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At least 1,747 records · Page 97

Morphological and crystallographic controls in the replacement of calcite and aragonite by cerussite and otavite

Mineral replacement reactions are essential solid-fluid interactions in natural and industrial processes including metasomatism, diagenesis, and metamorphism, and sequestration of metal toxins from polluted water. In this paper, we explore the morphological evolution of aragonite and calcite (polymorphs of CaCO 3 ) during their replacement by cerussite (PbCO 3 , an isomorph of aragonite) and otavite (CdCO 3 , an isomorph of calcite) in acidic aqueous solutions (with initial pH 3 to 4). Observations using scanning electron and synchrotron-based transmission X-ray microscopies reveal the formation of pseudomorphic shells (~5 to 10 µm thick) of cerussite and otavite when Pb 2+ is reacted with either calcite or aragonite and when Cd 2+ is reacted with aragonite. The formation of pore space at the substrate-precipitate interface and within the precipitate is found to be key in promoting chemical exchange between the dissolving phase and the solution. In contrast, minimal reactivity is observed when Cd 2+ is reacted with calcite. These results demonstrate that the lack of substrate-precipitate epitaxy (either because of inconsistent symmetries or due to large lattice constant mismatch) is a critical factor that enables replacement of primary CaCO 3 minerals by Pb- or Cd-bearing secondary minerals while the presence of epitaxial relationships inhibit those reactions. When calcite and aragonite coexist, the replacement of aragonite by cerussite and otavite occurs preferentially over calcite. We postulate that the relative reactivity of calcite and aragonite to Pb 2+ and Cd 2+ can be determined by interplay between morphological and crystallographic properties of CaCO 3 materials as well as solution chemistry. Our results demonstrate that coupled dissolution-precipitation processes of carbonate minerals play an important role in controlling mobility and bioavailability of lead and cadmium in environments where acidic metal-contaminated water interacts with carbonate-rich rocks and soils.

58 GEOSCIENCES↗

Investigating New Particle Formation and Growth Over an Urban Location in the Eastern Mediterranean

Abstract This study investigates the new particle formation (NPF) events at an urban location in the Eastern Mediterranean. Particle size distribution, particulate chemical composition, and gaseous pollutants were monitored in Rehovot, Israel (31°53″N 34°48″E) during two campaigns: from April 29 to 3 May 2021 (Campaign 1) and from May 3 to 11 May 2023 (Campaign 2), coinciding with an intensive bonfire burning festival. The organic aerosols (OA) source apportionment identified two major factors—Hydrocarbon‐like OA and Biomass‐burning OA—as well as two secondary factors—MO‐OOA (more oxidized‐oxygenated OA) and LO‐OOA (low oxidized oxygenated OA). NPF events were frequently observed during the day (mostly well‐defined nucleation events) and at night (burst of ultrafine mode particles without any discernible growth). A condensation sink value of (9.4 ± 4.0) × 10 −3 s −1 during Campaign 1 and (14.2 ± 6.0) × 10 −3 s −1 during Campaign 2 was obtained. The daytime events were associated with enhanced sulfuric acid proxy concentrations of (2–12) × 10 6 molecules cm −3 , suggesting the role of gas‐phase photochemistry in promoting NPF. A novel approach of hybrid positive matrix factorization analysis was used to deconvolve the chemical species responsible for the observed events. The results suggest the involvement of multiple components, including ammonium sulfate and MO‐OOA, in the nucleation; Nitrate, HOA and LO‐OOA participate in the subsequent particle growth for the daytime events. Nighttime events involve only semi‐volatile species (LO‐OOA, HOA and nitrate) along with ammonium sulfate.

