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At least 361 records · Page 20

Volcanism, global catastrophe and mass mortality

The effects of very large volcanic eruptions are well documented in many studies, mostly based on observations made on three historic eruptions, Laki 1783; Tambora 1815 and Krakatau 1883. Such eruptions have effects that are catastrophic locally and measurable globally, but it is not clear that even the largest volcanic eruptions have had global catastrophic effects, nor caused mass extinctions. Two different types of volcanic eruption were considered as likely to have the most serious widespread effects: large silicic explosive eruptions producing hundreds or thousands of cubic kilometers of pyroclastic materials, and effusive basaltic eruptions producing of approximately 100 cubic kilometers of lava. In both cases, the global effects are climatic, and attributable to production of stratospheric aerosols. Other possibilities need to be explored. Recent research on global change has emphasized the extreme sensitivity of the links between oceanic circulation, atmospheric circulation and climate. In particular, it was argued that the pattern of ocean current circulation (which strongly influences climate) is unstable; it may rapidly flip from one pattern to a different one, with global climatic consequences. If volcanism has been a factor in global environmental change and a cause of mass extinctions, it seems most likely that it has done so by providing a trigger to other processes, for example by driving oceanic circulation from one mode to another.

Francis, P. W.↗

Weak bump quasars

Research into the optical, ultraviolet and infrared continuum emission from quasars and their host galaxies was carried out. The main results were the discovery of quasars with unusually weak infrared emission and the construction of a quantitative estimate of the dispersion in quasar continuum properties. One of the major uncertainties in the measurement of quasar continuum strength is the contribution to the continuum of the quasar host galaxy as a function of wavelength. Continuum templates were constructed for different types of host galaxy and individual estimates made of the decomposed quasar and host continua based on existing observations of the target quasars. The results are that host galaxy contamination is worse than previously suspected, and some apparent weak bump quasars are really normal quasars with strong host galaxies. However, the existence of true weak bump quasars such as PHL 909 was confirmed. The study of the link between the bump strength and other wavebands was continued by comparing with IRAS data. There is evidence that excess far infrared radiation is correlated with weaker ultraviolet bumps. This argues against an orientation effect and implies a probable link with the host galaxy environment, for instance the presence of a luminous starburst. However, the evidence still favors the idea that reddening is not important in those objects with ultraviolet weak bumps. The same work has led to the discovery of a class of infrared weak quasars. Pushing another part of the envelope of quasar continuum parameter space, the IR-weak quasars have implications for understanding the effects of reddening internal to the quasars, the reality of ultraviolet turnovers, and may allow further tests of the Phinney dust model for the IR continuum. They will also be important objects for studying the claimed IR to x-ray continuum correlation.

Wilkes, B. J.↗

Chemical Compositions and Abundance Anomalies in Stellar Coronae ADP99

We have been investigating different statistical methods for analysing the metal abundances of sources with low S/N. A Bayesian technique has been developed that determines the most probable line-to-continuum ratio in the source, thereby leading to the metallicity. This method is a promising approach with which to mine the ASCA archive. Some of this work has now been published in conference proceedings. The flavour of the project has changed very slightly in the last year owing to the increasing availability of several good quality Chandra HETG and LETG spectra for stars for which we had reduced and analysed ASCA data. The Chandra grating spectra in principle provide a means of calibrating the results from the low resolution ASCA spectra and we have started some work toward that goal. One paper concerning abundance ratios in active stars is appearing shortly in conference proceedings and is being readied for publication in a main-stream astrophysical journal. This paper demonstrates for the first time that abundance anomalies cannot be categorized simply in terms of First Ionization Potential (FIP) or inverse-FIP based effects. Different Ne enhancements are found in different star types but a link between enhancement factors and stellar properties is not obvious. The publication noted as in preparation in an earlier report, finding strong Ne enhancements in active stars, is now published. These results will again be used to "calibrate" low resolution results for which line ratio techniques cannot be employed.

