Transient deep-water oxygenation recorded by rare Mesoproterozoic phosphorites, South Urals

The Mesoproterozoic deep ocean is thought to have been largely anoxic, dominated by ferruginous conditions. Phosphate was scavenged from the water column by iron oxyhydroxides, and dissolved nitrate was rapidly reduced along the redoxcline. Primary productivity was therefore generally low, and eukaryotic life was restricted to oxic marine margins. This model is supported by new nitrogen isotope data from the Lower Riphean (ca. 1.55 Ga) strata of the South Ural Mountains, where we find evidence for strong redox stratification, coupled with low organic carbon content. In contrast, unconformably overlying siliciclastic sedimentary rocks of Middle Riphean age (ca. 1.33 Ga) preserve a rare occurrence of apatite concretions, associated with relatively high concentrations of organic carbon (up to 4 wt%). The Pb-Pb isochron age for the apatite concretions of the Zigazino-Komarovo Formation is 1330 ± 20 Ma (MSWD = 3.7). We measured nitrogen isotope ratios across this interval and found δ¹⁵N values up to + 7.6‰, which are similar to those in modern upwelling zones and indicative of a significant nitrate reservoir. These observations are most parsimoniously explained by upwelling of phosphate- and nitrate-bearing waters, suggesting that the deep ocean was at least regionally and temporarily oxygenated. The lack of redox-sensitive trace element enrichment in these strata and the general scarcity of apatite accumulations in the Mesoproterozoic sedimentary record suggest that oxic deep-waters were not a global and persistent phenomenon, but our results confirm that oxic, nutrient-rich refugia existed in Mesoproterozoic oceans and were perhaps important for the radiation of early eukaryotes.