Bioessential element-depleted ocean following the euxinic maximum of the end-Permian mass extinction

Abstract

We describe variations in trace element compositions that occurred on the deep seafloor of palaeo-superocean Panthalassa during the end-Permian mass extinction based on samples of sedimentary rock from one of the most continuous Permian–Triassic boundary sections of the pelagic deep sea exposed in north-eastern Japan. Our measurements revealed low manganese (Mn) enrichment factor (normalised by the composition of the average upper continental crust) and high cerium anomaly values throughout the section, suggesting that a reducing condition already existed in the depositional environment in the Changhsingian (Late Permian). Other redox-sensitive trace-element (vanadium [V], chromium [Cr], molybdenum [Mo], and uranium [U]) enrichment factors provide a detailed redox history ranging from the upper Permian to the end of the Permian. A single V increase (representing the first reduction state of a two-step V reduction process) detected in uppermost Changhsingian chert beds suggests development into a mildly reducing deep-sea condition less than 1 million years before the end-Permian mass extinction. Subsequently, a more reducing condition, inferred from increases in Cr, V, and Mo, developed in overlying Changhsingian grey siliceous claystone beds. The most reducing sulphidic condition is recognised by the highest peaks of Mo and V (second reduction state) in the uppermost siliceous claystone and overlying lowermost black claystone beds, in accordance with the end-Permian mass extinction event. This significant increase in Mo in the upper Changhsingian led to a high Mo/U ratio, much larger than that of modern sulphidic ocean regions. This trend suggests that sulphidic water conditions developed both at the sediment–water interface and in the water column. Above the end-Permian mass extinction horizon, Mo, V and Cr decrease significantly. On this trend, we provide an interpretation of drawdown of these elements in seawater after the massive element precipitation event during the end-Permian maximum development of the reducing water column. A decrease in the Mo/U ratio despite enrichment of Mo and U also supports that of Mo. Calculations of the total amounts of these elements precipitated compared with the global seawater inventory suggest that when more than 6–10% of the global ocean became euxinic as much as the study section, most of the dissolved elements would precipitate into sediments, resulting in a global element-depleted seawater condition. Mo, V, and Cr act as bioessential elements for both primary producers and animals. The continuing reducing water column and the lack of bioessential elements could have had a considerable effect on primary producer turnover and marine life metabolism not only in the pelagic environment, but also in surrounding marine environments.