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Fluctuations in marine oxygen concentrations have been invoked as a primary driver for changes in biodiversity throughout Earth history. Expansions in reducing marine conditions are commonly invoked as key causal mechanisms for mass extinctions, while increases in marine oxygenation are becoming an increasingly common causal mechanism invoked for biodiversification events. Here we utilize a multiproxy approach to constrain local and global marine paleoredox conditions throughout the late Cambrian-Early Ordovician from two drill core successions in Baltoscandia. Local paleoredox proxies such as manganese concentrations and iron speciation reveal that both sites in the Baltic paleobasin had persistently anoxic and predominantly euxinic (anoxic and sulfidic) bottom water conditions throughout the study interval. Corresponding trace metal datasets indicate nuanced contraction and expansion of global anoxic and euxinic conditions along continental margins during the late Cambrian-Early Ordovician. Lastly, thallium isotope data from these locally reducing sections suggest a global expansion of oxygenated shelf and deeper marine environments from the late Cambrian into the Early Ordovician. This evidence for increasingly oxic marine environments coincides with increases in burrowing depth and tiering in marine animals, as well as diversification of body fossils throughout this ~8-million-year interval. The collective geochemical datasets provide some of the first direct paleoredox evidence for an increase in marine oxygen concentrations as a key mechanism for the Ordovician radiation of marine life., (© 2023 John Wiley & Sons Ltd.)

Ediacaran sediments record an unusual global carbon cycle perturbation that has been linked to widespread oceanic oxygenation, the Shuram negative C isotope excursion (NCIE). However, proxy-based estimates of global ocean redox conditions during this event have been limited largely due to proxy specificity (e.g., euxinic sediments for Mo and U isotopes). Modern global seawater documents a homogenous Tl isotope composition (ε 205 Tl = -6.0) due to significant manganese oxide burial, which is recorded in modern euxinic sediments. Here, we provide new data documenting that sediments deposited beneath reducing but a non-sulfidic water column from the Santa Barbara Basin (ε 205 Tl = -5.6 ± 0.1) also faithfully capture global seawater Tl isotope values. Thus, the proxy utilization of Tl isotopes can extend beyond strictly euxinic settings. Second, to better constrain the global redox conditions during the Shuram NCIE, we measured Tl isotopes of locally euxinic and ferruginous shales of the upper Doushantuo Formation, South China. The ε 205 Tl values of these shales exhibit a decreasing trend from ≈-3 to ≈-8, broadly coinciding with the onset of Shuram NCIE. There are ε 205 Tl values (-5.1 to -7.8) during the main Shuram NCIE interval that approach values more negative than modern global seawater. These results suggest that manganese oxide burial was near or even greater than modern burial fluxes, which is likely linked to an expansion of oxic conditions. This ocean oxygenation may have been an important trigger for the Shuram NCIE and evolution of Ediacaran-type biota. Subsequently, Tl isotopes show an increasing trend from the modern ocean value to values near the modern global inputs or even heavier (ε 205 Tl ≈ -2.5 ~ 0.4), occurring prior to recovery from the NCIE. These records may suggest that there was a decrease in the extent of oxygenated conditions in the global oceans during the late stage of the Shuram NCIE., (© 2020 John Wiley & Sons Ltd.)

By about 2.0 billion years ago (Ga), there is evidence for a period best known for its extended, apparent geochemical stability expressed famously in the carbonate-carbon isotope data. Despite the first appearance and early innovation among eukaryotic organisms, this period is also known for a rarity of eukaryotic fossils and an absence of organic biomarker fingerprints for those organisms, suggesting low diversity and relatively small populations compared to the Neoproterozoic era. Nevertheless, the search for diagnostic biomarkers has not been performed with guidance from paleoenvironmental redox constrains from inorganic geochemistry that should reveal the facies that were most likely hospitable to these organisms. Siltstones and shales obtained from drill core of the ca. 1.3-1.4 Ga Roper Group from the McArthur Basin of northern Australia provide one of our best windows into the mid-Proterozoic redox landscape. The group is well dated and minimally metamorphosed (of oil window maturity), and previous geochemical data suggest a relatively strong connection to the open ocean compared to other mid-Proterozoic records. Here, we present one of the first integrated investigations of Mesoproterozoic biomarker records performed in parallel with established inorganic redox proxy indicators. Results reveal a temporally variable paleoredox structure through the Velkerri Formation as gauged from iron mineral speciation and trace-metal geochemistry, vacillating between oxic and anoxic. Our combined lipid biomarker and inorganic geochemical records indicate at least episodic euxinic conditions sustained predominantly below the photic zone during the deposition of organic-rich shales found in the middle Velkerri Formation. The most striking result is an absence of eukaryotic steranes (4-desmethylsteranes) and only traces of gammacerane in some samples-despite our search across oxic, as well as anoxic, facies that should favor eukaryotic habitability and in low maturity rocks that allow the preservation of biomarker alkanes. The dearth of Mesoproterozoic eukaryotic sterane biomarkers, even within the more oxic facies, is somewhat surprising but suggests that controls such as the long-term nutrient balance and other environmental factors may have throttled the abundances and diversity of early eukaryotic life relative to bacteria within marine microbial communities. Given that molecular clocks predict that sterol synthesis evolved early in eukaryotic history, and (bacterial) fossil steroids have been found previously in 1.64 Ga rocks, then a very low environmental abundance of eukaryotes relative to bacteria is our preferred explanation for the lack of regular steranes and only traces of gammacerane in a few samples. It is also possible that early eukaryotes adapted to Mesoproterozoic marine environments did not make abundant steroid lipids or tetrahymanol in their cell membranes., (© 2019 John Wiley & Sons Ltd.)

The ocean-atmosphere system is typically envisioned to have gone through a unidirectional oxygenation with significant oxygen increases in the earliest (ca. 635 Ma), middle (ca. 580 Ma), or late (ca. 560 Ma) Ediacaran Period. However, temporally discontinuous geochemical data and the patchy metazoan fossil record have been inadequate to chart the details of Ediacaran ocean oxygenation, raising fundamental debates about the timing of ocean oxygenation, its purported unidirectional rise, and its causal relationship, if any, with the evolution of early animal life. To better understand the Ediacaran ocean redox evolution, we have conducted a multi-proxy paleoredox study of a relatively continuous, deep-water section in South China that was paleogeographically connected with the open ocean. Iron speciation and pyrite morphology indicate locally euxinic (anoxic and sulfidic) environments throughout the Ediacaran in this section. In the same rocks, redox sensitive element enrichments and sulfur isotope data provide evidence for multiple oceanic oxygenation events (OOEs) in a predominantly anoxic global Ediacaran-early Cambrian ocean. This dynamic redox landscape contrasts with a recent view of a redox-static Ediacaran ocean without significant change in oxygen content. The duration of the Ediacaran OOEs may be comparable to those of the oceanic anoxic events (OAEs) in otherwise well-oxygenated Phanerozoic oceans. Anoxic events caused mass extinctions followed by fast recovery in biologically diversified Phanerozoic oceans. In contrast, oxygenation events in otherwise ecologically monotonous anoxic Ediacaran-early Cambrian oceans may have stimulated biotic innovations followed by prolonged evolutionary stasis., (© 2016 John Wiley & Sons Ltd.)