconid crises. This nannoconid decline has been observed in Tethyan sections along with the

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Weissert Event. A positive trend in the δ18Obel-data agrees with a late Valanginian cooling that has

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been postulated based on independent proxies from the Boreal Realm and the Tethys.

Keywords

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earliest Cretaceous (Ryazanian – Hauterivian); Sr-isotope stratigraphy; biostratigraphy; calcareous

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nannofossils; Weissert Event; stable isotopes (δ13C, δ18O)

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Highlights

• We present an integrated stratigraphy for the lowermost Cretaceous

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• The Boreal calcareous nannofossil zonation of the Valanginian is re-calibrated • The upper Valanginian Weissert Event is reflected by a 1.2‰ positive shift in the δ13Cbel-data • The positive shift in the oxygen isotope data agrees with a Valanginian cooling

1. Introduction The earliest Cretaceous (Berriasian – Hauterivian) is an interval characterised by a distinctive provincialism of marine biota, causing the evolution of endemic floras and faunas in different parts of the world. The Indo-Pacific, the Tethys and the Boreal Realm show in parts geographically bound marine assemblages limited to these oceans (e.g. Remane, 1991; Wimbledon et al., 2011). This situation applies for the Tethys (nowadays southern France, Switzerland, northern Italy) and the southern part of the Boreal Realm (northern Germany, Poland, North Sea, Great Britain). Both areas show close faunal links throughout the Early – Middle Jurassic and the Aptian –

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ACCEPTED MANUSCRIPT Campanian. A Late Jurassic – Early Cretaceous sea-level low-stand caused the closure of gateways, hampered thereby migration and resulted in biogeographic isolation (e. g. Haq et al., 1988; Michael, 1979; Scotese, 1991). This in turn led to the widespread evolution of endemic taxa.

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The biogeographic restrictions culminated in Tithonian – Berriasian times, an interval for which two different stage names are being used. The Berriasian stage, defined in the Tethys, corresponds to

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the upper Volgian and Ryazanian (Zakharov et al., 1996) in the northern parts of the Boreal Realm

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(Siberia, Greenland, Svalbard, in some cases also used in England). These biogeographic differences resulted in major problems for biostratigraphical correlations of the uppermost Jurassic

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and lowermost Cretaceous sedimentary sequences of both realms biostratigraphically (Remane, 1991; Zakharov et al., 1996). Discussions regarding these problems have been going on for nearly

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100 years (Mazenot, 1939; Wimbledon et al., 2011) without finding a practicable solution yet. The provincialism ultimately resulted in two different ammonite zonation schemes used for

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subdividing the Tithonian – Early Cretaceous succession of the northern Tethys (Kilian, 1907-1913)

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and the Boreal Realm (Koenen, 1902, 1907). Even in more recent biostratigraphic zonation schemes (e.g. Hoedemaeker, 1987, 1991; Rawson, 1995; Rawson et al., 1996; Rawson and

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Hoedemaeker et al., 1999; Thieuloy, 1977) the correlation of the two realms is limited to rare phases of faunal exchange. Further refinement of the correlations is therefore needed. Two different zonation schemes were established also for calcareous nannofossils, calibrated to the regional ammonite zonations. Most widely used for the Tethys are the nannofossil zonation schemes by Sissingh (1977, 1978) and Bralower et al. (1989). Two zonation schemes are available.for the Boreal. The LK zonation (LK standing for Lower and Kreide, German for Cretaceous) of Jeremiah (2001) is based mainly on boreholes from the Central North Sea Basin, England, the Netherlands and Germany. The BC (Boreal Cretaceous) zonation of Bown et al. (1998) compiles studies by Perch-Nielsen (1979), Jakubowski (1987), Crux (1989) and Mutterlose (1991). For the lowermost Cretaceous (Ryazanian – Hauterivian) the BC zonation is based on material from sections in northeast England, northwest Germany, North Sea cores (Moray Firth Basin, off northeast Scotland, offshore Norway) and the Barents Sea. The correlation with the Boreal ammonite zonation is provided by outcrops where both calcareous nannofossils and

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ACCEPTED MANUSCRIPT ammonites are available, particularly the Speeton section in northeast England and outcrops in northwest Germany. Geochemical proxy data (87Sr/86Sr, δ13C) can be used to overcome the stratigraphic

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problems caused by geographically restricted index taxa, provided that an influence of regional processes on the isotope signature can be ruled out. The Sr-isotope ratio (87Sr/86Sr) is an efficient

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stratigraphic tool for correlating marine sediments on a global scale due to the long residence time

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of Sr in seawater (e. g. Elderfield, 1986; Peterman et al., 1970; Veizer, 1989). The varying Sr/86Sr-signature of seawater as reflected in marine carbonates is not affected by fractionation

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during incorporation. It results from the input of heavy radiogenic Sr due to continental weathering, and the amount of light, non-radiogenic Sr released by hydrothermal activity associated with

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submarine volcanism (Allègre et al., 2010; Veizer, 1989).

Recently, Mutterlose et al. (2014) presented 87Sr/86Sr-curves for the lowermost Cretaceous

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(Berriasian - Barremian), compiling data measured on belemnites from Tethyan (Vocontian Basin,

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Bodin et al., 2009; McArthur et al., 2007) and Boreal sections (Speeton, McArthur et al., 2004). All belemnites have been collected bed-by-bed, thus allowing a calibration with the existing regional

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ammonite zonation scheme.

In the current study, 87Sr/86Sr-data are obtained from 28 belemnite specimens collected from the Lower Cretaceous (Ryazanian – Barremian) Rødryggen section on Wollaston Forland (NorthEast Greenland). The section has been studied with respect to its biostratigraphy. Alsen (2006) established an ammonite biostratigraphic zonation for the Valanginian of North-East Greenland. Pauly et al. (2012a) provided a detailed calcareous nannofossil zonation for Wollaston Forland. Using the Sr-isotope data a reliable correlation to the biostratigraphic zonation of the Tethys can be achieved. Further we present a high-resolution record of Ryazanian to Hauterivian stable isotope ratios (δ13Cbel, δ18Obel) of 102 belemnite specimens covering the positive carbon isotope excursion interval (CIE) of the Valanginian “Weissert” Event (Erba et al., 2004). The Weissert Event is well established in the Tethys (Channell et al., 1993; Gréselle et al., 2011; Kujau et al., 2012; Lini et al., 1992; Weissert et al., 1998), but has also been documented from the western Atlantic and the Pacific (Bornemann and Mutterlose, 2008; Erba et al., 2004; Lini

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ACCEPTED MANUSCRIPT et al., 1992), and from the European and Russian parts of the Boreal Realm (Meissner et al., 2015; Nunn et al., 2010; Price and Mutterlose, 2004,). The stratigraphic position of the isotope anomaly is a well constrained isochronous event (Channell et al., 1993; Hennig et al., 1999; Lini et al., 1992;

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Weissert and Erba, 2004), which makes it a useful stratigraphic tool. The CIE goes along with the drowning of carbonate platforms (Föllmi, 2012; Föllmi et al., 2006;

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Weissert et al., 1998; Wortmann and Weissert, 2000) and changes in calcareous nannofossil

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assemblages. Among these the dramatic decline of nannoconids is perhaps the most prominent (eg. Bersezio et al., 2002; Bornemann and Mutterlose, 2008; Channell et al., 1993; Erba and

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Tremolada, 2004; Barbarin et al., 2012).

