Palaeotemperatures indicated by Upper Jurassic (Kimmeridgian-Tithonian) fossils from Mallorca determined by oxygen isotope composition

PALAEO , ELSEVIER

Palaeogeography, Palaeoclimatology, Palaeoecology 110 (1994) 1 10

Palaeotemperatures indicated by Upper Jurassic (Kimmeridgian-Tithonian) fossils from Mallorca determined by oxygen isotope composition G . D . Price, B.W. Sellwood * Postgraduate Research lnstitute fi)r Sedimentology, The UniversiO,. P.O. Box 227, Whiteknights, Reading, RG6 2AB. Ulx"

Received 17 September 1993; revised and accepted 1 December 1993

Abstract

The oxygen and carbon composition of calcite has been determined for belemnites, ammonite aptychi and the matrix surrounding these fossils, from the Kimmeridgian-Tithonian of Mallorca. Petrography, cathodoluminescence and trace element analyses indicate that both ammonite aptychi and matrix has been diagenetically altered whereas the belemnites have undergone minimal or no modification. The belemnites give the heaviest oxygen isotope values of +0.04 to -0.99%,, PDB and lighter values of -0.71 to 3.98%0 PDB come from the ammonite aptychi and matrix. The carbon isotopic compositions obtained from all the fossils are positive and are similar to those derived from modern marine shallow-water skeletons. Palaeotemperatures calculated on the basis of the oxygen isotopic composition of the belemnites give a range of values from 13.6' to 16°C. These results agree with Late Jurassic palaeotemperatures from similar palaeolatitudes.

1. Introduction

Palaeotemperature investigations using oxygen isotopic ratios in skeletal materials pioneered by Urey (1947) and Epstein et al. (1953) are now well established (e.g. Marshall, 1992; Hudson and Anderson, 1989). The method is based on the observation that the ratio of the two stable isotopes of oxygen (1~'O and 1sO), when precipitated in carbonate from a surrounding solution, is temperature dependent (Spicer and Corfield, 1992). However the preservation of the palaeotemperature record can be affected by post-depositional isotopic exchange caused by diagenesis and factors such as 'vital effects' and large scale variations in * Corresponding author. 0031-0182/94/$7.00 ~) 1994 Elsevier Science B.V. All rights reserved SSDI 01~31-0182(93)E0201-4

the isotopic composition of surface sea water need to be considered when interpreting oxygen isotope data (Marshall, 1992). Reconstructions of past global temperatures have been largely based upon oxygen isotopic data and palaeobotanical studies (e.g. Parrish and Spicer, 1988). The Mesozoic Era has often been described as warm and equable (Hallam, 1985; 1993), high latitudes have typically been considered areas of relative warmth, whilst the temperatures of low latitudes are thought to have been similar to those of today. Many studies have concentrated upon the Cretaceous period because of the greater availability of well preserved material suitable for oxygen isotope analysis. Recently palaeoclimate models have been proposed for the Late Jurassic (e.g. Valdes and Sellwood, 1992; Valdes, 1993: Moore et al.,

2

G.D. Price, B. W. Sellwood/Palaeogeography, Palaeoclimatology, Palaeoecology 110 (1994) 1-10

1992a,b) but to constrain such models accurate ocean palaeotemperatures are required. The objectives of this paper are firstly to investigate diagenetic and isotopic variations in a number of different Kimmeridgian-Tithonian calcareous macrofossils, together with the surrounding matrix from an originally mid-palaeolatitudinal site, the island of Mallorca, in order to identify which organisms provide the most 'reasonable' palaeotemperatures. The diagenetic responses of the different macrofossils are assessed through applica-

tion of chemical analyses, stable isotopic analyses and cathodoluminescence (CL). The results of these studies are compared with the published data for the Late Jurassic.

2. Regional geology and sampling The samples for this study were collected from the Kimmeridgian-Tithonian Ammonitico Rosso from Cala Fornells, Mallorca (Fig. 1).

N

/ .....

A,icA.rE'[

~

~PUER~

q

Belie / ,,'"/'caL J

--

~

60*

I

I

'~

) ~lk"Nf ~r.~--Bo,..ri.

_

\ t

-

--

60*

Fig. 1. Sketch map showing locality of study area (Cala Fornells) and Mallorca in relation to Southern Europe and to the Tethys ocean during the Late Jurassic. Palaeocontinental reconstruction modified from Smith and Briden, (1977).

