Isotopic evidence for changes in the mercury and zinc cycles during Oceanic Anoxic Event 2 in the northwestern Tethys, Austria

Abstract

The Cenomanian-Turonian Oceanic Anoxic Event 2 (OAE 2, ca. 94 Ma) was one of the most extreme carbon cycle and climatic perturbations of the Phanerozoic Eon. Widespread deposition of organic-rich shales during OAE 2 has been attributed to a rapid rise in atmospheric CO2, global heating, and marine anoxia triggered by intense large igneous province (LIP) volcanism. Here, we present new Hg and Zn elemental and isotopic analyses from samples spanning OAE 2 in a hemipelagic section from Rehkogelgraben, Austria, which was part of the north-western Tethys. We compare our data to existing records from a range of sites to constrain the relative timing, magnitude and geographic extent of the perturbation. We find a prominent Hg concentration peak and an overall positive Δ199Hg excursion, with no correlation between Hg content and organic matter (OM), Mn-Fe-oxyhydroxides, and/or clay minerals. We interpret this to indicate a terrestrial volcanic origin of Hg. The Hg excursion is coincident with an osmium (Os) isotope excursion, and together, this supports a global period of intense LIP volcanism. The δ66Zn record from the Rehkogelgraben section decreases abruptly by ~0.5‰ prior to the onset of OAE 2, a change recorded consistently among all reference sections. Combined with the Hg data, we interpret this to result from isotopically light Zn sourced from LIP activity. However, the second negative excursion in δ66Zn during the Plenus Cold Event (PCE), which is recorded in the proto-North Atlantic and adjacent areas and has been attributed to Zn released from OM during re‑oxygenation, is not recorded in this section. We suggest that the cool, oxygenated deep water mass did not invade the Penninic Ocean in the northwestern Tethys. Alternatively, this excursion could be missing in our section due to the presence of carbonate-free sediments during the PCE. After the PCE, the positive excursion in δ66Zn recorded in all sections reveals a recovery of the atmosphere-ocean system. Our findings highlight the significance of spatial and temporal variations in Hg and Zn isotopes during OAE 2.