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2. Geological setting

In the Early Cretaceous the Greenland-Norwegian Seaway was part of a gateway between the

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Tethys in the south and the Arctic Ocean in the north (fig. 1). It formed during a rifting event that

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started in the late Bajocian (Middle Jurassic) and culminated in the latest Jurassic to earliest Cretaceous (Surlyk, 1978, 2003). The Upper Jurassic and Lower Cretaceous sediments in North-

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East Greenland are represented by up to three kilometres of siliciclastics. Conglomerates and pebbly sandstones are common in the near shore settings, and gradually finer grained sediments were deposited further off-shore (Pauly et al., 2012b; Surlyk, 1978, 2003). The fossiliferous mudand marlstones of the Ryazanian - Hauterivian Albrechts Bugt Member and Rødryggen Member are the distal sediments of the late rifting phase. Due to a Ryazanian drowning event and a subsequent transgression they were deposited on top of the coarse clastics that represent the synrift deposits (Surlyk and Clemmensen, 1975; Surlyk, 1978, 2003).

3. Section The 138 samples analysed here were collected in the Rødryggen section (Pal4/2001, locality 5) in the northern part of the Wollaston Forland in North-East Greenland (N74°32'47.1'', W.19°50'35.5'') during field campaigns from 2000 to 2011. The interval considered here comprises 27 m of Lower Cretaceous sediments, which include 22 m of yellowish mudstones of the Albrechts

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ACCEPTED MANUSCRIPT Bugt Member in the lower part and 5 m claret-coloured silty mudstones of the Rødryggen Member in the upper part (fig 2). For more detailed descriptions of the section see Alsen (2006), Alsen & Mutterlose (2009) and Pauly et al. (2012a, b). The ammonite biostratigraphy of the section has

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been established by Alsen (2006) and Alsen and Mutterlose (2009), assigning the entire succession to the upper Ryazanian to lower Hauterivian. A detailed calcareous nannofossil

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Members as early Ryazanian to late Hauterivian (fig. 3).

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zonation has been published by Pauly et al. (2012a), dating the Albrechts Bugt and Rødryggen

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4. Material and methods

A total of 138 belemnite rostra, collected bed by bed throughout the section, have been

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sampled for major and minor element analysis. Based on the results, 28 samples have been selected for 87Sr/ 86Sr isotope analysis. All 138 samples have been analysed for their stable isotope

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composition (δ13Cbel, δ18Obel). Taxonomically the rostra have been assigned to the genera

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Pachyteuthis, Acroteuthis and Cylindroteuthis (table 1). After having split the rostra in halves dorsoventrally, carbonate powder samples were

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obtained by hand-drilling under a stereomicroscope with a 0.3 mm drill-bit. For analyses, portions of clear calcite were selected. The margins, the apical line and the apex, which are most prone to alteration, were avoided.

Major and minor element analysis (Ca, Mg, Sr, Fe, Mn) was performed at the RuhrUniversität Bochum on an ICP-OES (iCap 6500 Thermo Electron Corporation) on 1.5 mg of sample powder dissolved in 3 M HNO3. Element composition can indicate post-depositional alteration of the belemnite calcite (e.g. Rosales et al., 2004; Veizer and Fritz, 1976; Wierzbowski et al., 2013). Here belemnite samples with Mn-content >50 ppm, Fe-content >200 ppm and/or Strontium contents <1000 ppm were considered diagenetically altered and excluded from further consideration. Strontium isotope ratios (87Sr/86Sr) were determined using a 7-collector Thermal Ionisation Mass spectrometer (TIMS) MAT262 in 3-collector dynamic mode at the Ruhr-Universität Bochum. A detailed description of the sample preparation procedure is given by Meissner et al. (2015) and

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ACCEPTED MANUSCRIPT references therein. As standard reference material to test the repeatability of the measurements NIST NBS 987 and USGS EN-1 were used. The average 87Sr/86Sr-values of the standards were 0.710247 ± 0.000032 2σ (n=276) and 0.709162 ± 0.000026 2σ (n=247), respectively. The

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precision of the sample measurements was better than 0.000007 2σ. The stable isotope compositions (13C/12C, 18O/16O) were measured at the GeoZentrum

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Nordbayern, Friedrich-Alexander Universität Erlangen-Nürnberg. Reproducibility and accuracy is

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better than ± 0.07‰ for both δ13Cbel and δ18Obel. For details see Joachimski et al. (2001). The stable isotope data are given in per mil (‰) relative to V-PDB (Vienna Pee Dee Belemnite). The

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belemnite specimens are stored at the Ruhr-University Bochum.

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5. Results 5.1 Element composition

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Of the belemnites analysed, 33 specimens have Mn-contents exceeding the threshold values

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of 50 ppm and have thus been excluded. Seventeen samples have Fe-concentrations above the threshold of 200 ppm, all but three of these also contain more than 50 ppm Mn. No belemnite

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specimen showed Sr-content below 1000 ppm. In total, 36 of the 138 belemnite samples were excluded from further consideration based on their element composition. The results of element composition and isotope analyses are listed in table 1, samples with element compositions beyond the thresholds are marked in grey.

5.2 Strontium isotopes The 87Sr/86Sr-data from Greenland presented here (n=28; fig. 2) range from 0.707274 (sample GI-123773; 0 m) in the lowermost part of the succession to 0.707486 (sample GI-123819; 27.1 m) in the uppermost part. The resulting curve (LOESS smoothed, factor 0.3) has a steady gradient over the larger part of the section (0-21.5 m). In the upper part (21. 5 - 24 m) it shows a break and a short interval of a more rapid increase of the Sr-isotope ratios. In the uppermost part (25 - 27 m) the Sr-curve comes back to the former gradient.

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ACCEPTED MANUSCRIPT 5.3 Stable carbon and oxygen isotopes The δ13Cbel-data from the 102 belemnite samples considered can be best described dividing the studied interval in two parts (fig. 2). The values from the lower part (0 – 11 m) scatter around a

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mean of 0.03‰, in the upper part (12.7 – 27.1 m) they are more positive with a mean of 0.82‰. Statistical testing (t-test) shows that the difference between the data from the lower and upper part

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is significant with 95% confidence.

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The δ18Obel-data show a shift towards heavier values ~19 m above the base of the section (fig.2). The data from the lower part of the section (0-16 m) vary around a mean of -0.16‰. In the

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upper part (16-27.1 m) the mean value is 0.68‰. The statistical significance of the difference between the δ18Obel-data (difference of means 0.84‰) was checked with a t-test at the 95%-

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confidence level.

