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Description
The unusual physical properties and formation conditions attributed to h-, i-, m-, and n-nanodiamond polymorphs has resulted in their receiving much attention in the materials and planetary science literature. Their identification is based on diffraction features that are absent in ordinary cubic (c-) diamond (space group: Fd-3m). We show, using

The unusual physical properties and formation conditions attributed to h-, i-, m-, and n-nanodiamond polymorphs has resulted in their receiving much attention in the materials and planetary science literature. Their identification is based on diffraction features that are absent in ordinary cubic (c-) diamond (space group: Fd-3m). We show, using ultra-high-resolution transmission electron microscope (HRTEM) images of natural and synthetic nanodiamonds, that the diffraction features attributed to the reported polymorphs are consistent with c-diamond containing abundant defects. Combinations of {113} reflection and <011> rotation twins produce HRTEM images and d-spacings that match those attributed to h-, i-, and m-diamond. The diagnostic features of n-diamond in TEM images can arise from thickness effects of c-diamonds. Our data and interpretations strongly suggest that the reported nanodiamond polymorphs are in fact twinned c-diamond. We also report a new type of twin (<121> rotational), which can give rise to grains with dodecagonal symmetry. Our results show that twins are widespread in diamond nanocrystals. A high density of twins could strongly influence their applications.
ContributorsNemeth, Peter (Author) / Garvie, Laurence (Author) / Buseck, Peter (Author) / College of Liberal Arts and Sciences (Contributor) / School of Earth and Space Exploration (Contributor) / Center for Meteorite Studies (Contributor)
Created2015-12-16
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Description
Lonsdaleite, also called hexagonal diamond, has been widely used as a marker of asteroidal impacts. It is thought to play a central role during the graphite-to-diamond transformation, and calculations suggest that it possesses mechanical properties superior to diamond. However, despite extensive efforts, lonsdaleite has never been produced or described as

Lonsdaleite, also called hexagonal diamond, has been widely used as a marker of asteroidal impacts. It is thought to play a central role during the graphite-to-diamond transformation, and calculations suggest that it possesses mechanical properties superior to diamond. However, despite extensive efforts, lonsdaleite has never been produced or described as a separate, pure material. Here we show that defects in cubic diamond provide an explanation for the characteristic d-spacings and reflections reported for lonsdaleite. Ultrahigh-resolution electron microscope images demonstrate that samples displaying features attributed to lonsdaleite consist of cubic diamond dominated by extensive {113} twins and {111} stacking faults. These defects give rise to nanometre-scale structural complexity. Our findings question the existence of lonsdaleite and point to the need for re-evaluating the interpretations of many lonsdaleite-related fundamental and applied studies.
Created2014-11-01
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Description
Meteorites provide an opportunity to reconstruct the history of the SolarSystem. Differentiated meteorites, also called achondrites, are the result of melting and differentiation processes on their parent body. Stable isotopic compositions of differentiated meteorites and their components have added to the understanding of physical parameters, such as temperature, pressure, and redox conditions relevant to

Meteorites provide an opportunity to reconstruct the history of the SolarSystem. Differentiated meteorites, also called achondrites, are the result of melting and differentiation processes on their parent body. Stable isotopic compositions of differentiated meteorites and their components have added to the understanding of physical parameters, such as temperature, pressure, and redox conditions relevant to differentiation processes on planetesimals and planets in the early Solar System. In particular, Fe and Si isotopes have proven to be useful in advancing the understanding of physical and chemical processes during planetary accretion and subsequent evolution. In this work, I developed a new method to simultaneously purify Fe and Si from a single aliquot of sample while ensuring consistently high yields and accurate and precise isotopic measurements. I then measured the Fe isotope compositions and Si contents of metals from aubrite meteorites to infer the structure and thermal evolution of their asteroidal parent body. Thereafter, I determined the combined Si and Fe isotope compositions of aubrite metals and the Horse Creek iron meteorite, and compared the magnitude of Si and Fe isotope fractionation factors between metal and silicates for both enstatite chondrites and aubrites to estimate the effect of high-temperature core formation that occurred on the aubrite parent body. I additionally assessed whether correlated Si and Fe isotope systematics can be used to trace core formation and partial melting processes for the aubrite parent body, angrite parent body, Mars, Vesta, Moon, and Earth. Finally, I measured the combined Fe and Si isotope composition of a variety of ungrouped achondrites and brachinites that record different degrees of differentiation under different redox conditions to evaluate the role of differentiation and oxygen fugacity in controlling their Fe and Si isotope compositions. Taken together, this comprehensive dataset reveals the thermal evolution of the aubrite parent body, provides insights into the factors controlling the Fe and Si isotope compositions of various planetary materials, and helps constrain the bulk starting composition of planets and planetesimals.
ContributorsRay, Soumya (Author) / Wadhwa, Meenakshi (Thesis advisor) / Garvie, Laurence (Committee member) / Till, Christy (Committee member) / Hervig, Richard (Committee member) / Schrader, Devin (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Information about the elemental composition of a planetary surface can be determined using nuclear instrumentation such as gamma-ray and neutron spectrometers (GRNS). High-energy Galactic Cosmic Rays (GCRs) resulting from cosmic super novae isotropically bombard the surfaces of planetary bodies in space. When GCRs interact with a body’s surface, they can

