Glacial episodes have been linked to Ordovician–Silurian extinction events, but cooling itself may not be solely responsible for these extinctions. Teratological (malformed) assemblages of fossil plankton that correlate precisely with the extinction events can help identify alternate drivers of extinction. Here we show that metal poisoning may have caused these aberrant morphologies during a late Silurian (Pridoli) event. Malformations coincide with a dramatic increase of metals (Fe, Mo, Pb, Mn and As) in the fossils and their host rocks. Metallic toxins are known to cause a teratological response in modern organisms, which is now routinely used as a proxy to assess oceanic metal contamination. Similarly, our study identifies metal-induced teratology as a deep-time, palaeobiological monitor of palaeo-ocean chemistry. The redox-sensitive character of enriched metals supports emerging ‘oceanic anoxic event' models. Our data suggest that spreading anoxia and redox cycling of harmful metals was a contributing kill mechanism during these devastating Ordovician–Silurian palaeobiological events.
This paper focuses on the use of in situ and ex situ characterisation techniques to provide evidences of carbon species on a commercial iron-based Fischer-Tropsch synthesis catalyst as well as other indices of potential deactivation mechanisms. In situ XANES measurements demonstrate that re-oxidation or transformation of the active iron phase, i.e. the Hägg carbide phase, was not a significant deactivation mechanism at the studied conditions. Sintering of Hägg carbide nanoparticles is significant with increasing temperatures and time on stream. The sintering mechanism is proposed to be a hydrothermally-assisted process. In situ DRIFTS indicates the presence of different carbon species on the catalyst surface such as aliphatic hydrocarbons from wax products and oxygenate compounds such as alcohols, aldehydes/ketones and carboxylate species. Carboxylate species are resistant towards hydrogenation at 280°C. The presence of different carbon species on the surface after wax product extraction is evident from TPH-MS measurements. GC-MS analysis shows that the strongly adsorbed carbon species remaining on the catalyst surface from wax products are mainly α-olefins and branched carboxylic species. The interaction of oxygenate compounds, especially carboxylate species with iron oxide, may form stable complexes limiting further iron catalyst carburization. STEM-EDX analysis shows that carbon is preferentially located on iron particles.
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