Metals from spacecraft reentry in stratospheric aerosol particles.

Large increases in the number of low earth orbit satellites are projected in the coming decades [L. Schulz, K.-H. Glassmeier, Adv. Space Res. 67, 1002-1025 (2021)] with perhaps 50,000 additional satellites in orbit by 2030 [GAO, Large constellations of satellites: Mitigating environmental and other effects (2022)]. When spent rocket bodies and defunct satellites reenter the atmosphere, they produce metal vapors that condense into aerosol particles that descend into the stratosphere. So far, models of spacecraft reentry have focused on understanding the hazard presented by objects that survive to the surface rather than on the fate of the metals that vaporize. Here, we show that metals that vaporized during spacecraft reentries can be clearly measured in stratospheric sulfuric acid particles. Over 20 elements from reentry were detected and were present in ratios consistent with alloys used in spacecraft. The mass of lithium, aluminum, copper, and lead from the reentry of spacecraft was found to exceed the cosmic dust influx of those metals. About 10% of stratospheric sulfuric acid particles larger than 120 nm in diameter contain aluminum and other elements from spacecraft reentry. Planned increases in the number of low earth orbit satellites within the next few decades could cause up to half of stratospheric sulfuric acid particles to contain metals from reentry. The influence of this level of metallic content on the properties of stratospheric aerosol is unknown.

Design and testing of a sew-free origami mask for improvised respiratory protection.

Respiratory aerosols with diameters smaller than 100µm have been confirmed as important vectors for the spread of diseases such as SARS-CoV-2. While disposable and cloth masks afford some protection, they are typically inefficient at filtering these aerosols and require specialized fabrication devices to produce. We describe a fabrication technique that makes use of a folding procedure (origami) to transform any filtration material into a mask. These origami masks can be fabricated by non-experts at minimal cost and effort, provide adequate filtration efficiencies, and are easily scaled to different facial sizes. Using a mannequin fit test simulator, we demonstrate that these masks can provide filtration efficiencies of over 90% while simultaneously providing greater comfort as demonstrated by pressure drops of <20 Pa. We also quantify mask leakage by measuring the variations in filtration efficiency and pressure drop when masks are sealed to the mannequin face compared to when the mask is unsealed but positioned to achieve the best fit. While leakage generally trended with pressure drop, some of the best performing mask media achieved <10% reduction in filtration efficiency due to leakage. Because this mask can provide high filtration efficiencies at low pressure drop compared to commercial alternatives, it is likely to promote greater mask wearing tolerance and acceptance.

The role of low-volatility organic compounds in initial particle growth in the atmosphere.

About half of present-day cloud condensation nuclei originate from atmospheric nucleation, frequently appearing as a burst of new particles near midday. Atmospheric observations show that the growth rate of new particles often accelerates when the diameter of the particles is between one and ten nanometres. In this critical size range, new particles are most likely to be lost by coagulation with pre-existing particles, thereby failing to form new cloud condensation nuclei that are typically 50 to 100 nanometres across. Sulfuric acid vapour is often involved in nucleation but is too scarce to explain most subsequent growth, leaving organic vapours as the most plausible alternative, at least in the planetary boundary layer. Although recent studies predict that low-volatility organic vapours contribute during initial growth, direct evidence has been lacking. The accelerating growth may result from increased photolytic production of condensable organic species in the afternoon, and the presence of a possible Kelvin (curvature) effect, which inhibits organic vapour condensation on the smallest particles (the nano-Köhler theory), has so far remained ambiguous. Here we present experiments performed in a large chamber under atmospheric conditions that investigate the role of organic vapours in the initial growth of nucleated organic particles in the absence of inorganic acids and bases such as sulfuric acid or ammonia and amines, respectively. Using data from the same set of experiments, it has been shown that organic vapours alone can drive nucleation. We focus on the growth of nucleated particles and find that the organic vapours that drive initial growth have extremely low volatilities (saturation concentration less than 10(-4.5) micrograms per cubic metre). As the particles increase in size and the Kelvin barrier falls, subsequent growth is primarily due to more abundant organic vapours of slightly higher volatility (saturation concentrations of 10(-4.5) to 10(-0.5) micrograms per cubic metre). We present a particle growth model that quantitatively reproduces our measurements. Furthermore, we implement a parameterization of the first steps of growth in a global aerosol model and find that concentrations of atmospheric cloud concentration nuclei can change substantially in response, that is, by up to 50 per cent in comparison with previously assumed growth rate parameterizations.

