Lithium isotopic constraints on the evolution of continental clay mineral factory and marine oxygenation in the earliest Paleozoic Era.

The evolution of oxygen cycles on Earth's surface has been regulated by the balance between molecular oxygen production and consumption. The Neoproterozoic-Paleozoic transition likely marks the second rise in atmospheric and oceanic oxygen levels, widely attributed to enhanced burial of organic carbon. However, it remains disputed how marine organic carbon production and burial respond to global environmental changes and whether these feedbacks trigger global oxygenation during this interval. Here, we report a large lithium isotopic and elemental dataset from marine mudstones spanning the upper Neoproterozoic to middle Cambrian [~660 million years ago (Ma) to 500 Ma]. These data indicate a dramatic increase in continental clay formation after ~525 Ma, likely linked to secular changes in global climate and compositions of the continental crust. Using a global biogeochemical model, we suggest that intensified continental weathering and clay delivery to the oceans could have notably increased the burial efficiency of organic carbon and facilitated greater oxygen accumulation in the earliest Paleozoic oceans.

Mercury isotopes show vascular plants had colonized land extensively by the early Silurian.

The colonization and expansion of plants on land is considered one of the most profound ecological revolutions, yet the precise timing remains controversial. Because land vegetation can enhance weathering intensity and affect terrigenous input to the ocean, changes in terrestrial plant biomass with distinct negative Δ199Hg and Δ200Hg signatures may overwrite the positive Hg isotope signatures commonly found in marine sediments. By investigating secular Hg isotopic variations in the Paleozoic marine sediments from South China and peripheral paleocontinents, we highlight distinct negative excursions in both Δ199Hg and Δ200Hg at Stage level starting in the early Silurian and again in the Carboniferous. These geochemical signatures were driven by increased terrestrial contribution of Hg due to the rapid expansion of vascular plants. These excursions broadly coincide with rising atmospheric oxygen concentrations and global cooling. Therefore, vascular plants were widely distributed on land during the Ordovician-Silurian transition (~444 million years), long before the earliest reported vascular plant fossil, Cooksonia (~430 million years).

Rapid marine oxygen variability: Driver of the Late Ordovician mass extinction.

The timing and connections between global cooling, marine redox conditions, and biotic turnover are underconstrained for the Late Ordovician. The second most severe mass extinction occurred at the end of the Ordovician period, resulting in ~85% loss of marine species between two extinction pulses. As the only "Big 5" extinction that occurred during icehouse conditions, this interval is an important modern analog to constrain environmental feedbacks. We present a previously unexplored thallium isotope records from two paleobasins that record global marine redox conditions and document two distinct and rapid excursions suggesting vacillating (de)oxygenation. The strong temporal link between these perturbations and extinctions highlights the possibility that dynamic marine oxygen fluctuations, rather than persistent, stable global anoxia, played a major role in driving the extinction. This evidence for rapid oxygen changes leading to mass extinction has important implications for modern deoxygenation and biodiversity declines.

Low oxygen levels with high redox heterogeneity in the late Ediacaran shallow ocean: Constraints from I/(Ca + Mg) and Ce/Ce* of the Dengying Formation, South China.

Most previous studies focused on the redox state of the deep water, leading to an incomplete understanding of the spatiotemporal evolution of the redox-stratified ocean during the Ediacaran-Cambrian transition. In order to decode the redox condition of shallow marine environments during the late Ediacaran, this study presents I/(Ca + Mg), carbon and oxygen isotope, major, trace, and rare earth element data of subtidal to peritidal dolomite from the Dengying Formation at Yangba, South China. In combination with the reported radiometric and biostratigraphic data, the Dengying Formation and coeval successions worldwide are subdivided into a positive δ13 C excursion (up to ~6‰) in the lower part (~551-547 Ma) and a stable δ13 C plateau (generally between 0‰ and 3‰) in the middle-upper part (~547-541 Ma). The overall low I/(Ca + Mg) ratios (<0.5 µmol/mol) and slightly negative to no Ce anomalies (0.80 < [Ce/Ce*]SN < 1.25), point to low-oxygen levels in shallow marine environments at Yangba. Moreover, four pulsed negative excursions in (Ce/Ce*)SN (between 0.62 and 0.8) and the associated two positive excursions in I/(Ca + Mg) ratios (up to 2.02 µmol/mol) are observed, indicative of weak oxygenations in the shallow marine environments. The comparison with other upper Ediacaran shallow water successions worldwide reveals that the (Ce/Ce*)SN and I/(Ca + Mg) values generally fall in the Precambrian range but their temporal trends differ among these successions (e.g., Ce anomaly profiles significantly different between Yangba and the Yangtze Gorge sections), which point to low oxygen levels with high redox heterogeneity in the surface ocean. This is consistent with the widespread anoxia as revealed by low δ238 U values reported by previous studies. Thus, the atmospheric oxygen concentrations during the late Ediacaran are estimated to be very low, similar to the case during the most Mesoproterozoic to early Neoproterozoic period.