G.D. Price, B. V~ Sellwood/Palaeogeography, Palueoclimatology, Palaeoecology 110 (1994) 1 10

Palaeogeographic reconstructions by Smith and Briden (1977) place the Mallorca area between 25 and 30~'N during the Tithonian. Three different fossil types have been obtained for analysis: pygopid brachiopods, ammonite aptychi and belemnites. In addition, the matrix surrounding these fossil components has been also analysed. Brachiopods and belemnites are considered by Marshall (1992) to both have a high potential to record original isotopic signatures. This is because the original organisms precipitated low-Mg calcite skeletons which were relatively resistant to diagenesis. They also have well defined internal structures and consequently diagenetic alteration can be recognised more easily (see P o p p e t al., 1986a,b). Ammonite aptychi are thought to have been the calcitic part of the ammonite jaw apparatus (they may have also served as operculae (Lehmann and Kulicki, 199(I)) and have a widespread occurrence in the Upper Jurassic-Lower Cretaceous Alpine-Mediterranean province. They are often well preserved and are more abundant than ammonites, because of their calcite composition. It was hoped that they may also preserve their original isotopic compositions, and hence be of use in palaeotemperature determination. The Ammonitico Rosso is a red, nodular marly limestone facies particularly widespread in the Alpine-Mediterranean region and is a stratigraphically condensed pelagic carbonate. Estimated sedimentation rates are thought to be in the range of a few millimetres per 10 years, the nodularity resulting from sub-surface dissolution of aragonite and subsequent precipitation as limestone rich nodules (Jenkyns, 1974). The Ammonitieo Rosso at Cala Fornells has been interpreted to be of Kimmeridgian to Tithonian age (Jenkyns el al., 1990). It contains in its lower part globergerinid foraminifera which are common in the Oxfordian and ammonites suggesting ages as old as Bajocian-Bathonian (Fig. 2). In its upper portion it contains the brachiopod Pygope reflecting a Tithonian age. It is overlain by regularly bedded white Maiolica Limestone containing the large coccolithophorid Nannoconus, Towards the base, these white limestones yield Tithonian calpionellids and the free swimming crinoid Saccocoma.

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3. Analytical procedures The brachiopod, belemnite and ammonite aptychi samples were carefully scraped clean and shell material was separated from the surrounding matrix using a vibro etching instrument. Due to the poor state of preservation of the ammonites it was impossible to completely separate them from the surrounding matrix. Half of each sample was made into a polished thin section for examination by CL, standard optical petrography and carbonate staining. The other half of the sample was then further divided. Between 5 and 10rag was extracted from the fossils for oxygen and carbon isotope analysis. These were reacted with 100% phosphoric acid (H3PO4) at 25C. The liberated CO2 was then analysed on a VG Sira series I I mass spectrometer, following the method of McCrea (1950). Standard correction procedures of Craig (1957) were applied. Results are reported in the standard 6 notation in per mil (%,) relative to the PDB standard. Reproducibility for both 61~O and ~13C is better than _+0.1%,, based upon multiple sample analysis. A portion of the shell material was ground to a powder for analysis for X-ray diffraction (XRD) to determine bulk mineralogy. Elemental concentrations (for Mn, Sr, Mg and Fe) were determined by inductively coupled )lasma (ICP) spectrometry analysis on the (diluted phosphoric acid residues.

4. Results 4.1. Petrographic examination

The belemnites are seen to have a well defined internal structure with little sign of alteration. Under CL areas of bright luminescence reveal a concentric internal structure (Fig. 3a). These may have been formed where Mn-rich invasive fluids permeated the belemnite after burial along lines of possible weakness. Additionally, CL analysis shows thin sparry calcite veins cross-cutting a few of the belemnites. Such features have also been observed by Spaeth et al. (1971) and may be the result of secondary calcite infillings, the belemnite siphuncle acting as a 'pipe' enabling solutions to penetrate into the chambers.