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6. Discussion

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6.1 The Ryazanian-Valanginian boundary The good match of the Sr-isotope ratios from Greenland with the Sr-curve based on data

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from southeast France, Spain and northeast England (Mutterlose et al., 2014) is encouraging regarding the potential of belemnite calcite to preserve the “global” 87Sr/86Sr-ratio of Early Cretaceous seawater. The new Sr-data from Greenland help calibrating the different biostratigraphic zonation schemes of the lowermost Cretaceous. Our stratigraphic interpretation of the Sr-isotope curve agrees with the total range of the Rødryggen section suggested by biostratigraphy (Ryazanian - Barremian). A comparison of the Sr-, the calcareous nannofossil- and the ammonite stratigraphy of the Rødryggen section reveals, however, considerable discrepancies. Particularly the position of the Ryazanian / Valanginian boundary is not conclusive (fig 2). The new Sr-data presented here place the Ryazanian / Valanginian boundary ~2 m above the base of the Albrechts Bugt Member (~2 m above the base of the section). This is in agreement with the ammonite biostratigraphy, while nannofossil biostratigraphy defines the base of the Valanginian 6.4 m higher in the section (fig. 2). This discrepancy of the ammonite and Sr-isotope based ages on one hand and the nannofossil findings on the other might be explained by a down-

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ACCEPTED MANUSCRIPT slope transport of the ammonites and belemnites. The Rødryggen section crops out in a low, gently sloping hillside exposed to precipitation, freezing and thawing. The fossils appear to weather out from the calcareous mudstones rather fast, and some downhill transport of macrofossils with

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solifluction at the hills surface can be expected. The nannofossil samples have been taken by digging a trench into the hillside to a depth considered unaffected by solifluction and weathering

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(Pauly et al., 2012a). The sequence of the macrofossils, which are lying in a sensible stratigraphic

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order, suggests them, however, to be lying at or close to their original stratigraphical level (Alsen, 2006).

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Three calcareous nannofossil events, which occur shortly after each other (from bottom to top: last occurrence (=LO) Sollasites arcuatus, first occurrence (=FO) Triquetrorhabdulus

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shetlandensis, FO Micrantholithus speetonensis) have been observed in a number of localities in the North Sea and off Norway. These events define the Ryazanian / Valanginian boundary interval

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in the nannofossil zonations commonly used (Bown et al., 1998; Crux, 1989; Jakubowski, 1987;

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Jeremiah, 2001), with S. arcuatus confined to the uppermost Ryazanian and T. shetlandensis and M. speetonensis appearing in the lowermost Valanginian. All three nannofossil events have been

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observed in the Rødryggen section in this very sequence (Pauly et al., 2012a). It is therefore unlikely that they occur in North-East Greenland with a time-delay relative to the sites in the North Sea and Norwegian Sea. An explanation for the discrepancy regarding the position of the Ryazanian-Valanginian boundary has to be found elsewhere. The correlation of the calcareous nannofossil zonation scheme commonly used for the Boreal lowermost Cretaceous (BC zonation of Bown et al. (1998), Ryazanian - lower Valanginian) is based virtually exclusively on the ammonite biostratigraphy of the Speeton section. The Speeton section covers most of the Lower Cretaceous from the Ryazanian to the Albian but is highly incomplete showing stratigraphic gaps and condensed intervals. Based on "crushed fragments" of Platylenticeras found in the lower D4 beds (= Paratollia beds) by Doyle (Kemper, 1971; Kemper et al., 1981; see fig. 3), these beds have been correlated with the lowermost Valanginan Platylenticeras beds of Germany, the Pseudogarniera undulatoplicatilis zone of the Russian Platform and North-East Greenland and the Tirnovella

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ACCEPTED MANUSCRIPT pertransiens zone of the Tethys. These correlations are supported by the palynomorph Oligosphaeridium complex. O. complex makes it's first appearance in the Tethys in the lower middle T. pertransiens zone (Leereveld, 1997), in northern Germany in the Platylenticeras

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heteropleurum subzone (Below, 1981), in Speeton in the lower/middle Paratollia beds (near boundary D5/D4, precise position unknown; Duxbury, 1977) and in Greenland in the upper P.

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undulatoplicatilis zone (Piasecki, pers. comm., fig. 3).

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In Speeton, S. arcuatus is limited to the upper Ryazanian D6I to D6A beds (fig. 3). The overlying D5 and D4C beds are barren of nannofossils (Crux, 1989). The true stratigraphic range

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of S. arcuatus may therefore extend higher up in the section. According to the integrated stratigraphic data from nannofossils, ammonites, palynomorphs and Sr-isotopes presented here,

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the LO of S. arcuatus has to be placed in the lower Valanginian (fig. 3). This shifts the base of the Boreal nannofossil zone BC3 from uppermost Ryazanian into the lower Valanginian.

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Accepting the position of the Ryazanian / Valanginian boundary in the Rødryggen section

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indicated by Sr-isotope data and ammonite biostratigraphy, the FO of S. arcuatus however seems to be diachronous. In Speeton it is present already in the Ryazanian P. albidum ammonite zone

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(D6I bed), while in the Rødryggen section it is first observed in the basal P. undulatoplicatilis zone (Pauly et al., 2012a, fig. 3). The available Sr-isotope data support the diachroneity: Belemnite samples from the D7A and D6A beds of Speeton have a 87/86Sr of 0.707264 and 0.707265 (McArthur et al., 2004), respectively, corresponding to the late Berriasian (Mutterlose et al., 2014). In the Rødryggen section a belemnite (sample GI-123786) found directly below the FO of S. arcuatus gave a Sr-ratio of 0.707317, corresponding to an early Valanginian age. Preservation of the nannofossils as an explanation for the absence of S. arcuatus in the upper Ryazanian of the Rødryggen section can be ruled out. The entire upper Ryazanian and lower Valanginian are characterised by good to moderate preservation and comparatively high absolute nannofossil abundances (Pauly et al., 2012a,b).

6.2 The Weissert Event and the Valanginian nannoconid decline The ~1.5‰ positive carbon isotope excursion (CIE) of the Valanginian Weissert Event (Erba

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ACCEPTED MANUSCRIPT et al., 2004) is commonly used for stratigraphy and correlation. The CIE has been observed in marine bulk rock samples (Bornemann and Mutterlose, 2008; Channell et al., 1993; Gréselle et al., 2011; Lini et al., 1992; Weissert and Erba, 2004) and biogenic carbonates (Price & Mutterlose,

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2004) as well as in marine organic matter and terrestrial deposits (Gröcke et al., 2005 ; Nunn et al., 2010). The onset and maximum is recorded in the lowermost upper Valanginian, in the Tethyan

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Saynoceras verrucosum ammonite zone (Weissert and Erba, 2004).

