Christiaan G.C. van Baak

Identification and environmental interpretation of diagenetic and biogenic greigite in sediments: A lesson from the Messinian Black Sea

Greigite (Fe3S4) is a widespread authigenic magnetic mineral in anoxic sediments and is also commonly biosynthesized by magnetotactic bacteria in aqueous environments. While the presence of fossilized bacterial magnetite (Fe3O4) has now been widely demonstrated, the preservation of greigite magnetofossils in the geological record is only poorly constrained. Here we investigate Mio-Pliocene sediments of the former Black Sea to test whether we can detect greigite magnetofossils and to unravel potential environmental controls on greigite formation. Our magnetic analyses and transmission electron microscope (TEM) observations indicate the presence of both diagenetic and bacterial greigite, and suggest a potentially widespread preservation of greigite magnetofossils in ancient sediments, which has important implications for assessing the reliability of paleomagnetic records carried by greigite. TEM-based chemical and structural analyses also indicate the common presence of nickel-substituted diagenetic iron sulfide crystals with a ferrimagnetic greigite structure. In addition, our cyclostratigraphic framework allows correlation of magnetic properties of Messinian Black Sea sediments (Taman Peninsula, Russia) to global climate records. Diagenetic greigite enhancements appear to be climatically controlled, with greigite mainly occurring in warm/wet periods. Diagenetic greigite formation can be explained by variations in terrigenous inputs and dissolved pore water sulfate concentrations in different sedimentary environments. Our analysis demonstrates the usefulness of greigite for studying long-term climate variability in anoxic environments. Key Points: We provide evidence for the presence of biogenic greigite in ancient sediments Diagenetic greigite enhancements are climatically controlled Greigite is a paleoenvironmental indicator in anoxic environments

Mediterranean outflow pump: An alternative mechanism for the Lago-mare and the end of the Messinian Salinity Crisis

The final stage of the Messinian salinity crisis (MSC) was characterized by brackish-water “Lago-mare” conditions in the intermediate and marginal basins of the Mediterranean Sea. The presence of Paratethyan (former Black Sea) fauna in these deposits has fueled long-lasting controversies over the connectivity between the Mediterranean and Paratethys and contemporary sea-level drops in both basins. Here, we use the results of sub-precessional climate simulations to calculate the freshwater budget of the Mediterranean and Paratethys in the Messinian. We show that, during the MSC, the freshwater budget of Paratethys was positive, while the Mediterranean was negative. Using these numerical constraints, we propose a Mediterranean outflow pump as an alternative scenario for the two most dramatic hydrological changes in the MSC: (1) the Halite–Lago-mare transition and (2) the Pliocene reestablishment of marine conditions. Following the maximum MSC lowstand during halite formation, progressive Mediterranean sea-level rise resulting from African river runoff and overspill from both the Atlantic and Paratethys eventually reached the level of the Paratethys sill. A density contrast at this gateway caused dense Mediterranean waters to flow into the Paratethys, driving a compensatory return flow. This “pump” mechanism significantly enhanced Paratethyan inflow to the Mediterranean, creating suitable conditions for the Lago-mare fauna to migrate and thrive. When the Mediterranean sea level finally reached the height of the Gibraltar sill, Mediterranean outflow restarted there and enhanced exchange with the Atlantic Ocean. During this reorganization of the circulation, brackish and hypersaline waters were pumped out of the Mediterranean, and open-marine conditions were reestablished without major flooding of the basin at the Miocene-Pliocene boundary.

A Greigite-Based Magnetostratigraphic Time Frame for the Late Miocene to Recent DSDP Leg 42B Cores from the Black Sea

Throughout the Late Neogene, the Black Sea experienced large paleoenvironmental changes, switching between (anoxic) marine conditions when connected to the Mediterranean Sea and (oxic) freshwater conditions at times of isolation. We create a magnetostratigraphic time frame for three sites drilled during Deep Sea Drilling Project (DSDP) Leg 42B to the Black Sea (drilled in 1975). At the time, magnetostratigraphic dating was impossible because of the presence of the little understood iron sulfide mineral greigite (in sediments a precursor to pyrite) as magnetic carrier. Our rock-magnetic results indicate that only anoxic conditions result in poor magnetic signal, likely as a result of pyrite formation in the water column rather than in the sediment. The magnetostratigraphic results indicate that Hole 379A, drilled in the basin center, has a continuous sedimentary record dating back to 1.3 Ma. Hole 380/380A is subdivided into three consistent intervals, 0-700 mbsf, 700-860 mbsf and 860-1075 mbsf. The top unit covers the Pleistocene but the magnetostratigraphy is likely compromised by the presence of mass transport deposits. The middle unit spans between 4.3 and 6.1 Ma and records continuous deposition at ~10 cm/kyr. The lower unit lacks the independent age constraints to correlate the obtained magnetostratigraphy. Hole 381 is drilled on the Bosporus slope and as a result, hiatuses are common. A correlation to the nearby Hole 380/380A is proposed, but indicates deposits cannot straightforwardly be traced across the slope. Our improved age model does not support the original interpretation based on these cores of a desiccation of the Black Sea during the Messinian salinity crisis.