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At least 91 records · Page 5

In Situ Determination of Siderophile Trace Elements in Metals and Sulfides in Enstatite Achondrites

Enstatite meteorites are identified by their extremely reduced mineralogy (1) and similar oxygen isotope composition (2). The enstatite meteorite clan incorporates both EH and EL chondrites, as well as a wide variety of enstatite achondrites, such as aubrites or anomalous enstatite meteorites (e.g. Mt. Egerton, Shallowater, Zaklodzie, NWA 2526). The role of nebular versus planetary processes in the formation of enstatite meteorites is still under debate (e.g. 3-5). Past studies showed a significant influence of metal segregation in the formation of enstatite achondrites. Casanova et al. (6) suggested incomplete metal-silicate segregation during core formation and attributed the unfractionated siderophile element patterns in aubrites metals to a lack of fractional crystallization in a planetary core. Recent studies suggest a significant role of impact melting in the formation of primitive enstatite chondrites (7) and identified NWA 2526 as a partial melt residue of an enstatite chondrite (8). To understand the nature of siderophile element-bearing phases in enstatite achondrites, establish links between enstatite achondrites and enstatite chondrites (9), and constrain planetary differentiation on their respective parent bodies and their petrogenetic histories, we present laser ablation ICP-MS measurements of metal and sulfide phases in Shallowater, Mt. Egerton, and the aubrites Aubres, Cumberland Falls, and Mayo Belwa.

vanAcken, D.↗

Re-Os Isotopic Constraints on the Chemical Evolution and Differentiation of the Martian Mantle

The (187)Re-187Os isotopic systematics of SNC meteorites, thought to be from Mars, provide valuable information regarding the chemical processes that affected the Martian mantle, particularly with regard to the relative abundances of highly siderophile elements (HSE). Previously published data (Birck and Allegre 1994, Brandon et al. 2000), and new data obtained since these studies, indicate that the HSE and Os isotopic composition of the Martian mantle was primarily set in its earliest differentiation history. If so, then these meteorites provide key constraints on the processes that lead to variation in HSE observed in not only Mars, but also Earth, the Moon and other rocky bodies in the Solar System. Processes that likely have an effect on the HSE budgets of terrestrial mantles include core formation, magma ocean crystallization, development of juvenile crust, and the addition of a late veneer. Each of these processes will result in different HSE variation and the isotopic composition of mantle materials and mantle derived lavas. Two observations on the SNC data to present provide a framework for which to test the importance of each of these processes. First, the concentrations of Re and Os in SNC meteorites indicate that they are derived from a mantle that has similar concentrations to the Earth's mantle. Such an observation is consistent with a model where a chondritic late veneer replenished the Earth and Martian mantles subsequent to core formation on each planet. Alternative models to explain this observation do exist, but will require additional data to test the limitations of each. Second, Re-Os isotopic results from Brandon et al. (2000) and new data presented here, show that initial yos correlates with variations in the short-lived systems of (182)Hf- (182)W and (142)Sm-142Nd in the SNC meteorites (epsilon(sub W) and epsilon(sub 142Nd)). These systematics require an isolation of mantle reservoirs during the earliest differentiation history of Mars, and subsequent inefficient mixing between these reservoirs. These data show that models for the origin of isotopic variation for SNC meteorites require at least two long-lived mantle reservoirs, and possibly three. The range in the projected present day gamma(sub Os) of these reservoirs is from -5.4+/-2.6, to +4+/-1. The isotopic systematics of these reservoirs may be linked to development of cumulate crystal piles in a Martian magma ocean and variable amounts of late stage intercumulus melt. In this model, fractional crystallization of olivine and possibly other phases with slightly subchondritic Re/Os, from a solidifying magma ocean, resulted in a lower Re/Os ratio early cumulates, and a resultant low gamma(sub Os). Later cumulates or evolved melts crystallized with higher Re/Os ratios to produce the mantle reservoir(s) with consequent higher gamma(sub Os). Crystallization of the Martian magma ocean followed earliest core formation, as indicated by the correlation of epsilon(sub W) with epsilon(sub 142Nd) and initial gamma(sub Os).