Information about the elemental composition of a planetary surface can be determined using nuclear instrumentation such as gamma-ray and neutron spectrometers (GRNS). High-energy Galactic Cosmic Rays (GCRs) resulting from cosmic super novae isotropically bombard the surfaces of planetary bodies in space. When GCRs interact with a body’s surface, they can liberate neutrons in a process called spallation, resulting in neutrons and gamma rays being emitted from the planet’s surface; how GCRs and source particles (i.e. active neutron generators) interact with nearby nuclei defines the nuclear environment. In this work I describe the development of nuclear detection systems and techniques for future orbital and landed missions, as well as the implications of nuclear environments on a non-silicate (icy) planetary body. This work aids in the development of future NASA and international missions by presenting many of the capabilities and limitations of nuclear detection systems for a variety of planetary bodies (Earth, the Moon, metallic asteroids, icy moons). From bench top experiments to theoretical simulations, from geochemical hypotheses to instrument calibrations—nuclear planetary science is a challenging and rapidly expanding multidisciplinary field. In this work (1) I describe ground-truth verification of the neutron die-away method using a new type of elpasolite (Cs2YLiCl6:Ce) scintillator, (2) I explore the potential use of temporal neutron measurements on the surface of Titan through Monte-Carlo simulation models, and (3) I report on the experimental spatial efficiency and calibration details of the miniature neutron spectrometer (Mini-NS) on board the NASA LunaH-Map mission. This work presents a subset of planetary nuclear science and its many challenges in humanity's ongoing effort to explore strange new worlds.
ContributorsHeffern, Lena Elizabeth (Author) / Hardgrove, Craig (Thesis advisor) / Elkins-Tanton, Linda (Committee member) / Parsons, Ann (Committee member) / Garvie, Laurence (Committee member) / Holbert, Keith (Committee member) / Lyons, James (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Characterizing the surface mineralogy of asteroids is critical to constraining their formation history and provides insight into the processes of planetary formation. One method of determining the surface mineralogy of asteroids is comparison of their visible to near-infrared reflectance (VNIR) spectra with laboratory spectra from meteorites and minerals. Subsequent in-situ

Characterizing the surface mineralogy of asteroids is critical to constraining their formation history and provides insight into the processes of planetary formation. One method of determining the surface mineralogy of asteroids is comparison of their visible to near-infrared reflectance (VNIR) spectra with laboratory spectra from meteorites and minerals. Subsequent in-situ investigation of these asteroids by spacecraft can supplement or supersede interpretations derived from Earth-based observations.I investigated a suite of aubrites, sulfide minerals, and metal-rich chondrites in a variety of forms (hand samples, powders, and slabs) to identify similarities with ‘spectrally featureless’ asteroids. I collected VNIR spectra and powder X-ray diffraction patterns of these samples and compared their overall reflectance and spectral slope with X-complex and T-, L-, and D-type asteroid spectra. The Psyche Mission will orbit asteroid (16) Psyche beginning in 2026. I provide a pre-flight assessment of the surface composition of Psyche by comparing spectra of Psyche to a large spectral library of possible surface analog materials (e.g., iron meteorites, mesosiderites, pallasites, sulfides, enstatite, ordinary, and metal-rich chondrites, endmember silicates, and mixtures of silicates, metal, and sulfides). Spectra of Psyche are generally consistent with iron meteorite powder, mixtures of iron meteorite powder and low-Fe, low-Ca pyroxene, sulfide minerals, and the CH/CBb chondrite Isheyevo. Next, I demonstrate some anticipated capabilities of the Psyche Multispectral Imager by comparing spectral parameters derived from Imager-convolved data to those from high resolution laboratory spectra. I offer preliminary strategies for classifying surface composition based on Imager filter ratios and overall reflectance. Last, I present an assessment of a benchtop, commercial-off-the-shelf (COTS) version of the Psyche Imager. The COTS Imager uses the same model CCD and a similar f-number commercial camera lens. I measured the gain, full well, linearity, read noise, quantum efficiency, and modulation transfer function to compare with eventual calibration data from the flight Imager. I validate the results of a radiometric model developed for the flight Imager with signal measurements from the COTS Imager. This work demonstrates that the COTS Imager is an effective testbed for validating Imager requirements and developing software and procedures for eventual calibration of the flight instrument.
ContributorsDibb, Steven (Author) / Bell, James (Thesis advisor) / Hardgrove, Craig (Committee member) / Garvie, Laurence (Committee member) / Elkins-Tanton, Linda (Committee member) / Bose, Maitrayee (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Energy use within urban building stocks is continuing to increase globally as populations expand and access to electricity improves. This projected increase in demand could require deployment of new generation capacity, but there is potential to offset some of this demand through modification of the buildings themselves. Building