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The dataset from the Rødryggen section shows a large scatter of the δ13Cbel values. A possible explanation lies in the origin of the data from different ontogenetic layers of different

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belemnite genera (Acroteuthis, Pachyteuthis and Cylindroteuthis). Despite the large scatter, a positive shift in the δ13Cbel data can be clearly distinguished (fig. 3). The maximum of the positive

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carbon isotope excursion is, however, not clearly recorded in the δ13Cbel-data presented here, as only few belemnite specimens cover the CIE interval.

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A marked decline in the abundance of nannoconids, large and heavily calcified nannoliths of

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unknown taxonomic affiliation, preceeds the CIE in the Tethys (southeast France and northern Italy, Barbarin et al., 2012; Bersezio et al., 2002; Erba et al., 2004; Gréselle et al., 2011), central Atlantic

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(Bornemann and Mutterlose, 2008) and Pacific Ocean (ODP Hole 1149B, Erba et al., 2004). Pauly et al. (2012b) describe a decline of nannoconids in the lowermost Valanginian of the Rødryggen section. By using the re-calibrated Valanginian nannofossil zonation discussed here, this decline falls into the upper lower Valanginian. In agreement with the observations in low latitudinal settings, the decline of nannoconid abundance is just preceding the δ13Cbel shift towards higher mean values (fig.4).

6.3 The lower / upper Valanginian boundary The discrepancy of the ammonite and calcareous nannofossil biostratigraphy regarding the lower / upper Valanginian transition in the Rødryggen section can not be resolved by the 87Sr/86Sr dataset presented here, due to the low sample resolution in this interval (fig. 2). The onset of the positive CIE has been dated as early late Valanginian in other sections. By extrapolating these observations to the Rødryggen section, the lower / upper Valanginian boundary is positioned

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ACCEPTED MANUSCRIPT between 11-13 m above the base of the Albrechts But Member. This datum is in agreement with the ammonite zonation, but it conflicts with the LO of M. speetonensis (17 m above base of the section). In the Boreal LK and BC nannofossil zonation schemes, the LO of M. speetonensis marks

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the base of the upper Valanginian (fig. 2). For the Boreal Valanginian, few sections allow for correlation of nannofossil events to the

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ammonite zonation. One is the Speeton section, where the upper Valanginian is missing (Neale,

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1962; Rawson, 1971). In the sections in northern Germany, the first abundant and consistent nannofossil floras occur in basal upper Valanginian (Mutterlose, 1991). In the Wąwał section in

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central Poland M. speetonensis has been observed in only one sample belonging to the Prodichotomites hollwedensis ammonite zone (Mutterlose, 1993). Our observations imply, that the

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LO of M. speetonensis has been imprecisely correlated due to stratigraphic limitations of the outcrops. The integrated chemo- and biostratigraphic data from the Rødryggen section suggest

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that M. speetonensis ranges into the late Valanginian.

6.4 The Valanginian / Hauterivian boundary

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The position of the Valanginian / Hauterivian boundary established by Alsen (2006) and Alsen and Mutterlose (2009) based on ammonite biostratigraphy deviates by 6 m from the one suggested by calcareous nannofossils and Sr-isotope stratigraphy. By definition the base of the Hauterivian is drawn at the first occurrence of Acanthodiscus radiatus (Thieuloy, 1977; Mutterlose, 1996), an ammonite species common in the Tethys but also known from the Boreal Realm. In northwest Germany, A. radiatus first appears in the upper Endemoceras amblygonium zone (Kemper et al., 1981; Mutterlose, 1984, 1996). In Speeton this event is positioned even higher, in the Endemoceras regale zone (Rawson, 1971). The inclusion of the lower part of the E. amblygonium zone in the Valanginian, which has consequently been suggested (Kemper et al., 1981; Rawson, 1983; Rawson and Hoedemaeker et al., 1999), is supported by the Sr-isotope data of McArthur et al. (2007) and Mutterlose et al. (2014). The nannofossil Eprolithus antiquus, which defines the base of nannofossil zone BC7 (Crux, 1989; Bown et al., 1998), consistently appears in northwest Germany in the E. amblygonium to

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ACCEPTED MANUSCRIPT Endemoceras noricum zone (Mutterlose, 1991), in Speeton in the upper E. amblygonium zone (fig. 3). It is found also in the North Sea (Jeremiah, 2001) and in northeast Greenland (Pauly et al., 2012a). A short-lived earlier occurrence of E. antiquus has been observed in the upper Valanginian

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of the West Netherlands Basin and Lower Saxony Basin. Despite this scattered Valanginian occurrence, E. antiquus is regarded as a reliable nannofossil marker for the base of the

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Hauterivian.

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In the Rødryggen section the lowermost Hauterivian is very condensed. This is reflected by a break in the Sr-isotope curve (fig. 2). The closely spaced occurrences of the nannofossil marker

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species for nannofossil zones BC6 to BC8 document that the lowermost Hauterivian zones BC6 and BC7 are represented by 0.4 m of sediment at most.

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Due to the condensed nature of the lowermost Hauterivian, E. antiquus was observed by Pauly et al. (2012a) in one sample only (sample 469464, 21.9 m above base of the Albrechts Bugt

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Member). The corresponding Sr-isotope values (0.707382, 21.3 m; 0.707399, 21.7 m) agree well

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with the Sr-isotope ratio of about 0.70739 given in the compiled Sr-curve of Mutterlose et al. (2014) for the Valanginian / Hauterivian boundary. Our Sr-data therefore clearly support the position of the

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base of the Hauterivian as suggested by nannofossil biostratigraphy. Based on ammonite fragments identified as Simbirskites sp., Alsen (2006) and Alsen and Mutterlose (2009) placed the base of the Hauterivian 6 m further down in the section. In contrast to the ammonite specimens found in the Rødryggen Member which can be clearly identified as Simbirskites, the ammonite fragments from the Albrechts Bugt Member are poorly preserved. Their identification as Simbirskites sp. did not unequivocally withstand re-examination.

6.5 Lowermost Cretaceous paleotemperatures The δ18Obel-data presented here show an increase from average values of 0‰ in the upper Ryazanian and lower Valanginian to ~1‰ in the upper Valanginian and lower Hauterivian (fig. 2). A similar trend has been observed in the δ18Obel-data from southeast France and Spain (McArthur et al., 2007), northern Germany (Podlaha et al., 1998), Western Siberia (Price and Mutterlose, 2004)

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ACCEPTED MANUSCRIPT and Arctic Svalbard (Price and Nunn, 2010). This increase is independently supported by oxygen isotope data from bulk rock carbonate (northern Italy; Weissert and Erba, 2004) and fish teeth from southeast France (Barbarin et al., 2012).

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Provided that it has not been diagenetically altered, the δ18O of biogenic calcite is the result of ambient sea-water temperatures during calcification and the oxygen isotope composition of the

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water it precipitates from. The δ18O of seawater is influenced by the volume of polar ice and the

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salinity, which in turn is the result of evaporation and freshwater input.