Drake, Jeremy↗

Atmospheric Circulation Anomalies During Two Persistent North American Droughts: 1932-1939 and 1948-1957

We use an early twentieth century (1908-1958) atmospheric reanalysis, based on assimilation of surface and sea level pressure observations, to contrast atmospheric circulation during two periods of persistent drought in North America: 1932-1939 (the Dust Bowl) and 1948-1957. Primary forcing for both droughts is believed to come from anomalous sea surface temperatures (SSTs): a warm Atlantic and a cool eastern tropical Pacific. For boreal winter (October-March) in the 1950s, a stationary wave pattern originating from the tropical Pacific is present, with positive centers over the north Pacific and north Atlantic ocean basins and a negative center positioned over northwest North America and the tropical/subtropical Pacific. This wave train is largely absent for the 1930s drought; boreal winter height anomalies are organized much more zonally, with positive heights extending across northern North America. For boreal summer (April-September) during the 1930s, a strong upper level ridge is centered over the Great Plains; this feature is absent during the 1950s and appears to be linked to a weakening of the Great Plains low-level jet (GPLLJ). Subsidence anomalies are co-located over the centers of each drought: in the central Great Plains for the 1930s and in a band extending from the southwest to the southeastern United States for the 1950s. The location and intensity of this subsidence during the 1948-1957 drought is a typical response to a cold eastern tropical Pacific, but for 1932-1939 deviates in terms of the expected intensity, location, and spatial extent. Overall, circulation anomalies during the 1950s drought appear consistent with the expected response to the observed SST forcing. This is not the case for the 1930s, implying some other causal factor may be needed to explain the Dust Bowl drought anomalies. In addition to SST forcing, the 1930s were also characterized by massive alterations to the land surface, including regional-scale devegetation from crop failures and intensive wind erosion and dust storms. Incorporation of these land surface factors into a general circulation model greatly improves the simulation of precipitation and subsidence anomalies during this drought, relative to simulations with SST forcing alone. Even with additional forcing from the land surface, however, the model still has difficulty reproducing some of the other circulation anomalies, including weakening of the GPLLJ and strengthening of the upper level ridge during AMJJAS. This may be due to either weaknesses in the model or uncertainties in the boundary condition estimates. Still, analysis of the circulation anomalies supports the conclusion of an earlier paper (Cook et al. in Proc Natl Acad Sci 106:4997, 2009), demonstrating that land degradation factors are consistent with the anomalous nature of the Dust Bowl drought.

Cook, Benjamin↗

Designer Fluorescent Redoxmer Self‐Reports Side Reactions in Nonaqueous Redox Flow Batteries

The state of health (SOH) is a critical measure for evaluating and predicting performance of redox flow batteries (RFBs). However, diagnosing SOH of RFBs is often challenging due to the overwhelming complexity of the electrolytes and associated electrochemical reactions. Designing active molecules or redoxmers that can autonomously exhibit property changes upon specific stimuli may provide a viable way for early diagnosis of SOH. Herein, a dimerized redoxmer, DGL-N-CH 3 , was designed and synthesized by linking blue-green fluorescent monomers through a diglycolamide linker. While DGL-N-CH 3 still maintains similar electrochemical behavior and strong fluorescence, we observe a unique side reaction when cycling DGL-N-CH 3 in H-cells, which leads to a side product, NHCH 3 -BzNSN via linker cleavage. Interestingly, NHCH 3 -BzNSN also emits fluorescence but at a longer wavelength. By taking advantage of this unique fluorescent change that corresponds to the growth of NHCH 3 -BzNSN, we successfully established the capacity decay of DGL-N-CH 3 H-cell cycling, exemplifying a proof-of-concept self-reporting redoxmer design towards in situ SOH monitoring.