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G.D. Price, B. VK Sellwood/Palaeogeography, Palaeoclimatology, Palaeoecology 110 (1994) 1-10

MACROFAUNA

AGE

~o O.°I--

II~ E--

Z ,,¢

WZ ~O

.(~__

I~~ ~ ; )

=~ ~*o" ~r, .i-

SLUMPING / DISCONTINUITY

Grey-greenmarls

XQ

~

IP.,~

Purple-red marls

Z ¢[

~

LIMESTONE a NODULAR LIMESTONE -"~ MARL a NODULAR MARL

0.00 L-.-L.J-..L.J-# ~

|

°~

i®

5-~__~-r~P~_/--~'

PROMINENT HARDGROUND

Iron stainedwith large corrodedammonites

(~

AMMONITEI~APTYCHI

~ > ' BELEMNITE

4 - l"-~---~_-~

(~

BRACHIOPOD

~ > BIVALVE OI-

~=

I

SOLITARY CORAL

I ' ' ' I I I I I I

(¢E "*O

SAMPLED HORIZON O ~55~-~'~,' ~

chaotic

marly

limestones

Fig. 2. Vertical section through Ammonitico Rosso sequence at Cala Fornells, showing main lithologies, fossils and ages. Modified from Prescott (1989).

The pygopid brachiopod samples displayed a well defined fibrous structure obscured only in places by inclusion rich zones. CL revealed some luminescent areas within the brachiopod, particularly along the outer shell margins. Luminescent calcite is also visible, seen as possible replacements of single fibrous brachiopod crystals (Fig. 3b). These are areas most commonly seen where the shell has been fractured (i.e. areas that were more susceptible to diagenetic alteration). Silicification has also affected a few brachiopod samples and appears to be non-selective, in textural terms. The ammonite samples are poorly preserved, the shell material being highly fragmented and with sparry calcite filling the entire shell structure. No aragonite has been detected by XRD analysis and, in concert with the petrographic evidence, this suggests wholesale replacement. Examination of the ammonite aptychi reveals a ribbed outer surface and coarse cellular, honeycomb interior (Fig. 3c). The honeycomb interior consists of

irregularly shaped chambers with walls that are composed of calcite. Under CL the chamber walls can be seen to be largely non-luminescing calcite but the chambers are filled with zoned luminescent calcite cements (Fig. 3d) and luminescent micritic matrix. Some of the chambers also remain free of any cement, whilst others show complete replacement by silica. The matrix surrounding the fossil components contains abundant fine debris from the planktonic crinoid Saccocoma. In addition occasional luminescent brachiopod fragments and foraminifera are present. CL examination clearly shows the presence of small amounts of authigenic and possibly detrital quartz within a largely dully luminescing matrix. 5. Elemental data

Within this study the abundances of four trace elements (strontium, iron, manganese, and magne-

G.D. Price, B. ~ Sellwood/Palaeogeography, Palaeoclimatolo~y, Palaeoecology l lO (1994) I lO

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Fig. 3. (a) CL Photomicrograph of belemnite rostrum showing concentric internal structure highlighted by thin highly luminescent zones (avoided during sampling) within luminescent matrix (scale bar is 0.5 mm). (b) CL photomicrograph of Pygopid brachiopod fragment displaying a fibrous structure, picked out by luminescence (scale bar is 100 ~tm). (c) CL photomicrograph of ammonite aptychi revealing a coarse honeycomb internal region composed of irregularly shaped chambers (scale bar is 200 ~tm). (d) CL photomicrograph of honeycomb interior of ammonite aptychi displaying irregularly shaped chambers with non/dull luminescing calcite walls filled with zoned luminescent calcite cements (scale bar is 100 ~tmt.

sium) have been assessed. These four have been used because firstly it has been shown (e.g. Brand and Veizer, 1980; Veizer, 1983) that their presence, or absence, can reflect the degree of diagenetic alteration. Secondly Mn and Fe, in particular, are known to be the main activator and quencher ions in terms of luminescence. Therefore trace element analysis can be fully integrated with the petrographic studies. Trace element analyses also permit comparisons with other studies from different successions (e.g. Pirrie and Marshall, 1992a,b) thus allowing the results to be quality controlled. The trace element data are given in Table 1 with Mn contents ranging from 8 to 361 ppm. The

belemnites clearly have the lowest values, with a range from 8 to 40 ppm. These values compare closely with predicted Mn concentrations. 30 ppm, of calcites precipitated in equilibrium with sea water (Veizer, 1974, 1983 ). The belemnites also have Mn contents similar to modern molluscs such as the cephalopod Nautilus pompilius, which according to Brand (1983) precipitated its (aragonite) shell in equilibrium with the ambient seawater. Higher Mn values are recorded for the ammonite and matrix samples, whilst the highest values (up to 361 ppm) tend to be recorded for the ammonite aptychi. Strontium values in all samples range from 144