Clumped isotope data of belemnite calcite from Western Siberia suggest increased δ18O of

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seawater and / or decreased precipitation and riverine input coincident with low late Valanginian temperatures (Price and Passey, 2013). Intervals of cool climate with at least seasonally low water

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temperatures in the earliest Cretaceous are supported by the occurrence of glendonites and dropstones in the upper lower and upper Valanginian (Frakes and Francis, 1988; Kemper and

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Schmitz, 1975; Price and Nunn, 2010).This late Valanginian cooling is reflected in the oxygen

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isotope data from Greenland presented here. Our data document a shift towards heavier (=colder)

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δ18Obel values, which postdates the onset and the peak of the CIE.

7. Conclusions

This study presents a correlation of strontium and carbon isotope (87Sr/86Sr, δ13Cbel) based stratigraphy within the framework of existing ammonite- and nannofossil zonations of the lowermost Cretaceous. The stratigraphic range of the Rødryggen section (Wollaston Forland, North-East Greenland) resulting from the Sr-isotope stratigraphy (Ryazanian - Barremian) agrees with the results from biostratigraphy. Mismatches regarding stage/ substage boundaries resulted in a reconsideration of the nannofossil biostratigraphy of the Boreal Lower Cretaceous. The correlation of the nannofossil zonation of this interval is based primarily on material from the Ryazanian - Hauterivian of Speeton (northern England), a section which is in part very condensed or incomplete. The average increase of about 1.2‰ in the δ13Cbel-data matches records of the carbon isotope excursion associated with the upper Valanginian Weissert Event from other areas of the world. The

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ACCEPTED MANUSCRIPT isotope anomaly is isochronous and well-established in stratigraphic correlation. Here it is a valuable datum for the determination of the lower / upper Valanginian boundary. Based on the available stratigraphic data we conclude the following. a) The first occurrence (FO) of

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the nannofossil Sollasites arcuatus is probably diachronous. b) The last occurrence (LO) of S. arcuatus, which defines the base of nannofossil zone BC3 has been falsely assigned to the latest

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Ryazanian and is in fact early Valanginian of age. c) The LO of Micrantholithus speetonensis,

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marking the early / late Valanginian transition in Boreal nannofossil zonations, might actually be of late Valanginian age.

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By using the re-calibration of the Valanginian nannofossil zonation discussed here, the marked decline in the abundance of Nannoconus spp. in the Rødryggen section falls into the upper

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lower Valanginian. In agreement with the observations on the nannoconid decline associated with the Weissert Event in the Tethys, this decline just precedes the shift towards higher mean δ13Cbel.

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This makes the decrease in nannoconid abundance observed by Pauly et al. (2012b) the first

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documentation of the Valanginian nannoconid crisis in the Boreal Realm. The oxygen isotope record (δ18Obel) presented here shows an increase of 1‰ during the

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Valanginian. This agrees well with Lower Cretaceous oxygen isotope records from other areas of the Boreal Realm and the Tethys, as well as other geochemical and paleoecological proxies suggesting a late Valanginian cooling.

8. Acknowledgements

We appreciate logistic support by the Geological Survey of Denmark and Greenland (GEUS, Copenhagen). Thank you to all Danish colleagues involved for assistance and the enjoyable field campaigns in North-East Greenland. We are grateful to the staff of the labs of the FriedrichAlexander Universität Erlangen Nürnberg / GeoZentrum Nordbayern and of the Ruhr-Universität Bochum for element composition analysis and measurements of C-, O- and Sr-isotopes. Financial support of the German Research foundation (DFG, MU 667/38-1) is gratefully acknowledged. We appreciate the effort and time two unknown reviewers spent on improving the manuscript.

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ACCEPTED MANUSCRIPT 9. References

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10. Taxonomic Appendix

Nannofossils

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Eprolithus antiquus Perch-Nielsen, 1979a

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Micrantholithus speetonensis Perch-Nielsen, 1987 Nannoconus Kamptner, 1931

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Sollasites arcuatus Black, 1971a Tegumentum octiformis (Köthe, 1981) Crux, 1989

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Triquetrorhabdulus shetlandensis Perch-Nielsen, 1988

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Palynomorphs/ Dinoflagellate cysts

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Ammonites

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Oligosphaeridium complex (White, 1842) Davey and Williams, 1966

Acanthodiscus Uhlig, 1905

Acanthodiscus radiatus (Buguière, 1789) Busnardoites campylotoxus

Dichotomites Koenen, 1909

Dichotomites crassus, Kemper, 1978 Endemoceras Thiermann, 1963 Endemoceras amblygonium (Neumayr and Uhlig, 1881) Endemoceras noricum (Roemer, 1836) Paratollia Casey, 1973 Peregrinoceras Sazonova, 1971 Peregrinoceras albidum Casey, 1973 Platylenticeras Hyatt, 1900

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ACCEPTED MANUSCRIPT Polyptychites Pavlow, 1892 Polyptychites michalskii (Bogoslowsky, 1902) Saynoceras Munier-Chalmas, 1894

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Saynoceras verrucosum (D'Orbigny, 1841) Simbirskites Pavlow, 1894

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Tirnovella pertransiens (Sayn, 1901)

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Belemnites Acrotheutis Stolley, 1911

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Cylindrotheutis Bayle, 1878

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Pachytheutis Bayle, 1878

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ACCEPTED MANUSCRIPT Figure captions Fig. 1: Map of the Valanginian paleogeography, modified from Smith et al. (1994) showing the position of the Rødryggen section, Wollaston Forland, North-East Greenland. Indicated in grey are

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areas presumably above sea-level in the Valanginian; GNS = Greenland-Norwegian Seaway.

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Fig. 2: Lithic log of the Rødryggen section (Pal-4/2001, locality 5) with ammonite zones (Alsen,

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2006), calcareous nannofossil zonation (Pauly et al., 2012a), 87Sr/86Sr data (this study). Graphs on the right show belemnite stable isotope data (δ18Obel,δ13Cbel) in permil V-

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PDB (this study) and absolute abundance data of Nannoconus spp. of Pauly et al. (2012b) from the same section given as 107 specimen per gram of sediment. In the stable isotope data three

MA

belemnite genera are distinguished (Acroteuthis, Pachyteuthis, Cylindroteuthis). The arrows at the top mark the average stable isotope ratio value of each genus. Black (Pachyteuthis & Acr./Pachy.)

D

and grey lines (Acroteuthis & Cylindroteuthis) represent LOESS-smoothing (factor 0.4). Broken

TE

lines mark the 4m sampling gap, where no belemnite specimen were available.

AC CE P

Fig. 3: Correlation of ammonite and calcareous nannofossil zonations and the first occurrence of the palynomorph Oligosphaeridium complex of the lowermost Cretaceous of northern Germany, Speeton (northeast England) and the Wollaston Forland (North-East Greenland) to the Tethyan ammonite biostratigraphy. Ammonite zonations are from Alsen (2006) and Mutterlose et al. (2014), calcareous nannofossil biostratigraphy from Crux (1989), Mutterlose (1991), Pauly (2012a), Möller and Mutterlose (2014), and palynomorph stratigraphy from Leereveld (1997), Below (1981), Duxbury (1977) and Piasecki (pers.comm.).