Meteorology & Atmospheric Sciences↗

Oscillatory redox behavior in oxides: Cyclic surface reconstruction and reactivity modulation via the Mars–van Krevelen mechanism

The breaking of translational symmetry at oxide surfaces gives rise to coordinatively unsaturated cations/anions and surface restructuring—key factors that govern surface reactivity. Using direct in situ environmental transmission electron microscopy (TEM) observations along with atomistic modeling, we report oscillatory redox behavior in CuO under H 2 , where cyclic surface reconstruction and reactivity modulation occur via the Mars–van Krevelen (MvK) mechanism. We observe self-switching between oxygen-rich and oxygen-deficient surface reconstructions, alternately activating and deactivating the surface for H 2 O formation. During periods of chemical inactivity, the oxygen-deficient surface undergoes slow reoxidation via lattice oxygen diffusing from subsurface and bulk reservoirs, restoring the active oxygen-rich surface termination. The inherent disparity in chemical activity among undercoordinated surface ions, along with sluggish subsurface-to-surface oxygen replenishment, drives this oscillatory redox cycle, modulating H2-induced loss of lattice oxygen at the surface and its delayed replenishment from the subsurface. This creates spatiotemporally separated redox steps at the oxide surface. The phenomena and atomistic insights presented here have significant implications for manipulating the surface reactivity of oxides by tuning the separation of these redox steps.

36 MATERIALS SCIENCE↗

Rate constant for the reaction of O(3P) with diacetylene from 210 to 423 K

The absolute rate constant for the reaction of O(3P) with diacetylene (C4H2) has been measured as a function of pressure and temperature by the flash-photolysis/resonance-fluorescence method. At 298 K and below, no pressure dependence of the rate constant was observed, but at 423 K a moderate (factor-of-2) increase was detected in the range 3 to 75 torr Ar.Results at or near the high-pressure limit are represented by an Arrhenius expression over the temperature range 210 to 423 K. The results are compared with previous determinations, all of which employed the discharge-flow/mass-spectrometry technique. The mechanism of the reaction is considered, including both primary and secondary processes. The heats of formation of the reactants, adducts, and products for the O(3P) + C4H2 reaction are discussed and contrasted with those for O(3P) + C2H2.

Mitchell, M. B.↗

Interplanetary meteoroid debris in LDEF metal craters

The extraterrestrial meteoroid residue found lining craters in the Long Duration Exposure Facility (LDEF) aluminum and gold targets is highly variable in both quantity and type. In typical craters only a minor amount of residue is found and for these craters it is evident that most of the impacting projectile was ejected during crater formation. Less than 10 percent of the craters greater than 100 microns contain abundant residue consistent with survival of a major fraction of the projectile. In these cases the residue can be seen optically as a dark liner and it can easily be analyzed by SEM-EDX techniques. Because they are rare, the craters with abundant residue must be a biased sampling of the meteoroids reaching the earth. Factors that favor residue retention are low impact velocity and material properties such as high melting point. In general, the SEM-EDX observations of crater residues are consistent with the properties of chondritic meteorites and interplanetary dust particles collected in the stratosphere. Except for impacts by particles dominated by single minerals such as FeS and olivine, most of the residue compositions are in broad agreement with the major element compositions of chondrites. In most cases the residue is a thin liner on the crater floor and these craters are difficult to quantitatively analyze by EDX techniques because the electron beam excites both residue and underlying metal substrate. In favorable cases, the liner is thick and composed of vesicular glass with imbedded FeNi, sulfide and silicate grains. In the best cases of meteoroid preservation, the crater is lined with large numbers of unmelted mineral grains. The projectiles fragmented into micron sized pieces but the fragments survived without melting. In one case, the grains contain linear defects that appear to be solar flare tracks. Solar flare tracks are common properties of small interplanetary particles and their preservation during impact implies that the fragments were not heated above 600 C. We are investigating the meteoroid fragments in LDEF metal craters to determine the properties of interplanetary dust and to determine if there are meteoroid types that are overlooked or otherwise undetected in cosmic dust collections obtained from the stratosphere and polar ice.

Brownlee, D. E.↗

A hydrodynamic treatment of the tilted cold dark matter cosmological scenario

A standard hydrodynamic code coupled with a particle-mesh code is used to compute the evolution of a tilted cold dark matter (TCDM) model containing both baryonic matter and dark matter. Six baryonic species are followed, with allowance for both collisional and radiative ionization in every cell. The mean final Zel'dovich-Sunyaev y parameter is estimated to be (5.4 +/- 2.7) x 10 exp -7, below currently attainable observations, with an rms fluctuation of about (6.0 +/- 3.0) x 10 exp -7 on arcmin scales. The rate of galaxy formation peaks at a relatively late epoch (z is about 0.5). In the case of mass function, the smallest objects are stabilized against collapse by thermal energy: the mass-weighted mass spectrum peaks in the vicinity of 10 exp 9.1 solar masses, with a reasonable fit to the Schechter luminosity function if the baryon mass to blue light ratio is about 4. It is shown that a bias factor of 2 required for the model to be consistent with COBE DMR signals is probably a natural outcome in the present multiple component simulations.