Evidence for a vestigial nematic state in the cuprate pseudogap phase.

The CuO2 antiferromagnetic insulator is transformed by hole-doping into an exotic quantum fluid usually referred to as the pseudogap (PG) phase. Its defining characteristic is a strong suppression of the electronic density-of-states D(E) for energies |E| < [Formula: see text], where [Formula: see text] is the PG energy. Unanticipated broken-symmetry phases have been detected by a wide variety of techniques in the PG regime, most significantly a finite-Q density-wave (DW) state and a Q = 0 nematic (NE) state. Sublattice-phase-resolved imaging of electronic structure allows the doping and energy dependence of these distinct broken-symmetry states to be visualized simultaneously. Using this approach, we show that even though their reported ordering temperatures T DW and T NE are unrelated to each other, both the DW and NE states always exhibit their maximum spectral intensity at the same energy, and using independent measurements that this is the PG energy [Formula: see text] Moreover, no new energy-gap opening coincides with the appearance of the DW state (which should theoretically open an energy gap on the Fermi surface), while the observed PG opening coincides with the appearance of the NE state (which should theoretically be incapable of opening a Fermi-surface gap). We demonstrate how this perplexing phenomenology of thermal transitions and energy-gap opening at the breaking of two highly distinct symmetries may be understood as the natural consequence of a vestigial nematic state within the pseudogap phase of Bi2Sr2CaCu2O8.

Machine Learning Methods for Multiscale Physics and Urban Engineering Problems.

We present an overview of four challenging research areas in multiscale physics and engineering as well as four data science topics that may be developed for addressing these challenges. We focus on multiscale spatiotemporal problems in light of the importance of understanding the accompanying scientific processes and engineering ideas, where "multiscale" refers to concurrent, non-trivial and coupled models over scales separated by orders of magnitude in either space, time, energy, momenta, or any other relevant parameter. Specifically, we consider problems where the data may be obtained at various resolutions; analyzing such data and constructing coupled models led to open research questions in various applications of data science. Numeric studies are reported for one of the data science techniques discussed here for illustration, namely, on approximate Bayesian computations.

Topology in Nonlinear Mechanical Systems.

Many advancements have been made in the field of topological mechanics. The majority of the work, however, concerns the topological invariant in a linear theory. In this Letter, we present a generic prescription to define topological indices that accommodates nonlinear effects in mechanical systems without taking any approximation. Invoking the tools of differential geometry, a Z-valued quantity in terms of a topological index in differential geometry known as the Poincaré-Hopf index, which features the topological invariant of nonlinear zero modes (ZMs), is predicted. We further identify one type of topologically protected solitons that are robust to disorders. Our prescription constitutes a new direction of searching for novel topologically protected nonlinear ZMs in the future.

Composition of Ultrafine Particles in Urban Beijing: Measurement Using a Thermal Desorption Chemical Ionization Mass Spectrometer.

Ultrafine particles (UFPs) dominate the particle number population in the urban atmosphere and revealing their chemical composition is important. The thermal desorption chemical ionization mass spectrometer (TDCIMS) can semicontinuously measure UFP composition at the molecular level. We modified a TDCIMS and deployed it in urban Beijing. Radioactive materials in the TDCIMS for aerosol charging and chemical ionization were replaced by soft X-ray ionizers so that it can be operated in countries with tight regulations on radioactive materials. Protonated N-methyl-2-pyrrolidone ions were used as the positive reagent ion, which selectively detects ammonia and low-molecular weight-aliphatic amines and amides vaporized from the particle phase. With superoxide as the negative reagent ion, a wide range of inorganic and organic compounds were observed, including nitrate, sulfate, aliphatic acids with carbon numbers up to 18, and highly oxygenated CHO, CHON, and CHOS compounds. The latter two can be attributed to parent ions or the decomposition products of organonitrates and organosulfates/organosulfonates, respectively. Components from both primary emissions and secondary formation of UFPs were identified. Compared to the UFPs measured at forest and marine sites, those in urban Beijing contain more nitrogen-containing and sulfur-containing compounds. These observations illustrate unique features of the UFPs in the urban environment and provide insights into their origins.

Rapid growth of organic aerosol nanoparticles over a wide tropospheric temperature range.

