Decreasing extents of Archean serpentinization contributed to the rise of an oxidized atmosphere

At present, molecular hydrogen (H2) produced through Fe(II) oxidation during serpentinization of ultramafic rocks represents a small fraction of the global sink for O2 due to limited exposures of ultramafic rocks. In contrast, ultramafic rocks such as komatiites were much more common in the Early Earth and H2 production via serpentinization was a likely factor in maintaining an O2-free atmosphere throughout most of the Archean. Using thermodynamic simulations, this work quantifies the global O2 consumption attributed to serpentinization during the past 3.5 billion years. Results show that H2 generation is strongly dependent on rock compositions where serpentinization of more magnesian lithologies generated substantially higher amounts of H2. Consumption of >2 Tmole O2 yr−1 via low-temperature serpentinization of Archean continents and seafloor is possible. This O2 sink diminished greatly towards the end of the Archean as ultramafic rocks became less common and helped set the stage for the Great Oxidation Event.

Investigation of the γ′ Precipitates Dissolution in a Ni-Based Superalloy During Stress-Free Short-Term Annealing at High Homologous Temperatures

The equiaxed Ni-based superalloy René 108 was subjected to short-term annealing at five temperatures between 900 °C and 1100 °C. The phase composition, phase lattice parameters, microstructure, stereological parameters, and chemical composition of γ′ precipitates were investigated by thermodynamic simulations, X-ray diffraction, scanning and transmission electron microscopy, and energy-dispersive X-ray spectroscopy. Analysis of the γ and γ′ lattice parameters using the Nelson-Riley extrapolation function showed that the misfit parameter for temperatures 900 °C to 1050 °C is positive (decreasing from 0.32 to 0.11 pct). At 1100 °C, the parameter becomes negative, δ = − 0.18 pct. During the short-term annealing, γ′ precipitates dissolution occurred progressing more rapidly with increasing temperatures. The surface fraction of γ′ precipitates decreased with increasing temperature from 0.52 to 0.34. The dissolution of γ′ precipitates did not only proceed through uninterrupted thinning of each individual precipitate, but also included more complex mechanisms, including splitting. Based on transmission electron microscopy, it was shown that after γ′ precipitates dissolution, the matrix close to the γ/γ′ interface is strongly enriched in Co and Cr and depleted in Al.

The trisulfur radical ion S3•− controls platinum transport by hydrothermal fluids

Platinum group elements (PGE) are considered to be very poorly soluble in aqueous fluids in most natural hydrothermal–magmatic contexts and industrial processes. Here, we combined in situ X-ray absorption spectroscopy and solubility experiments with atomistic and thermodynamic simulations to demonstrate that the trisulfur radical ion S3•− forms very stable and soluble complexes with both PtII and PtIV in sulfur-bearing aqueous solution at elevated temperatures (∼300 °C). These Pt-bearing species enable (re)mobilization, transfer, and focused precipitation of platinum up to 10,000 times more efficiently than any other common inorganic ligand, such as hydroxide, chloride, sulfate, or sulfide. Our results imply a far more important contribution of sulfur-bearing hydrothermal fluids to PGE transfer and accumulation in the Earth’s crust than believed previously. This discovery challenges traditional models of PGE economic concentration from silicate and sulfide melts and provides new possibilities for resource prospecting in hydrothermal shallow crust settings. The exceptionally high capacity of the S3•− ion to bind platinum may also offer new routes for PGE selective extraction from ore and hydrothermal synthesis of noble metal nanomaterials.

Diffusion Simulation in SUS 430 Stainless Steel Interconnect with a MnCu Coating at 800°C

(MnCu)3O4 spinel coatings are good candidates for Cr-positioning protection on stainless steel interconnect. The spinel coatings can be formed by sputtering MnCu followed by a hot oxidation treatment. To understand how the elements diffuse in the MnCu-steel system, a homogenization diffusion-couple model was built with consideration for Mn oxidation at the coating surface. According to the simulation, the diffusion of Fe from the steel substrate to the MnCu coating occurred while Cr was almost trapped under the MnCu coating. Cu-rich metallic phase formed under the Mn-oxide layer early in the process. The solid solubility of Cr in such Cu phase was very low which can function as a Cr blocker so that Cr external oxidation can be inhibited. The inward diffusion of Mn from the coating to the substrate was caused by the formation of a Mn concentration peak at the interface which, based on thermodynamic simulations, was probably due to the dissolution of Mn with Fe and Cr.

CemGEMS – an easy-to-use web application for thermodynamic modeling of cementitious materials

Thermodynamic equilibrium calculations for cementitious materials enable predictions of stable phases and solution composition. In the last two decades, thermodynamic modelling has been increasingly used to understand the impact of factors such as cement composition, hydration, leaching, or temperature on the phases and properties of a hydrated cementitious system. General thermodynamic modelling codes such as GEM-Selektor have versatile but complex user interfaces requiring a considerable learning and training time. Hence there is a need for a dedicated tool, easy to learn and to use, with little to no maintenance efforts. CemGEMS (https://cemgems.app) is a free-to-use web app developed to meet this need, i.e. to assist cement chemists, students and industrial engineers in easily performing and visualizing thermodynamic simulations of hydration of cementitious materials at temperatures 0-99 °C and pressures 1-100 bar. At the server side, CemGEMS runs the GEMS code (https://gems.web.psi.ch) using the PSI/Nagra and Cemdata18 chemical thermodynamic data-bases (https://www.empa.ch/cemdata). The present paper summarizes the concepts of CemGEMS and its template data, highlights unique features of value for cement chemists that are not available in other tools, presents several calculated examples related to hydration and durability of cementitious materials, and compares the results with thermodynamic modelling using the desktop GEM-Selektor code.

The Fluid Mobilities of K and Zr in Subduction Zones: Thermodynamic Constraints

A subduction zone plays a critical role in forging continental crust via formation of arc magmas, which are characteristically enriched in large ion lithophile elements (LILEs) and depleted in high field strength elements (HFSEs). This trace element pattern results from the different mobilities of LILEs and HFSEs during slab-to-wedge mass transfer, but the mechanisms of trace element transfer from subducting crusts are not fully understood. In this study, thermodynamic simulations are carried out to evaluate the mobilities of K and Zr, as representative cases of LILE and HFSE, respectively, in slab fluids. The fluids buffered by basaltic eclogite can dissolve > 0.1 molal of K at sub-arc depths (~3 to 5.5 GPa). However, only minor amounts of K can be liberated by direct devolatilization of altered oceanic basalt, because sub-arc dehydration mainly takes place at temperatures < 600 °C (talc-out), wherein the fluid solubility of K is very limited (<0.01 molal). Therefore, serpentinite-derived fluids are required to flush K from the eclogite. The solubility of K can be enhanced by the addition of NaCl to the fluid, because fluid Na+ can unlock phengite-bonded K via a complex ion exchange. Finally, it is further confirmed that Zr and other HFSEs are immobile in slab fluids.