Brandon, Alan D.↗

Petrology and Geochemistry of a Mg- and Al-Rich Orthopyroxenite Xenolith in the EETA79001 Shergottite: Implications for Mars Crustal Evolution

EETA79001 is a Mars meteorite (SNC) consisting of multiple rock types, including two basalt types, olivine and pyroxene xenocrysts, and ultramafic xenoliths. This study is focused on the petrology and geochemistry of one orthopyroxenite xenolith in PTS 68, designated X-1. It consists of chemically homogeneous orthopyroxene cores with exceptionally high Mg/Fe (mg#=85) and Al. Cores are permeated by minute high-Si+Al glassy inclusions, some with augite microlites. Magnesian core areas are mantled by more Fe-rich orthopyroxene rims grading to pigeonite away from cores. The xenolith is transected by cross-cutting shear planes, some of pre-incorporation origin. Major and minor element composition and variation suggest that core areas are primarily igneous, crystallized from a high temperature mafic melt. However, nearly constant mg# across cores suggest metamorphic equilibration. Si+Al inclusions may result from, among other processes, exsolution of feldspathic material during subsolidus cooling, or may be solid materials (alkali feldspar) poikilitically enclosed by growing igneous orthopyroxene crystals. Late reaction with more fractionated melts produced Fe-rich mantles, the whole assemblage later cut by tectonic micro-shear planes. Raw electron microprobe data produced during this study are available on request from the author.

Berkley, John L.↗

Retaining Geochemical Signatures during Aragonite-Calcite Transformation at Hydrothermal Conditions

Transformation of aragonite, a mineral phase metastable at Earth’s surface, to calcite widely occurs in both sedimentary and metamorphic systems with the presence of an aqueous phase. The transformation process can affect geochemical signatures of aragonite (a protolith). This study focused on quantification of the retention of Mg/Ca and Sr/Ca ratios, and δ18O during the transformation process as well as evaluation of the transformation rate. To investigate the effect of transformation from aragonite to calcite on elemental and stable isotope ratios, we conducted a series of experiments in NaCl solutions at temperatures between 120 and 184 °C. Two additional experiments at 250 °C were conducted to estimate the transformation rate of aragonite to calcite. Protolith materials consist of (1) synthetic (Mg; Sr-bearing or non-Mg; Sr bearing) needle-shaped microcrystals of aragonite (<5 µm in size) and (2) larger chips (>100 µm in size) of natural aragonite. X-ray diffraction (XRD) showed that microcrystals successfully transformed to calcite within 30 h and scanning electron microscopy (SEM) yielded a change in the crystal size to >10 µm in rhombohedral shape. Electron backscatter diffraction (EBSD) of the larger aragonite chips showed that transformation to randomly oriented calcite occurred at the rims and along the cracks while the core retained an aragonite crystal structure. Isotope-ratio mass spectrometry (IRMS) analyses showed that calcite δ18O was controlled by temperature and δ18O of the solution. The obtained calibration curve of isotope fractionation factor versus temperature is consistent with other studies. Inductively coupled plasma optical emission spectroscopy (ICP-OES) analyses showed that calcite partially or completely retained Mg/Ca and Sr/Ca ratios through the transformation.

58 GEOSCIENCES↗

Directing Charge Carriers and Ferroelectric Domains at Lateral Interfaces in van der Waals Heterostructures

Emergent phenomena in traditional ferroelectrics are frequently observed at heterointerfaces. Accessing such functionalities in van der Waals ferroelectrics requires the formation of layered heterostructures, either vertically stacked (similar to oxide ferroelectrics) or laterally stitched (without equivalent in 3D-crystals). Here, we investigate lateral heterostructures of the ferroelectric van der Waals semiconductors SnSe and SnS. A two-step process produces ultrathin crystals comprising an SnSe core laterally joined to an SnS edge-band, as confirmed by Raman spectroscopy, transmission electron microscopy (TEM) imaging, and electron diffraction. TEM shows a moiré pattern across the SnSe core due to coverage by an ultrathin SnS layer. The ability of the lateral interface (IF) to direct excited carriers, probed by cathodoluminescence, shows electron transfer over 560 nm diffusion length from the SnS edge-band. Large, thin flakes supporting ferroelectricity allow investigating domains and domain wall interactions in uniform crystals and lateral heterostructures. Polarized optical microscopy of sub-20 nm flakes consistently shows ⟨110⟩ oriented stripe domains with mirror-twin domain walls. Heterostructures adopt two domain configurations, with domains either constrained to the SnSe core or propagating across the entire SnSe–SnS flakes. Furthermore, the combined results demonstrate multifunctional van der Waals heterostructures with high-quality IFs presenting extraordinary opportunities for manipulating carrier flows and ferroelectric domain patterns.

