Evolution of Earth's tectonic carbon conveyor belt.

Concealed deep beneath the oceans is a carbon conveyor belt, propelled by plate tectonics. Our understanding of its modern functioning is underpinned by direct observations, but its variability through time has been poorly quantified. Here we reconstruct oceanic plate carbon reservoirs and track the fate of subducted carbon using thermodynamic modelling. In the Mesozoic era, 250 to 66 million years ago, plate tectonic processes had a pivotal role in driving climate change. Triassic-Jurassic period cooling correlates with a reduction in solid Earth outgassing, whereas Cretaceous period greenhouse conditions can be linked to a doubling in outgassing, driven by high-speed plate tectonics. The associated 'carbon subduction superflux' into the subcontinental mantle may have sparked North American diamond formation. In the Cenozoic era, continental collisions slowed seafloor spreading, reducing tectonically driven outgassing, while deep-sea carbonate sediments emerged as the Earth's largest carbon sink. Subduction and devolatilization of this reservoir beneath volcanic arcs led to a Cenozoic increase in carbon outgassing, surpassing mid-ocean ridges as the dominant source of carbon emissions 20 million years ago. An increase in solid Earth carbon emissions during Cenozoic cooling requires an increase in continental silicate weathering flux to draw down atmospheric carbon dioxide, challenging previous views and providing boundary conditions for future carbon cycle models.

Alkaline magmas in shallow arc plutonic roots: a field and experimental investigation of hydrous cumulate melting in the southern Adamello batholith.

Despite the first-order importance of crystallisation-differentiation for arc magma evolution, several other processes contribute to their compositional diversity. Among them is the remelting of partly crystallised magmas, also known as cumulate melting or 'petrological cannibalism'. The impact of this process on the plutonic record is poorly constrained. We investigate a nepheline-normative dyke suite close to the Blumone gabbros, a large amphibole-gabbro unit of the Tertiary Southern Alpine Adamello igneous complex. The compositions of the studied dykes are characterised by low SiO2 (43-46 wt. %), MgO (5.0-7.2 wt. %), Ni (18-40 µg/g), and high Al2O3 (20.2-22.0 wt. %) contents. Phenocrystic plagioclase in these dykes exhibits major, trace, and Sr isotope compositions similar to Blumone cumulate plagioclase, suggesting a genetic link between the nepheline-normative dykes and the amphibole-gabbro cumulates. We tested this hypothesis by performing saturation experiments on a nepheline-normative dyke composition in an externally heated pressure vessel at 200 MPa between 975 and 1100 °C at fO2 conditions close to the Ni-NiO buffer. Plagioclase and spinel are near-liquidus phases at and above 1050 °C, contrasting with the typical near-liquidus olivine ± spinel assemblage in hydrous calc-alkaline basalts. The alkaline nature of the dykes results from the abundance of amphibole in the protolith, consistent with melting of amphibole-gabbro cumulates. We modelled the heat budget from the repeated injection of basaltic andesite into a partly crystallised amphibole-gabbro cumulate. The results of this model show that no more than 7% of the cumulate pile reaches temperatures high enough to produce nepheline-normative melts. We propose that such nepheline-normative dykes are a hallmark of hydrous cumulate melting in subvolcanic plumbing systems. Therefore, ne-normative dykes in arc batholiths may indicate periods with high magma fluxes. Supplementary Information: The online version contains supplementary material available at 10.1007/s00410-023-02047-3.

Changes in Aortic Diameter and Wall Strain in Progressing Abdominal Aortic Aneurysms.

OBJECTIVES: The analysis of wall strain opens new perspectives in the prediction of abdominal aortic aneurysm (AAA) rupture. This study investigates the capability of four-dimensional ultrasound (4D US) to detect and characterize changes in wall strain in the same patients during follow-up observations. METHODS: Eighteen patients were examined by 64 4D US scans during a median follow-up period of 24.5 months. After performing the 4D US and manual aneurysm segmentation, kinematic analysis was performed using a customized interface and evaluation of the mean and peak circumferential strain, as well as spatial heterogeneity. RESULTS: All aneurysms showed a continuous diameter growth with a mean rate of 4% per year (P < .001). The mean circumferential strain (MCS) tends to increase from a median 0.89% by 10.49% per year in follow-up independent of the aneurysm diameter (P = .063). The subgroup analysis reveals a cohort with increasing MCS and decreasing spatial heterogeneity, as well as a cohort with nonincreasing MCS and increasing spatial heterogeneity (P < .05). CONCLUSIONS: The 4D US is able to register the strain changes in AAA follow-up. The MCS tends to increase during the observation time in the entire cohort, but the changes were independent of the maximum aneurysm diameter. The kinematic parameters allow the entire AAA cohort to differentiate into two subgroups and provide additional information about the pathologic behavior of the aneurysm wall.

Genetic model of the El Laco magnetite-apatite deposits by extrusion of iron-rich melt.

Magnetite-apatite deposits are important sources of iron and other metals. A prominent example are the magnetite lavas at the El Laco volcano, Northern Chile. Their formation processes remain debated. Here, we test the genetic hypothesis that an Fe-rich melt separated from silicate magma and ascended along collapse-related fractures. We complement recent analyses with thermodynamic modelling to corroborate Fe-Si liquid immiscibility evident in melt inclusions at El Laco and present viscometry of Fe- and Si-rich melts to assess the time and length scales of immiscible liquid separation. Using a rock deformation model, we demonstrate that volcano collapse can form failure zones extending towards the edifice flanks along which the ore liquid ascends towards extrusion driven by vapour exsolution despite its high density. Our results support the proposed magmatic genesis for the El Laco deposits. Geochemical and textural similarities indicate magnetite-apatite deposits elsewhere form by similar processes.

Generation of basic centers in high-silica zeolites and their application in gas-phase upgrading of bio-oil.

High-silica zeolites have been reported recently as efficient catalysts for liquid- and gas-phase condensation reactions because of the presence of a complementary source of basicity compared to Al-rich basic zeolites. Herein, we describe the controlled generation of these active sites on silica-rich FAU, BEA, and MFI zeolites. Through the application of a mild base treatment in aqueous Na2CO3, alkali-metal-coordinating defects are generated within the zeolite whereas the porous properties are fully preserved. The resulting catalysts were applied in the gas-phase condensation of propanal at 673 K as a model reaction for the catalytic upgrading of pyrolysis oil, for which an up to 20-fold increased activity compared to the unmodified zeolites was attained. The moderate basicity of these new sites leads to a coke resistance superior to traditional base catalysts such as CsX and MgO, and comparable activity and excellent selectivity is achieved for the condensation pathways. Through strategic acid and base treatments and the use of magic-angle spinning NMR spectroscopy, the nature of the active sites was investigated, which supports the theory of siloxy sites as basic centers. This contribution represents a key step in the understanding and design of high-silica base catalysts for the intermediate deoxygenation of crude bio-oil prior to the hydrotreating step for the production of second-generation biofuels.

Towards liquid fuels from biosyngas: effect of zeolite structure in hierarchical-zeolite-supported cobalt catalysts.

Wax on, wax off: Bifunctional cobalt-based catalysts on zeolite supports are applied for the valorization of biosyngas through Fischer-Tropsch chemistry. By using these catalysts, waxes can be hydrocracked to shorter-chain hydrocarbons, increasing the selectivity towards the C5 -C11 (gasoline) fraction. The zeolite topology and the amount and strength of acid sites are key parameters to maximize the performance of these bifunctional catalysts, steering Fischer-Tropsch product selectivity towards liquid hydrocarbons.