The reason for the abundance of dolomite lithologies in Earth's early geological record compared to modern environments remains contentious. This study provides new insight into this Precambrian “dolomite problem” by revisiting one of the most controversial dolomite localities, the Beck Spring Dolomite, of Death Valley, USA. Consistent with some previous studies, petrographic evidence indicates that although the Beck Spring Dolomite now consists almost entirely of dolomite, it was originally precipitated largely as aragonite and high-Mg calcite. Depositional constituents (microbialites and ooids) were likely originally aragonitic, and early marine length-fast cements (now dolomite) are suggested to have precipitated as high-Mg calcite then replaced syntaxially by dolomite. Based on petrographic and geochemical evidence, we suggest that marine dolomitization was the dominant synsedimentary diagenetic process in the unit, and for the most part, involved syntaxial and mimetic replacement. Further, a length-slow fibrous dolomite generation was precipitated during the later stages of marine diagenesis as a primary marine dolomite cement. This is indicated by the length-slow crystallographic structure of the cement and from its preserved geochemical and cathodoluminescence growth zonation. This new evidence for Tonian marine dolomite precipitation reinforces the idea of Precambrian marine environmental conditions, including the chemical composition of seawater, promoting dolomite formation at this time. The trace metal geochemical composition of well-preserved marine components, especially dolomite marine cements, reveals information about redox conditions in this Tonian shallow seawater. In terms of rare earth element geochemistry, the Beck Spring Dolomite has no significant Ce anomaly, and a ubiquitous positive Eu anomaly, consistent with widespread oceanic anoxia during deposition. Furthermore, the relatively low levels of iron and chalcophile elements Co, Cu, Pb and Zn in marine components compared to other Neoproterozoic carbonates suggest euxinic conditions (both anoxic and sulphidic) prevailed during deposition of the Beck Spring Dolomite.
There has been extensive debate about the history of Earth's oxygenation and the role that land plant evolution played in shaping Earth's ocean–atmosphere system. Here we use the rare earth element patterns in marine carbonates to monitor the structure of the marine redox landscape through the rise and diversification of animals and early land plants. In particular, we use the relative abundance of cerium (Ceanom), the only redox-sensitive rare earth element, in well-preserved marine cements and other marine precipitates to track seawater oxygen levels. Our results indicate that there was only a moderate increase in oceanic oxygenation during the Ediacaran (average Cryogenian Ceanom = 1.1, average Ediacaran Ceanom = 0.62), followed by a decrease in oxygen levels during the early Cambrian (average Cryogenian Ceanom = 0.90), with significant ocean anoxia persisting through the early and mid Paleozoic (average Early Cambrian–Early Devonian Ceanom = 0.84). It was not until the Late Devonian that oxygenation levels are comparable to the modern (average of all post-middle Devonian Ceanom = 0.55). Therefore, this work confirms growing evidence that the oxygenation of the Earth was neither unidirectional nor a simple two-stage process. Further, we provide evidence that it was not until the Late Devonian, when large land plants and forests first evolved, that oxygen levels reached those comparable to the modern world. This is recorded with the first modern-like negative Ceanom (values <0.6) occurring at around 380 Ma (Frasnian). This suggests that land plants, rather than animals, are the ‘engineers’ responsible for the modern fully oxygenated Earth system.