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At least 1,603 records · Page 89

Arsenic attenuation in tailings at a former Cu-W-As mine, SW Finland

Nearly half a century after mine closure, release of As from the Ylöjärvi Cu–W–As mine tailings in groundwater and surface water run-off was observed. Investigations by scanning electron microscopy (SEM), electron microprobe analysis (EMPA), synchrotron-based micro-X-ray diffraction (μ-XRD), micro-X-ray absorption near edge structure (μ-XANES) and micro-extended X-ray absorption fine structure (μ-EXAFS) spectroscopy, and a sequential extraction procedure were performed to assess As attenuation mechanisms in the vadose zone of this tailings deposit. Results of SEM, EMPA, and sequential extractions indicated that the precipitation of As bearing Fe(III) (oxy)hydroxides (up to 18.4 wt.% As 2 O 5 ) and Fe(III) arsenates were important secondary controls on As mobility. The μ-XRD, μ-XANES and μ-EXAFS analyses suggested that these phases correspond to poorly crystalline and disordered As-bearing precipitates, including arsenical ferrihydrite, scorodite, kankite, and hydrous ferric arsenate (HFA). The pH within 200 cm of the tailings surface averaged 5.7, conditions which favor the precipitation of ferrihydrite. Poorly crystalline Fe(III) arsenates are potentially unstable over time, and their transformation to ferrihydrite, which contributes to As uptake, has potential to increase the As adsorption capacity of the tailings. Arsenic mobility in tailings pore water at the Ylöjärvi mine will depend on continued arsenopyrite oxidation, dissolution or transformation of secondary Fe(III) arsenates, and the As adsorption capacity of Fe(III) (oxy)hydroxides within this tailings deposit

Parviainen, Annika↗

Elucidating structural order and disorder phenomena in mullite-type Al{sub 4}B{sub 2}O{sub 9} by automated electron diffraction tomography

The crystal structure and disorder phenomena of Al{sub 4}B{sub 2}O{sub 9}, an aluminum borate from the mullite-type family, were studied using automated diffraction tomography (ADT), a recently established method for collection and analysis of electron diffraction data. Al{sub 4}B{sub 2}O{sub 9}, prepared by sol-gel approach, crystallizes in the monoclinic space group C2/m. The ab initio structure determination based on three-dimensional electron diffraction data from single ordered crystals reveals that edge-connected AlO{sub 6} octahedra expanding along the b axis constitute the backbone. The ordered structure (A) was confirmed by TEM and HAADF-STEM images. Furthermore, disordered crystals with diffuse scattering along the b axis are observed. Analysis of the modulation pattern implies a mean superstructure (AAB) with a threefold b axis, where B corresponds to an A layer shifted by ½a and ½c. Diffraction patterns simulated for the AAB sequence including additional stacking disorder are in good agreement with experimental electron diffraction patterns. - Graphical abstract: Crystal structure and disorder phenomena of B-rich Al{sub 4}B{sub 2}O{sub 9} studied by automated electron diffraction tomography (ADT) and described by diffraction simulation using DISCUS. - Highlights: • Ab-initio structure solution by electron diffraction from single nanocrystals. • Detected modulation corresponding mainly to three-fold superstructure. • Diffuse diffraction streaks caused by stacking faults in disordered crystals. • Observed streaks explained by simulated electron diffraction patterns.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Velocity- and pressure-based metrics for estimating strike injuries during fish passage through hydro turbines

Hydropower is a crucial source of clean and reliable energy worldwide, and its importance will continue to grow. To enhance the environmental sustainability of hydropower development and operations, it is essential to predict the strike injury rates of fish passing through turbines accurately and cost-effectively. However, conventional experiments involving a large number of live fish are still commonly conducted in practice, and previous attempts mainly focused on the dose-response relationships at an individual level or relative comparisons of biological characterization between different conditions. Thus, this study proposes two novel strike metrics based on velocity and pressure (M V and M P ) measured by the cutting-edge Sensor Fish (SF) technology, designed to quantify the biological effects of strikes and collisions between fish and rigid hydraulic structures. SF measurements and 48-hour survival rates of live fish from a study conducted at the Ice Harbor Dam on the Snake River were used to establish thresholds for the two proposed metrics. These metrics and thresholds were then applied to three additional SF studies conducted at hydropower facilities featuring Kaplan turbines within the Columbia River basin. Results from the application of the strike metrics indicate that the estimated survival rates derived from both metrics agree well with previously reported live fish survival rates. Furthermore, the study identified specific passage regions with elevated risks of fish mortality due to strikes and collisions. Overall, the proposed strike metrics present a reliable and cost-effective approach to reducing reliance on live fish and lowering costs in fish passage studies.