Nucleation and growth of aerosol particles from atmospheric vapors constitutes a major source of global cloud condensation nuclei (CCN). The fraction of newly formed particles that reaches CCN sizes is highly sensitive to particle growth rates, especially for particle sizes <10 nm, where coagulation losses to larger aerosol particles are greatest. Recent results show that some oxidation products from biogenic volatile organic compounds are major contributors to particle formation and initial growth. However, whether oxidized organics contribute to particle growth over the broad span of tropospheric temperatures remains an open question, and quantitative mass balance for organic growth has yet to be demonstrated at any temperature. Here, in experiments performed under atmospheric conditions in the Cosmics Leaving Outdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN), we show that rapid growth of organic particles occurs over the range from [Formula: see text]C to [Formula: see text]C. The lower extent of autoxidation at reduced temperatures is compensated by the decreased volatility of all oxidized molecules. This is confirmed by particle-phase composition measurements, showing enhanced uptake of relatively less oxygenated products at cold temperatures. We can reproduce the measured growth rates using an aerosol growth model based entirely on the experimentally measured gas-phase spectra of oxidized organic molecules obtained from two complementary mass spectrometers. We show that the growth rates are sensitive to particle curvature, explaining widespread atmospheric observations that particle growth rates increase in the single-digit-nanometer size range. Our results demonstrate that organic vapors can contribute to particle growth over a wide range of tropospheric temperatures from molecular cluster sizes onward.

C-H Arylation in the Formation of a Complex Pyrrolopyridine, the Commercial Synthesis of the Potent JAK2 Inhibitor, BMS-911543.

The development of an improved short and efficient commercial synthesis of the JAK2 inhibitor, a complex pyrrolopyridine, BMS-911543, is described. During the discovery and development of this synthesis, a Pd-catalyzed C-H functionalization was invented which enabled the rapid union of the key pyrrole and imidazole fragments. The synthesis of this complex, nitrogen-rich heterocycle was accomplished in only six steps (longest linear sequence) from readily available materials.

Molecular-Level Understanding of Synergistic Effects in Sulfuric Acid-Amine-Ammonia Mixed Clusters.

The abundance and basicity of a stabilizing base have shown to be key factors in sulfuric acid driven atmospheric new-particle formation. However, since experiments indicate that a low concentration of ammonia enhances particle formation from sulfuric acid and dimethylamine, which is a stronger base, there must be additional factors affecting the particle formation efficiency. Using quantum chemistry, we provide a molecular-level explanation for the synergistic effects in sulfuric acid-dimethylamine-ammonia cluster formation. Because of the capability of ammonia to form more intermolecular interactions than dimethylamine, it can act as a bridge-former in sulfuric acid-dimethylamine clusters. In many cluster compositions, ammonia is more likely to be protonated than dimethylamine, although it is a weaker base. By nanoparticle formation rate simulations, we show that due to the synergistic effects, ammonia can increase the particle formation rate by up to 5 orders of magnitude compared to the two-component sulfuric acid-amine system.

Multilevel Analysis of Child and Adolescent Subjective Well-Being Across 14 Countries: Child- and Country-Level Predictors.

This study tests an ecological, relationship-based model of children's subjective well-being with 9- to 14-year-old children (n = 25,906) from 14 countries across Africa, Asia, Europe, North America, and South America. Children completed the Children's Worlds survey, a self-report measure of contextual and well-being indicators. Multilevel modeling was used to predict children's well-being (life satisfaction and self-image) at two levels, child (age, gender, home context, family relationships, peer relationships, school context, teacher relationships, and neighborhood quality), and country (gross domestic product and income inequality). Findings indicated that intercepts varied significantly across countries. The majority of variance in children's well-being was attributed to child-level rather than country-level factors. Country-level factors did not strongly predict well-being but marginally improved model fit.

Commensurate 4a0-period charge density modulations throughout the Bi2Sr2CaCu2O8+x pseudogap regime.