25 ENERGY STORAGE↗

Biogeochemical control points of connectivity between a tidal creek and its floodplain

As global climates shift, coastal systems experience changes that alter function within the tidal zone. However, it remains uncertain how changes in tidal extent and magnitude will alter coastal biogeochemical cycling. We present high-frequency data collected in-situ along two transects across a tidal creek and floodplain to capture how changes in vertical and lateral connectivity act as biogeochemical control points. Using wavelet analysis, we identified short periods of strong vertical connectivity during spring tides followed by extended periods of floodplain isolation from tides. During a drier period, neap tides were linked to lateral creek-floodplain connectivity, detected by discharge of saline, oxygen-depleted groundwater to the creek on ebb tides. We estimate up to half of creek water throughout the tidal cycle was associated with floodplain drainage. From point measurements of carbon, nitrogen, and greenhouse gases along the creek-floodplain transect, we infer that lateral connectivity functions as a biogeochemically significant control point.

54 ENVIRONMENTAL SCIENCES↗

Zr 3 Mn 3 Sn 4 Ga: A new hetero-kagome bilayer antiferromagnet

Here, we report the magnetic and electrical transport properties of single-crystalline Zr 3 Mn 3 Sn 4 Ga, featuring two distinct kagome lattices: a non-magnetic breathing Zr 3 Sn 4 lattice and a magnetic intact Mn 3 Ga lattice. The material undergoes an antiferromagnetic phase transition at T N = 87 K, with neutron diffraction confirming commensurate ordering characterized by k = (1/3,1/3,0). Transport measurements show metallic behavior, a resistivity anomaly near T N , and 12% magnetoresistance at 2 K under 9 T. Deviations from the conventional second-order power law, along with negative magnetoresistance and nonlinear Hall slope variations near T N , suggest strong magneto-electronic coupling. Resonant photoemission spectroscopy identifies Zr 4d and Mn 3d orbitals as dominant contributors to the valence band, linking the material’s unique electronic properties to its kagome layers. Zr 3 Mn 3 Sn 4 Ga offers a valuable platform to study interactions between magnetism and topological electronic bands in hetero-kagome systems using the co- existence of magnetic and non-magnetic kagome layers and its tunable electronic structure.

Crystal structure↗

Spin skyrmion gaps as signatures of strong-coupling insulators in magic-angle twisted bilayer graphene

Abstract The flat electronic bands in magic-angle twisted bilayer graphene (MATBG) host a variety of correlated insulating ground states, many of which are predicted to support charged excitations with topologically non-trivial spin and/or valley skyrmion textures. However, it has remained challenging to experimentally address their ground state order and excitations, both because some of the proposed states do not couple directly to experimental probes, and because they are highly sensitive to spatial inhomogeneities in real samples. Here, using a scanning single-electron transistor, we observe thermodynamic gaps at even integer moiré filling factors at low magnetic fields. We find evidence of a field-tuned crossover from charged spin skyrmions to bare particle-like excitations, suggesting that the underlying ground state belongs to the manifold of strong-coupling insulators. From the spatial dependence of these states and the chemical potential variation within the flat bands, we infer a link between the stability of the correlated ground states and local twist angle and strain. Our work advances the microscopic understanding of the correlated insulators in MATBG and their unconventional excitations.

36 MATERIALS SCIENCE↗

Causal machine learning uncovers conditions for convective intensification driven by organic and sulfate aerosols

Aerosols are often hypothesized to invigorate deep convective clouds (DCCs), but observational evidence remains limited and inconclusive. Clarifying this hypothesis is critical for regions vulnerable to thunderstorms and flooding, particularly highly polluted coastal cities. Leveraging a novel causal discovery–inference pipeline and high-resolution observations near Houston, TX, we identify multiple causal pathways among aerosols (mostly organic and sulfate), DCCs, and meteorological factors. However, a direct causal link from aerosols to DCCs is found to be uncommon, occurring in less than 35% of analyzed scenarios, and is characterized by strong conditionality and nonlinearity. When aerosol impacts on DCCs do occur, they can be substantial, enhancing DCC core heights by approximately 1.7 km, with 92% of this effect concentrated in warmer-phase cloud regions. Notably, the presence of sea breezes and the inclusion of all measured aerosol particles each enhance DCCs in over 95% of aerosol-sensitive cases.