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G.D. Price, B. VK Sellwood/Palaeogeography, Palaeoclimatology, Palaeoecology 110 (1994) 1-10

Table 1 Carbon and oxygen isotopic compositions and trace elements of the fossils, together with calculated palaeotemperatures Form

Mineralogy

613C (PDB)

6180 (PDB)

Fe (ppm)

Mg (ppm)

Mn (ppm)

Sr (ppm)

Temp

Belemnite Belemnite Belemnite Belemnite Belemnite Belemnite

Calcite Calcite Calcite Calcite Calcite Calcite

0.97 1.51 1.49 1.32 - 0.45 - 2.03

-0.43 - 0.92 - 1.00 - 0.38 - 0.18 0.04

61 56 57

2270 2069 2298

20 40 19

945 950 941

0 0

1767 2131

10 8

996 1138

13.6 15.7 16.0 13.4 12.5 11.5

Am Aptychi Am Aptychi Am Aptychi Am Aptychi Am Aptychi Am Aptychi

Calcite* Calcite* Calcite* Calcite* Calcite* Calcite*

1.15 1.07 1.32 2.14 1.35

- 1.19 -0.71 -2.28 -3.98 -2.30

Matrix Matrix Matrix

Calcite* Calcite* Calcite*

1.66 1.39 1.67

- 2.30 - 2.66 -2.27

Brachiopod Ammonite Spar

Calcite Calcite Calcite

1.36 1.49 1.40

- 2.11 - 0.95 -6.32

1048 372 954 1097

3290 2465 3237 3313

351 174 361 349

291 253 302 293

447 455

2742 2882

237 247

152 161

245 736

2735 2170

226 282

144 198

16.8 14.8 21.1 27.2 21.4 21.2 22.5 21.1 20.4 15.8 34.3

*Denotes a trace of quartz present. to 1138 ppm. The lowest values are recorded for the a m m o n i t e and matrix samples (144-161 ) whilst intermediate ones are recorded f r o m the a m m o n i t e aptychi. The belemnites have substantially higher Sr values which range f r o m 941 to 1138 ppm. Veizer (1974) predicted that the Sr content o f calcite precipitated in equilibrium with seawater should be ~ 1100 ppm. O u r measurements from the belemnites are in g o o d agreement with the predicted value. The lowest Fe values are recorded f r o m the belemnite samples, (ranging f r o m 0 to 61 ppm). Higher values are recorded f r o m the a m m o n i t e and matrix samples, whilst the highest values are again recorded for the a m m o n i t e aptychi samples. Fe (and Mn) tend to be incorporated into calcite u n d e r reducing conditions. Such conditions occur only rarely in a depositional setting but are c o m m o n in diagenetic environments and they m a y be accompanied by a loss o f 'marine' M g and Sr (Veizer, 1983). Hence, the presence o f Fe and Mn, a n d / o r low a m o u n t s o f Sr and Mg, within some samples m a y be indicative o f a strong diagenetic overprint. The relatively low concentrations o f M n

and Fe, together with higher concentrations o f Sr and M g within the belemnites, compares closely with the trends recorded in belemnites by Pirrie and Marshall (1990a). These were o f Late Cretaceous age and are considered to have been unaffected by diagenesis.

6. lsotopes

The c a r b o n and oxygen isotopic compositions o f the fossils are given in Table 1, together with the calculated palaeotemperatures. The c a r b o n isotopic compositions derived from all the fossils are positive and are similar to measurements made on m o d e r n marine shallow-water skeletons (e.g. Brand et al., 1987; Keith et al., 1964). Two belemnites however have negative 613C values, possibly reflecting diagenetic alteration (although trace element trends suggest little modification by diagenesis). The range o f 6180 values obtained from the belemnites is -0.99%0 to 0.41%0 PDB. A greater variability o f 6180 values (-3.98%0 to -0.71%0 P D B ) is seen for the a m m o n i t e aptychi samples.