Biological characterization↗

Implementation of higher-order velocity mapping between marker particles and grid in the particle-in-cell code XGC

The global total-f gyrokinetic particle-in-cell code XGC, used to study transport in magnetic fusion plasmas or to couple with a core gyrokinetic code while functioning as an edge gyrokinetic code, implements a five-dimensional continuum grid to perform the dissipative operations, such as plasma collisions, or to exchange the particle distribution function information with a core code. To transfer the distribution function between marker particles and a rectangular two-dimensional velocity-space grid, XGC employs a bilinear mapping. The conservation of particle density and momentum is accurate enough in this bilinear operation, but the error in the particle energy conservation can become undesirably large and cause non-negligible numerical heating in a steep edge pedestal. In the present work we update XGC to use a novel mapping technique, based on the calculation of a pseudo-inverse, to exactly preserve moments up to the order of the discretization space. Here we describe the details of the implementation and we demonstrate the reduced interpolation error for a tokamak test plasma using first- and second-order elements with the pseudo-inverse method and comparing with the bilinear mapping.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Integrating computation and experiment to investigate photoelectrodes for solar water splitting at the microscopic scale.

CONSPECTUS: Photoelectrochemical water-splitting is a promising and sustainable way to store the energy of the sun in chemical bonds and use it to produce hydrogen gas, a clean fuel. The key components in photoelectrochemical cells (PECs) are photoelectrodes, including a photocathode that reduces water to hydrogen gas and a photoanode that oxidizes water to oxygen gas. Materials used in photoelectrodes for PECs must effectively absorb sunlight, yield photogenerated carriers, and exhibit electronic properties that enable the efficient shuttling of carriers to the surface to participate in relevant water-splitting reactions. Discovering and understanding the key characteristics of optimal photoelectrode materials is paramount to the realization of PEC technologies. Oxide-based photoelectrodes can satisfy many of these materials requirements, including stability in aqueous environments, band edges with reasonable alignment with the redox potentials for water splitting, and ease of synthesis. However, oxide photoelectrodes generally suffer from poor charge transport properties and considerable bulk electron-hole separation, and they have relatively large band gaps. Numerous strategies have been proposed to improve these aspects and understand how these improvements are reflected in the photoelectrochemical performance. Unfortunately, the structural and compositional complexity of multinary oxides accompanied by the inherent complexity of photoelectrochemical processes makes it challenging to understand the individual effects of composition, structure, and defects in the bulk and on the surface on a material's photoelectrochemical properties. The integration of experiment and theory has great potential to increase our atomic-level understanding of structure-composition-property relationships in oxide photoelectrodes. In this Account, we describe how integrating experiment and theory is beneficial for achieving scientific insights at the microscopic scale. We highlight studies focused on understanding the role of (i) bulk composition via solid-state solutions, intercalation, and comparison with isoelectronic compounds, (ii) dopants for both the anion and cation and their interactions with oxygen vacancies, and (iii) surface/interface structure in the photocurrent generation and photoelectrochemical performance in oxide photoelectrodes. In each instance, we outline strategies and considerations for integrating experiment and theory and describe how this integration led to valuable insights and new directions in uncovering structure-composition-property relationships. Our aim is to demonstrate the unique value of combining experiment and theory in studying photoelectrodes and to encourage the continued effort to bring experiment and theory in closer step with each other.

