Gareth Izon

Volcanism, mass extinction, and carbon isotope fluctuations in the middle permian of China

Middle Permian Extinction A major extinction in the Middle Permian 260 to 270 million years ago preceded the huge end-Permian extinction. Wignall et al. (p. 1179) present a detailed analysis of the Middle Permian event from rocks in southwest China. The extinction coincided with extensive nearby volcanic eruptions. A major drop in carbon isotope values followed the extinction event, implying massive disruption of the carbon cycle. Fossiliferous rocks from southwest China show that a major extinction in the Middle Permian coincided with extensive volcanic eruptions. The 260-million-year-old Emeishan volcanic province of southwest China overlies and is interbedded with Middle Permian carbonates that contain a record of the Guadalupian mass extinction. Sections in the region thus provide an opportunity to directly monitor the relative timing of extinction and volcanism within the same locations. These show that the onset of volcanism was marked by both large phreatomagmatic eruptions and extinctions amongst fusulinacean foraminifers and calcareous algae. The temporal coincidence of these two phenomena supports the idea of a cause-and-effect relationship. The crisis predates the onset of a major negative carbon isotope excursion that points to subsequent severe disturbance of the ocean-atmosphere carbon cycle.

Resolution of inter-laboratory discrepancies in Mo isotope data: an intercalibration

The molybdenum (Mo) stable isotope system has been applied to a variety of geochemical and environmental problems. In the absence of a universally accepted zero-delta reference material, different groups report their data relative to their adopted in-house standards. Rigorous comparison of results generated in different laboratories using different analytical approaches is only possible if the in-house standards are of identical Mo isotope composition. To determine potential isotopic differences among various standards, the δ98Mo (98Mo/95Mo) values of ten Mo standard solutions were measured as part of this study. For six of these solutions, four laboratories carried out an intercalibration. In contrast to previous results, δ98Mo of various in-house standards were found to differ by up to 0.37‰. Renormalisation of our new and published Mo-isotope data available for seawater taken from various sites and the USGS rock reference material SDO-1 relative to NIST-SRM-3134, provides a much better agreement among reported δ98Mo values for these samples. Relative to NIST-SRM-3134, the δ98Mo of SDO-1 is 0.80 ± 0.14‰ (2s), while oxic, open-ocean seawater is characterised by an average δ98Mo of 2.09 ± 0.10‰ (2s). This intercalibration provides a solid platform for comparing and amending existing δ98Mo values. In addition, we recommend that future Mo isotope studies adopt NIST-SRM-3134 as a universal zero-delta reference material.

Biological Regulation of Atmospheric Chemistry En Route to Planetary Oxygenation

Significance It has been proposed that enhanced methane fluxes to Earth’s early atmosphere could have altered atmospheric chemistry, initiating a hydrocarbon-rich haze reminiscent of Saturn’s moon Titan. The occurrence, cause, and significance of haze development, however, remain unknown. Here, we test and refine the “haze hypothesis” by combining an ultra-high-resolution sulfur- and carbon-isotope dataset with photochemical simulations to reveal the structure and timing of haze development. These data suggest that haze persisted for ∼1 million years, requiring a sustained biological driver. We propose that enhanced atmospheric CH4, implied by the presence of haze, could have had a significant impact on the escape of hydrogen from the atmosphere, effectively contributing to the terminal oxidation of Earth’s surficial environments ∼2.4 billion years ago. Emerging evidence suggests that atmospheric oxygen may have varied before rising irreversibly ∼2.4 billion years ago, during the Great Oxidation Event (GOE). Significantly, however, pre-GOE atmospheric aberrations toward more reducing conditions—featuring a methane-derived organic-haze—have recently been suggested, yet their occurrence, causes, and significance remain underexplored. To examine the role of haze formation in Earth’s history, we targeted an episode of inferred haze development. Our redox-controlled (Fe-speciation) carbon- and sulfur-isotope record reveals sustained systematic stratigraphic covariance, precluding nonatmospheric explanations. Photochemical models corroborate this inference, showing Δ36S/Δ33S ratios are sensitive to the presence of haze. Exploiting existing age constraints, we estimate that organic haze developed rapidly, stabilizing within ∼0.3 ± 0.1 million years (Myr), and persisted for upward of ∼1.4 ± 0.4 Myr. Given these temporal constraints, and the elevated atmospheric CO2 concentrations in the Archean, the sustained methane fluxes necessary for haze formation can only be reconciled with a biological source. Correlative δ13COrg and total organic carbon measurements support the interpretation that atmospheric haze was a transient response of the biosphere to increased nutrient availability, with methane fluxes controlled by the relative availability of organic carbon and sulfate. Elevated atmospheric methane concentrations during haze episodes would have expedited planetary hydrogen loss, with a single episode of haze development providing up to 2.6–18 × 1018 moles of O2 equivalents to the Earth system. Our findings suggest the Neoarchean likely represented a unique state of the Earth system where haze development played a pivotal role in planetary oxidation, hastening the contingent biological innovations that followed.