Theories based upon strong real space (r-space) electron-electron interactions have long predicted that unidirectional charge density modulations (CDMs) with four-unit-cell (4a0) periodicity should occur in the hole-doped cuprate Mott insulator (MI). Experimentally, however, increasing the hole density p is reported to cause the conventionally defined wavevector QA of the CDM to evolve continuously as if driven primarily by momentum-space (k-space) effects. Here we introduce phase-resolved electronic structure visualization for determination of the cuprate CDM wavevector. Remarkably, this technique reveals a virtually doping-independent locking of the local CDM wavevector at [Formula: see text] throughout the underdoped phase diagram of the canonical cuprate Bi2Sr2CaCu2O8 These observations have significant fundamental consequences because they are orthogonal to a k-space (Fermi-surface)-based picture of the cuprate CDMs but are consistent with strong-coupling r-space-based theories. Our findings imply that it is the latter that provides the intrinsic organizational principle for the cuprate CDM state.

Identifying risk and protective factors related to depressive symptoms among Northern Plains American Indian women cancer survivors.

Cancer is the leading cause of death among American Indian and Alaska Native (AIAN) women, and depressive symptoms have been linked to higher mortality, but research on depressive symptoms among AIAN cancer patients has been scant. The purpose of this exploratory study was, using the Framework of Historical Oppression, Resilience, and Transcendence, to examine risk and protective factors related to depressive symptoms in American Indian (AI) women cancer survivors. We examined the relationships of adverse childhood experiences (ACE), perceived health status, resilience, and social support with depressive symptoms in Northern Plains AI women cancer survivors. We used a cross-sectional design with purposive sampling of 73 female cancer survivors (aged 18 years or older) between June 2014 and February 2015. Hierarchical multiple regression was used to test three sets of variables in relation to depressive symptoms: (1) sociodemographics, (2) risk factors (ACE and perceived health), and (3) protective factors (psychological resilience and social support). Approximately 47 percent of participants had probable depressive symptoms. Depressive symptoms were inversely associated with perceived health, psychological resilience, and social support. These results support bolstering existing social support among AI cancer patients and survivors as well as prevention and intervention efforts that strengthen resilience.

Quantum Spin Liquid Intertwining Nematic and Superconducting Order in Fese.

Despite its seemingly simple composition and structure, the pairing mechanism of FeSe remains an open problem due to several striking phenomena. Among them are nematic order without magnetic order, nodeless gap and unusual inelastic neutron spectra with a broad continuum, and gap anisotropy consistent with orbital selection of unknown origin. Here we propose a microscopic description of a nematic quantum spin liquid that reproduces key features of neutron spectra. We then study how the spin fluctuations of the local moments lead to pairing within a spin-fermion model. We find the resulting superconducting order parameter to be nodeless s±d wave within each domain. Further we show that orbital dependent Kondo-like coupling can readily capture observed gap anisotropy. Our prediction calls for inelastic neutron scattering in a detwinned sample.

Coherent Superconductivity with a Large Gap Ratio from Incoherent Metals.

A mysterious incoherent metallic (IM) normal state with T-linear resistivity is ubiquitous among strongly correlated superconductors. Recent progress with microscopic models exhibiting IM transport has presented the opportunity for us to study new models that exhibit direct transitions into a superconducting state out of IM states within the framework of connected Sachdev-Ye-Kitaev "quantum dots." Here, local Sachdev-Ye-Kitaev interactions within a dot produce IM transport in the normal state, while local attractive interactions drive superconductivity. Through explicit calculations, we find two features of superconductivity arising from an IM normal state. First, despite the absence of quasiparticles in the normal state, the superconducting state still exhibits coherent superfluid transport. Second, the nonquasiparticle nature of the IM Green's functions produces a large enhancement in the ratio of the zero-temperature superconducting gap Δ and transition temperature T_{SC}, 2Δ/T_{SC}, with respect to its BCS value of 3.53.

Topology and Geometry of Spin Origami.

Kagome antiferromagnets are known to be highly frustrated and degenerate when they possess simple, isotropic interactions. We consider the entire class of these magnets when their interactions are spatially anisotropic. We do so by identifying a certain class of systems whose degenerate ground states can be mapped onto the folding motions of a generalized "spin origami" two-dimensional mechanical sheet. Some such anisotropic spin systems, including Cs_{2}ZrCu_{3}F_{12}, map onto flat origami sheets, possessing extensive degeneracy similar to isotropic systems. Others, such as Cs_{2}CeCu_{3}F_{12}, can be mapped onto sheets with nonzero Gaussian curvature, leading to more mechanically stable corrugated surfaces. Remarkably, even such distortions do not always lift the entire degeneracy, instead permitting a large but subextensive space of zero-energy modes. We show that for Cs_{2}CeCu_{3}F_{12}, due to an additional point group symmetry associated with the structure, these modes are "Dirac" line nodes with a double degeneracy protected by a topological invariant. The existence of mechanical analogs thus serves to identify and explicate the robust degeneracy of the spin systems.