Wang, Wennie↗

Copper uptake, intracellular localization, and speciation in marine microalgae measured by synchrotron radiation X-ray fluorescence and absorption microspectroscopy

Metal toxicity to aquatic organisms depends on the speciation of the metal and its binding to the critical receptor site(s) (biotic ligand) of the organism. The intracellular nature of the biotic ligand for Cu in microalgal cells was investigated using the high elemental sensitivity of microprobe synchrotron radiation X-ray fluorescence (SR-XRF) and X-ray absorption near-edge spectroscopy (XANES). The marine microalgae, Ceratoneis closterium , Phaeodactylum tricornutum , and Tetraselmis sp. were selected based on their varying sensitivities to Cu (72-h 50% population growth inhibitions of 8–47 μg Cu/L). Intracellular Cu in control cells was similar for all three species (2.5–3.2 × 10–15 g Cu/cell) and increased 4-fold in C. closterium and Tetraselmis sp. when exposed to copper, but was unchanged in P. tricornutum (72-h exposure to 19, 40, and 40 μg Cu/L, respectively). Whole cell microprobe SR-XRF identified endogenous Cu in the central compartment (cytoplasm) of control (unexposed) cells. After Cu exposure, Cu was colocated with organelles/granules dense in P, S, Ca, and Si and this was clearly evident in thin sections of Tetraselmis sp. XANES indicated coexistence of Cu(I) and Cu(II) in control and Cu-exposed cells, with the Cu ligand (e.g., phytochelatin) in P. tricornutum different from that in C. closterium and Tetraselmis sp. Here, this study supports the hypothesis that Cu(II) is reduced to Cu(I) and that polyphosphate bodies and phytochelatins play a significant role in the internalization and detoxification of Cu in marine microalgae.

54 ENVIRONMENTAL SCIENCES↗

Ultranarrow TaS 2 Nanoribbons

Imposing additional confinement in two-dimensional (2D) materials can yield further control over the associated electronic, optical, and topological properties. However, synthesis of ultra-narrow nanoribbons (NRs) remains a challenge, particularly for the transition metal dichalcogenides (TMDs), and synthesizing TMD NRs narrower than 50 nm has remained elusive. In this paper, we report the vapor-phase synthesis of ultra-narrow TaS 2 NRs. The NRs are grown within the hollow cavity of carbon nanotubes, thereby limiting their lateral dimensions and layer number, while simultaneously stabilizing them against the environment. The NRs reach the monolayer (ML) limit and exhibit widths as low as 2.5 nm. Atomic-resolution scanning transmission electron microscopy (STEM) reveals the detailed atomic structure of the ultra-narrow NRs and we observe a hitherto unseen atomic structure supermodulation phenomenon of ordered defect arrays within the NRs. First-principles calculations based on density functional theory (DFT) show the presence of flat bands, as well as edge- and boundary-localized states, and help identify the atomic configuration of the supermodulation. Nanotube-templated synthesis represents a unique, transferable, and broadly deployable route toward ultra-narrow TMD NR growth.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Static Polystyrene Gate Charge Density Modulation of Dinaphthothienothiophene with Tetrafluorotetracyanoquinodimethane Layer Doping: Evidence from Conductivity and Seebeck Coefficient Measurements and Correlations

We relate the static charging of organic field effect transistor (OFET) gate dielectric polymers, the resulting change in threshold voltage shift, and the modulation of thermoelectric properties of the transistor semiconductor. We utilize a bottom gate OFET structure with cross-linkable polystyrene and plain polystyrene (XLPS/PS) bilayer dielectrics and dinaphthothienothiophene (DNTT) organic molecular semiconductor with tetrafluorotetracyanoquinodimethane (F4TCNQ) doping layer. Conductivity and Seebeck coefficient are measured before and after charging. We find that the conductivity increases significantly, while the Seebeck coefficient decreases correspondingly in a trend of S ∝ ln(σ) after the dielectrics were negatively charged, resulting in an average of fivefold increase in power factor at the maximum charging level. Additionally, temperature-dependent conductivity measurements show that the activation energy decreases with the increasing conductivity. We calculate the Seebeck coefficient based on the activation energy and find the result is consistent with the Mott mobility edge model. This work confirms the charging mechanism in our previous published work, including the location of static charges in the bulk of the dielectric, and demonstrates modulation and enhancement of the thermoelectric properties of organic thermoelectric materials by adjacent chargeable dielectrics without changing the molecular microstructure or applying external gate voltage during operation.

