Kimberly V. Lau

Marine anoxia and delayed Earth system recovery after the end-Permian extinction

Significance The end-Permian mass extinction not only decimated taxonomic diversity but also disrupted the functioning of global ecosystems and the stability of biogeochemical cycles. Explaining the 5-million-year delay between the mass extinction and Earth system recovery remains a fundamental challenge in both the Earth and biological sciences. We use coupled records of uranium concentrations and isotopic compositions to constrain global marine redox conditions across the end-Permian extinction horizon and through the subsequent 17 million years of Earth system recovery. Our finding that the trajectory of biological and biogeochemical recovery corresponds to variations in an ocean characterized by extensive, shallow marine anoxia provides, to our knowledge, the first unified explanation for these observations. Delayed Earth system recovery following the end-Permian mass extinction is often attributed to severe ocean anoxia. However, the extent and duration of Early Triassic anoxia remains poorly constrained. Here we use paired records of uranium concentrations ([U]) and 238U/235U isotopic compositions (δ238U) of Upper Permian−Upper Triassic marine limestones from China and Turkey to quantify variations in global seafloor redox conditions. We observe abrupt decreases in [U] and δ238U across the end-Permian extinction horizon, from ∼3 ppm and −0.15‰ to ∼0.3 ppm and −0.77‰, followed by a gradual return to preextinction values over the subsequent 5 million years. These trends imply a factor of 100 increase in the extent of seafloor anoxia and suggest the presence of a shallow oxygen minimum zone (OMZ) that inhibited the recovery of benthic animal diversity and marine ecosystem function. We hypothesize that in the Early Triassic oceans—characterized by prolonged shallow anoxia that may have impinged onto continental shelves—global biogeochemical cycles and marine ecosystem structure became more sensitive to variation in the position of the OMZ. Under this hypothesis, the Middle Triassic decline in bottom water anoxia, stabilization of biogeochemical cycles, and diversification of marine animals together reflect the development of a deeper and less extensive OMZ, which regulated Earth system recovery following the end-Permian catastrophe.

Multiple episodes of extensive marine anoxia linked to global warming and continental weathering following the latest Permian mass extinction

Multiple episodes of extensive oceanic anoxia delayed the marine ecosystem recovery from the latest Permian mass extinction. Explaining the ~5-million-year delay in marine biotic recovery following the latest Permian mass extinction, the largest biotic crisis of the Phanerozoic, is a fundamental challenge for both geological and biological sciences. Ocean redox perturbations may have played a critical role in this delayed recovery. However, the lack of quantitative constraints on the details of Early Triassic oceanic anoxia (for example, time, duration, and extent) leaves the links between oceanic conditions and the delayed biotic recovery ambiguous. We report high-resolution U-isotope (δ238U) data from carbonates of the uppermost Permian to lowermost Middle Triassic Zal section (Iran) to characterize the timing and global extent of ocean redox variation during the Early Triassic. Our δ238U record reveals multiple negative shifts during the Early Triassic. Isotope mass-balance modeling suggests that the global area of anoxic seafloor expanded substantially in the Early Triassic, peaking during the latest Permian to mid-Griesbachian, the late Griesbachian to mid-Dienerian, the Smithian-Spathian transition, and the Early/Middle Triassic transition. Comparisons of the U-, C-, and Sr-isotope records with a modeled seawater PO43− concentration curve for the Early Triassic suggest that elevated marine productivity and enhanced oceanic stratification were likely the immediate causes of expanded oceanic anoxia. The patterns of redox variation documented by the U-isotope record show a good first-order correspondence to peaks in ammonoid extinctions during the Early Triassic. Our results indicate that multiple oscillations in oceanic anoxia modulated the recovery of marine ecosystems following the latest Permian mass extinction.

Uranium isotope evidence for an expansion of marine anoxia during the end‐Triassic extinction

The end-Triassic extinction coincided with an increase in marine black shale deposition and biomarkers for photic zone euxinia, suggesting that anoxia played a role in suppressing marine biodiversity. However, global changes in ocean anoxia are difficult to quantify using proxies for local anoxia. Uranium isotopes (δ238U) in CaCO3 sediments deposited under locally well-oxygenated bottom waters can passively track seawater δ238U, which is sensitive to the global areal extent of seafloor anoxia due to preferential reduction of 238U(VI) relative to 235U(VI) in anoxic marine sediments. We measured δ238U in shallow-marine limestones from two stratigraphic sections in the Lombardy Basin, northern Italy, spanning over 400 m. We observe a ∼0.7‰ negative excursion in δ238U beginning in the lowermost Jurassic, coeval with the onset of the initial negative δ13C excursion and persisting for the duration of subsequent high δ13C values in the lower-middle Hettangian stage. The δ238U excursion cannot be realistically explained by local mixing of uranium in primary marine carbonate and reduced authigenic uranium. Based on output from a forward model of the uranium cycle, the excursion is consistent with a 40–100-fold increase in the extent of anoxic deposition occurring worldwide. Additionally, relatively constant uranium concentrations point toward increased uranium delivery to the oceans from continental weathering, which is consistent with weathering-induced eutrophication following the rapid increase in pCO2 during emplacement of the Central Atlantic Magmatic Province. The relative timing and duration of the excursion in δ238U implies that anoxia could have delayed biotic recovery well into the Hettangian stage.