2D ferroelectrics↗

Zagami - Product of a two-stage magmatic history

Results of petrologic studies of new large samples of the Zagami shergottite are presented. Pyroxene crystals have homogeneous Mg-rich pigeonite and augite cores, overgrown by Fe-rich zoned pyroxene rims. Amphibole-bearing magmatic inclusions occur exclusively in the cores. It is concluded that Zagami experienced a two-stage crystallization history. The first stage occurred in a deep-seated, slowly cooling magma chamber. There, the homogeneous Mg-rich cores of the pyroxenes crystallized during relatively slow cooling. During the second stage, the Mg-rich pyroxenes were entrained into a magma that either intruded to the near-surface and cooled in a relatively thin dike or sill, or extruded to the surface and crystallized in a lava flow greater than 10 m thick, again without indications of crystal settling. The estimated depth of the magma chamber for Zagami of greater than 7.5 km and thickness of the putative lava flow of greater than 10 m are consistent with calculations and observations of volcanic constructs and flows in the Tharsis region of Mars.

Mccoy, Timothy J.↗

Application of Powder Diffraction Methods to the Analysis of the Atomic Structure of Nanocrystals: The Concept of the Apparent Lattice Parameter (ALP)

The applicability of standard methods of elaboration of powder diffraction data for determination of the structure of nano-size crystallites is analysed. Based on our theoretical calculations of powder diffraction data we show, that the assumption of the infinite crystal lattice for nanocrystals smaller than 20 nm in size is not justified. Application of conventional tools developed for elaboration of powder diffraction data, like the Rietveld method, may lead to erroneous interpretation of the experimental results. An alternate evaluation of diffraction data of nanoparticles, based on the so-called 'apparent lattice parameter' (alp) is introduced. We assume a model of nanocrystal having a grain core with well-defined crystal structure, surrounded by a surface shell with the atomic structure similar to that of the core but being under a strain (compressive or tensile). The two structural components, the core and the shell, form essentially a composite crystal with interfering, inseparable diffraction properties. Because the structure of such a nanocrystal is not uniform, it defies the basic definitions of an unambiguous crystallographic phase. Consequently, a set of lattice parameters used for characterization of simple crystal phases is insufficient for a proper description of the complex structure of nanocrystals. We developed a method of evaluation of powder diffraction data of nanocrystals, which refers to a core-shell model and is based on the 'apparent lattice parameter' methodology. For a given diffraction pattem, the alp values are calculated for every individual Bragg reflection. For nanocrystals the alp values depend on the diffraction vector Q. By modeling different a0tomic structures of nanocrystals and calculating theoretically corresponding diffraction patterns using the Debye functions we showed, that alp-Q plots show characteristic shapes which can be used for evaluation of the atomic structure of the core-shell system. We show, that using a simple model of a nanocrystal with spherical shape and centro-symmetric strain at the surface shell we obtain theoretical alp-Q values which match very well the alp-Q plots determined experimentally for Sic, GaN, and diamond nanopowders. The theoretical models are defined by the lattice parameter of the grain core, thickness of the surface shell, and the magnitude and distribution of the strain field in the surface shell. According to our calculations, the part of the diffraction pattern measured at relatively low diffraction vectors Q (below 10/angstrom) provides information on the surface strain, whle determination of the lattice parameters in the grain core requires measurements at large Q-values (above 15 - 20/angstrom).

