Abstract.A detailed geochemical analysis was performed on the upper part of the Maiolica Formation in the Breggia (southern Switzerland) and Capriolo sections (northern Italy). The analysed sediments consist of well-bedded, partly siliceous, pelagic carbonate, which lodges numerous thin, dark and organic-rich layers. Stable-isotope, phosphorus, organic-carbon and a suite of redox-sensitive trace-element contents (RSTE: Mo, U, Co, V and As) were measured. The RSTE pattern and C org :P tot ratios indicate that most organic-rich layers were deposited under dysaerobic rather than anaerobic conditions and that latter conditions were likely restricted to short intervals in the latest Hauterivian, the early Barremian and the pre-Selli early Aptian.
A detailed stratigraphical and geochemical analysis was performed on the upper part of the Maiolica Formation outcropping in the Breggia (southern Switzerland) and Capriolo sections (northern Italy). In these localities, the Maiolica Formation consists of well-bedded, partly siliceous, pelagic, micritic carbonate, which lodges numerous thin, dark and organic-rich layers. Stable-isotope, phosphorus, organic-carbon and a suite of redox-sensitive trace-metal contents (RSTE: Mo, U, Co, V and As) were measured. Higher densities of organic-rich layers were identified in the uppermost Hauterivian, lower Barremian and the Barremian-Aptian boundary intervals, whereas the upper Barremian interval and the interval immediately following the Barremian-Aptian boundary interval are characterized by lower densities of organic-rich layers. TOC contents, RSTE pattern and C<sub>org</sub>:P<sub>tot</sub> ratios indicate that most layers were deposited under dysaerobic rather than anaerobic conditions and that latter conditions were likely restricted to short intervals in the latest Hauterivian, the early Barremian and the pre-Selli early Aptian. <br><br> Correlations are possible with organic-rich intervals in central Italy (the Gorgo a Cerbara section) and the Boreal northwest German Basin, and with the facies and drowning pattern in the evolution of the Helvetic segment of the northern Tethyan carbonate platform. Our data and correlations suggest that the latest Hauterivian witnessed the progressive installation of dysaerobic conditions in the Tethys, which went along with the onset in sediment condensation, phosphogenesis and platform drowning on the northern Tethyan margin, and which culminated in the Faraoni anoxic episode. This brief episode is followed by further episodes of dysaerobic conditions in the Tethys and the northwest German Basin, which became more frequent and progressively stronger in the late early Barremian. Platform drowning persisted and did not halt before the latest early Barremian. The late Barremian witnessed diminishing frequencies and intensities in dysaerobic conditions, which went along with the progressive installation of the Urgonian carbonate platform. Near the Barremian-Aptian boundary, the increasing density in dysaerobic episodes in the Tethyan and northwest German Basins is paralleled by a change towards heterozoan carbonate production on the northern Tethyan shelf. The following return to more oxygenated conditions is correlated with the second phase of Urgonian platform growth and the period immediately preceding and corresponding to the Selli anoxic episode is characterized by renewed platform drowning and the change to heterozoan carbonate production. Changes towards more humid climate conditions were likely the cause for the repetitive installation of dys- to anaerobic conditions in the Tethyan and Boreal basins and the accompanying changes in the evolution of the carbonate platform towards heterozoan carbonate-producing ecosystems and platform drowning
The global silica cycle is an important component of the long-term climate system, yet its controlling factors are largely uncertain due to poorly constrained proxy records. Because radiolarians and other organisms preferentially extract lighter 28 Si from the ocean, the δ 30 Si of biosiliceous tests can thus be used for a potential proxy of productivity. Additionally, δ 30 Si of oceanic silica could have reflected changes in the isotopic ratio of sources and sinks. Here we show δ 30 Si records measured by secondary ion mass spectrometer (SIMS) in radiolarian silica, precipitated inside radiolarian molds in early Mesozoic bedded chert of the Inuyama section, central Japan. Range of measured δ 30 Si between-0.3 and 2 ‰ is consistent with that of modern and Cenozoic radiolarian tests. Relatively large intra-chert bed variability up to ~ 0.8 ‰ (1SD) support that δ 30 Si of the Mesozoic radiolarian molds are not perfectly homogenized in a chert bed during diagenesis. We found an overall inverse correlation between 10-Myr scale δ 30 Si and biogenic silica (BSi) burial flux, which contradicts with a conventional interpretation of δ 30 Si as paleoproductivity proxy, despite the lowresolution and scattered our δ 30 Si records. Although most of the factors controlling oceanic δ 30 Si are difficult to be constrained, this inverse relation might be explained by changes in δ 30 Si of mafic/felsic rock weathering ratio, which inferred from paleogeography. Further high-resolution δ 30 Si records will allow a better understanding of the past silica cycle.