Nitrogen fixation sustained productivity in the wake of the Palaeoproterozoic Great Oxygenation Event

The marine nitrogen cycle is dominated by redox-controlled biogeochemical processes and, therefore, is likely to have been revolutionised in response to Earth-surface oxygenation. The details, timing, and trajectory of nitrogen cycle evolution, however, remain elusive. Here we couple nitrogen and carbon isotope records from multiple drillcores through the Rooihoogte–Timeball Hill Formations from across the Carletonville area of the Kaapvaal Craton where the Great Oxygenation Event (GOE) and its aftermath are recorded. Our data reveal that aerobic nitrogen cycling, featuring metabolisms involving nitrogen oxyanions, was well established prior to the GOE and that ammonium may have dominated the dissolved nitrogen inventory. Pronounced signals of diazotrophy imply a stepwise evolution, with a temporary intermediate stage where both ammonium and nitrate may have been scarce. We suggest that the emergence of the modern nitrogen cycle, with metabolic processes that approximate their contemporary balance, was retarded by low environmental oxygen availability.The response of biogeochemical nitrogen cycle to Earth-surface oxygenation remains poorly known. Here, the authors show that aerobic nitrogen cycling was pervasive prior to the Great Oxygenation Event (GOE), but its evolution was complex, with diazotrophy prevailing and sustaining productivity after the GOE.

Vivianite formation in methane-rich deep-sea sediments from the South China Sea

Phosphorus is often invoked as the ultimate limiting nutrient, modulating primary productivity on geological timescales. Consequently, along with nitrogen, phosphorus bioavailability exerts a fundamental control on organic carbon production, linking all the biogeochemical cycles across the Earth system. Unlike nitrogen that can be microbially fixed from an essentially infinite atmospheric reservoir, phosphorus availability is dictated by the interplay between its sources and sinks. While authigenic apatite formation has received considerable attention as the dominant sedimentary phosphorus sink, the quantitative importance of reduced iron-phosphate minerals, such as vivianite, has only recently been acknowledged, and their importance remains underexplored. Combining microscopic and spectroscopic analyses of handpicked mineral aggregates with sediment geochemical profiles, we characterize the distribution and mineralogy of iron-phosphate minerals present in methane-rich sediments recovered from the northern South China Sea. Here, we demonstrate that vivianite authigenesis is pervasive in the iron-oxide-rich sediments below the sulfate–methane transition zone (SMTZ). We hypothesize that the downward migration of the SMTZ concentrated vivianite formation below the current SMTZ. Our observations support recent findings from non-steady-state post-glacial sedimentary successions, suggesting that iron reduction below the SMTZ, probably driven by iron-mediated anaerobic oxidation of methane (Fe-AOM), is coupled to phosphorus cycling on a much greater spatial scale than previously assumed. Calculations reveal that vivianite acts as an important burial phase for both iron and phosphorus below the SMTZ, sequestering approximately half of the total reactive iron pool. By extension, sedimentary vivianite formation could serve as a mineralogical marker of Fe-AOM, signalling low-sulfate availability against methanogenic and ferruginous backdrop. Given that similar conditions were likely present throughout vast swathes of Earth’s history, it is possible that Fe-AOM and vivianite authigenesis may have modulated methane and phosphorus availability on the early Earth, as well as during later periods of expanded marine oxygen deficiency. A better understanding of vivianite authigenesis, therefore, is fundamental to test long-standing hypotheses linking climate, atmospheric chemistry and the evolution of the biosphere.