Cen, Renyue↗

The Development of Vestibular Connections in Rat Embryos in Microgravity

Existing experimental embryological data suggests that the vestibular system initially develops in a very rigid and genetically controlled manner. Nevertheless, gravity appears to be a critical factor in the normal development of the vestibular system that monitors position with respect to gravity (saccule and utricle). In fact several studies have shown that prenatal exposure to microgravity causes temporary deficits in gravity-dependent righting behaviors, and prolonged exposure to hypergravity from conception to weaning causes permanent deficits in gravity-dependent righting behaviors. Data on hypergravity and microgravity exposure suggest some changes in the otolith formation during development, in particular the size although these changes may actually vary with the species involved. In adults exposed to microgravity there is a change in the synaptic density in the otic sensory epithelia suggesting that some adaptation may occur there. However, effects have also been reported in the brainstem. Several studies have shown synaptic changes in the lateral vestibular nucleus and in the nodulus of the cerebellum after neonatal exposure to hypergravity. We report here that synaptogenesis in the medial vestibular nucleus is retarded in developing rat embryos that were exposed to microgravity from gestation days 9 to 19.

Bruce, Laura L.↗

Design and Development of 256x256 Linear Mode Low-Noise Avalanche Photodiode Arrays

A larger format photodiode array is always desirable for many LADAR imaging applications. However, as the array format increases, the laser power or the lens aperture has to increase to maintain the same flux per pixel thus increasing the size, weight and power of the imaging system. In order to avoid this negative impact, it is essential to improve the pixel sensitivity. The sensitivity of a short wavelength infrared linear-mode avalanche photodiode (APD) is a delicate balance of quantum efficiency, usable gain, excess noise factor, capacitance, and dark current of APD as well as the input equivalent noise of the amplifier. By using InA1As as a multiplication layer in an InP-based APD, the ionization coefficient ratio, k, is reduced from 0.40 (lnP) to 0.22, and the excess noise is reduced by about 50%. An additional improvement in excess noise of 25% was achieved by employing an impact-ionization-engineering structure with a k value of 0.15. Compared with the traditional InP structure, about 30% reduction in the noise-equivalent power with the following amplifier can be achieved. Spectrolab demonstrated 30-um mesa APD pixels with a dark current less than 10 nA and a capacitance of 60 fF at gain of 10. APD gain uninformity determines the usable gain of most pixels in an array, which is critical to focal plane array sensitivity. By fine tuning the material growth and device process, a break-down-voltage standard deviation of 0.1 V and gain of 30 on individual pixels were demonstrated in our 256x256 linear-mode APD arrays.

Yuan, Ping↗

Coupling Fractional Thermal Runaway Calorimetry (FTRC) Results with Statistical Analysis Methods

Important factors to consider when optimizing Lithium-ion (Li-ion) battery thermal management systems, from a battery safety perspective, include the total energy released during a single cell thermal runaway (TR) event and the fraction of the total energy that is released through the cell casing versus through the ejecta material. A fractional thermal runaway calorimeter (FTRC) was used to examine the TR behavior of the following 18650-format Li-ion cells: (1) Molicel 18650-J, (2) LG 18650-HG2, (3) Samsung 18650-30Q, (4) 3.35 Ah LG 18650 test cell, (5) Sony 18650-VC7, and (6) LG 18650-MJ1. These cells were intentionally selected to represent a variety of manufacturers, chemistries, capacities, and safety features. Because of the large number of random and non-random variables associated with the FTRC results, a linear regression model, developed using engineering statistical methods, was utilized to provide final interpretation of the TR behavior for each cell type and design variable combination.

