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Creators/Authors contains: "Walter, Michael"

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  1. The increasing demand for optical technologies with dynamic spectral control has driven interest in chromogenic materials, particularly for applications in tunable infrared metasurfaces. Phase-change materials such as vanadium dioxide and germanium–antimony–tellurium, for instance, have been widely used in the infrared regime. However, their reliance on thermal and electrical tuning introduces challenges such as high power consumption, limited emissivity tuning, and slow modulation speeds. Photochromic materials may offer an alternative approach to dynamic infrared metasurfaces, potentially overcoming these limitations through rapid, light-induced changes in their optical properties. This manuscript explores the potential of thiazolothiazole-embedded polymers, known for their reversible photochromic transitions and strong infrared absorption changes, for use in tunable infrared metasurfaces. The material exhibits low absorption and a strong photochromic contrast in the spectral range from 1500 cm−1 to 1700 cm−1, making it suitable for dynamic infrared light control. This manuscript reports on infrared imaging experiments demonstrating the photochromic contrast in thiazolothiazole-embedded polymer, and thereby provides compelling evidence for its potential applications in dynamic infrared metasurfaces. 
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    Free, publicly-accessible full text available June 1, 2026
  2. Sublithospheric diamonds and the inclusions they may carry crystallize in the asthenosphere, transition zone, or uppermost lower mantle (from 300 to ∼800 km), and are the deepest minerals so far recognized to form by plate tectonics. These diamonds are distinctive in their deformation features, low nitrogen content, and inclusions of these major mantle minerals: majoritic garnet, clinopyroxene, ringwoodite, CaSi perovskite, ferropericlase, and bridgmanite or their retrograde equivalents. The stable isotopic compositions of elements within these diamonds (δ11B, δ13C, δ15N) and their inclusions (δ18O, δ56Fe) are typically well outside normal mantle ranges, showing that these elements were either organic (C) or modified by seawater alteration (B, O, Fe) at relatively low temperatures. Metamorphic minerals in cold slabs are effective hosts that transport C as CO3 and H as H2O, OH, or CH4 below the island arc and mantle wedge. Warming of the slab generates carbonatitic melts, supercritical aqueous fluids, or metallic liquids, forming three types of sublithospheric diamonds. Diamond crystallization occurs by movement and reduction of mobile fluids as they pass through host mantle via fractures—a process that creates chemical heterogeneity and may promote deep focus earthquakes. Geobarometry of majoritic garnet inclusions and diamond ages suggest upward transport, perhaps to the base of mantle lithosphere. From there, diamonds are carried to Earth's surface by eruptions of kimberlite magma. Mineral assemblages in sublithospheric diamonds directly trace Earth's deep volatile cycle, demonstrating how the hydrosphere of a rocky planet can connect to its solid interior.▪Sublithospheric diamonds from the deep upper mantle, transition zone, and lower mantle host Earth's deepest obtainable mineral samples.▪Low-temperature seawater alteration of the ocean floor captures organic and inorganic carbon at the surface eventually to become some of the most precious gem diamonds.▪Subduction transports fluids in metamorphic minerals to great depth. Fluids released by slab heating migrate, react with host mantle to induce diamond crystallization, and may trigger earthquakes.▪Sublithospheric diamonds are powerful tracers of subduction—a plate tectonic process that deeply recycles part of Earth's planetary volatile budget. 
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  3. Fe2O3produced in a deep magma ocean in equilibrium with core-destined alloy sets the early redox budget and atmospheric composition of terrestrial planets. Previous experiments (≤28 gigapascals) and first-principles calculations indicate that a deep terrestrial magma ocean produces appreciable Fe3+but predict Fe3+/ΣFe ratios that conflict by an order of magnitude. We present Fe3+/ΣFe of glasses quenched from melts equilibrated with Fe alloy at 38 to 71 gigapascals, 3600 to 4400 kelvin, analyzed by synchrotron Mössbauer spectroscopy. These indicate Fe3+/ΣFe of 0.056 to 0.112 in a terrestrial magma ocean with mean alloy-silicate equilibration pressures of 28 to 53 gigapascals, producing sufficient Fe2O3to account for the modern bulk silicate Earth redox budget and surficial conditions near or more oxidizing than the iron-wüstite buffer, which would stabilize a primitive CO- and H2O-rich atmosphere. 
