Reconstruction of Phanerozoic climate using carbonate clumped isotopes and implications for the oxygen isotopic composition of seawater.

The oxygen isotope ratio 18O/16O (expressed as a δ18OVSMOW value) in marine sedimentary rocks has increased by ~8‰ from the early Paleozoic to modern times. Interpretation of this trend is hindered by ambiguities in the temperature of formation of the carbonate, the δ18Oseawater, and the effects of postdepositional diagenesis. Carbonate clumped isotope measurements, a temperature proxy, offer constraints on this problem. This thermometer is thermodynamically controlled in cases where carbonate achieves an equilibrium internal distribution of isotopes and is independent of the δ18O of the water from which the carbonate grew; therefore, it has a relatively rigorous chemical-physics foundation and can be applied to settings where the δ18O of the water is not known. We apply this technique to an exceptionally well-preserved Ordovician carbonate record from the Baltic Basin and present a framework for interpreting clumped isotope results and for reconstructing past δ18Oseawater. We find that the seawater in the Ordovician had lower δ18Oseawater values than previously estimated, highlighting the need to reassess climate records based on oxygen-isotopes, particularly where interpretations are based on assumptions regarding either the δ18Oseawater or the temperature of deposition or diagenesis. We argue that an increase in δ18Oseawater contributed to the long-term rise in the δ18O of marine sedimentary rocks since the early Paleozoic. This rise might have been driven by a change in the proportion of high- versus low-temperature water-rock interaction in the earth's hydrosphere as a whole.

Morphological variation suggests that chitinozoans may be fossils of individual microorganisms rather than metazoan eggs.

Chitinozoans are organic-walled microfossils widely recorded in Ordovician to Devonian (ca 485-359 Mya) marine sediments and extensively used in high-resolution biostratigraphy. Their biological affinity remains unknown, but most commonly, they are interpreted as eggs of marine metazoans. Here, we provide new insights into their palaeobiology from three lines of inquiry. We examine morphological variation of a new, well-preserved Late Ordovician species, Hercochitina violana; analyse a compiled dataset of measurements on 378 species representing all known chitinozoan genera; and compare these data with the size variation of eggs of both extinct and extant aquatic invertebrates. The results indicate that the magnitude of size variation within chitinozoan species is larger than observed in fossil and modern eggs. Additionally, delicate morphological structures of chitinozoans, such as prosome and complex ornamentation, are inconsistent with the egg hypothesis. Distinct and continuous morphological variation in H. violana is more plausibly interpreted as an ontogenetic series of individual microorganisms, rather than as eggs.

Glendonite occurrences in the Tremadocian of Baltica: first Early Palaeozoic evidence of massive ikaite precipitation at temperate latitudes.

The Tremadocian (Early Ordovician) is currently considered a time span of greenhouse conditions with tropical water surface temperature estimates, interpolated from oxygen isotopes, approaching 40 °C. In the mid-latitude Baltoscandian Basin, conodonts displaying low δ18O values, which suggest high temperatures (>40 °C) in the water column, are in contrast with the discovery of contemporaneous glendonite clusters, a pseudomorph of ikaite (CaCO3·6H2O) traditionally considered as indicator of near-freezing bottom-water conditions. The massive precipitation of this temperature sensitive mineral is associated with transgressive conditions and high organic productivity. As a result, the lower Tremadocian sediments of Baltoscandia apparently contain both "greenhouse" pelagic signals and near-freezing substrate indicators. This paradox points to other primary controlling mechanisms for ikaite precipitation in kerogenous substrates, such as carbonate alkalinity, pH and Mg/Ca ratios, as recently constrained by laboratory experiments. Preservation of "hot" conodonts embedded in kerogenous shales rich in δ18O-depleted glendonites suggests both the onset of sharp thermal stratification patterns in a semi-closed basin and the assumed influence of isotopically depleted freshwater yielded by fluvial systems.