Energy use within urban building stocks is continuing to increase globally as populations expand and access to electricity improves. This projected increase in demand could require deployment of new generation capacity, but there is potential to offset some of this demand through modification of the buildings themselves. Building stocks are quasi-permanent infrastructures which have enduring influence on urban energy consumption, and research is needed to understand: 1) how development patterns constrain energy use decisions and 2) how cities can achieve energy and environmental goals given the constraints of the stock. This requires a thorough evaluation of both the growth of the stock and as well as the spatial distribution of use throughout the city. In this dissertation, a case study in Los Angeles County, California (LAC) is used to quantify urban growth, forecast future energy use under climate change, and to make recommendations for mitigating energy consumption increases. A reproducible methodological framework is included for application to other urban areas.

In LAC, residential electricity demand could increase as much as 55-68% between 2020 and 2060, and building technology lock-in has constricted the options for mitigating energy demand, as major changes to the building stock itself are not possible, as only a small portion of the stock is turned over every year. Aggressive and timely efficiency upgrades to residential appliances and building thermal shells can significantly offset the projected increases, potentially avoiding installation of new generation capacity, but regulations on new construction will likely be ineffectual due to the long residence time of the stock (60+ years and increasing). These findings can be extrapolated to other U.S. cities where the majority of urban expansion has already occurred, such as the older cities on the eastern coast. U.S. population is projected to increase 40% by 2060, with growth occurring in the warmer southern and western regions. In these growing cities, improving new construction buildings can help offset electricity demand increases before the city reaches the lock-in phase.
ContributorsReyna, Janet Lorel (Author) / Chester, Mikhail V (Thesis advisor) / Gurney, Kevin (Committee member) / Reddy, T. Agami (Committee member) / Rey, Sergio (Committee member) / Arizona State University (Publisher)
Created2016
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Description
The beginning of our Solar System, including events such as the formation of the first solids as well as the accretion and differentiation of planetary bodies, is recorded in meteoritic material. This record can be deciphered using petrographic, geochemical and isotopic investigations of different classes of meteorites and their components.

The beginning of our Solar System, including events such as the formation of the first solids as well as the accretion and differentiation of planetary bodies, is recorded in meteoritic material. This record can be deciphered using petrographic, geochemical and isotopic investigations of different classes of meteorites and their components. In this dissertation, I have investigated a variety of isotope systematics in chondritic and achondritic meteorites to understand processes that have shaped our Solar System. Specifically, the investigations conducted here are in two main areas: 1) Hydrogen isotope systematics in a meteorite representing the freshest known sample of the martian crust, and 2) Isotopic studies (specifically relating to high resolution chronology, nucleosynthetic anomalies and mass-dependent fractionations) in calcium-aluminum-rich inclusions, which are thought to be the earliest-formed solids in the Solar System. Chapter 1 of this dissertation presents a review of the hydrogen isotopic compositions of various planetary bodies and reservoirs in the Solar System, which could serve as tracers for the volatile sources. Chapter 2 focuses on an investigation of the hydrogen isotopic systematics in the freshest martian meteorite fall, Tissint, using the Cameca IMS-6f secondary ion mass spectrometer (SIMS). These first two chapters comprise the first part of this dissertation. The second part is comprised of chapters 3 through 6 and is focused on isotopic analyses of Calcium-Aluminum-rich Inclusions (CAIs). Chapter 3 is a review of CAIs, which record some of the earliest processes that occurred in the solar nebula. Chapter 4 presents the results of an investigation of the 26Al-26Mg short-lived chronometer (half-life ~0.72 Ma) in two CAIs and their Wark-Lovering (WL) rims from a CV3 carbonaceous chondrite using the Cameca NanoSIMS 50L. Chapter 5 is focused on the results of a study of the Zr isotope compositions of a suite of 15 CAIs from different carbonaceous chondrites using multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), in order to identify nucleosynthetic anomalies in the CAI-forming region. Chapter 6 focuses on the mass-dependent Mg isotopic compositions measured in 11 CAIs from the Allende CV3 carbonaceous chondrite using MC-ICPMS, to evaluate effects of thermal processing on CAIs.
ContributorsMane, Prajkta (Author) / Wadhwa, Meenakshi (Thesis advisor) / Hervig, Richard (Committee member) / Desch, Steven (Committee member) / Garvie, Laurence (Committee member) / Bell, James (Committee member) / Arizona State University (Publisher)
Created2016
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Description
This study explores how bulk composition and oxygen fugacity (fO2) affect the partitioning of sulfur between the molten mantle and core of an early planetesimal. The model can be used to determine the range of potential sulfur concentrations in the asteroid (16) Psyche, which is the target of the National