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  4. Talc is expected to be an important water carrier in Earth's upper mantle, and understanding its electrical and seismic properties under high pressure and temperature conditions is required to detect possible talc‐rich regions in subduction zones imaged using geophysical observations. We conducted acoustic and electrical experiments on natural talc aggregates at relevant pressure‐temperature conditions. Compressional wave velocity (Vp) was measured using ultrasonic interferometry in a Paris‐Edinburgh press at pressures up to 3.4 GPa and temperatures up to 873 K. Similar Vp values are obtained regardless of the initial crystallographic preferred orientation of the samples, which can be explained by talc grain reorientation during the experiment, with the (001) plane becoming perpendicular to the uniaxial compression axis. Electrical conductivity of the same starting material was determined using impedance spectroscopy in a multi‐anvil press up to 6 GPa and 1263 K. Two conductivity jumps are observed, at ∼860–1025 K and ∼940–1080 K, depending on pressure, and interpreted as talc dehydroxylation and decomposition, respectively. Electrical anisotropy is observed at low temperature and decreases with increasing pressure (∼10 at 1.5 GPa and ∼2 at 3.5 GPa). Comparison of acoustic and electrical results with geophysical observations in central Mexico supports the presence of a talc‐bearing layer atop the subducted Cocos plate. 
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    Free, publicly-accessible full text available November 1, 2025
  5. Decades of measurements of the thermophysical properties of hot metals show that pulsed Joule heating is an effective method to heat solid and liquid metals that are chemically reactive or difficult to contain. To extend such measurements to hundreds of GPa pressure, pulsed heating methods have recently been integrated with diamond anvil cells. The recent design used a low-side switch and active electrical sensing equipment that was prone to damage and measurement error. Here, we report the design and characterization of new electronics that use a high-side switch and robust, passive electrical sensing equipment. The new pulse amplifier can heat ∼5 to 50 μm diameter metal wires to thousands of kelvin at tens to hundreds of GPa using diamond anvil cells. Pulse durations and peak currents can each be varied over three orders of magnitude, from 5 µs to 10 ms and from 0.2 to 200 A. The pulse amplifier is integrated with a current probe. Two voltage probes attached to the body of a diamond anvil cell are used to measure voltage in a four-point probe geometry. The accuracy of four-point probe resistance measurements for a dummy sample with 0.1 Ω resistance is typically better than 5% at all times from 2 µs to 10 ms after the beginning of the pulse. 
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  6. In the current plate tectonic regime, thermal modeling, petrology, and seismology show that subsurface portions of cold slabs carry some of their volatiles into the deep upper mantle, mantle transition zone, and uppermost lower mantle avoiding the devolatilization occurring with normal arc and wedge subduction. Slab crustal remnants at these depths can melt by intersecting their carbonated solidus whereas slab mantle remnants can devolatilize by warming and metamorphosing to ‘dryer’ mineral assemblages. Since fluid release and earthquake production (“dehydration embrittlement”) operates down to ~300 km depths in all subduction zones, we propose, that deep-focus earthquakes trace the places of fluid release at deeper levels (350 to 750 km). Fluids in faults related to earthquake generation will become diamond-forming as they react with mantle rocks along the fault walls. Diamonds thus formed will record deformation produced by mantle convection and slab buckling during mantle storage. Lithospheric diamonds, stored in static ancient continental keels, lack the connection to this type of geodynamic regime that is evident for sublithospheric diamonds. However, a comparison between the two diamond types suggests a geologic model for lithospheric diamond formation in the ancient past. Lithospheric diamonds and sublithospheric diamonds both contain evidence for the recycling of sediments or surficial rocks that have equilibrated at low temperatures with seawater. The known way to inject these materials into diamond-forming regions is slab subduction. Hence both diamond