static gate, Seebeck coefficient, organic semicond↗

Chiral structures of electric polarization vectors quantified by X-ray resonant scattering

Resonant elastic X-ray scattering (REXS) offers a unique tool to investigate solid-state systems providing spatial knowledge from diffraction combined with electronic information through the enhanced absorption process, allowing the probing of magnetic, charge, spin, and orbital degrees of spatial order together with electronic structure. A new promising application of REXS is to elucidate the chiral structure of electrical polarization emergent in a ferroelectric oxide superlattice in which the polarization vectors in the REXS amplitude are implicitly described through an anisotropic tensor corresponding to the quadrupole moment. Here, we present a detailed theoretical framework and analysis to quantitatively analyze the experimental results of Ti L-edge REXS of a polar vortex array formed in a PbTiO 3 /SrTiO 3 superlattice. Based on this theoretical framework, REXS for polar chiral structures can become a useful tool similar to x-ray resonant magnetic scattering (XRMS), enabling a comprehensive study of both electric and magnetic REXS on the chiral structures.

36 MATERIALS SCIENCE↗

Paradoxical roles of hydrogen in electrochemical performance of graphene: High rate capacity and atomistic origins

Atomic hydrogen exists ubiquitously in graphene materials made by chemical methods. Yet determining the effect of hydrogen on the electrochemical performance of graphene remains a significant challenge. Here we report the experimental observations of high rate capacity in hydrogen-treated 3-dimensional (3D) graphene nanofoam electrodes for lithium ion batteries. Structural and electronic characterization suggests that defect sites and hydrogen play synergistic roles in disrupting sp 2 graphene to facilitate fast lithium transport and reversible surface binding, as evidenced by the fast charge-transfer kinetics and increased capacitive contribution in hydrogen-treated 3D graphene. In concert with experiments, multiscale calculations reveal that defect complexes in graphene are prerequisite for low-temperature hydrogenation, and that the hydrogenation of defective or functionalized sites at strained domain boundaries plays a beneficial role in improving rate capacity by opening gaps to facilitate easier Li penetration. Additional reversible capacity is provided by enhanced lithium binding near hydrogen-terminated edge sites. Furthermore, these findings provide qualitative insights in helping the design of graphene-based materials for high-power electrodes.

25 ENERGY STORAGE↗

Dynamic Wavelength-Tunable Photodetector Using Subwavelength Graphene Field-Effect Transistors

The holy grail of photodetector technology is dynamic wavelength tunability. Because of its atomic thickness and unique properties, graphene opens up new paradigms to realize this concept, but so far this has been elusive experimentally. We employ detailed quantum transport modeling of photocurrent in graphene field-effect transistors (including realistic electromagnetic fields) to show that wavelength tunability is possible by dynamically changing the gate voltage. We also reveal the phenomena that govern the behavior of this type of device and show significant departure from the simple expectations based on vertical transitions. We find strong focusing of the electromagnetic fields at the contact edges over the same length scale as the band-bending. Both of these spatially-varying potentials lead to an enhancement of non-vertical optical transitions, which dominate even in the absence of phonon or impurity scattering. Furthermore, we show that the vanishing density of states near the Dirac point leads to contact blocking and a gate-dependent modulation of the photocurrent. Several of the effects discussed here should be applicable to a broad range of one- and two-dimensional materials and devices.

36 MATERIALS SCIENCE↗

The Close AGN Reference Survey (CARS)

