Creating Reactivity with Unstable Endmembers using Pressure and Temperature: Synthesis of Bulk Cubic Mg0.4 Fe0.6 N.

Alloy and nitride solid solutions are prominent for structural, energy and information processing applications. There are frequently however barriers to making them. We remove barriers to reactivity here using pressure with a new synthetic approach. We target pressures where the reasons for cubic endmember nitride instability can become the driving force for cubic nitride solid solution stability. Using this approach we form a novel rocksalt Mg0.4 Fe0.6 N solid solution at between 15 and 23 GPa and up to 2500 K. This is a system where, neither an alloy nor a nitride solid solution form at ambient conditions and bulk MgN and FeN endmembers do not form, either at ambient or at high pressure. The new nitride is formed, by removing endmember lattice mismatch with pressure, allowing a stabilizing redistribution of valence electrons upon heating. This approach can be employed for a range of normally unreactive systems. Mg, Fe and enhanced nitrogen presence, may also indicate a richer reaction chemistry in our planets interior.

Lattice thermal conductivity of lower mantle minerals and heat flux from Earth's core.

The amount of heat flowing from Earth's core critically determines the thermo-chemical evolution of both the core and the lower mantle. Consisting primarily of a polycrystalline aggregate of silicate perovskite and ferropericlase, the thermal boundary layer at the very base of Earth's lower mantle regulates the heat flow from the core, so that the thermal conductivity (k) of these mineral phases controls the amount of heat entering the lowermost mantle. Here we report measurements of the lattice thermal conductivity of pure, Al-, and Fe-bearing MgSiO(3) perovskite at 26 GPa up to 1,073 K, and of ferropericlase containing 0, 5, and 20% Fe, at 8 and 14 GPa up to 1,273 K. We find the incorporation of these elements in silicate perovskite and ferropericlase to result in a ∼50% decrease of lattice thermal conductivity relative to the end member compositions. A model of thermal conductivity constrained from our results indicates that a peridotitic mantle would have k = 9.1 ± 1.2 W/m K at the top of the thermal boundary layer and k = 8.4 ± 1.2 W/m K at its base. These values translate into a heat flux of 11.0 ± 1.4 terawatts (TW) from Earth's core, a range of values consistent with a variety of geophysical estimates.

Tools for interpretation of wastewater SARS-CoV-2 temporal and spatial trends demonstrated with data collected in the San Francisco Bay Area.

Wastewater surveillance for severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) RNA can be integrated with COVID-19 case data to inform timely pandemic response. However, more research is needed to apply and develop systematic methods to interpret the true SARS-CoV-2 signal from noise introduced in wastewater samples (e.g., from sewer conditions, sampling and extraction methods, etc.). In this study, raw wastewater was collected weekly from five sewersheds and one residential facility. The concentrations of SARS-CoV-2 in wastewater samples were compared to geocoded COVID-19 clinical testing data. SARS-CoV-2 was reliably detected (95% positivity) in frozen wastewater samples when reported daily new COVID-19 cases were 2.4 or more per 100,000 people. To adjust for variation in sample fecal content, four normalization biomarkers were evaluated: crAssphage, pepper mild mottle virus, Bacteroides ribosomal RNA (rRNA), and human 18S rRNA. Of these, crAssphage displayed the least spatial and temporal variability. Both unnormalized SARS-CoV-2 RNA signal and signal normalized to crAssphage had positive and significant correlation with clinical testing data (Kendall's Tau-b (τ)=0.43 and 0.38, respectively), but no normalization biomarker strengthened the correlation with clinical testing data. Locational dependencies and the date associated with testing data impacted the lead time of wastewater for clinical trends, and no lead time was observed when the sample collection date (versus the result date) was used for both wastewater and clinical testing data. This study supports that trends in wastewater surveillance data reflect trends in COVID-19 disease occurrence and presents tools that could be applied to make wastewater signal more interpretable and comparable across studies.

Correlation between structural and semiconductor-metal changes and extreme conditions materials chemistry in Ge-Sn.

High pressure and temperature experiments on Ge-Sn mixtures to 24 GPa and 2000 K reveal segregation of Sn from Ge below 10 GPa whereas Ge-Sn agglomerates persist above 10 GPa regardless of heat treatment. At 10 GPa Ge reacts with Sn to form a tetragonal P4(3)2(1)2 Ge(0.9)Sn(0.1) solid solution on recovery, of interest for optoelectronic applications. Using electron diffraction and scanning electron microscopy measurements in conjunction with a series of tailored experiments promoting equilibrium and kinetically hindered synthetic conditions, we provide a step by step correlation between the semiconductor-metal and structural changes of the solid and liquid states of the two elements, and whether they segregate, mix or react upon compression. We identify depletion zones as an effective monitor for whether the process is moving toward reaction or segregation. This work hence also serves as a reference for interpretation of complex agglomerates and for developing successful synthesis conditions for new materials using extremes of pressure and temperature.

Synthesis of a nitrogen-stabilized hexagonal Re(3)ZnN(x) phase using high pressures and temperatures.

High pressure can induce profound changes in solids. A significant barrier to new alloys and ceramics, however, is that targeted starting materials may not react with each other, even with the help of pressure. We use nitrogen, in a new capacity, to incorporate two otherwise unreactive elements, Re and Zn, in the same structure when pressure alone does not suffice, without nitrogen altering the resulting backbone structure. Synthesis experiments up to 20 GPa and 1800 K show that while no Re-Zn alloy or solid solution is formed, a novel Re(3)ZnN(x) ordered solid solution is formed, at 20 GPa, with nitrogen occupying Re-coordinated cages. We put forth that unlike pure Re(3)Zn, our novel hexagonal Re(3)ZnN(x) structure is stabilized by nitrogen bond formation with rhenium. Pressure lifts the pronounced ambient Zn anisotropy, making it more compatible with Re and likely facilitating incorporation of the structure-stabilizing nitrogen anion. This methodology and result denote further options for removing impasses to material preparation, thus opening new avenues for synthesis. These can also be pursued with other ions including carbon, hydrogen, and oxygen, in addition to nitrogen.

Tuning between mixing and reactivity in the Ge-Sn system using pressure and temperature.

No bulk GeSn crystal existed prior to this work. Near 10 GPa the two elements resemble each other both electronically and structurally. Synthesis experiments at 10 GPa and 1500 K followed by annealing at 770 K using Ge and Sn starting materials and ex-situ analysis using transmission electron microscopy, scanning electron microscopy, and X-ray diffraction document the recovery of a Ge(0.9)Sn(0.1) solid solution (space group P4(3)2(1)2, a = 6.014 (1) A, c = 7.057 (1) A, Z = 12).