A model for the decrease in amplitude of carbon isotope excursions across the Phanerozoic

The geological cycling of carbon ties together the ocean-atmosphere carbon pool, Earths biosphere, and Earths sedimentary reservoirs. Perturbations to this coupled system are recorded in the carbon-isotopic (δ13C) composition of marine carbonates. Large amplitude δ13C excursions are typically treated as individual events and interpreted accordingly. However, a recent compilation of Phanerozoic carbon isotopic data reveals that δ13C excursions are a ubiquitous feature of the geologic record, and thus should be considered in concert. Analysis indicates that Phanerozoic carbon isotope excursions, as a whole, have characteristic durations of 0.5 to 10 M.yr. and exhibit declining amplitude over time. These commonalities suggest a shared underlying control. Here we demonstrate that sinusoidal modulation of the sensitivity of organic carbon and phosphate burial in a simple numerical model of the geologic carbon cycle results in large, asymmetric δ13C oscillations that exhibit their largest amplitudes in the 0.5 to 10 M.yr. period range. As anoxia is known to strongly modulate the C:P burial ratio of organic matter in sediments, we propose that sea-level oscillations were the primary source of sinusoidal modulation for the geologic carbon cycle, and that their degree of influence on the carbon cycle was determined by the state of oxygenation of bottom waters overlying the continental shelves. When oxygen minimum zones (OMZs) were large, shallow, and prone to expansion, sea-level changes would have had the capacity to drive large changes in the areal extent of OMZs in contact with the sea-floor, resulting in strong leverage on the burial sensitivity of organic carbon and phosphate, and thus on δ13C. Progressive oxygenation of the oceans, which was facilitated by biological innovations, resulted in a decline in the amplitude of δ13C excursions over the Phanerozoic, and the biogeochemical stabilization of the Earth System.

Global perturbation of the marine calcium cycle during the Permian-Triassic transition

A negative shift in the calcium isotopic composition of marine carbonate rocks spanning the end-Permian extinction horizon in South China has been used to argue for an ocean acidification event coincident with mass extinction. This interpretation has proven controversial, both because the excursion has not been demonstrated across multiple, widely separated localities, and because modeling results of coupled carbon and calcium isotope records illustrate that calcium cycle imbalances alone cannot account for the full magnitude of the isotope excursion. Here, we further test potential controls on the Permian-Triassic calcium isotope record by measuring calcium isotope ratios from shallow-marine carbonate successions spanning the Permian-Triassic boundary in Turkey, Italy, and Oman. All measured sections display negative shifts in δ44/40Ca of up to 0.6‰. Consistency in the direction, magnitude, and timing of the calcium isotope excursion across these widely separated localities implies a primary and global δ44/40Ca signature. Based on the results of a coupled box model of the geological carbon and calcium cycles, we interpret the excursion to reflect a series of consequences arising from volcanic CO2 release, including a temporary decrease in seawater δ44/40Ca due to short-lived ocean acidification and a more protracted increase in calcium isotope fractionation associated with a shift toward more primary aragonite in the sediment and, potentially, subsequently elevated carbonate saturation states caused by the persistence of elevated CO2 delivery from volcanism. Locally, changing balances between aragonite and calcite production are sufficient to account for the calcium isotope excursions, but this effect alone does not explain the globally observed negative excursion in the δ13C values of carbonate sediments and organic matter as well. Only a carbon release event and related geochemical consequences are consistent both with calcium and carbon isotope data. The carbon release scenario can also account for oxygen isotope evidence for dramatic and protracted global warming as well as paleontological evidence for the preferential extinction of marine animals most susceptible to acidification, warming, and anoxia.

The Late Permian to Late Triassic Great Bank of Guizhou: An isolated carbonate platform in the Nanpanjiang Basin of Guizhou Province, China

The Late Permian to Late Triassic Great Bank of Guizhou (GBG) in southwest China is one of the few isolated carbonate platforms in the world that exposes an essentially complete record of initiation, development, and drowning across multiple platform-to-basin transects. The platform is exceptionally exposed in cross section at the surface by a faulted syncline that rotated strata to a dip angle of approximately 65°. Platform development spanned the end-Permian extinction and Triassic recovery that marks the transition from Paleozoic to Mesozoic styles of carbonate sediment production, providing a rare opportunity to assess the impact of global changes in carbonate factory types at a single locality. In addition, regional basin controls such as differential siliciclastic sediment input and varied antecedent topography provided mechanisms for lateral variability in platform morphology that can be investigated along exposures in several geographic sectors. Consequently, the GBG preserves a record of temporal and spatial variability in platform architecture that offers an unparalleled opportunity to investigate the controls on isolated carbonate platform morphology. A better understanding of these mechanisms is critical for improving predictive geologic models in exploration and field-development settings. The GBG also serves as a key outcrop analog for Early Triassic oolite reservoirs in the Middle East and China, the steep microbial-boundstone slopes of Carboniferous platforms in Kazakhstan, and the Permian platforms of Texas and New Mexico.