The oxygen isotope (δ 18 O) analysis of carbonate fossils is widely applied for palaeoceanographic analysis, whereas that of siliceous fossils is only limited partly due to technical constraints and uncertain fractionation factors. Here we used a secondary ion mass spectrometer (SIMS) for δ 18 O of radiolarian silica, precipitated inside radiolarian molds in Mesozoic radiolarites from Japan, Italy, Switzerland and Romania in order to examine its potential for palaeoceanographic proxy. 507 measurements of the isotopic oxygen signature relative to the Vienna Standard Mean Ocean Water (δ 18 OVSMOW) of 53 chert samples range between 19.8 to 35.3 ‰ overlapping with that of modern and Cenozoic radiolarian tests in the equatorial Pacific. Relatively large intra-chert variability supports that δ 18 O of the Mesozoic radiolarian tests are not perfectly homogenized within a chert bed during the diagenetic segregation. The temporal changes in the δ 18 O values of radiolarians (δ 18 Oradiolarians) show an Early-Middle Triassic slight positive excursion, a Late Triassic high plateau, an Early Jurassic negative excursion with up to 8 ‰ , a Middle Jurassic slight positive excursion, and a few light values for the Cretaceous despite of their low resolution. A comparison of δ 18 O between radiolarian molds, conodont apatite, and the low magnesium calcium shells show overall similar secular variations during the Triassic, but different trends was observed during the Early Jurassic. Because our data is low-resolution, further cross check of δ 18 Oradiolarians is necessary to use as a proxy for paleoceanography.
The end-Triassic mass extinction event (ETE) is considered to be linked with the emplacement of the Central Atlantic magmatic province (CAMP), yet their temporal relation and underlying nature of global environmental and biotic changes remain controversial. A drastic radiolarian faunal turnover was associated with deep-sea acidification and changes in the chemical composition of pelagic terrigenous components, which were interpreted as the results of increased CAMP-derived materials, such as Fe2O3/Al2O3, MgO/Al2O3, and SiO2/Al2O3, without statistical tests. Here, we re-examined these CAMP-like signatures in terms of changes in the chemical composition of the Triassic–Jurassic pelagic deep-sea chert succession in Japan. Our newly compiled dataset suggests that changes in Fe2O3/Al2O3 and MgO/Al2O3 across the ETE were not significant, and thus, they may not be appropriate proxies for CAMP-derived material, potentially due to the dissolution of iron by ocean acidification and the formation of chlorite during diagenesis, respectively. Decreased SiO2/Al2O3 was also considered to have been reflected in increased CAMP-related dust flux and/or decreased biosiliceous productivity, but a slight increase in the Al2O3/TiO2 ratio (a biosiliceous productivity proxy) and an increase in shale bed thickness (dust flux proxy) across the radiolarian ETE imply increased eolian dust flux rather than decreased productivity. Furthermore, statistically significant Na enrichment at the radiolarian ETE level might be related to CAMP volcanism and/or associated changes in the source areas of eolian dust.
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