Walker, William↗

Highly Siderophile Elements as Tracers for the Subcontinental Mantle Evolution Beneath the Southwestern USA: The San Carlos and Kilbourne Hole Peridotite Xenoliths Revisited

Peridotite xenoliths from San Carlos, Arizona, and Kilbourne Hole, New Mexico, have been studied since the 1970 s to give insights into melting and metasomatism in the subcontinental mantle beneath the southwestern USA. More recently, the highly siderophile elements (HSE; Os, Ir, Ru, Rh, Pt, Pd, and Re) and the included Re-Os isotope system have been established as powerful tools for the study of mantle processes because of their range in compatibility during mantle melting and their siderophile and chalcophile geochemical behavior. Model aluminachron Re-Os ages for San Carlos and Kilbourne Hole, as well as for the nearby Dish Hill and Vulcan's Throne sites, give consistent depletion ages of around 2.2 Ga. This age can be interpreted as a single large scale mantle melting event linked to crustal formation and continental growth under the southwestern USA. Highly siderophile elements, however, may be added to depleted peridotites via melt-rock interaction, especially the more incompatible and hence mobile Pt, Pd, and Re. This may result in overprinting of the signature of melt extraction, thus abating the usefulness of Re-Os mantle extraction model ages. A comprehensive characterization of the suite of mantle xenoliths from the SW USA in terms of HSE concentrations is thus necessary to re-assess the Re-Os system for dating purposes. San Carlos peridotites are depleted to moderately fertile, as indicated by their bulk Al2O3 contents between 0.66 wt% and 3.13 wt%. Bulk Os-187/Os-188 in San Carlos peridotites range from 0.1206 to 0.1357. In contrast, Kilbourne Hole peridotites tend to be more fertile with Al2O3 between 2.11 and 3.78 wt%, excluding one extremely depleted sample with 0.30 wt% Al2O3, and have Os-187/Os-188 between 0.1156 and 0.1272, typical for mantle peridotites. No large fractionation between the more compatible HSE Os, Ir, and Ru are observed. The more incompatible HSE Re, Pd, and to a minor extent, Pt, however, are depleted in a number of samples by factors of up to 4 for Pt, 6 for Pd, and 20 for Re, compared to primitive mantle estimates. This is in agreement with previous studies from the same locales, which demonstrated the presence of different populations of mantle xenoliths having undergone various degrees of melt extraction. The depletion of the more incompatible elements (Re, Pd, and Pt) also suggests that the HSE budgets of the SW USA peridotites were primarily established by extraction of basaltic melt, and reflect only minor influence from later episodes of metasomatism. Model Re-Os ages obtained from San Carlos and Kilbourne Hole xenoliths may thus reflect ages of crustal formation and mantle depletion in the SW USA region.

vanAcken, D.↗

Rare Earth Element Measurements of Melilite and Fassaite in Allende Cai by Nanosims

The rare earth elements (REEs) are concentrated in CAIs by approx. 20 times the chondritic average [e.g., 1]. The REEs in CAIs are important to understand processes of CAI formation including the role of volatilization, condensation, and fractional crystallization [1,2]. REE measurements are a well established application of ion microprobes [e.g., 3]. However the spatial resolution of REE measurements by ion microprobe (approx.20 m) is not adequate to resolve heterogeneous distributions of REEs among/within minerals. We have developed methods for measuring REE with the NanoSIMS 50L at smaller spatial scales. Here we present our initial measurements of REEs in melilite and fassaite in an Allende Type-A CAI with the JSC NanoSIMS 50L. We found that the key parameters for accurate REE abundance measurements differ between the NanoSIMS and conventional SIMS, in particular the oxide-to-element ratios, the relative sensitivity factors, the energy distributions, and requisite energy offset. Our REE abundance measurements of the 100 ppm REE diopside glass standards yielded good reproducibility and accuracy, 0.5-2.5 % and 5-25 %, respectively. We determined abundances and spatial distributions of REEs in core and rim within single crystals of fassaite, and adjacent melilite with 5-10 m spatial resolution. The REE abundances in fassaite core and rim are 20-100 times CI abundance but show a large negative Eu anomaly, exhibiting a well-defined Group III pattern. This is consistent with previous work [4]. On the other hand, adjacent melilite shows modified Group II pattern with no strong depletions of Eu and Yb, and no Tm positive anomaly. REE abundances (2-10 x CI) were lower than that of fassaite. These patterns suggest that fassaite crystallized first followed by a crystallization of melilite from the residual melt. In future work, we will carry out a correlated study of O and Mg isotopes and REEs of the CAI in order to better understand the nature and timescales of its formation process and subsequent metamorphic history.