Significant fluctuation in the global sulfate reservoir and oceanic redox state during the Late Devonian event.

Ocean sulfate concentration might have fluctuated greatly throughout the Earth's history and may serve as a window into perturbations in the ocean-atmosphere system. Coupling high-resolution experimental results with an inverse modeling approach, we, here, show an unprecedented dynamic in the global sulfate reservoir during the Frasnian-Famennian (F-F) boundary event, as one of the "Big five" Phanerozoic biotic crises. Notably, our results indicate that, in a relatively short-time scale (∼200 thousand years), seawater sulfate concentration would have dropped from several mM before the Upper Kellwasser Horizon (UKH) to an average of 235 ± 172 µM at the end of the UKH (more than 100 times lower than the modern level) as the result of evaporite deposition and euxinia, and returned to around mM range after the event. Our findings indicate that the instability in the global sulfate reservoir and nutrient-poor oceans may have played a major role in driving the Phanerozoic biological crises.

Timing and pacing of the Late Devonian mass extinction event regulated by eccentricity and obliquity.

The Late Devonian envelops one of Earth's big five mass extinction events at the Frasnian-Famennian boundary (374 Ma). Environmental change across the extinction severely affected Devonian reef-builders, besides many other forms of marine life. Yet, cause-and-effect chains leading to the extinction remain poorly constrained as Late Devonian stratigraphy is poorly resolved, compared to younger cataclysmic intervals. In this study we present a global orbitally calibrated chronology across this momentous interval, applying cyclostratigraphic techniques. Our timescale stipulates that 600 kyr separate the lower and upper Kellwasser positive δ13C excursions. The latter excursion is paced by obliquity and is therein similar to Mesozoic intervals of environmental upheaval, like the Cretaceous Ocean-Anoxic-Event-2 (OAE-2). This obliquity signature implies coincidence with a minimum of the 2.4 Myr eccentricity cycle, during which obliquity prevails over precession, and highlights the decisive role of astronomically forced "Milankovitch" climate change in timing and pacing the Late Devonian mass extinction.

Biogenic Iron-Rich Filaments in the Quartz Veins in the Uppermost Ediacaran Qigebulake Formation, Aksu Area, Northwestern Tarim Basin, China: Implications for Iron Oxidizers in Subseafloor Hydrothermal Systems.

Fe-(oxyhydr)oxide-encrusted filamentous microstructures produced by microorganisms have been widely reported in various modern and ancient extreme environments; however, the iron-dependent microorganisms preserved in hydrothermal quartz veins have not been explored in detail because of limited materials available. In this study, abundant well-preserved filamentous microstructures were observed in the hydrothermal quartz veins of the uppermost dolostones of the terminal-Ediacaran Qigebulake Formation in the Aksu area, northwestern Tarim Basin, China. These filamentous microstructures were permineralized by goethite and hematite as revealed by Raman spectroscopy and completely entombed in chalcedony and quartz cements. Microscopically, they are characterized by biogenic filamentous morphologies (commonly 20-200 µm in length and 1-5 µm in diameter) and structures (curved, tubular sheath-like, segmented, and mat-like filaments), similar to the Fe-oxidizing bacteria (FeOB) living in modern and ancient hydrothermal vent fields. A previous study revealed that quartz-barite vein swarms were subseafloor channels of low-temperature, silica-rich, diffusive hydrothermal vents in the earliest Cambrian, which contributed silica to the deposition of the overlying bedded chert of the Yurtus Formation. In this context, this study suggests that the putative filamentous FeOB preserved in the quartz veins might have thrived in the low-temperature, silica- and Fe(II)-rich hydrothermal vent channels in subseafloor mixing zones and were rapidly fossilized by subsequent higher-temperature, silica-rich hydrothermal fluids in response to waning and waxing fluctuations of diffuse hydrothermal venting. In view of the occurrence in a relatively stable passive continental margin shelf environment in Tarim Block, the silica-rich submarine hydrothermal vent system may represent a new and important geological niche favorable for FeOB colonization, which is different from their traditional habitats reported in hydrothermal vent systems at oceanic spreading centers or volcanic seamounts. Thus, these newly recognized microfossils offer a new clue to explore the biological signatures and habitat diversity of microorganisms on Earth and beyond.