Research paper

Stable isotope and trace element stratigraphy across the Permian–Triassic transition: A redefinition of the boundary in the Velebit Mountain, Croatia

We present a map that correlates tectonic units between Alps and western Turkey accompanied by a text providing access to literature data, explaining the concepts used for defining the mapped tectonic units, and first-order paleogeographic inferences. Along-strike similarities and differences of the Alpine-Eastern Mediterranean orogenic system are discussed. The map allows (1) for superimposing additional information, such as e.g., post-tectonic sedimentary basins, manifestations of magmatic activity, onto a coherent tectonic framework and (2) for outlining the major features of the Alpine-Eastern Mediterranean orogen. Dinarides-Hellenides, Anatolides and Taurides are orogens of opposite subduction polarity and direction of major transport with respect to Alps and Carpathians, and polarity switches across the Mid-Hungarian fault zone. The Dinarides-Hellenides-Taurides (and Apennines) consist of nappes detached from the Greater Adriatic continental margin during Cretaceous and Cenozoic orogeny. Internal units form composite nappes that passively carry ophiolites obducted in the latest Jurassic–earliest Cretaceous or during the Late Cretaceous on top of the Greater Adriatic margin successions. The ophiolites on top of composite nappes do not represent oceanic sutures zones, but root in the suture zones of Neotethys that formed after obduction. Suturing between Greater Adria and the northern and eastern Neotethys margin occupied by the Tisza and Dacia mega-units and the Pontides occurred in the latest Cretaceous along the Sava-İzmir-Ankara-Erzincan suture zones. The Rhodopian orogen is interpreted as a deep-crustal nappe stack formed in tandem with the Carpatho-Balkanides fold-thrust belt, now exposed in a giant core complex exhumed in late Eocene to Miocene times from below the Carpatho-Balkan orogen and the Circum-Rhodope unit. Its tectonic position is similar to that of the Sakarya unit of the Pontides. We infer that the Rhodope nappe stack formed due to north-directed thrusting. Both Rhodopes and Pontides are suspected to preserve the westernmost relics of the suture zone of Paleotethys.

The Permian–Triassic mass extinction (PTME) is not only a dramatic loss in biodiversity and major change in ecosystem structures, but also coincided with the formation of abundant unusual sedimentary structures. Of these, ooids were widespread in shallow marine carbonate settings during the Permian–Triassic (P–Tr) transition, and giant ooids occurred more frequently at this critical period than any time during the Phanerozoic. Global review of 43 oolite-bearing Permian–Triassic boundary (PTB) sections with reliable biostratigraphic controls indicates that ooids occurred mostly in coincidence with the latest Permian extinction (LPE) and its immediate aftermath. Ooids became widespread over extensive regions just after the LPE during the interval corresponding to the conodont Hindeodus changxingensis Zone. They persisted into the earliest Triassic until the conodont Isarcicella isarcica Zone. In addition, oolites are often found in association with microbialites in low-latitude shallow-marine settings. Proliferation of ooids over the P–Tr transition indicates an extensive range of warm waters with high level of carbonate saturation state that prevailed in the oceans during that time. The latest Permian ooids were usually small (0.3 to 0.7 mm in diameter), aragonitic, poorly preserved and recrystallized, while moderately to well-preserved morphology, bimineralic, and oversized forms usually occurred in the I. isarcica Zone of the earliest Triassic and afterwards. Widespread aragonitic ooids in the end of the Permian reinforce the scenario that an “aragonite sea” period may have resulted in the dramatic losses of skeletal organisms that precipitated low-Mg calcite and hampered their recovery in the aftermath. The anomalous primary mineralogy of Lower Triassic ooids implies that previously assumed stable seawater composition during the Early Triassic needs to be revaluated.

A combined study of trace elements, carbon and oxygen isotopes was carried out for Carboniferous marine limestones from the Lower Yangtze platform in South China. The results provide insights into the influence of terrigenous input to Paleotethyan seawater, from which pure and impure carbonates precipitated. In terms of the correlations between the concentrations of elements with different properties, variable extents of two-component mixing are evident between seawater and terrigenous detritus. This is quantitatively dictated by such parameters as the calcite–seawater partition coefficients (D_X) and the seawater–continental upper crust partition coefficients (K_X). Water-soluble elements with high and medium K_X values, such as Na, Mg, P, V, Cr, Ni, Cu, Zn, Sr, Mo and U, are susceptible to incorporation into carbonate lattices, and thus their concentrations represent the geochemical composition of paleoseawater. In contrast, water-insoluble elements with low K_X values, such as Be, Al, Sc, Co, Ga, Cs, REE, Hf and Th, cannot be incorporated into carbonate lattices, thus providing a proxy for contributions from terrigenous material.

The Carboniferous marine limestones from a stratigraphic profile exhibit three positive and three negative δ¹³C excursions from the late Visean to Gzhelian. These δ¹³C excursions generally match those of contemporaneous carbonates elsewhere in the world, which can be linked to the alternative occurrences of cold and warm paleoclimates in the Carboniferous. The lowest δ¹³C values in the profile are generally associated with the lowest values of Y/Ho and the highest values of (Nd/Yb)_PAAS, Th, Sc and insoluble residue. This indicates a significant contribution from the terrigenous material to the negative δ¹³C excursions. The effect from the warm paleoclimate is also indicated by high chemical indices of alteration for the insoluble residue from the three intervals of high terrigenous input. On the other hand, the positive δ¹³C excursions are associated with the decreases of terrigenous input. Therefore, the incorporation of terrigenous material into the epicontinental seawater is temporally linked to the paleoclimatic change on continental margins adjacent to the Paleotethyan seawater.

