δ18O of carbonate, quartz and phosphate from belemnite guards:: implications for the isotopic record of old fossils and the isotopic composition of ancient seawater

Belemnite guards of Cretaceous and Jurassic age were found to contain varying amounts of quartz deposited both on the external surface and inside the rostrum. The oxygen isotopic composition of coexisting carbonate, quartz and phosphate from the same rostrum was measured according to well-established techniques. None of these compounds showed isotopic values in equilibrium with one another. Assuming delta(18)O values of the diagenetic water within the range of meteoric waters, the delta(18)O(SiO2) yield temperatures in agreement with the apparent secondary origin of this phase. The delta(18)O(CO32-) range, with a certain continuity, between -10.8 and +0.97 PDB-1 with most of the intermediate values being within the range of the carbonate isotopic values of Mesozoic fossils. The most positive isotopic results obtained from phosphate are close to +23/+24 parts per thousand (V-SMOW). They can hardly be related to a secondary origin of the phosphate, or to the presence of diagenetic effects, since these results are among the most positive ever measured on phosphate. As far as we know there is no widespread diagenetic process determining an O-18 enrichment of phosphate. The very low concentration of phosphate did not allow the determination of its mineralogical composition. All the available delta(18)O(PO43-) values from belemnite and non-belemnite fossils of marine origin of Tertiary and Mesozoic age are reported along with the newly measured belemnites. The following conclusions may be drawn from the data reported: (1) the pristine oxygen isotope composition of fossil marine organisms (either carbonate or phosphate) may easily undergo fairly large changes because of oxygen isotope exchange processes with diagenetic water; this process is apparent even in the case of geologically recent fossils; (2) the delta(18)O(PO43-) of belemnite rostra seems to be, at least in the case of the most positive results, in isotopic equilibrium with environmental water because of the similarity between the results from Cretaceous belemnites and the results from Cretaceous and Lower Tertiary pelecypods and fish teeth; 3) if so, the only feasible interpretation that can be suggested for the O-18 enriched data is the possibility of a relatively large variation of the oxygen isotopic composition of ocean paleowater from Jurassic to recent time. (C) 2002 Elsevier Science B.V. All rights reserved.