54 ENVIRONMENTAL SCIENCES↗

Computing Bottleneck Structures at Scale for High-Precision Network Performance Analysis

The Theory of Bottleneck Structures is a recently-developed framework for studying the performance of data networks. It describes how local perturbations in one part of the network propagate and interact with others. This framework is a powerful analytical tool that allows network operators to make accurate predictions about network behavior and thereby optimize performance. Previous work implemented a software package for bottleneck structure analysis, but applied it only to toy examples. In this work, we introduce the first software package capable of scaling bottleneck structure analysis to production-size networks. Here, we benchmark our system using logs from ESnet, the Department of Energy's high-performance data network that connects research institutions in the U.S. Using the previously published tool as a baseline, we demonstrate that our system achieves vastly improved performance, constructing the bottleneck structure graphs in 0.21 s and calculating link derivatives in 0.09 s on average. We also study the asymptotic complexity of our core algorithms, demonstrating good scaling properties and strong agreement with theoretical bounds. These results indicate that our new software package can maintain its fast performance when applied to even larger networks. They also show that our software is efficient enough to analyze rapidly changing networks in real time. Overall, we demonstrate the feasibility of applying bottleneck structure analysis to solve practical problems in large, real-world data networks.

benchmark↗

Assessing carbon storage capacity and saturation across six central US grasslands using data–model integration

Abstract. Future global changes will impact carbon (C) fluxes and pools in most terrestrial ecosystems and the feedback of terrestrial carbon cycling to atmospheric CO2. Determining the vulnerability of C in ecosystems to future environmental change is thus vital for targeted land management and policy. The C capacity of an ecosystem is a function of its C inputs (e.g., net primary productivity – NPP) and how long C remains in the system before being respired back to the atmosphere. The proportion of C capacity currently stored by an ecosystem (i.e., its C saturation) provides information about the potential for long-term C pools to be altered by environmental and land management regimes. We estimated C capacity, C saturation, NPP, and ecosystem C residence time in six US grasslands spanning temperature and precipitation gradients by integrating high temporal resolution C pool and flux data with a process-based C model. As expected, NPP across grasslands was strongly correlated with mean annual precipitation (MAP), yet C residence time was not related to MAP or mean annual temperature (MAT). We link soil temperature, soil moisture, and inherent C turnover rates (potentially due to microbial function and tissue quality) as determinants of carbon residence time. Overall, we found that intermediates between extremes in moisture and temperature had low C saturation, indicating that C in these grasslands may trend upwards and be buffered against global change impacts. Hot and dry grasslands had greatest C saturation due to both small C inputs through NPP and high C turnover rates during soil moisture conditions favorable for microbial activity. Additionally, leaching of soil C during monsoon events may lead to C loss. C saturation was also high in tallgrass prairie due to frequent fire that reduced inputs of aboveground plant material. Accordingly, we suggest that both hot, dry ecosystems and those frequently disturbed should be subject to careful land management and policy decisions to prevent losses of C stored in these systems.

58 GEOSCIENCES↗

Preliminary analysis of WL experiment number 701: Space environment effects on operating fiber optic systems

A brief overview of the analysis performed on WL Experiment number 701 is presented, highlighting the successful operation of the first know active fiber optic links orbited in space. Four operating fiber optic links were exposed to the space environment for a period exceeding five years, situated aboard and external to the Long Duration Exposure Facility (LDEF). Despite the prolonged space exposure to radiation, wide temperature extremums, atomic oxygen interactions, and micrometeorite and debris impacts, the optical data links performed well within specification limits. Early Phillips Laboratory tests and analyses performed on the experiment and its recovered magnetic tape data strongly indicate that fiber optic application in space will have a high success rate.

