Formula omitted], [formula omitted] and [formula omitted] evolution of Phanerozoic seawater

Abstract

A total of 2128 calcitic and phosphatic shells, mainly brachiopods with some conodonts and belemnites, were measured for their δ18O, δ13C and 87Sr/86Sr values. The dataset covers the Cambrian to Cretaceous time interval. Where possible, these samples were collected at high temporal resolution, up to 0.7 Ma (one biozone), from the stratotype sections of all continents but Antarctica and from many sedimentary basins. Paleogeographically, the samples are mostly from paleotropical domains. The scanning electron microscopy (SEM), petrography, cathodoluminescence and trace element results of the studied calcitic shells and the conodont alteration index (CAI) data of the phosphatic shells are consistent with an excellent preservation of the ultrastructure of the analyzed material. These datasets are complemented by extensive literature compilations of Phanerozoic low-Mg calcitic, aragonitic and phosphatic isotope data for analogous skeletons. The oxygen isotope signal exhibits a long-term increase of δ18O from a mean value of about −8‰ (PDB) in the Cambrian to a present mean value of about 0‰ (PDB). Superimposed on the general trend are shorter-term oscillations with their apexes coincident with cold episodes and glaciations. The carbon isotope signal shows a similar climb during the Paleozoic, an inflexion in the Permian, followed by an abrupt drop and subsequent fluctuations around the modern value. The 87Sr/86Sr ratios differ from the earlier published curves in their greater detail and in less dispersion of the data. The means of the observed isotope signals for 87Sr/86Sr, δ18O, δ13C and the less complete δ34S (sulfate) are strongly interrelated at any geologically reasonable (1 to 40 Ma) time resolution. All correlations are valid at the 95% level of confidence, with the most valid at the 99% level. Factor analysis indicates that the 87Sr/86Sr, δ18O, δ13C and δ34S isotope systems are driven by three factors. The first factor links oxygen and strontium isotopic evolution, the second 87Sr/86Sr and δ34S, and the third one the δ13C and δ34S. These three factors explain up to 79% of the total variance. We tentatively identify the first two factors as tectonic, and the third one as a (biologically mediated) redox linkage of the sulfur and carbon cycles. On geological timescales (≥1 Ma), we are therefore dealing with a unified exogenic (litho-, hydro-, atmo-, biosphere) system driven by tectonics via its control of (bio)geochemical cycles.