G.D. Price, B. W. Sellwood/Palaeogeography, Palaeoclimatology, Palaeoecoh)gy 110 (1994) 1 10

The lightest value (-6.32%0 PDB) came from a sample of calcite spar. Calcite palaeotemperatures (Table 1) were calculated using the equation of Epstein et al. (1953) and Craig (1965) and modified by Anderson and Arthur (1983). This expresses the oxygen isotopic composition of the water, 6w, directly relative to the (Standard Mean Ocean Water) SMOW standard: T ('C)= 16.0-4.14(6c-~v)+0.13(6c-6~) 2 where 3c equals the oxygen isotopic composition of the calcite with respect to the PDB international standard and 6w equals the oxygen isotopic composition of the water from which the calcite was precipitated with respect to the SMOW standard. This formula is derived from measurement of the isotopic composition of molluscs grown under different conditions and is used in preference to the equation of O'Neil, Clayton and Mayeda (1969) which was derived using inorganic calcite precipitated over a range of 0 ° 500°C. In calculating the temperatures, it has been assumed that the Jurassic seawater within which the specimens grew was free from icecaps (Ager, 1975; Frakes, 1979) and would have been isotopically lighter than at present. Therefore a 61sO of - 1 . 2 % 0 PDB (equivalent to -1.0%0 SMOW) is thought to be more appropriate (Shackleton and Kennet, 1975).

7. Discussion

The affect of diagenetic alteration upon the macrofossil and matrix samples has been assessed using petrographic and geochemical data. Relatively low Mn and Fe concentrations and higher Sr and Mg levels, in conjunction with petrographical analysis showing low levels of luminescence, confirm that the belemnites have undergone little or no diagenetic alteration. They accordingly should provide the most 'reasonable' palaeotemperatures. However care must taken when using CL to identify diagenetic alteration. Recent work carried out by Barbin et al. (1991), showed that shell material was often luminescent regardless ot" mineralogical composition and con-

7

cluded that luminescence was not a reliable indicator of diagenetic alteration. A second consideration is that Fe and Mn may not have been present in the fluid causing the diagenesis (Marshall, 1992). Therefore an integrated approach using microscopy, together with geochemical techniques, is essential in assessing the degree of diagenetic alteration. Petrographic analysis of the ammonite aptychi reveals three main states of preservation of the internal honeycomb structure: ( l j chambers infilled by luminescent zoned cements and/or micritic matrix, (2) chambers lacking cement or (3) chambers replaced by silica. These states arc reflected in the variable trace element and oxygen isotope values (Table 1). Carbon values appear to have remained more or less unaltered. This may reflect an internal origin for the cement. The internal honeycomb structure of the ammonite aptychi makes them highly susceptible to nonskeletal carbonate contamination (cements and micritic matrix) and therefore great care needs to be taken when using them to provide original isotopic seawater signatures. We consider them to be far less reliable than belemnites. The original porosity of belemnite rostra is unknown (S~elen, 1989). The rostrum may have been porous (Spaeth et al., 1971: Veizer, 1974) and therefore an early low-Mg calcite cement would make original porosity difficult to recognise (Sa~len, 1989). This would consequently mask the seawater palaeotemperature signal. However the nature of the preservation of the spar-filled porosity within the ammonite aptychi may provide a clue to the original belemnite porosity. If the belemnites were porous, the internal pores might have followed the same diagenetic path as the ammonite aptychi, and consequently display a similar chemical and isotopic signature. Their largely different signatures demonstrates that they have not, and therefore might confirm that they had possessed a very low, or zero, original porosity. Petrographic and geochemical analysis of the ammonite, brachiopod and matrix samples indicates that they have been subjected to a degree of diagenetic alteration rendering them of little value for the determination of marine palaeotemper-

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G.D. Price, B. W. Sellwood/Palaeogeography, Palaeoclimatology, Palaeoecology 110 (1994) 1-10

atures. The 6180 value of the ammonite is close to those of the belemnites. This is surprising because both textural and elemental analysis indicates that complete recrystallisation has occurred. In such a situation much lighter isotopic values (indicative of diagenesis) might be expected. However, this may be because of the inversion of the relatively unstable aragonite to more stable calcite, during early (?marine) diagenesis. In such a case, very little shift in the isotopic values would have taken place, particularly if precipitation occurred under conditions that were close to isotopic equilibrium with seawater (Popp et al., 1986b).