26

MA

NU

SC

RI

PT

ACCEPTED MANUSCRIPT

AC CE P

TE

D

Figure 1

27

Figure 2

AC CE P

TE

D

MA

NU

SC

RI

PT

ACCEPTED MANUSCRIPT

28

Figure 3

AC CE P

TE

D

MA

NU

SC

RI

PT

ACCEPTED MANUSCRIPT

29

ACCEPTED MANUSCRIPT Table 1

original sample no. depth [m] sample no.

identification

GI-123773

W1

0.00

Pachyteuthis sp.

389460

2488

1445

80

34.9

-0.80

GI-123773

W2

0.00

Acroteuthis sp.

386750

1910

1531

97

37.3

1.33

0.67

GI-123773

W3

0.00

Acroteuthis sp.

390240

1666

1612

73

14.2

0.93

-2.42

GI-123774

W4

0.50

Pachyteuthis sp.

396330

553

1563

41

5.1

0.05

1.65

GI-123774

W5 (1)

0.50

Pachyteuthis sp.

397760

1424

1442

42

6.7

0.36

-0.18

GI-123774

W5 (2)

0.50

Pachyteuthis sp.

0.46

-0.14

GI-123774

W6

0.50

Pachyteuthis sp.

395820

1199

1248

86

24.6

-0.46

0.44

GI-123775

W7

0.90

Pachyteuthis sp.

388290

3430

1454

96

52.4

-2.68

-1.08

GI-123775

W8

0.90

Pachyteuthis sp.

394140

1371

1437

70

24.5

1.26

-1.43

GI-123775

W9

0.90

Pachyteuthis sp.

393710

1591

1453

89

12.5

-0.61

0.32

GI-123776

W10 (1)

1.50

Cylindroteuthis sp.

391930

1239

1656

65

5.7

0.41

0.55

GI-123776

W10 (2)

1.50

Cylindroteuthis sp.

0.46

0.64

GI-123776

W11

1.50

Cylindroteuthis sp.

395490

1284

1326

57

6.4

0.59

-1.39

GI-123776

W12

1.50

Pachyteuthis sp.

387390

2524

1336

124

36.1

-1.08

0.62

GI-123777

W13

2.00

Pachyteuthis sp.

392780

1455

61

22.2

-0.51

0.37

GI-123777

W14

2.00

Pachyteuthis sp.

389350

1736

1282

126

39.5

-0.11

0.28

GI-123777

W15 (1)

2.00

Pachyteuthis sp.

389420

1489

1362

49

12.9

0.27

0.21

W15 (2)

2.00

Pachyteuthis sp.

0.32

0.22

GI-123778

W16

2.50

Pachyteuthis sp.

384010

2730

1788

80

42.6

-0.11

-0.72

GI-123778

W17 (1)

2.50

Pachyteuthis sp.

2473

1293

103

25.3

-0.62

0.01

W17 (2)

2.50

Pachyteuthis sp.

D

Table 1

-0.63

-0.04

GI-123778

W18

2.50

Pachyteuthis sp.

394010

915

1750

60

10.8

1.21

-1.63

GI-123779 GI-123779

W19 W20

2.80 2.80

Pachyteuthis sp. Pachyteuthis sp.

387500 384060

2765 4073

1764 1473

176 210

97.6 56.2

0.65 -2.41

-3.94 -1.33

GI-123779

W21

2.80

Pachyteuthis sp.

392230

1596

1236

67

21.1

0.23

0.30

394150

1160

1380

87

22.4

-0.12

1.01

-0.11

1.06

W22 (1)

3.15

W22 (2)

3.15

Acroteuthis/ Pachyteuthis sp. Acroteuthis/ Pachyteuthis sp.

PT

RI

SC

NU

1182

MA

387880

TE

AC CE P

GI-123780

13 13 Ca [ppm] Mg [ppm] Sr [ppm] Fe [ppm] Mn [ppm] δ C [‰] δ C [‰]

87

Sr/86Sr

-0.03 ####### #######

#######

#######

#######

#######

GI-123780

W23

3.15

Acroteuthis/ Pachytheutis sp.

GI-123780

W24

3.15

Acroteuthis/ Pachyteuthis sp.

388260

3081

1404

105

70.8

-1.77

-0.24

GI-123781

W25

3.40

Pachyteuthis sp.

380380

2766

1329

190

59.9

-1.64

-0.68

GI-123781

W26

3.40

Pachyteuthis sp.

391440

2579

1378

68

20.4

-1.39

-0.14

GI-123781

W27 (1)

3.40

Pachyteuthis sp.

394090

2048

1455

73

85.8

-0.70

-0.31

W27 (2)

3.40

Pachyteuthis sp.

-0.65

-0.27

GI-123782

W28

3.70

Pachyteuthis sp.

388550

1427

1288

44

6.5

0.57

-2.11

GI-123782

W29

3.70

Acroteuthis sp.

390360

2119

1431

93

31.6

0.06

0.07

GI-123782

W30

3.70

Acroteuthis sp.

396950

980

1329

54

12.4

-0.87

0.51

#######

GI-123783

W31

4.00

Acroteuthis sp.

339830

753

1518

70

37.7

2.33

-2.57

#######

GI-123783

W32 (1)

4.00

Pachyteuthis sp.

393690

939

1620

49

7.1

0.28

0.11

W32 (2)

4.00

Pachyteuthis sp.

0.26

-0.09

GI-123783

W33

4.00

Pachyteuthis sp.

393710

1414

1496

39

27.8

-0.05

0.08

GI-123784

W34

4.40

Pachyteuthis sp.

386220

2241

1664

45

8.9

-0.30

0.02

389290

3717

1356

214

63.6

-2.12

-2.05

30

ACCEPTED MANUSCRIPT W35

4.40

Pachyteuthis sp.

387590

2519

1538

63

22.8

0.07

-1.16

GI-123784

W36

4.40

Pachyteuthis sp.

389140

2530

1330

248

115

-1.79

0.22

GI-123785

W37

4.70

Pachyteuthis sp.

388780

2183

1482

60

11

-0.36

-0.70

GI-123785

W38 (1)

4.70

Pachyteuthis sp.

392250

1097

1371

135

61.2

-0.18

0.84

W38 (2)

4.70

Pachyteuthis sp.

-0.04

0.83

GI-123785

W39

4.70

Pachyteuthis sp.

388910

1664

1371

113

GI-123786

W40

4.90

Pachyteuthis sp.

390620

1260

1322

44

GI-123786

W41

4.90

Pachyteuthis sp.

383740

3851

1594

77

36.8

0.80

-1.33

GI-123786

W42

4.90

Pachyteuthis sp.

386520

2620

1473

75

18.1

0.28

-0.43

GI-123787

W43 (1)

6.20

Pachyteuthis sp.

390700

905

1734

6.5

1.65

-0.49

W43 (2)

6.20

Pachyteuthis sp.

