(Table 1) Stable carbon isotope record and calculated recycled DIC for sediment core ANDRA_HTM102

The prominent negative stable carbon isotope excursion in both carbonate and organic carbon recorded in organic-rich sediments deposited during the Toarcian oceanic anoxic event (OAE) has commonly been explained by recycling of 13C-depleted CO2 (the so-called Küspert model). More recently, the massive release of 13C-depleted methane or other forms of 13C-depleted carbon was also proposed to account for the observed negative d13C excursions in organic carbon of terrigenous as well as of marine origin. The occurrence of diagenetic products of the carotenoid isorenieratene (isorenieratane and other aryl isoprenoids) in Toarcian black shales has been regarded as supporting evidence for the Küspert hypothesis as they point to strong stratification of the epicontinental seas. A section of a drill core straddling the Toarcian of the Paris Basin (Cirfontaine-en-Ornois) contained intact isorenieratane, providing evidence that photosynthetic green sulphur bacteria were present at the time of deposition, even prior to the OAE. However, the isorenieratane abundances are very low in the section where the negative d13C excursion in organic carbon and phytane, a chemical fossil derived from chlorophyll, occurs. The abundance of the isorenieratene derivatives increases, once the d13C records have shifted to more positive values. The d13C of isorenieratane (generally circa -13.1 ± 0.5 per mil) indicates that the respired CO2 contribution at the chemocline was low and is thus not likely to be the main cause of the prominent up to 7per mil negative d13C shift recorded in Toarcian organic carbon records.

Long chain diols and diol indices of surface sediments of the Iberian Atlantic margin

Long chain diols are lipids that have gained interest over the last years due to their high potential to serve as biomarkers and diol indices have been proposed to reconstruct upwelling conditions and sea surface temperature (SST). However, little is known about the sources of the diols and the mechanisms impacting their distribution. Here we studied the factors controlling diol distributions in the Iberian Atlantic margin, which is characterized by a dynamic continental shelf under the influence of upwelling of nutrient-rich cold deep waters, and fluvial input. We analyzed suspended particulate matter (SPM) of the Tagus river, marine SPM and marine surface sediments along five transects off the Iberian margin, as well as riverbank sediments and soil from the catchment area of the Tagus river. Relatively high fractional abundances of the C32 1,15-diol (normalized with respect to the 1,13- and 1,15-diols) were observed in surface sediments in front of major river mouths and this abundance correlates strongly with the BIT index, a tracer for continental input of organic carbon. Together with an even higher fractional abundance of the C32 1,15-diol in the Tagus river SPM, and the absence of long chain diols in the watershed riverbank sediments and soils, we suggest that this long chain diol is produced in-situ in the river. Further support for this hypothesis comes from the small but distinct stable carbon isotopic difference of 1.3? with the marine C28 1,13-diol. The 1,14-diols are relatively abundant in surface sediments directly along the northern part of the coast, close to the upwelling zone, suggesting that Diol Indices based on 1,14-diols would work well as upwelling tracers in this region. Strikingly, we observed a significant difference in stable carbon isotopic composition between the monounsaturated C30:1 1,14- and the saturated C28 1,14-diol (3.8±0.7 per mil), suggesting different sources, in accordance with their different distributions. In addition, the Long chain Diol Index (LDI), a proxy for sea surface temperature, was applied for the surface sediments. The results correlate well with satellite SSTs offshore but reveal a significant discrepancy with satellite-derived SSTs in front of the Tagus and Sado rivers. This suggests that river outflow might compromise the applicability of this proxy.