We describe variations in trace element compositions that occurred on the deep seafloor of palaeo-superocean Panthalassa during the end-Permian mass extinction based on samples of sedimentary rock from one of the most continuous Permian–Triassic boundary sections of the pelagic deep sea exposed in north-eastern Japan. Our measurements revealed low manganese (Mn) enrichment factor (normalised by the composition of the average upper continental crust) and high cerium anomaly values throughout the section, suggesting that a reducing condition already existed in the depositional environment in the Changhsingian (Late Permian). Other redox-sensitive trace-element (vanadium [V], chromium [Cr], molybdenum [Mo], and uranium [U]) enrichment factors provide a detailed redox history ranging from the upper Permian to the end of the Permian. A single V increase (representing the first reduction state of a two-step V reduction process) detected in uppermost Changhsingian chert beds suggests development into a mildly reducing deep-sea condition less than 1 million years before the end-Permian mass extinction. Subsequently, a more reducing condition, inferred from increases in Cr, V, and Mo, developed in overlying Changhsingian grey siliceous claystone beds. The most reducing sulphidic condition is recognised by the highest peaks of Mo and V (second reduction state) in the uppermost siliceous claystone and overlying lowermost black claystone beds, in accordance with the end-Permian mass extinction event. This significant increase in Mo in the upper Changhsingian led to a high Mo/U ratio, much larger than that of modern sulphidic ocean regions. This trend suggests that sulphidic water conditions developed both at the sediment–water interface and in the water column. Above the end-Permian mass extinction horizon, Mo, V and Cr decrease significantly. On this trend, we provide an interpretation of drawdown of these elements in seawater after the massive element precipitation event during the end-Permian maximum development of the reducing water column. A decrease in the Mo/U ratio despite enrichment of Mo and U also supports that of Mo. Calculations of the total amounts of these elements precipitated compared with the global seawater inventory suggest that when more than 6–10% of the global ocean became euxinic as much as the study section, most of the dissolved elements would precipitate into sediments, resulting in a global element-depleted seawater condition. Mo, V, and Cr act as bioessential elements for both primary producers and animals. The continuing reducing water column and the lack of bioessential elements could have had a considerable effect on primary producer turnover and marine life metabolism not only in the pelagic environment, but also in surrounding marine environments.

Redox sensitive elements serve as useful proxies of the oxygenation state of ancient environments, but their interpretation may not always be straightforward. To evaluate the inherent complexities, rare earths and yttrium (REY), iodine, and major element concentrations are determined in two carbonate sections spanning the Permian–Triassic (P–Tr) transition in Demirtas, Turkey and Cili, South China. We use major oxides to identify non-seawater REY sources such as siliciclastics, Fe-oxides, phosphates and diagenetic fluids. Additionally, we employ Y/Ho ratio, La anomaly, and light rare earth element depletion to identify which samples preserve a seawater-like REY_SN distribution. In contrast to past interpretations, we find that the P–Tr boundary microbialites in both sections contain REY signatures indicative of deposition in an oxic environment. These boundary microbialites have their base at the extinction horizon and are widespread within the Tethyan region. In the Cili section, the underlying Permian limestone also preserves a seawater-like REY signature with a negative Ce anomaly. This indicates that the water column was oxygenated both before and after the extinction event. The Permian limestone in the Demirtas section does not preserve a seawater-like REY_SN distribution, so the absence of a Ce anomaly cannot be used to distinguish prevailing redox conditions during deposition. However, in these samples, we find the presence of a diverse Permian benthic community sufficient to identify deposition in an oxic environment. The geochemical evidence for a continuously oxic environment during the deposition of the boundary microbialite presented in this study strongly supports work done using ostracods as redox indicators within the boundary microbialite in South China. The microbialite has been proposed as a disaster facies, in part resulting from the exclusion of grazers. Although anoxia is one of the suggested mechanisms for the exclusion of grazers, we find that it is not supported by geochemical and biotic evidence.

The end of the Permian was a time of crisis that culminated in the Earth's greatest mass extinction. There is much speculation as to the cause for this catastrophe. Here we provide a full suite of high-resolution and coeval geochemical results (trace and rare earth elements, carbon, oxygen, strontium and clumped isotopes) reflecting ambient seawater chemistry and water quality parameters leading up to the end‐Permian crisis. Preserved brachiopod low-Mg calcite-based seawater chemistry, supplemented by data from various localities, documents a sequence of interrelated primary events such as coeval flows of Siberian Trap continental flood basalts and emission of carbon dioxide leading to warm and extreme Greenhouse conditions with sea surface temperatures (SST) of ~ 36 °C for the Late Permian. Although anoxia has been advanced as a cause for the mass extinction, most biotic and geochemical evidence suggest that it was briefly relevant during the early phase of the event and only in areas of upwelling, but not a general cause. Instead, we suggest that renewed and increased end‐Permian Siberian Trap volcanic activity, about 2000 years prior to the extinction event, released massive amounts of carbon dioxide and coupled with thermogenic methane emissions triggered extreme global warming and increased continental weathering. Eventually, these rapidly discharged greenhouse gas emissions, less than 1000 years before the event, ushered in a global Hothouse period leading to extreme tropical SSTs of ~ 39 °C and higher. Based on these sea surface temperatures, atmospheric CO₂ concentrations were about 1400 ppmv and 3000 ppmv for the Late and end‐Permian, respectively. Leading up to the mass extinction, there was a brief interruption of the global warming trend when SST dropped, concurrent with a slight, but significant recovery in biodiversity in the western Tethys. It is possible that emission of volcanic sulfate aerosols resulted in brief cooling just after the onset of intensified warming during the end of the Permian. After aerosol deposition, global warming resumed and the biotic decline proceeded, and was accompanied by suboxia, in places of the surface ocean which culminated in the greatest mass extinction in Earth history.