1.64

-0.49

original sample no. depth [m] sample no.

identification

GI-123787

W44

6.20

Pachyteuthis sp.

392590

GI-123787

W45

6.20

Pachyteuthis sp.

388100

GI-123788

W46

6.50

Pachyteuthis sp.

GI-123788

W47

6.50

GI-123788

W48 (1)

52

-0.92

0.07

9.4

-0.31

-0.64

RI

SC

NU

Table 1 (cont.)

PT

GI-123784

34

40

5.9

-0.52

0.21

1475

1295

110

32.8

-0.06

-1.15

389380

2356

1518

151

28.4

0.39

-0.12

Pachyteuthis sp.

396060

1968

1616

76

26.4

-0.24

0.81

6.50

Pachyteuthis sp.

3133

1838

237

118

-0.65

-4.39

W48 (2)

6.50

Pachyteuthis sp.

-0.72

-4.36

GI-123789

W49

7.00

Pachyteuthis sp.

391440

1240

1458

87

21.6

-0.91

-0.16

GI-123789

W50

7.00

Pachyteuthis sp.

390770

1709

1455

43

13.2

-0.84

0.29

GI-123789

W51

7.00

Cylindroteuthis sp.

393150

1011

1753

40

5.3

-1.35

388400

GI-123790

W52

7.30

Cylindroteuthis sp.

388520

2227

1431

61

13.1

0.22

0.05

394100

962

1472

57

7.2

0.98

0.47

0.96

0.56

W53 (1)

7.30

W53 (2)

7.30

GI-123790

W54

7.30

GI-123791

W55

7.70

GI-123791

W56

7.70

GI-123791

W57

7.70

GI-123792

W58 (1)

8.00

W58 (2)

8.00

GI-123792

W59

8.00

GI-123792

W60

8.00

GI-123793

W61

8.50

GI-123793

W62

8.50

GI-123793

W63

8.50

GI-123794

W64 (1)

9.00

384570

TE

AC CE P

GI-123790

Acroteuthis/ Pachyteuthis sp. Acroteuthis/ Pachyteuthis sp. Acroteuthis/ Pachyteuthis sp. Acroteuthis/ Pachyteuthis sp. Acroteuthis/ Pachyteuthis sp. Acroteuthis/ Pachyteuthis sp. Acroteuthis/ Pachyteuthis sp. Acroteuthis/ Pachyteuthis sp. Acroteuthis/ Pachyteuthis sp. Acroteuthis/ Pachyteuthis sp. Acroteuthis/ Pachyteuthis sp. Acroteuthis/ Pachyteuthis sp. Acroteuthis/ Pachyteuthis sp. Acroteuthis/ Pachyteuthis sp.

1314

MA

1206

D

13 13 Ca [ppm] Mg [ppm] Sr [ppm] Fe [ppm] Mn [ppm] δ C [‰] δ C [‰]

381420

1407

1378

121

50.4

-1.08

0.58

383610

1456

1312

61

25

0.26

0.18

385680

958

1678

57

3.6

1.88

0.64

384940

774

1370

43

2.7

-1.08

-0.97

378930

2032

1470

68

29

-0.84

-0.19

-0.78

-0.06

385530

809

1683

45

4.7

1.30

0.28

383820

983

1503

48

11.6

2.62

-0.66

384370

1249

1449

112

36.5

0.83

0.03

381570

1976

1336

66

24.4

0.26

-0.01

382510

1354

1309

71

12.5

-1.21

0.56

382820

1159

1349

58

32.6

-0.51

0.53

31

#######

87

Sr/86Sr

#######

#######

#######

ACCEPTED MANUSCRIPT W64 (2)

9.00

GI-123794

W65

9.00

GI-123794

W66

9.00

GI-123795

W67

GI-123795 GI-123795

Acroteuthis/ Pachyteuthis sp. Acroteuthis/ Pachyteuthis sp.

-0.57

0.53

3322

1511

92

30.6

0.11

-0.67

Pachyteuthis sp.

383040

1304

1301

47

10.9

-0.85

0.19

9.50

Pachyteuthis sp.

384650

1631

1472

109

15.3

-0.33

-0.57

W68

9.50

Acroteuthis sp.

389370

709

1325

66

20.8

1.07

-0.21

9.50 9.50 10.00 10.00 10.00 11.00 11.00 11.00 12.00 12.70

Acroteuthis sp.

385750

2259

1479

215

119

Acroteuthis sp.

389740 392100 390510 385600 383390

2047 1613 1859 2067 1734

1274 1226 1481 1205 1654

136 52 95 130 80

GI-123798 GI-123799

W69 (1) W69 (2) W70 W71 W72 W73 W74 (1) W74 (2) W75 W76

Acroteuthis sp.

394380 389980

1117 1029

1449 1476

119 99

136 36.7

-0.89 -0.82 0.38 0.32 0.25 -1.69 -0.17 -0.20 0.79 1.57

-0.96 -1.01 -0.23 0.21 -1.75 -0.88 0.75 0.76 -0.39 -0.52

GI-123799

W77

12.70

Acroteuthis sp.

383790

1948

1341

203

202

0.43

-0.04

GI-123799

W78

12.70

Acroteuthis sp.

388870

824

1510

132

29.9

1.57

-0.12

388640

1185

1264

46

8.9

1.08

-0.02

388650

1007

1465

25

5.0

1.32

-0.66

Acroteuthis sp. Acroteuthis sp.

Acroteuthis sp.

GI-118554

CM8

13.10

Acroteuthis or Cylindroteuthis sp.

GI-123800

CM7

13.50

Acroteuthis sp.

Table 1 (cont.) identification

13 13 Ca [ppm] Mg [ppm] Sr [ppm] Fe [ppm] Mn [ppm] δ C [‰] δ C [‰]

#######

#######

#######

#######

#######

87

Sr/86Sr

D

original sample no. depth [m] sample no.

NU

Acroteuthis sp.

32.7 11.6 37.2 72.7 31.3

RI

Acroteuthis sp.

SC

Acroteuthis sp.

MA

GI-123796 GI-123796 GI-123796 GI-123797 GI-123797

PT

374750

391810

1662

1407

392480

580

1414

46 25

4.4

no powder left after Sr 1.18 0.06

393630

735

1374

15

3.1

-0.18

1.56

389960

1009

1705

24

2.2

3.77

-0.32

Cylindroteuthis sp.

392690

1041

1250

56

7

1.66

0.56

19.00

Cylindroteuthis sp.

396120

590

1234

73

112

-1.02

0.05

W82 (1)

19.00

Cylindroteuthis sp.

395380

1380

1627

87

110

2.11

-2.72

GI-123801

W82 (2) W83

19.00 19.00

Acroteuthis sp.

395770

481

1465

88

51.3

2.12 2.43

-2.64 0.73

GI-123802

W84

20.00

Acroteuthis sp.

392600

1066

1143

118

45.5

1.06

1.19

GI-123803

W85

20.80

Cylindroteuthis sp.