Active galactic nuclei (AGN) are thought to be responsible for the suppression of star formation in massive ~10 10 M ⊙ galaxies. While this process is a key feature in numerical simulations of galaxy formation, it has not been unambiguously confirmed in observational studies yet. The characterization of the star formation rate (SFR) in AGN host galaxies is challenging as AGN light contaminates most SFR tracers. Furthermore, the various SFR tracers are sensitive to different timescales of star formation from approximately a few to 100 Myr. We aim to obtain and compare SFR estimates from different tracers for AGN host galaxies in the Close AGN Reference Survey (CARS) to provide new observational insights into the recent SFR history of those systems. We constructed integrated panchromatic spectral energy distributions to measure the far infrared (FIR) luminosity as a tracer for the recent (< 100 Myr) SFR. In addition we used the integral-field unit observation of the CARS targets to employ the Hα luminosity decontaminated by AGN excitation as a proxy for the current (< 5 Myr) SFR. We find that significant differences in specific SFR of the AGN host galaxies as compared with the larger galaxy population disappear once cold gas mass, in addition to stellar mass, is used to predict the SFR for a specific AGN host. Only a tentative trend with the inclination of the host galaxy remains, such that SFR appears slightly lower than expected when the galaxies of unobscured AGN appear more edge-on along our line-of-sight, particular for dust-insensitive FIR-based SFRs. We identify individual galaxies with a significant difference in their SFR which can be related to a recent enhancement or decline in their SFR history that might be related to various processes including interactions, gas consumption, outflows, and AGN feedback. AGN can be present in various stages of galaxy evolution which makes it difficult to relate the SFR solely to the impact of the AGN. Our study shows that stellar mass alone is an insufficient parameter to estimate the expected SFR of an AGN host galaxy compared to the underlying non-AGN galaxy population. We do not find any strong evidence for a global positive or negative AGN feedback in the CARS sample. However, there is tentative evidence that (1) the relative orientation of the AGN engine with respect to the host galaxies might alter the efficiency of AGN feedback and that (2) the recent SFH is an additional tool to identify rapid changes in galaxy growth driven by the AGN or other processes.

79 ASTRONOMY AND ASTROPHYSICS↗

Field effect in the quantum Hall regime of a high mobility graphene wire

In graphene-based electronic devices like in transistors, the field effect applied thanks to a gate electrode allows tuning the charge density in the graphene layer and passing continuously from the electron to the hole doped regime across the Dirac point. Homogeneous doping is crucial to understand electrical measurements and for the operation of future graphene-based electronic devices. However, recently theoretical and experimental studies highlighted the role of the electrostatic edge due to fringing electrostatic field lines at the graphene edges [P. Silvestrov and K. Efetov, Phys. Rev. B 77, 155436 (2008); F. T. Vasko and I. V. Zozoulenko, Appl. Phys. Lett. 97, 092115 (2010)]. This effect originates from the particular geometric design of the samples. A direct consequence is a charge accumulation at the graphene edges giving a value for the density, which deviates from the simple picture of a plate capacitor and also varies along the width of the graphene sample. Entering the quantum Hall regime would, in principle, allow probing this accumulation thanks to the extreme sensitivity of this quantum effect to charge density and the charge distribution. Moreover, the presence of an additional and counter-propagating edge channel has been predicted [P. Silvestrov and K. Efetov, Phys. Rev. B 77, 155436 (2008)] giving a fundamental aspect to this technological issue. In this article, we investigate this effect by tuning a high mobility graphene wire into the quantum Hall regime in which charge carriers probe the electrostatic potential at high magnetic field close to the edges. We observe a slight deviation to the linear shift of the quantum Hall plateaus with magnetic field and we study its evolution for different filling factors, which correspond to different probed regions in real space. We discuss the possible origins of this effect including an increase of the charge density towards the edges.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Image segmentation of nanoscale Zernike phase contrast X-ray computed tomography images

Zernike phase contrast is a useful technique for nanoscale X-ray computed tomography (CT) imaging of materials with a low X-ray absorption coefficient. It enhances the image contrast by phase shifting X-ray waves to create changes in amplitude. However, it creates artifacts that hinder the use of traditional image segmentation techniques. We propose an image restoration method that models the X-ray phase contrast optics and the three-dimensional image reconstruction method. We generate artifact-free images through an optimization problem that inverts this model. Though similar approaches have been used for Zernike phase contrast in visible light microscopy, this optimization employs an effective edge detection method tailored to handle Zernike phase contrast artifacts. We characterize this optics-based restoration method by removing the artifacts in and thresholding multiple Zernike phase contrast X-ray CT images to produce segmented results that are consistent with the physical specimens. We quantitatively evaluate and compare our method to other segmentation techniques to demonstrate its high accuracy.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Self-cavity lasing in optically pumped single crystals of p-sexiphenyl