Ito, M.↗

Gas permeation properties of amorphous zeolitic imidazolate framework membranes made by atomic/molecular layer deposition

Amorphous metal-organic framework (MOF) membranes are desirable because they may retain some of the molecular sieving properties of their crystalline counterparts while being free of grain boundary defects, which often hinder the consistent achievement of high membrane performance. However, current methods, like melting and compression, for fabricating amorphous MOF membranes involve multi-step processes that require the formation of a crystalline membrane first, that is then amorphized, and therefore, could be challenging to scale. Here, we utilize atomic/molecular layer deposition (ALD/MLD) of diethylzinc (DEZ) and 2-methylimidazole (2mIm) to directly synthesize ultrathin amorphous zeolitic imidazolate framework (aZIF) deposits on γ-alumina-coated α-alumina supports. As the number of ALD/MLD cycles increased from 10 to 300, gas permeances decreased while ideal selectivities increased. Mixture separation factors for C3H6/C3H8, CO2/N2, and H2/C3H8 as high as 4, 37, and 194, respectively, were obtained. At 200 °C and 2.5 bar equimolar feed of H2 and C3H8, a H2/C3H8 mixture separation factor of 185 is obtained with an H2 permeance of ca. 4.15x10-8 mol/m2-s-Pa (124 GPU). Additionally, the membrane achieves a CO2/N2 mixture separation factor of 37 at 25 °C and 1 bar with a CO2 permeance of ca. 3.96x10-8 mol/m2-s-Pa (118 GPU). Considering the vast array of compositionally distinct aZIFs that can be potentially deposited by this approach, an enormously large parameter space for membrane design is emerging to be explored.

36 MATERIALS SCIENCE↗

Initial tests of large format sensors for the ATLAS ITk strip tracker

For the construction of the Inner Tracker (ITk) as part of the phase-II upgrade programme of the ATLAS detector for the High-Luminosity (HL) LHC, batches of Long Strip (LS) and Short Strip (SS) n + -in-p type micro-strip sensors have been produced by Hamamatsu Photonics and Infineon. The full size sensors measure approximately 98 × 98 mm 2 and are designed and engineered for tolerance against the 9.7 × 10 14 1 MeV n eq /cm 2 fluence expected at the HL-LHC, including a safety factor of 1.5. Each sensor has 2 or 4 columns of 1280 individual channels arranged at 75.5 μ m horizontal pitch. To ensure the sensors comply with their specifications, a Quality Control (QC) procedure has been implemented, comprising measurements on every individual sensor as well as on a sample basis. Every sensor is subjected to an initial visual inspection, after which the full surface of the sensor is captured with very high resolution by an automated camera setup. Non-contact metrology is performed to obtain the sensor surface profile. Electrical measurements establishing the reverse bias leakage current and depletion voltage are then conducted automatically. Sample sensors from every batch are subjected to 40 h of leakage stability checks in controlled atmosphere, and tests on every channel measuring leakage current, coupling capacitance and bias resistance are done. The recorded results are uploaded to a production database following data quality checks. In this paper, QC test validation data and the compiled results for the first batches of production grade sensors are presented. The QC protocol was validated, and the first production sensors were confirmed to be within specification. The results are compared to those from the previous generation of prototype sensors.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Tailoring the Intermediate Phase to Control Formation of γ‑CsPbI3 Films

Controlling the crystallization pathway of inorganic CsPbI3 perovskite is essential for achieving high efficiency and stability in optoelectronic devices. Here, we report a solvent-engineering strategy that combines an antisolvent process with vacuum treatment (AVT) to modulate evaporation dynamics of the precursor, guiding the formation of highly oriented (CH3)2NH2PbI3 (DMAPbI3) and Cs4PbI6 intermediate phases. Synchrotron and in situ analyses revealed correlations between intermediate orientation and γ-CsPbI3 crystallinity. This directional crystallization pathway promotes vertical alignment and grain enlargement in γ-CsPbI3 films, resulting in fewer voids, lower defect densities, and reduced tensile strain. Photovoltaic devices based on AVT-processed films achieved a power conversion efficiency of 18.47% with a fill factor of 83.14% and retained 101.9% of their initial efficiency after 526 h without encapsulation. This study first reports that the quality of DMAPbI3 and Cs4PbI6 intermediates, controlled by combination of antisolvent and vacuum treatment, plays a crucial role in achieving high-quality γ-CsPbI3 films.