Palosz, B.↗

High-Pressure Melting Experiments of Fe 3 C and a Thermodynamic Model of Fe-C Liquids for the Earth's Core

Melting experiments of Fe 3 C were conducted to 85 GPa in laser-heated diamond anvil cells with in situ X-ray diffraction and post-experiment textural observation. From the determined pressure-temperature conditions of the melting curve for Fe 3 C, together with literature data on the melting point of diamond and eutectic point of the system Fe-Fe 3 C/Fe 7 C 3 under high pressures, we established a self-consistent thermodynamic model for high-pressure melting of the system Fe-C including the mixing parameters for liquids. The results show that mixing of Fe and C liquids is negatively nonideal from 1 bar to the pressure at the center of the Earth. The departure from ideal mixing becomes progressively larger with increasing pressure, which leads to greatly stabilized liquids under core pressures. The modeled carbon content in eutectic melts under core pressures is 3.3–4.4 wt%. From the Gibbs free energy, we derived an internally consistent parameters for Fe-C outer cores which included the crystallizing points at their bottoms, isentropic thermal profiles, and densities and longitudinal seismic wave speeds (Vp). While the addition of carbon in excess of the eutectic melt composition effectively reduces the density of iron liquid, the Vp of iron liquid is not greatly changed. Therefore, the low density and high Vp of PREM relative to pure iron cannot be reconciled by an Fe-C liquid. Therefore, the Earth's core cannot be approximated by the system Fe-C and should include another light element.

58 GEOSCIENCES↗

Low-loss low thermo-optic coefficient Ta 2 O 5 on crystal quartz planar optical waveguides

Optical resonator-based frequency stabilization plays a critical role in ultra-low linewidth laser emission and precision sensing, atom clocks, and quantum applications. However, there has been limited success in translating traditional bench-top stabilization cavities to compact on-chip integrated waveguide structures that are compatible with photonic integration. The challenge lies in realizing waveguides that not only deliver low optical loss but also exhibit a low thermo-optic coefficient and frequency noise stability. Given the problematic sources of frequency noise within dielectrics, such as thermorefractive noise, resonators with small thermo-optic response are desirable for on-chip reference cavities. We report the first demonstration of a Ta 2 O 5 (tantala) waveguide core fabricated on a crystal quartz substrate lower cladding with TEOS-PECVD SiO 2 upper cladding. This waveguide offers significant advantages over other waveguides in terms of its low thermo-optic coefficient and reduced thermorefractive-related frequency noise. We describe the waveguide structure and key design parameters as well as fabrication considerations for processing tantala on quartz waveguides. We report a waveguide thermo-optic coefficient of -1.14 × 10 -6 RIU/K, a value that is over 6 times smaller in magnitude than that of SiO 2 -substrate tantala waveguides, with a propagation loss of 1.19 dB/cm at 1550 nm and <1.33 dB/cm across the 1525 nm–1610 nm wavelength range. Within a 1.6 mm radius ring resonator, we demonstrate a 2.54 × 10 5 intrinsic Q factor. With the potential for very low loss and the ability to control the thermal response, this waveguide platform takes a key step toward creating thermally stable integrated resonators for on-chip laser frequency stabilization and other applications.

42 ENGINEERING↗

Unveiling the effect of Ni on the formation and structure of Earth’s inner core

Ni is the second most abundant element in the Earth’s core. Yet, its effects on the inner core’s structure and formation process are usually disregarded because of its electronic and size similarity with Fe. Using ab initio molecular dynamics simulations, we find that the bcc phase can spontaneously crystallize in liquid Ni at temperatures above Fe’s melting point at inner core pressures. The melting temperature of Ni is shown to be 700 to 800 K higher than that of Fe at 323 to 360 GPa. hcp, bcc, and liquid phase relations differ for Fe and Ni. Ni can be a bcc stabilizer for Fe at high temperatures and inner core pressures. A small amount of Ni can accelerate Fe’s crystallization at core pressures. These results suggest that Ni may substantially impact the structure and formation process of the solid inner core.

58 GEOSCIENCES↗

Shell-mediated control of surface chemistry of highly stoichiometric magnetite nanoparticles