Organic single-crystal self-cavities are prepared by solution growth of p-sexiphenyl (p-6P). Based on Fabry-Pérot feedback inside a quasi-lozenge-shaped platelet crystal, edge-emitting laser is obtained under optical pumping. The multimode lasing band appears at the 0-1 or 0-2 vibronic progressions depending on the excitation conditions which affect the self-absorption effect. Cavity-size dependence of amplified spontaneous emission (ASE) is investigated with laser-etched single crystals of p-6P. As the cavity length of square-shaped crystal is reduced from 100 to 10 μm, ASE threshold fluence is decreased probably due to size-dependent light confinement in the crystal cavity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Listening to temperature: Ultrasonic non-destructive identification of material phase and temperature

In the chemical transport field, such as petro-chemicals or food processing, there is a need to quantify the spatially varying temperature and phase state of the material within a cylindrical vessel, such as a pipeline, using non-invasive techniques. Using ultrasonic signals, which vary in time-of-flight, intensity, and wave characteristics based on the temperature and phase of a material, an automated technique is presented which can provide a non-axisymmetric map of the phase and temperature inside a cylindrical vessel within a single plane using exclusively information from the through-transmission wave and the external temperature profile. This research demonstrates the approach using an amorphous wax, due to its stable nature and ability to be reheated many times without changing the properties of the wax. Due to its amorphous nature, the wax transitions from a solid to a low-viscosity fluid over a range of temperatures. This behavior is similar to that of a thermoplastic and a slurry experiencing curing. As the spatial temperature within a container of wax increases the time of flight for an ultrasonic signal will change. Finally, results presented indicate the ability of the investigated technique to map the temperature and phase change of the wax based solely on the ultrasonic signals and knowledge of the external temperature on the outer edge of the vessel.

36 MATERIALS SCIENCE↗

In situ detection of RF breakdown on microfabricated surface ion traps

We report microfabricated surface ion traps are a principal component of many ion-based quantum information science platforms. The operational parameters of these devices are pushed to the edge of their physical capabilities as the experiments strive for increasing performance. When the applied radio-frequency (RF) voltage is increased excessively, the devices can experience damaging electric discharge events known as RF breakdown. We introduce two novel techniques for in situ detection of RF breakdown, which we implemented while characterizing the breakdown threshold of surface ion traps produced at Sandia National Laboratories. In these traps, breakdown did not always occur immediately after increasing the RF voltage, but often minutes or even hours later. This result is surprising in the context of the suggested mechanisms for RF breakdown in vacuum. Additionally, the extent of visible damage caused by breakdown events increased with the applied voltage. To minimize the probability for damage when RF power is first applied to a device, our results strongly suggest that the voltage should be ramped up over the course of several hours and monitored for breakdown.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

THE EXTREME SPIN OF THE BLACK HOLE IN CYGNUS X-1

The compact primary in the X-ray binary Cygnus X-1 was the first black hole to be established via dynamical observations. We have recently determined accurate values for its mass and distance, and for the orbital inclination angle of the binary. Building on these results, which are based on our favored (asynchronous) dynamical model, we have measured the radius of the inner edge of the black hole's accretion disk by fitting its thermal continuum spectrum to a fully relativistic model of a thin accretion disk. Assuming that the spin axis of the black hole is aligned with the orbital angular momentum vector, we have determined that Cygnus X-1 contains a near-extreme Kerr black hole with a spin parameter a{sub *} > 0.95 (3{sigma}). For a less probable (synchronous) dynamical model, we find a{sub *} > 0.92 (3{sigma}). In our analysis, we include the uncertainties in black hole mass, orbital inclination angle, and distance, and we also include the uncertainty in the calibration of the absolute flux via the Crab. These four sources of uncertainty totally dominate the error budget. The uncertainties introduced by the thin-disk model we employ are particularly small in this case given the extreme spin of the black hole and the disk's low luminosity.

79 ASTRONOMY AND ASTROPHYSICS↗