Stable oxygen isotope data of Thoracosphaera heimii in surface sediment samples of the equatorial Atlantic and South Atlantic

To investigate the potential use of the stable isotope composition of the vegetative cysts of the photosynthetic dinoflagellate Thoracosphaera heimii for quantitative palaeotemperature reconstructions a method has been developed to purify T. heimii cysts from sediment samples. Stable oxygen and carbon isotopes have been measured on T. heimii cysts from 21 surface sediment samples from the equatorial Atlantic and South Atlantic Oceans. Calculated temperatures based on the palaeotemperature equation for inorganic calcite precipitation generally reflect mean annual temperatures of the upper water column, notably of thermocline depths. Although the present results suggest that the isotopic composition of T. heimii shells might be formed in equilibrium with the seawater in which the shells are being formed, future investigations are required to determine possible effects of metabolic and kinetic processes on the fractionation process. This pilot study therefore forms the basis for future investigations on the development of this tool and the determination of a species-specific palaeotemperature equation. The wide geographic and stratigraphic distribution of T. heimii cysts in sediments, the stable position of T. heimii within the water column and the high resistance of its cysts against calcite dissolution underline its potential for a wide usability in palaeotemperature reconstructions.

(Table 1) Bulk Fe isotope values and pyrite framboids sizes of Cenomanian-Turonian samples

Organic carbon-rich shales from localities in England, Italy, and Morocco, which formed during the Cenomanian-Turonian oceanic anoxic event (OAE), have been examined for their total organic carbon (TOC) values together with their carbon, nitrogen, and iron isotope ratios. Carbon isotope stratigraphy (d13Corg and d13Ccarb) allows accurate recognition of the strata that record the oceanic anoxic event, in some cases allowing characterization of isotopic species before, during, and after the OAE. Within the black shales formed during the OAE, relatively heavy nitrogen isotope ratios, which correlate positively with TOC, suggest nitrate reduction (leading ultimately to denitrification and/or anaerobic ammonium oxidation). Black shales deposited before the onset of the OAE in Italy have unusually low bulk d57Fe values, unlike those found in the black shale (Livello Bonarelli) deposited during the oceanic anoxic event itself: These latter conform to the Phanerozoic norm for organic-rich sediments. Pyrite formation in the pre-OAE black shales has apparently taken place via dissimilatory iron reduction (DIR), within the sediment, a suboxic process that causes an approximately -2 per mil fractionation between a lithogenic Fe(III)oxide source and Fe(II)aq. In contrast, bacterial sulfate reduction (BSR), at least partly in the water column, characterized the OAE itself and was accompanied by only minor iron isotope fractionation. This change in the manner of pyrite formation is reflected in a decrease in the average pyrite framboid diameter from ~10 to ~7 µm. The gradual, albeit irregular increase in Fe isotope values during the OAE, as recorded in the Italian section, is taken to demonstrate limited isotopic evolution of the dissolved iron pool, consequent upon ongoing water column precipitation of pyrite under euxinic conditions. Given that evidence exists for both nitrate and sulfate reduction during the OAE, it is evident that redox conditions in the water column were highly variable, in both time and space.