7.1. Palaeotemperatures The belemnites provide ocean temperatures ranging from 13.4 ° to 16°C, with an average of 14.7°C, for a site located on the northern margin of the Tethys between palaeolatitudes 25 ° and 30°N. However, the palaeoecology of belemnites is relatively unclear and hence the range of their palaeodepth habitats is still controversial (Doyle, 1992). An additional factor which may effect the oxygen isotope ratio are 'vital effects'. Benthic and planktonic foraminifera, and coccoliths, can often show departures from isotopic equilibrium (e.g. Shackleton et al., 1973; Duplessy et al., 1970; Dudley et al., 1986). To determine whether extinct organisms, without direct modern counterparts, such as belemnites, show vital effects is more difficult. Urey et al. (1951) proposed that there were no vital effects for any of the molluscs they examined, reconfirmed recently by Marshall (1992). A further factor which will effect the determined palaeotemperatures are uncertainties in the isotopic composition of the Jurassic seawater and we have assumed that 160 rich icecaps were absent. Furthermore palaeoclimate models (e.g. Parrish et al., 1982; Moore et al., 1992a,b) predict moderate-to-high rainfall along Gondwana's Tethyan coast which, in conjunction with possible increased runoff rates, would have isotopically lightened surface waters by an undeterminable amount. The oxygen isotope values (and calculated palaeotemperatures) obtained from belemnites from this study are in general agreement with

other belemnite-derived isotope values obtained from the Mediterranean-north European region (Table2). The choice of temperature equation, and the isotopic composition of seawater, is critical when trying to correlate ocean temperatures. As noted above a modified version of the Epstein et al. (1953) equation was used and the temperatures obtained from other studies, seen in Table 2, have been recalculated using this temperature equation and a 6180 of -1%0 SMOW is assumed for Jurassic seawater. The KimmeridgianTithonian (Mallorca) seawater temperatures and the data presented in Table 2 agree closely with the predicted Late Jurassic Tethyan sea surface temperatures (SST) of Moore et al. (1992a; at 280 ppm atmospheric CO2). However, they are significantly cooler than SST's predicted by Moore et al. (1992a) at l l 2 0 p p m atmospheric CO2 (a 'greenhouse' Earth). The latter model provides a better fit with regard to the distribution of corals (Beauvais, 1973, 1992; Flagel and Fltigel-Kahler, 1992). The belemnite palaeotemperatures may therefore be a record of cooler sub-surface waters, whilst the reefs are recording warmer surface temperatures.

8. Conclusions

Mineralogical, trace element and stable isotope analyses suggest that the belemnites are giving the best palaeotemperature information. However, caution must be used in the interpretation of such temperatures because of often unquantifiable environmental factors affecting the temperature equation such as freshwater runoff and evaporation. Analysis of the ammonite aptychi, brachiopods and matrix suggests that these materials have all been subjected to post-deposition diagenesis and are therefore unsuitable for ocean palaeotemperature analysis. The calculated Mallorcan (belemnite) palaeotemperature range for Kimmeridgian-Tithonian seawater is 13.4 to 16°C. This range is in general agreement with published temperatures from similar palaeolatitudes and agrees well with modelled Tethyan palaeotemperatures.

G.D. Price. B. gd Sellwood/Palaeogeography. Palaeoelimatology, Palaeoecolo~,v 110 : 1994) 1 10

~)

Table 2 Belemnite-derived oxygen and carbon isotope values and calculated palaeotemperatures from the Mediterranean northern European region Location

Fossil

Age

6~sO (PDB)

Temp.

Source

Skye, Scotland, U K Skye, Scotland, U K Huntington, England, U K Calvert Pit, Oxford, UK Arc (Doubs), France Rodoche. Perte a Bovay. Switzerland Braunegg, Aarau, Switzerland Pechora Basin, Russia

Cvlindroteuthis Belemnite rostra Cylimlroteuthis puzosiana Cvlimlroteuthis puzosiana Belemnites hastatus Belemnites hastatus

Callovian Callovian Oxfordian Oxfordian Late Oxfordian Late Oxfordian

1.3 -- 0.92 1.1 1.64 -- 1.46 2.22

17.2 15.7 16.4 18.6 17.9 21).9

FUll et al. 11970) Urey et al. t 1951 ) Bowen ( 1961 Bowen ( 1961 Bowen (1961 Bowen (1961

Belemnites subhastatus Belemnite rostra

- 1.74 -0.(19

19.0 C 12.1 (7

Bowcn ( 1961 Berlin et al. ( 9 6 7 )

Hundsruck. G e r m a n y

Belemnites hastatus

- (I.91

15.6 (_2

Bowen ( 1961

Sos'wt Basin, Urals, Russia Moscow. Russia

Betemnite rostra Belemnite rostra

Late Oxfordian Oxfordian Early Kimmeridgian Early Kimmeridgian Late Kimmeridgian Volgian

-. 0.11 0.37

12.2 C 10.1 (_7

Berlin el al. (1967) Price (unpubl.)