types may have formed by variants of this same process that differ in depth and style over geologic time. Lithospheric diamonds are different from sublithospheric diamonds in critical ways: higher average N content, ages extending into the Paleoarchean, inclusion assemblages indicating formation at lower pressure, and lack of ubiquitous deformation features. Nitrogen content is the key to relating lithospheric diamonds to the subducting slab. Nitrogen occurs in clays and sediments at the slab surface or uppermost crust. Regardless of whether the slab is hot or cold during subduction, nitrogen will be removed into a mantle wedge if one exists. Additionally, diamonds will not survive in the melts/fluids generated in the wedge under oxidizing conditions. For sublithospheric diamonds, their low to non-existent nitrogen content occurs because they are derived from slab fluids/melts once nitrogen has been largely removed or from rocks deeper in the slab where nitrogen is scarce. The much higher nitrogen in lithospheric diamonds suggests that they formed from fluids/melts derived near the slab surface that contained N. In the Archean, such slabs must have subducted close to the nascent mantle keel with no mantle wedge so the fluids could be directly reduced by the mantle keel. We propose a gradual temporal change from shallow, keel-adjacent, mantle-wedge-poor subduction that produced lithospheric diamonds starting in the Paleoarchean to wedge-avoiding, cold and deep subduction that produced sublithospheric diamonds in the Paleozoic. This temporal change is consistent with many geologic features: an early stagnant lid and a buoyant Archean oceanic lithosphere; the slab-imbrication, advective thickening, and diamond-richness of portions of mantle keels; and anomalously diamond-rich ancient eclogites. 
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  7. Abstract The relative roles of protoplanetary differentiation versus late accretion in establishing Earth’s life-essential volatile element inventory are being hotly debated. To address this issue, we employ first-principles calculations to investigate nitrogen (N) isotope fractionation during Earth’s accretion and differentiation. We find that segregation of an iron core would enrich heavy N isotopes in the residual silicate, while evaporation within a H2-dominated nebular gas produces an enrichment of light N isotope in the planetesimals. The combined effect of early planetesimal evaporation followed by core formation enriches the bulk silicate Earth in light N isotopes. If Earth is comprised primarily of enstatite-chondrite-like material, as indicated by other isotope systems, then late accretion of carbonaceous-chondrite-like material must contribute ~ 30–100% of the N budget in present-day bulk silicate Earth. However, mass balance using N isotope constraints shows that the late veneer contributes only a limited amount of other volatile elements (e.g., H, S, and C) to Earth. 
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  8. Free, publicly-accessible full text available June 1, 2026
  9. The solidification of a deep magma ocean occurred early in Earth’s history. Although the initial amount of H2O in Earth’s magma ocean is predicted to be low (e.g., <3000 ppm), as an incompatible element it becomes highly enriched (e.g. >10 wt%) in the final few percent of crystallization. In order to understand how a hydrous magma ocean would crystallize at the top of the lower mantle, we determined liquidus phase relations in the MgO-FeOCaO-Al2O3-SiO2-H2O system at 24 GPa. We find that the bridgmanite (brg) + stishovite (st) + melt and bridgmanite (brg) + ferropericlase (fp) + melt cotectic boundary curves trend to Mg-rich melt compositions with decreasing temperature and extend to very high H2O contents (~80 mol% H2O). The brg+st+melt curve is a subtraction curve at < ~18 mol% H2O and a reaction curve at higher H2O contents, whereas the brg+fp+melt is a subtraction curve throughout its length. The density of melts along the two cotectics leads to neutral buoyancywith respect to shallow lower mantle and transition zone minerals at H2O contents up to ~25 mol%. A transient melt-rich layer can form at the top of the lower mantle during late-stage crystallization in a mushy magma ocean when melt percolation dominates. When crystallization exceeds ~98%, hydrous melts (>25 mol% H2O) become buoyant and can percolate into and hydrate the mantle transition zone. 
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