Magnetite (Fe 3 O 4 ) nanoparticles are one of the most studied nanomaterials for different nanotechnological and biomedical applications. However, Fe 3 O 4 nanomaterials gradually oxidize to maghemite (γ-Fe 2 O 3 ) under conventional environmental conditions leading to changes in their functional properties that determine their performance in many applications. Here we propose a novel strategy to control the surface chemistry of monodisperse 12 nm magnetite nanoparticles by means of a 3 nm-thick Zn-ferrite epitaxial coating in core/shell nanostructures. We have carried out a combined Mössbauer spectroscopy, dc magnetometry, X-ray photoelectron spectroscopy and spatially resolved electron energy loss spectroscopy study on iron oxide and Fe 3 O 4 /Zn 0.6 Fe 2.4 O 4 core/shell nanoparticles aged under ambient conditions for 6 months. Our results reveal that while the aged iron oxide nanoparticles consist of a mixture of γ-Fe 2 O 3 and Fe 3 O 4 , the Zn-ferrite-coating preserves a highly stoichiometric Fe 3 O 4 core. Therefore, the aged core/shell nanoparticles present a sharp Verwey transition, an increased saturation magnetization and the possibility of tuning the effective anisotropy through exchange-coupling at the core/shell interface. The inhibition of the oxidation of the Fe 3 O 4 cores can be accounted for in terms of the chemical nature of the shell layer and an epitaxial crystal symmetry matching between the core and the shell.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Mechanistic Investigation of Enhanced Catalytic Selectivity toward Alcohol Oxidation with Ce Oxysulfate Clusters

Ceria-based materials have been highly desired in photocatalytic reactions due to their easily redox property and strong oxygen storage and transfer ability. Herein, we report the structures of one CeCe 70 oxysulfate cluster and four MCe 70 clusters (M = Cu, Ni, Co, Fe) with the same Ce 70 core. As noted, single crystal X-ray diffraction confirmed the structures of CeCe 70 and the MCe 70 series, while Raman spectroscopy indicated an increase in oxygen defects upon the introduction of Cu and Fe ions. The clusters catalyzed the oxidation of 4-methoxybenzyl alcohol under ultraviolet light. CuCe 70 and FeCe 70 exhibited enhanced reactivity compared to CeCe 70 and improved aldehyde selectivity compared to control experiments. In comparison with their homogeneous congeners, the CeCe 70 /MCe 70 clusters altered the location of radical generation from the bulk solution to the clusters’ surfaces. Mechanistic studies highlight the role of oxygen defects and specific transition metal introduction for efficient photocatalysis. Furthermore, the mechanistic pathway in this study provides insight on how to select or design a highly selective catalyst for photocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Results from a synthetic model of the ITER XRCS-Core diagnostic based on high-fidelity x-ray ray tracing

A high-fidelity synthetic diagnostic has been developed for the ITER core x-ray crystal spectrometer diagnostic based on x-ray ray tracing. This synthetic diagnostic has been used to model expected performance of the diagnostic, to aid in diagnostic design, and to develop engineering tolerances. The synthetic model is based on x-ray ray tracing using the recently developed xicsrt ray tracing code and includes a fully three-dimensional representation of the diagnostic based on the computer aided design. The modeled components are: plasma geometry and emission profiles, highly oriented pyrolytic graphite pre-reflectors, spherically bent crystals, and pixelated x-ray detectors. Plasma emission profiles have been calculated for Xe 44+ , Xe 47+ , and Xe 51+ , based on an ITER operational scenario available through the Integrated Modelling & Analysis Suite database, and modeled within the ray tracing code as a volumetric x-ray source; the shape of the plasma source is determined by equilibrium geometry and an appropriate wavelength distribution to match the expected ion temperature profile. All individual components of the x-ray optical system have been modeled with high-fidelity producing a synthetic detector image that is expected to closely match what will be seen in the final as-built system. Particular care is taken to maintain preservation of photon statistics throughout the ray tracing allowing for quantitative estimates of diagnostic performance.

47 OTHER INSTRUMENTATION↗

Phase Separation in Ultramassive White Dwarfs

We report ultramassive white dwarfs are extreme endpoints of stellar evolution. Recent findings, such as a missing multi-Gyr cooling delay for a number of ultramassive white dwarfs and a white dwarf with a quasi-Chandrasekhar mass, motivate a better understanding of their evolution. A key process still subject to important uncertainties is the crystallization of their dense cores, which are generally assumed to be constituted of 16 O, 20 Ne, and a mixture of several trace elements (most notably 23 Na and 24 Mg). In this work, we use our recently developed Clapeyron integration technique to compute accurate phase diagrams of three-component mixtures relevant to the modeling of O/Ne ultramassive white dwarfs. We show that, unlike the phase separation of 22 Ne impurities in C/O cores, the phase separation of 23 Na impurities in O/Ne white dwarfs cannot lead to the enrichment of their cores in 23 Na via a distillation process. This severely limits the prospect of transporting large quantities of 23 Na toward the center of the star, as needed in the white dwarf core-collapse mechanism recently proposed by Caiazzo et al. We also show that despite representing ≈10% of the ionic mixture, 23 Na and 24 Mg impurities only have a negligible impact on the O/Ne phase diagram, and the two-component O/Ne phase diagram can be safely used in white dwarf evolution codes. We provide analytic fits to our high-accuracy O/Ne phase diagram for implementation in white dwarf models.