Direct phase-sensitive identification of a d-form factor density wave in underdoped cuprates.

The identity of the fundamental broken symmetry (if any) in the underdoped cuprates is unresolved. However, evidence has been accumulating that this state may be an unconventional density wave. Here we carry out site-specific measurements within each CuO2 unit cell, segregating the results into three separate electronic structure images containing only the Cu sites [Cu(r)] and only the x/y axis O sites [Ox(r) and O(y)(r)]. Phase-resolved Fourier analysis reveals directly that the modulations in the O(x)(r) and O(y)(r) sublattice images consistently exhibit a relative phase of π. We confirm this discovery on two highly distinct cuprate compounds, ruling out tunnel matrix-element and materials-specific systematics. These observations demonstrate by direct sublattice phase-resolved visualization that the density wave found in underdoped cuprates consists of modulations of the intraunit-cell states that exhibit a predominantly d-symmetry form factor.

Risk and protective factors for depressive symptoms among American Indian older adults: adverse childhood experiences and social support.

OBJECTIVES: Despite efforts to promote health equity, many American Indian and Alaska Native (AI/AN) populations, including older adults, experience elevated levels of depression. Although adverse childhood experiences (ACE) and social support are well-documented risk and protective factors for depression in the general population, little is known about AI/AN populations, especially older adults. The purpose of this study was to examine factors related to depression among a sample of AI older adults in the midwest. METHOD: Data were collected using a self-administered survey completed by 233 AIs over the age of 50. The survey included standardized measures such as the Geriatric Depression Scale-Short Form, ACE Questionnaire, and the Multidimensional Scale of Perceived Social Support. Hierarchical multivariate regression analyses were conducted to evaluate the main hypotheses of the study. RESULTS: Two dimensions of ACE (i.e., childhood neglect, household dysfunction) were positively associated with depressive symptoms; social support was negatively associated with depressive symptoms. Perceived health and living alone were also significant predictors. CONCLUSION: ACE may play a significant role in depression among AI/AN across the life course and into old age. Social support offers a promising mechanism to bolster resilience among AI/AN older adults.

The effect of additives on the zinc carbenoid-mediated cyclopropanation of a dihydropyrrole.

The synthesis of a key intermediate in the preparation of oral antidiabetic drug Saxagliptin is discussed with an emphasis on the challenges posed by the cyclopropanation of a dihydropyrrole. Kinetic studies on the cyclopropanation show an induction period that is consistent with a change in the structure of the carbenoid reagent during the course of the reaction. This mechanistic transition is associated with an underlying Schlenk equilibrium that favors the formation of monoalkylzinc carbenoid IZnCH2I relative to dialkylzinc carbenoid Zn(CH2I)2, which is responsible for the initiation of the cyclopropanation. The factors influencing reaction rates and diastereoselectivities are discussed with the aid of DFT computational studies. The rate accelerations observed in the presence of Brønsted acid-type additives correlate with the minimization of the undesired induction period and offer insights for the development of a robust process.

Secondary organic aerosol formation and organic nitrate yield from NO3 oxidation of biogenic hydrocarbons.

The secondary organic aerosol (SOA) mass yields from NO3 oxidation of a series of biogenic volatile organic compounds (BVOCs), consisting of five monoterpenes and one sesquiterpene (α-pinene, ß-pinene, Δ-3-carene, limonene, sabinene, and ß-caryophyllene), were investigated in a series of continuous flow experiments in a 10 m(3) indoor Teflon chamber. By making in situ measurements of the nitrate radical and employing a kinetics box model, we generate time-dependent yield curves as a function of reacted BVOC. SOA yields varied dramatically among the different BVOCs, from zero for α-pinene to 38-65% for Δ-3-carene and 86% for ß-caryophyllene at mass loading of 10 µg m(-3), suggesting that model mechanisms that treat all NO3 + monoterpene reactions equally will lead to errors in predicted SOA depending on each location's mix of BVOC emissions. In most cases, organonitrate is a dominant component of the aerosol produced, but in the case of α-pinene, little organonitrate and no aerosol is formed.