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At least 613 records · Page 34

Deep Roots Supply Reactivity and Enhance Silicate Weathering in the Bedrock Vadose Zone

In upland environments, roots commonly extend deep below soil into partially saturated bedrock. This Bedrock Vadose Zone (BVZ) has been shown to store and circulate water, host organic carbon respiration and serve as a critical source of rock-derived nutrients. However, the extent to which deep roots influence chemical weathering rates remains poorly understood. Here, we report 4 years of depth-resolved major ion chemistry over a 16-m thick BVZ hosting a deep rhizosphere in a catchment subject to a Mediterranean climate. These data allow development and validation of a reactive transport model (RTM), revealing that the timescales of water storage and drainage in the BVZ are sufficient to facilitate substantial chemical weathering of the shale bedrock. However, observed solute concentrations are only reproduced by the RTM when we explicitly include measured rates of CO 2(g) production meters below soil driven by the deeply rooted forest. By combining direct observations and a process-based RTM we conclude that the carbon respiration promoted by deep roots significantly enhances chemical weathering rates in the BVZ, constituting 43% ± 3% of total solute flux from the base of the BVZ to the water table.

Osorio‐Leon, Ivan D. [University of Illinois Urban↗

Examining normal modes as fundamental heat carriers in amorphous solids: The case of amorphous silicon

Normal mode decomposition of atomic vibrations has been used to provide microscopic understanding of thermal transport in amorphous solids for decades. In normal mode methods, it is naturally assumed that atoms vibrate around their equilibrium positions, and that individual normal modes are the fundamental vibrational excitations transporting heat. With the abundance of predictions from normal mode methods and experimental measurements now available, we carefully analyze these calculations in amorphous silicon, a model amorphous solid. We find a number of discrepancies, suggesting that treating individual normal modes as fundamental heat carriers may not be accurate in amorphous solids. Furthermore, our classical and ab initio molecular dynamics simulations of amorphous silicon demonstrate a large degree of atomic diffusion, especially at high temperatures, leading to the conclusion that thermal transport in amorphous solids could be better described starting from the perspectives of liquid physics rather than from crystalline solids.

36 MATERIALS SCIENCE↗

Accelerated oxidation during 1350°C cycling of ytterbium silicate environmental barrier coatings

We report environmental barrier coatings (EBCs) will be needed to protect SiC-based ceramic matrix composite components for the next generation of high-efficiency industrial gas turbines (IGTs). The IGT application will require ≥25 kh lifetimes, and little data are available on EBC failure mechanisms, particularly at ≥1300°C. Initial 1-h furnace cycle testing at 1350°C in 90 vol% H 2 O/10 vol% air was conducted ≥1000 cycles on thermally sprayed ytterbium disilicate (YbDS) coatings with and without an Si bond coating. By ≥1000 h, both EBCs formed thick, highly cracked, and fully crystalline cristobalite scales. Comparison of thermally grown oxide (TGO) microstructure and kinetics to isothermal rates of Si and SiC steam oxidation indicated a departure from slow-growing parabolic growth to more rapid rates of silica formation. Possible mechanisms and implications for this acceleration are discussed.

36 MATERIALS SCIENCE↗

Steam oxidation and microstructural evolution of rare earth silicate environmental barrier coatings

A primary failure mode for environmental barrier coatings (EBCs) on SiC ceramic matrix composites (CMCs) is the oxidation of the intermediate Si-bond coating, where the formation of SiO 2 at the bond coating–EBC interface results in debonding and spallation. This work compares the microstructure evolution and steam oxidation kinetics of the Si-bond coating beneath yttrium/ytterbium disilicate ((Y/Yb)DS) and ytterbium disilicate/monosilicate (YbDS/YbMS) EBCs to better understand the impact of EBC composition on oxidation kinetics. After 500 1-h cycles at 1350°C, (Y/Yb)DS displayed a decreasing concentration of the monosilicate minor phase and increasing concentration of porosity as furnace cycling time increased, whereas the YbDS/YbMS EBC displayed negligible microstructural evolution. For both EBC systems, thermally grown oxide growth rates in steam were found to increase by approximately an order magnitude compared to dry air oxidation. The (Y/Yb)DS EBC displayed a reduced steam oxidation rate compared to YbDS/YbMS.

36 MATERIALS SCIENCE↗

Silicate coprecipitation reduces green rust crystal size and limits dissolution-precipitation during air oxidation

Green rusts (GR) are mixed-valence iron (Fe) hydroxides which form in reducing redox environments like riparian and wetland soils and shallow groundwater. In these environments, silicon (Si) can influence Fe oxides’ chemical and physical properties but its role in GR formation and subsequent oxidative transformation have not been studied starting at initial nucleation. Green rust sulfate [GR(SO 4 )] and green rust carbonate [GR(CO 3 )] were both coprecipitated from salts by base titration in increasing % mol Si (0, 1, 10, and 50). The minerals were characterized before and after rapid (24 h) aqueous air-oxidation by x-ray diffraction (XRD), scanning electron microscopy (SEM), Fe extended x-ray absorption fine structure spectroscopy (EXAFS), and N 2 -BET surface area. Results showed that only GR(SO4) or GR(CO3) was formed at every tested Si concentration. Increasing % mol Si caused decreased plate size and increased surface area in GR(CO3) but not GR(SO4). GR plate basal thickness was not changed at any condition indicating a lack of Si interlayering. Air oxidation of GR(SO4) at all % mol Si contents transformed by dissolution and reprecipitation into lepidocrocite and goethite, favoring ferrihydrite with higher % Si content. Air oxidation of GR(CO3) transformed into magnetite and goethite but increasing Si caused GR to oxidize while retaining its hexagonal plate structure via solid-state oxidation. Our results indicate that Si has the potential to cause GR to form in smaller particles and upon air oxidation, Si can either stabilize the plate structure or alter transformation to ferrihydrite.

36 MATERIALS SCIENCE↗