79 ASTRONOMY AND ASTROPHYSICS↗

Parent-body models for the formation of iron meteorites.

The iron meteorites appear to have formed by both igneous and non-igneous processes in asteroid-sized parent bodies. Evidence regarding the IIIA-IIIB irons (the most common iron meteorite group) favors their having originated as a central core, which experienced fractional crystallization during solidification. A reevaluation of available data does not confirm earlier reports of variable cooling rates within group IIIA. Members of group IA-IB contain chondritic silicates, have short I-Xe formation intervals and do not show evidence of fractional crystallization. They appear to have formed nonigneously by inhomogeneous agglomeration and accretion of solar nebular condensates.

Wasson, J. T.↗

Isotopic And Geochemical Investigations Of Meteorites

The primary goals of our research over the past four years are to constrain the timing of certain early planetary accretion/differentiation events, and to constrain the proportions and provenance of materials involved in these processes. This work was achieved via the analysis and interpretation of long- and short-lived isotope systems, and the study of certain trace elements. Our research targeted these goals primarily via the application of the Re-187, Os-187, Pt-190 Os-186 Tc-98 Ru-99 and Tc-99 Ru-99 isotopic systems, and the determination/modeling of abundances of the highly siderophile elements (HSE; including Re, Os, Ir, Ru, Pd, Pt, and maybe Tc). The specific events we examined include the segregation and crystallization histories of asteroidal cores, the accretion and metamorphic histories of chondrites and chondrite components, and the accretionary and differentiation histories of Mars and the Moon.

Walker, Richard J.↗

Compositional zoning of the Otowi Member of the Bandelier Tuff, Valles caldera, New Mexico, USA

The Otowi Member of the Bandelier Tuff erupted at ca. 1.60 Ma from the Valles caldera (New Mexico, USA). It consists of as much as 400 km 3 (dense rock equivalent) of strongly differentiated high-silica rhyolite and shows systematic upward variations in crystallinity, mineral chemistry, and trace element concentrations through its thickness, but the major element composition is almost constant and is near the low-pressure granite minimum. Incompatible trace elements in whole pumice fragments and glasses show well-correlated linear covariations. Upward zoning to lower abundances of incompatible trace elements is accompanied by development of overgrowths on quartz and alkali feldspar, although earlier-formed interiors of quartz and feldspar have near-constant compositions throughout the tuff, modified by cation diffusion in the case of feldspar. Melt inclusions in remnant quartz cores show diverse Pb isotope ratios, pointing to a wide range of distinct protoliths that contributed rhyolitic melt to the Otowi magma. Mineral thermometers suggest a modest temperature gradient through the melt body, perhaps of 40 °C, at the time of eruption. Chemical, textural, and mineralogical variations and volume-composition relations through the tuff are consistent with an origin for zoning by melting of a high-crystallinity cumulate layer beneath cognate supernatant liquid to produce denser, remobilized liquid of accumulative composition (i.e., the “modified mush model”). Melting may have occurred in several episodes. The latest of these episodes, probably thousands of years prior to eruption, introduced new rhyolitic liquid into the system and was associated with a thermal excursion, recorded in core compositions of pyroxene, during which much of the earlier crystal mass was dissolved. This left inherited cores and interiors of accumulated quartz and feldspar mantled with new growth having less-evolved compositions (higher Ti, Sr, and Ba). Changing solubility of zircon during cumulate melting produced a reversal of Zr concentrations. There is no clear petrologic evidence of a recharge eruption trigger; nonetheless, compositional zoning resulted mainly from repeated recharge-induced remobilization of quartz-feldspar cumulate. The Otowi system was built, evolved, and modified by several events over the course of a few hundred thousand years.

Wolff, J. A.↗