This study explores how bulk composition and oxygen fugacity (fO2) affect the partitioning of sulfur between the molten mantle and core of an early planetesimal. The model can be used to determine the range of potential sulfur concentrations in the asteroid (16) Psyche, which is the target of the National Aeronautics and Space Administration/Arizona State University Psyche Mission. This mission will be our visit to an M-type asteroid, thought to be dominantly metallic.

The model looks at how oxygen fugacity (fO2), bulk composition, temperature, and pressure affect sulfur partitioning in planetesimals using experimentally derived equations from previous studies. In this model, the bulk chemistry and oxygen fugacity of the parent body is controlled by changing the starting material, using ordinary chondrites (H, L, LL) and carbonaceous chondrites (CM, CI, CO, CK, CV). The temperature of the planetesimal is changed from 1523 K to 1873 K, the silicate mobilization and total melting temperatures, respectively; and pressure from 0.1 to 20 GPa, the core mantle boundary pressures of Vesta and Mars, respectively.

The final sulfur content of a differentiated planetesimal core is strongly dependent on the bulk composition of the original parent body. In all modeled cores, the sulfur content is above 5 weight percent sulfur; this is the point at which the least amount of other light elements is needed to form an immiscible sulfide liquid in a molten core. Early planetesimal cores likely formed an immiscible sulfide liquid, a eutectic sulfide liquid, or potentially were composed of mostly troilite, FeS.
ContributorsBercovici, Hannah La'ia (Author) / Elkins-Tanton, Linda T. (Thesis advisor) / Garvie, Laurence (Committee member) / Wadhwa, Meenakshi (Committee member) / Arizona State University (Publisher)
Created2020
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Description

A globally integrated carbon observation and analysis system is needed to improve the fundamental understanding of the global carbon cycle, to improve our ability to project future changes, and to verify the effectiveness of policies aiming to reduce greenhouse gas emissions and increase carbon sequestration. Building an integrated carbon observation

A globally integrated carbon observation and analysis system is needed to improve the fundamental understanding of the global carbon cycle, to improve our ability to project future changes, and to verify the effectiveness of policies aiming to reduce greenhouse gas emissions and increase carbon sequestration. Building an integrated carbon observation system requires transformational advances from the existing sparse, exploratory framework towards a dense, robust, and sustained system in all components: anthropogenic emissions, the atmosphere, the ocean, and the terrestrial biosphere. The paper is addressed to scientists, policymakers, and funding agencies who need to have a global picture of the current state of the (diverse) carbon observations.

We identify the current state of carbon observations, and the needs and notional requirements for a global integrated carbon observation system that can be built in the next decade. A key conclusion is the substantial expansion of the ground-based observation networks required to reach the high spatial resolution for CO2 and CH4 fluxes, and for carbon stocks for addressing policy-relevant objectives, and attributing flux changes to underlying processes in each region. In order to establish flux and stock diagnostics over areas such as the southern oceans, tropical forests, and the Arctic, in situ observations will have to be complemented with remote-sensing measurements. Remote sensing offers the advantage of dense spatial coverage and frequent revisit. A key challenge is to bring remote-sensing measurements to a level of long-term consistency and accuracy so that they can be efficiently combined in models to reduce uncertainties, in synergy with ground-based data.

