Suboxic deep seawater in the late Paleoproterozoic: Evidence from hematitic chert and iron formation related to seafloor-hydrothermal sulfide deposits, central Arizona, USA

A current model for the evolution of Proterozoic deep seawater composition involves a change from anoxic sulfide-free to sulfidic conditions 1.8 Ga. In an earlier model the deep ocean became oxic at that time. Both models are based on the secular distribution of banded iron formation (BIF) in shallow marine sequences. We here present a new model based on rare earth elements, especially redox-sensitive Ce, in hydrothermal silica–iron oxide sediments from deeper-water, open-marine settings related to volcanogenic massive sulfide (VMS) deposits. In contrast to Archean, Paleozoic, and modern hydrothermal iron oxide sediments, 1.74 to 1.71 Ga hematitic chert (jasper) and iron formation in central Arizona, USA, show moderate positive to small negative Ce anomalies, suggesting that the redox state of the deep ocean then was at a transitional, suboxic state with low concentrations of dissolved O2 but no H2S. The presence of jasper and/or iron formation related to VMS deposits in other volcanosedimentary sequences ca. 1.79–1.69 Ga, 1.40 Ga, and 1.24 Ga also reflects oxygenated and not sulfidic deep ocean waters during these time periods. Suboxic conditions in the deep ocean are consistent with the lack of shallow-marine BIF ∼ 1.8 to 0.8 Ga, and likely limited nutrient concentrations in seawater and, consequently, may have constrained biological evolution.