Taylor, E. W.↗

Carbon Dioxide Cycling And The Climate of Ancient Earth

The continental cycle of silicate weathering and metamorphism dynamically buffers atmospheric CO2 and climate. Feedback is provided by the strong temperature dependence of silicate weathering. Here we argue that hydrothermal alteration of oceanic basalts also dynamically buffers CO2. The oceanic cycle links with the mantle via subduction and the midocean ridges. Feedback is provided by the dependence of carbonatization on dissolved carbonates in seawater. Unlike the continental cycle, the oceanic cycle has no thermostat. Currently the continental cycle is more important, but earlier in Earth's history, especially if heat flow were higher than it is now, more vigorous plate tectonics would have made the oceanic cycle dominant. We find that CO2 greenhouses thick enough to defeat the faint early sun are implausible and that, if no other greenhouse gases are invoked, very cold climates are expected for much of the Proterozoic and the Archean. We echo current fashion and favor biogenic methane as the chief supplement to CO2. Fast weathering and probable subduction of abundant impact ejecta would have reduced CO2 levels still further in the Hadean. Despite its name, the Hadean would have been the coldest era in the history of the Earth.

Zahnle, Kevin↗

Carbon Dioxide Cycling and the Climate of Ancient Earth

The continental cycle of silicate weathering and metamorphism dynamically buffers atmospheric CO2 and climate. Feedback is provided by the strong temperature dependence of silicate weathering. Here we argue that hydrothermal alteration of oceanic basalts also dynamically buffers CO2. The oceanic cycle links with the mantle via subduction and the midocean ridges. Feedback is provided by the dependence of carbonatization on dissolved carbonates in seawater. Unlike the continental cycle, the oceanic cycle has no thermostat. Currently the continental cycle is more important, but earlier in Earth's history, especially if heat flow were higher than it is now, more vigorous plate tectonics would have made the oceanic cycle dominant. We find that CO2 greenhouses thick enough to defeat the faint early Sun are implausible and that, if no other greenhouse gases are invoked, very cold climates are expected for much of the Proterozoic and the Archean. We echo current fashion and favor biogenic methane as the chief supplement to CO2. Fast weathering and probable subduction of abundant impact ejecta would have reduced CO2 levels still further in the Hadean. Despite its name, the Hadean would have been the coldest era in the history of the Earth.

Zahnle, Kevin↗

New Estimates of Ice and Oxygen Fluxes Across the Entire Lid of Lake Vostok From Observations of Englacial Radio Wave Attenuation

Over deep Antarctic subglacial lakes, spatially varying ice thickness and the pressure‐dependent melting point of ice result in distinct areas of melting and freeze‐on at the ice‐water interface, that is, at the lake lid. These ice mass fluxes drive lake circulation and, because basal Antarctic ice contains air clathrate, affect the input of oxygen to the lake, with implications for subglacial life. Inferences of rates of melting and freeze‐on, that is, accretion rates, from radar layer tracking and geodesy are limited in spatial coverage and resolution. Here we develop a new method to estimate accretion rate, and the resulting oxygen input at a lake lid, using airborne radar data over Lake Vostok together with ice‐temperature and chemistry data from the Vostok ice core. Because the lake lid is a coherent reflector of known reflectivity (at our radar frequency), we can infer depth‐averaged radio wave attenuation in the ice, with a spatial resolution of ~1 km along flight lines. Spatial variation in attenuation depends mostly on variation in ice temperature near the lid, which in turn varies strongly with ice mass flux at the lid. We model ice temperature versus depth with ice mass flux as a parameter, thus linking that flux to observed depth‐averaged attenuation. The resulting map of melt and accretion rates independently reproduces features known from earlier studies but now covers the entire lid. We find that freeze‐on is dominant when integrated over the lid, with an ice imbalance of 0.05 to 0.07 cu.km/year, which is robust against uncertainties.

