Bleuenn Gueguen

A shale-hosted Cr isotope record of low atmospheric oxygen during the Proterozoic

The emergence and expansion of animal life on Earth represents a dramatic shift in the structure and complexity of the biosphere. A lack of firm constraints on surface oxygen levels during the mid-Proterozoic has resulted in heated debate as to whether the rise and earliest diversification of animals was directly linked to a change in environmental oxygen levels or, instead, simply reflects the timing of innovations in gene expression and developmental regulation and was independent of a direct environmental trigger. Here, we present chromium (Cr) isotope data from marine black shales that provide evidence for minimal Cr oxidation throughout the mid-Proterozoic leading up to the diversification of eukaryotes and the rise of animals during the late Neoproterozoic. This observation requires very low background oxygen levels (<1% of present atmospheric levels). Accepting previously proposed estimates of p O2 levels needed to induce Cr isotope fractionation, our data provide support for the persistence of an Earth system in which baseline atmospheric p O2 would have been low enough to inhibit the diversification of animals until ca. 800 Ma. More generally, evidence for a delayed rise of atmospheric oxygen strongly suggests that environmental factors have played a fundamental role in controlling the emergence and expansion of complex life on Earth.

Integrated geochemical-petrographic insights from component-selective δ238U of Cryogenian marine carbonates

Emerging geochemical proxies have improved our understanding of the broad-scale history of Earth’s oxygenation. However, paleoredox work does not always include extensive consideration of sample preservation and paleoenvironmental setting. This is particularly an issue with marine carbonates, which although being potentially ideal ocean redox archives, are commonly altered during diagenesis. Here we provide new insight into the robustness of uranium isotopes (238U/235U ratios: δ238U values) as paleoredox tracers by determining texture-specific δ238U values from a well-described Cryogenian (Balcanoona) reef complex in South Australia. We found high variability in δ238U values between different carbonate components, even within a single sample. Petrographically, the best-preserved components from the Balcanoona reef are marine cements, which have a mean δ238U value of −0.23‰, essentially unfractionated from riverine inputs. These values are interpreted as reflecting a marine system with widespread anoxic and iron-rich settings. Less-well-preserved phases have δ238U values spanning almost the entire extent of the documented isotopic range. This integrated petrographic-geochemical work demonstrates the need for petrographic analysis and careful sample selection on a case-by-case basis in future carbonate metal isotope geochemistry.

Tracking the rise of eukaryotes to ecological dominance with zinc isotopes

The biogeochemical cycling of zinc (Zn) is intimately coupled with organic carbon in the ocean. Based on an extensive new sedimentary Zn isotope record across Earths history, we provide evidence for a fundamental shift in the marine Zn cycle ~800 million years ago. We discuss a wide range of potential drivers for this transition and propose that, within available constraints, a restructuring of marine ecosystems is the most parsimonious explanation for this shift. Using a global isotope mass balance approach, we show that a change in the organic Zn/C ratio is required to account for observed Zn isotope trends through time. Given the higher affinity of eukaryotes for Zn relative to prokaryotes, we suggest that a shift toward a more eukaryote-rich ecosystem could have provided a means of more efficiently sequestering organic-derived Zn. Despite the much earlier appearance of eukaryotes in the microfossil record (~1700 to 1600 million years ago), our data suggest a delayed rise to ecological prominence during the Neoproterozoic, consistent with the currently accepted organic biomarker records.