Bringing tight observational constraints on fossil fuel and land use change emissions will be the biggest challenge for deployment of a policy-relevant integrated carbon observation system. This will require in situ and remotely sensed data at much higher resolution and density than currently achieved for natural fluxes, although over a small land area (cities, industrial sites, power plants), as well as the inclusion of fossil fuel CO2 proxy measurements such as radiocarbon in CO2 and carbon-fuel combustion tracers. Additionally, a policy-relevant carbon monitoring system should also provide mechanisms for reconciling regional top-down (atmosphere-based) and bottom-up (surface-based) flux estimates across the range of spatial and temporal scales relevant to mitigation policies. In addition, uncertainties for each observation data-stream should be assessed. The success of the system will rely on long-term commitments to monitoring, on improved international collaboration to fill gaps in the current observations, on sustained efforts to improve access to the different data streams and make databases interoperable, and on the calibration of each component of the system to agreed-upon international scales.

ContributorsCiais, P. (Author) / Dolman, A. J. (Author) / Bombelli, A. (Author) / Duren, R. (Author) / Peregon, A. (Author) / Rayner, P. J. (Author) / Miller, C. (Author) / Gobron, N. (Author) / Kinderman, G. (Author) / Marland, G. (Author) / Gruber, N. (Author) / Chevallier, F. (Author) / Andres, R. J. (Author) / Balsamo, G. (Author) / Bopp, L. (Author) / Breon, F. -M. (Author) / Broquet, G. (Author) / Dargaville, R. (Author) / Battin, T. J. (Author) / Borges, A. (Author) / Bovensmann, H. (Author) / Buchwitz, M. (Author) / Butler, J. (Author) / Canadell, J. G. (Author) / Cook, R. B. (Author) / DeFries, R. (Author) / Engelen, R. (Author) / Gurney, Kevin (Author) / Heinze, C. (Author) / Heimann, M. (Author) / Held, A. (Author) / Henry, M. (Author) / Law, B. (Author) / Luyssaert, S. (Author) / Miller, J. (Author) / Moriyama, T. (Author) / Moulin, C. (Author) / Myneni, R. (Author) / College of Liberal Arts and Sciences (Contributor)
Created2013-11-30
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Description

Novel hydride chemistries are employed to deposit light-emitting Ge1-y Snyalloys with y ≤ 0.1 by Ultra-High Vacuum Chemical Vapor Deposition (UHV-CVD) on Ge-buffered Si wafers. The properties of the resultant materials are systematically compared with similar alloys grown directly on Si wafers. The fundamental difference between the two systems is a fivefold

Novel hydride chemistries are employed to deposit light-emitting Ge1-y Snyalloys with y ≤ 0.1 by Ultra-High Vacuum Chemical Vapor Deposition (UHV-CVD) on Ge-buffered Si wafers. The properties of the resultant materials are systematically compared with similar alloys grown directly on Si wafers. The fundamental difference between the two systems is a fivefold (and higher) decrease in lattice mismatch between film and virtual substrate, allowing direct integration of bulk-like crystals with planar surfaces and relatively low dislocation densities. For y ≤ 0.06, the CVD precursors used were digermane Ge2H6 and deuterated stannane SnD4. For y ≥ 0.06, the Ge precursor was changed to trigermane Ge3H8, whose higher reactivity enabled the fabrication of supersaturated samples with the target film parameters. In all cases, the Ge wafers were produced using tetragermane Ge4H10 as the Ge source. The photoluminescence intensity from Ge1-y Sny /Ge films is expected to increase relative to Ge1-y Sny /Si due to the less defected interface with the virtual substrate. However, while Ge1-y Sny /Si films are largely relaxed, a significant amount of compressive strain may be present in the Ge1-y Sny /Ge case. This compressive strain can reduce the emission intensity by increasing the separation between the direct and indirect edges. In this context, it is shown here that the proposed CVD approach to Ge1-y Sny /Ge makes it possible to approach film thicknesses of about 1  μm, for which the strain is mostly relaxed and the photoluminescence intensity increases by one order of magnitude relative to Ge1-y Sny /Si films. The observed strain relaxation is shown to be consistent with predictions from strain-relaxation models first developed for the Si1-x Gex /Si system. The defect structure and atomic distributions in the films are studied in detail using advanced electron-microscopy techniques, including aberration corrected STEM imaging and EELS mapping of the average diamond–cubic lattice.

ContributorsSenaratne, Charutha Lasitha (Author) / Gallagher, J. D. (Author) / Jiang, Liying (Author) / Aoki, Toshihiro (Author) / Smith, David (Author) / Menéndez, Jose (Author) / Kouvetakis, John (Author) / Department of Chemistry and Biochemistry (Contributor)
Created2014-10-07