Acknowledgements This research was funded by NERC (grant GR3/7939) as part of the Mesozoic climate modelling project. A.M. Ziegler and J. Veizer refereed an earlier version of the manuscript and made many helpful suggestions for its improvement. This paper is Reading University PRIS contribution number 334.

References Ager. D.V., 1975. The Jurassic world ocean, lu: K. Finstad and R.C. Selley (Editors), Proc. Jurassic Northern North Sea Symp. Norw. Pet. Soc., Oslo, pp. 1 29. Anderson. T.F. and Arthur, M.A., 1983. Stable isotopes of oxygen and carbon and their application to sedimentologic and palaeoenvironmental problems. In: M.A. A u t h u r et al. (Editors), Stable Isotopes in Sedimentary Geology. SEPM Short Course, l(/,pp. 1-1 1-151. Barbin, V.. Ramseyer, K., Debenay, J.P,, Schein, E. Roux, M. and l)ecrouez, D., 1991. Cathodoluminescence of Recent biogenic carbonates: an environmental and ontogenetic fingerprint. Geol. Mag., 128:19 26. Beauvais, L., 1973. Upper Jurassic hermatypic corals. In: A. Hallam (Editor,) Atlas of Paleobiogeography. Elsevier, Amsterdam, pp. 317 328. Beauwfis, L., 1992. Palaeobiogeography of the Early Cretaceous corals, Palaeogeogr., Palaeoclimatol., Palaeoecol., l(12: 253 "2.71.

(" (av) (7 (avt (' C (" C

Berlim T.S., Naydin, D.P.. Saks, V.N., Teis. R.V. and Khabakov, A.V., 1967. Jurassic and Cretaceous climate in northern USSR, 1¥om paleotemperature determinations. Ira. Geol. Rev., 9:1080 1092. Bowem R., 1961. Paleotemperature analysis of Belemnoidca and Jurassic Paleoclimatology. J. Geol., 69:3(19 32(/. Brand, U., 1983. Geochemical analysis of Nautilus pompilius from Fiji, South Pacific. Mar, Geol., 53:M1 M5. Brand, U. and Veizer, J., 1980. Chemical diagenesis of a m u l t i c o m p o n e m system I. Trace elements. J. Sedimen|. Petrol., 50:1219 1236. Brand, U., Morrison, J.O., Brand. N. and Brand. E.. 1987. Isotopic variation in the shells of Recent marine invertebrates from the Canadian Pacific Coast. Chem. Geol. t Isot. Geosc. Sect.), 65:137 145. Craig, H.. 1957. Isotopic standards for carbon and oxygen and correction factors for mass spectrometer analysis of carbon dioxide. Geochim. Cosmochim. Acta. 12:133 149. Craig. H.. 1965. The measurement of Oxygen Isotope Palaeotemperatures. In: E, Tongiorgi (Editor), Stable Isotopes in Oceanographic Studies and Palaeotemperatures. Consiglio Nazionale delle Richerche. kabortorio di Geologia Nucleare. Pisa, pp. 161 182. Doyle, P. 1992. A review of the biogeography of Cretaceous belemnites. Palaeogeogr., Palaeoclmmtol., Palaeoecol., ~)2: 207 216. Dudley, W.C., Blackwelder, P., Brand, 1,. and Duplessy, J.(., 1986. Stable isotopic composition of coccoliths. Mar. Micropaleontol., 10:1 8. Duplessy, J.C., Lalou, C. and Vinot, A . C , 1970 Differential isotopic fractionation in benthic l\~rammifera and paleotemperatures reassessed. Science, 168:250 251. Epstein. S.. Buchsbaum. R., Lowenstam, H.A. and I Jrey, H.('.,

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