394220

2010

1268

96

14.4

1.41

0.92

GI-123803

W86

20.80

Cylindroteuthis sp.

394430

1379

1548

83

11.4

-0.13

0.54

GI-123803

W87 (1)

20.80

Cylindroteuthis sp.

392750

2165

1120

85

14.7

-0.54

0.91

-0.52

0.97

3022 1475 1079

1512 1441 1183

920 228 81

431 27.2 26.4

-1.56 0.95 0.45

-0.47 0.62 0.30

GI-123800 GI-118555

W79 CM6

13.50 14.50

Acroteuthis sp.

GI-118558

CM5

18.50

? Pachyteuthis sp.

GI-123801

CM4

19.00

Acroteuthis sp.

GI-123801

W80

19.00

GI-123801

W81

GI-123801

AC CE P

TE

sp. indet.

7.4

#######

W87 (2)

20.80

Cylindroteuthis sp.

GI-123803 GI-123804 GI-123804

W88 W89 W90

20.80 21.30 21.30

Acroteuthis sp.

?

381160 391590 394000

GI-123804

W91

21.30

Acroteuthis sp.

393430

2036

1223

56

4.9

0.60

0.18

#######

GI-123805

W92 (1)

21.70

Acroteuthis sp.

393020

1791

1287

59

5.6

0.52

1.30

#######

W92 (2)

21.70

Acroteuthis sp.

0.45

1.30

GI-123805

W93

21.70

Acroteuthis sp.

393690

1093

1734

56

8.3

2.13

0.94

GI-123805 GI-123806 GI-123807 GI-123807

W94 W95 W96 W97 (1)

21.70 22.00 22.70 22.70

Acroteuthis sp.

394800 397400 391000 394660

1381 791 2262 1436

1194 1260 1133 1266

118 101 272 106

82.8 27.1 91.5 5.5

0.80 0.63 -0.50 1.09

-0.39 0.57 0.79 1.36

Acroteuthis sp.

Acroteuthis sp. Acroteuthis sp. Acroteuthis sp.

32

#######

ACCEPTED MANUSCRIPT 22.70 22.70 23.30 23.30 23.30 23.90 23.90

GI-123809

W103

23.90

GI-123809

W104

23.90

GI-123810

W105

GI-123810

W106

GI-123810

390310 384590 385690 392510 388230

1791 2004 1820 1491 923

Acroteuthis sp.

385550

1802

Acroteuthis sp.

382970

1359

24.40

Acroteuthis sp.

383000

1890

1143

67

24.40

Acroteuthis sp.

375900

3624

1201

106

W107 (1)

24.40

Acroteuthis sp.

379400

2371

1126

542

W107 (2)

24.40

Acroteuthis sp.

GI-123811

W108

24.70

Acroteuthis sp.

386260

907

GI-123814

W109

25.00

Acroteuthis sp.

380280

1973

1146

87

GI-123812

W110

25.00

Acroteuthis sp.

381370

2330

1086

162

GI-123813

W112

25.50

Acroteuthis sp.

389400

2302

1168

114

GI-123813

W113 (1)

25.50

Acroteuthis sp.

387540

2509

1238

76

GI-123814

W113 (2) W114

25.50 25.50

Acroteuthis sp.

390910

1425

1402

63

GI-123814

W115

25.90

Acroteuthis sp.

383510

2025

1129

26.15 26.15 26.15 26.15 26.30 26.30 26.30

Acroteuthis sp.

386590 362120 390850

2482 2189 1411

1341 1127 1425

D

W97 (2) W98 W99 W100 W101 W102 (1) W102 (2)

Acroteuthis sp.

GI-123807 GI-123808 GI-123808 GI-123808 GI-123809

2167 1794 1914

1156 1156 1124

Acroteuthis sp. Acroteuthis sp. Acroteuthis sp.

1356 1319 1063 1075 1580

63 176 70 225 49

14.2 18.4 22.8 116 7.8

1578

56

26.1

1285

472

Acroteuthis sp. Acroteuthis sp.

Acroteuthis sp. Acroteuthis sp.

392130 393000 389340

Acroteuthis sp.

NU

1.32 0.60 0.88 1.07 0.78 1.06 0.92

0.97

1.39

0.71

0.48

6.2

1.16

1.00

136

-0.07

0.57

-0.05

0.25

RI

175

327

0.37 0.90

10.1

0.83

0.69

#######

47.3

-0.44

0.76

#######

100

1.09

0.58

20.1

0.04

1.01

19.1

0.06 1.55

1.01 0.62

1310

513

-0.14

0.38

162 482 64

94.5 315 4.9

568 75 49

16.8 2.9 4.6

0.82 -0.08 3.02 2.95 1.04 0.88 0.47

0.82 0.74 -2.02 -1.99 0.71 0.29 0.71

13.6

GI-123817

W122

26.50

Acroteuthis sp.

391880

1409

1159

105

5.8

0.71

0.78

GI-123817

W123 (1)

26.50

Acroteuthis sp.

391960

1795

1276

59

3.4

1.06

0.46

1.01

0.39

AC CE P

identification

Ca [ppm] Mg [ppm] Sr [ppm] Fe [ppm] Mn [ppm] δ13C [‰] δ13C [‰]

W123 (2)

26.50

GI-123817

W124

26.50

Acroteuthis sp.

391710

1801

1265

60

9.7

0.94

0.92

GI-123817

W125

26.50

Acroteuthis sp.

387520

1460

1122

215

45.8

0.68

0.89

GI-123818

W126

26.75

Acroteuthis sp.

387550

1616

1014

92

15.6

-0.50

0.72

GI-123818

W127

26.75

Acroteuthis sp.

388740

2272

1155

148

84.5

0.86

1.20

GI-123818

W128 (1)

26.75

Acroteuthis sp.

389740

2056

1099

181

55.8

0.34

0.70

0.21

0.66

1.55

1.37

W128 (2)

26.75

GI-123819

W129

27.10

Acroteuthis sp.

394410

910

1263

52

3.4

GI-123819

W130 (1)

27.10

Acroteuthis sp.

390950

2080

1207

55

5.5

GI-123819 GI-123819

W130 (2) W131 W132 (1) W132 (2)

390530 385630 387470 389370

2093 3470 2365 2346

1208 1299 1288 1288

93 166 107 128

27.5 82.6 37.3 48

Acroteuthis sp.

33

#######

1.33

69

original sample no. depth [m] sample no.

27.10 27.10

#######

0.03

SC

1182

1.06 1.13 0.20 -0.35 -0.14 0.56 0.44

PT

Acroteuthis sp.

MA

W116 W117 W118 (1) W118 (2) GI-123816 W119 GI-123816 W120 GI-123816 W121 Table 1 (cont.)

Acroteuthis sp.

TE

GI-123815 GI-123815 GI-123815

Acroteuthis sp.

#######

87

Sr/86Sr

#######

####### -0.57 -0.08

0.31 0.25