Search

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 geological calcium cycle is linked to the geological carbon cycle through the weathering and burial of carbonate rocks. As a result, calcium (Ca) isotope ratios (44Ca/40Ca, expressed as δ44/40Ca) can help to constrain ancient carbon cycle dynamics if Ca cycle behavior can be reconstructed. However, the δ44/40Ca of carbonate rocks is influenced not only by the δ44/40Ca of seawater but also by diagenetic processes and fractionation associated with carbonate precipitation. In this study, we investigate the dominant controls on carbonate δ44/40Ca in Upper Permian to Middle Triassic limestones (ca. 253 to 244 Ma) from south China and Turkey. This time interval is ideal for assessing controls on Ca isotope ratios in carbonate rocks because fluctuations in seawater δ44/40Ca may be expected based on several large carbon isotope (δ13C) excursions ranging from − 2 to + 8‰. Parallel negative δ13C and δ44/40Ca excursions were previously identified across the end-Permian extinction horizon. Here, we find a second negative excursion in δ44/40Ca of ~ 0.2‰ within Lower Triassic strata in both south China and Turkey; however, this excursion is not synchronous between regions and thus cannot be interpreted to reflect secular change in the δ44/40Ca of global seawater. Additionally, δ44/40Ca values from Turkey are consistently 0.3‰ lower than contemporaneous samples from south China, providing further support for local or regional influences. By measuring δ44/40Ca and Sr concentrations ([Sr]) in two stratigraphic sections located at opposite margins of the Paleo-Tethys Ocean, we can determine whether the data represent global conditions (e.g., secular variations in the δ44/40Ca of seawater) versus local controls (e.g., original mineralogy or diagenetic alteration). The [Sr] and δ44/40Ca data from this study are best described statistically by a log-linear correlation that also exists in many previously published datasets of various geological ages. Using a model of early marine diagenetic water-rock interaction, we illustrate that this general correlation can be explained by the chemical evolution of bulk carbonate sediment samples with different initial mineralogical compositions that subsequently underwent recrystallization. Although early diagenetic resetting and carbonate mineralogy strongly influence the carbonate δ44/40Ca values, the relationship between [Sr] and δ44/40Ca holds potential for reconstructing first-order secular changes in seawater δ44/40Ca composition.

On shallow-marine carbonate buildups in south China, Turkey, and Japan, uppermost Permian skeletal limestones are truncated by an erosional surface that exhibits as much as 10 cm of topography, including overhanging relief. Sedimentary facies, microfabrics, carbon isotopes, and cements together suggest that erosion occurred in a submarine setting. Moreover, biostratigraphic data from south China demonstrate that the surface postdates the uppermost Permian sequence boundary at the global stratotype section and truncates strata within the youngest known Permian conodont zone. The occurrences of similar truncation surfaces at the mass-extinction horizon on carbonate platforms across the global tropics, each overlain by microbial buildups, and their association with a large negative excursion in 513C further suggest a causal link between erosion of shallow-marine carbonates and mass extinction. Previously proposed to account for marine extinctions, the hypothesis of rapid carbon release from sedimentary reservoirs or the deep ocean can also explain the petrographic observations. Rapid, unbuffered carbon release would cause submarine carbonate dissolution, accounting for erosion of uppermost Permian skeletal carbonates, and would be followed by a pulse of high carbonate saturation, explaining the precipitation of microbial limestones containing upward-growing carbonate crystal fans. Models for other carbon-release events suggest that at least 5 x [10.sup.18] g of carbon, released in Keywords: extinction, carbonate platform, carbon cycle, microbialite, calcification.

Four volcanic-ash beds bracket the Early-Middle Triassic boundary, as defined by conodont biostratigraphy, in a stratigraphic section in south China. High-precision U-Pb dates of single zircons allow us to place the Early to Middle Triassic (Olenekian-Anisian) boundary at 247.2 Ma. Magnetic-reversal stratigraphy allows global correlation. The new dates constrain the Early Triassic interval characterized by delayed biotic recovery and carbon-cycle instability to ~5 m.y. This time constraint must be considered in any model for the end-Permian extinction and subsequent recovery. Keywords: U-Pb geochronology, conodont, biostratigraphy, Permian, Triassic, extinction.

The end‐Permian extinction and its aftermath altered carbonate factories globally for millions of years, but its impact on platform geometries remains poorly understood. Here, the evolution in architecture and composition of two exceptionally exposed platforms in the Nanpanjiang Basin are constrained and compared with geochemical proxies to evaluate controls on platform geometries. Geochemical proxies indicate elevated siliciclastic and nutrient fluxes in the basal Triassic, at the Induan—Olenekian boundary and in the uppermost Olenekian. Cerium/Ce* shifts from high Ce/Ce* values and a lack of Ce anomaly indicating anoxia during the Lower Triassic to a negative Ce anomaly indicating oxygenation in the latest Olenekian and Anisian. Uranium and Mo depletion represents widespread anoxia in the world's oceans in the Early Triassic with progressive oxygenation in the Anisian. Carbonate factories shifted from skeletal in the Late Permian to abiotic and microbial in the Early Triassic before returning to skeletal systems in the Middle Triassic, Anisian coincident with declining anoxia. Margin facies shifted to oolitic grainstone in the Early Triassic with development of giant ooids and extensive marine cements. Anisian margins, in contrast, are boundstone with a diverse skeletal component. The shift in platform architecture from ramp to steep, high‐relief, flat‐topped profiles is decoupled from carbonate compositions having occurred in the Olenekian prior to the onset of basin oxygenation and biotic stabilisation of the margins. A basin‐wide synchronous shift from ramp to high‐relief platforms points to a combination of high subsidence rate and basin starvation coupled with high rates of abiotic and microbial carbonate accumulation and marine cement stabilisation of oolitic margins as the primary causes for margin up‐building. High sea water carbonate saturation resulting from a lack of skeletal sinks for precipitation, and basin anoxia promoting an expanded depth of carbonate supersaturation, probably contributed to marine cement stabilisation of margins that stimulated the shift from ramp to high‐relief platform architecture. [ABSTRACT FROM AUTHOR]