Yoon, Geon Woo↗

Development of Solar Cells with Trapezoidal Grid Fingers

In concentrator solar cells, traditional metallic contacts cover a substantial portion of the device area, resulting in reflected light that diminishes the amount of current collected. In this paper, we developed trapezoidal front grid fingers to decrease the optical shadowing and the resulting loss of the device short-circuit current. By using a negative photoresist, a thick metal layer can be deposited by metal evaporation. The formation of an organic and metallic reflective deposit under the negative sloped photoresist is observed, though. By removing this deposit, a similar short-circuit current to typical Ni/Au contacts deposited by electrodeposition is obtained. Even though the Ti/Al grid fingers have larger width, they have the same effective shadowing due to the trapezoidal shape. At high concentration, a higher efficiency is obtained as well due to a high fill factor and improved open circuit voltage.

14 SOLAR ENERGY↗

Unveiling enhanced oxidation resistance and mechanical integrity of multicomponent ultra–high temperature carbides

The development of a new class of multicomponent ultra-high temperature ceramics (MC-UHTCs), often referred to as high-entropy UHTCs, has gained increased interest due to the possibility of improved thermomechanical and oxidation properties. In this study, a systematic approach by gradual addition in the UHTC components ranging from a binary to a dense quaternary (Ta,Nb,Hf,Ti)C is synthesized using spark plasma sintering (SPS). The solid solutioning was the critical factor in homogenizing the composition in the multicomponent system. The segregation of NbC and HfC was seen in binary and ternary UHTC systems, while a single-phase homogeneity was observed in the quaternary UHTC improving its hardness up to 34.8 GPa. The presence of closely spaced slip lines in the MC-UHTCs enhances resistance to indentation damage up to 72% at an applied load of 200 N. The formation of complex mixed oxide phase of Hf6Ta2O17 ensued in the lower to negligible oxidation even up to 3 min of plasma exposure with temperature exceeding 2800°C. In sum, though the entropy remains medium (0.96R) for the selected system, the quaternary UHTC system undoubtedly has significantly better thermomechanical performance when compared to established baseline UHTCs. Furthermore, this raises the debate on the justification for calling a multicomponent system a “high entropy” to be seen in a new light. The developed MC-UHTCs elicits the paradigm of this new class of UHTCs expanding their potential in thermal protection systems for hypersonic applications.

36 MATERIALS SCIENCE↗

First-Principles Thermodynamic Assessments of Sr-Containing Secondary Phase Formation in La1-xSrxMnO3±δ Perovskites for Solid Oxide Cell Applications

Sr-secondary phase formation is a potentially significant degradation mode threatening solid-oxide cell (SOC) commercial viability. A first-principles thermodynamic study was performed for rhombohedral perovskite (La1-xSrx) MnO3±δ (LSM) to assess its stability against Sr secondary phase formation in SOC applications. In this work, the Sr secondary phase formation reaction free energies were determined by combining ab initio lattice dynamics calculations for the solid phases and an ab initio thermodynamics approach for the gas phases. Furthermore, this approach goes beyond previous thermodynamic modeling studies by integrating first-principles based point-defect equilibria into the analyses. The modeling results indicate an increased tendency to form SrO oxide from LSM upon decreasing the oxygen partial pressure. Additionally, enhancing factors to form the Sr-related secondary phase from the associated SrO activity in LSM are further quantified by considering the equilibrium of SrO reacting with contaminant gas species as a function of temperature and gas pressure.

Defect and phase stability↗

Formation of the muonic helium atom /alpha particle-muon-electron/ and observation of its Larmor precession

Experiments are described in which it proved possible to form the muonic helium atom by stopping polarized negative muons in a helium gas with a 2% xenon admixture at a pressure of 14 atm. The observed Larmor precession amplitudes are plotted against the gyromagnetic ratio for both muons and antimuons stopped in He + 2% Xe. In addition, a non-zero residual polarization of 0.06 plus or minus 0.01 was measured for muons stopped in pure helium gas, which corresponds to a depolarization factor of 18 plus or minus 3.

Souder, P. A.↗