Evidence for benthic oxygen production in Neoarchean lacustrine stromatolites

The evolution of oxygenic photosynthesis fundamentally altered the global environment, but the history of this metabolism prior to the Great Oxidation Event (GOE) at ca. 2.4 Ga remains unclear. Increasing evidence suggests that non-marine microbial mats served as localized "oxygen oases" for hundreds of millions of years before the GOE, though direct examination of redox proxies in Archean lacustrine microbial deposits remains relatively limited. We report spatially distinct patterns of positive and negative cerium (Ce) anomalies in lacustrine stromatolites from the 2.74 Ga Ventersdorp Supergroup (Hartbeesfontein Basin, South Africa), which indicate that dynamic redox conditions within ancient microbial communities were driven by oxygenic photosynthesis. Petrographic analyses and rare earth element signatures support a primary origin for Ce anomalies in stromatolite oxides. Oxides surrounding former bubbles entrained in mats (preserved as fenestrae) exhibit positive Ce anomalies, while oxides in stromatolite laminae typically contain strong negative Ce anomalies. The spatial patterns of Ce anomalies in Ventersdorp stromatolites are most parsimoniously explained by localized Ce oxidation and scavenging around oxygen bubbles produced by photosynthesis in microbial mats. Our new data from Ventersdorp stromatolites supports the presence of oxygenic photosynthesis similar to 300 m.y. before the GOE, and add to the growing evidence for early oxygen oases in Archean non-marine deposits.