Ocean oxygenation and ecological restructuring caused by the late Paleozoic evolution of land plants

The dramatic increase in ocean-atmosphere oxygen levels during the Devonian and Mississippian is increasingly linked to the diversification of land plants, yet the timing and extent of this event remain uncertain. This study uses the redox-sensitive rare earth element cerium (cerium anomaly—Ce/Ce*) to investigate ocean redox conditions during the deposition of globally distributed Paleozoic carbonate strata. Our Paleozoic Ce/Ce* record suggests that Cambrian, Ordovician, and Silurian oceans had relatively low O2 levels (mean Ce/Ce* = 0.86 ± 0.10, 0.91 ± 0.14, and 0.91 ± 0.10 [±1σ], respectively). In contrast, short-lived ocean oxygenation events, possibly related to the diversification of small land plants, likely occurred throughout the Early and Middle Devonian (mean Ce/Ce* = 0.80 ± 0.07 and 0.58 ± 0.14, respectively). “Modern” Ce/Ce* values (<0.36) first occurred during the Late Devonian, suggesting that the main phase of Devonian and Mississippian oceanic oxygenation was related to the evolution of large vascular plants and the first forests. Despite this, the significant variability of Ce/Ce* values during this time suggests that shallow marine settings were susceptible to redox instability, possibly caused by upwelling of anoxic deep waters. This redox instability potentially provides evidence of a mechanism for contemporaneous mass extinction and metazoan reef collapse events. Development of strongly oxic conditions during the Late Devonian may have resulted in the demise of many Paleozoic-type organisms, facilitated the radiation of the modern evolutionary fauna, and established the modern oxygenated ocean-atmosphere system.