Dale P. Winebrenner↗

A Cross‐Linked Flexible Metaferroelectrolyte Regulated by 2D/2D Perovskite Heterostructures for High‐Performance Compact Solid‐State Sodium Batteries

Abstract To address the issues of limited ionic conductivity and poor interface stability at room and low temperatures in solid‐state electrolytes, a robust intrinsic ferroelectrolyte or nanoferroelectrolyte strategy for engineering solid‐state flexible ferroelectric composite electrolytes utilizing strongly coupled intrinsic ion conducting 2D/2D sodium‐rich anti‐perovskite (NaRAP)/ferroelectric perovskite heterostructures is introduced. Herein, highly scalable PVDF‐based metaferroelectrolytes with Na 2.99 Ba 0.005 OCl/Ca 2 Na 2 Nb 5 O 16 − (CNNO − ) nanosheets into a ferroelectric poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) matrix, through an in situ cross‐linking and spontaneous bridging method, for compact solid‐state sodium batteries (SSBs), are reported. Benefiting from unique well‐dispersed 3D ferroelectric coupled network and the Na 2.99 Ba 0.005 OCl/CNNO − ‐induced PVDF‐HFP ferroelectric β phase, the Na + flux is regulated, thereby inhibiting Na dendrite growth at the interface. Notably, the optimized PH‐5% NC metaferroelectrolyte exhibits rapid ion transport (1.11 × 10 −4 S cm −1 at 25 °C), a wide electrochemical window (> 4.8V), superior conformal mechanical compatibility, improved flexibility, good elasticity and flame retardancy. The solid‐state Na 3 V 2 (PO 4 ) 3 /PH‐5% NC/Na batteries present a stable cycling performance (remaining 56.4 mAh g −1 after 500 cycles at 1 C) even at 0 °C, potential for cost‐effective, safe, stable and compact SSB energy storage over 600 Wh L −1 , vastly surpassing 365 Wh L −1 of the current commercial sodium‐ion liquid‐electrolyte batteries.

Chemistry↗

Understanding why poly(acrylic acid) works: decarbonylation and cross-linking provide an ionically conductive passivation layer in silicon anodes

Poly(acrylic acid) (PAA) is commonly used as a binder for fabricating silicon (Si) anode active materials in lithium-ion batteries due to its useful properties including high polar solvent solubility, good rheology, and strong adhesive properties. However, the role and evolution of PAA during electrode fabrication, cycling, and calendar aging are not well understood. In this work, we reveal the evolution of PAA during electrode curing and relate its chemical change to the final electrode properties and performance. These studies are made possible using two types of in situ attenuated total reflectance-infrared Fourier transform (ATR-FTIR) spectroscopy: thermal ATR-FTIR to probe the cross-linking reaction, and ATR-FTIR spectroelectrochemistry of three-dimensional composite electrodes, a unique technique developed herein that probes the solvation dynamics of lithium ions at the silicon anode interface under electrochemical polarization. Specifically, we show that PAA undergoes a thermally-mediated, cross-linking decarbonylation reaction to form an ether-based network polymer. To show the importance of the polyether moieties, we synthesize partially esterified PAA analogues that do not undergo this cross-linking decarbonylation reaction and correlate the degree of cross-linking to half-cell performance metrics. Finally, we unveil the mechanism of the polyether binder performance through in situ ATR-FTIR spectroelectrochemistry and show that PAA acts as an interfacial material that conducts lithium-ions, limits solvent molecule access to the Si surface, and stabilizes the electrode against parasitic lithium inventory loss at high state of charge for an extended period of time.

25 ENERGY STORAGE↗

Carbamoylation as an Effective Tool in the Analysis of the Soman Nerve Agent Marker Pinacolyl Alcohol in Soil Matrices by EI-GC-MS and LC-HRMS

Pinacolyl alcohol (PA) is a Schedule 2 chemical commonly featured in most proficiency tests (PTs) administered by the Organisation for the Prohibition of Chemical Weapons (OPCW) due to its direct as well as forensic link to the nerve agent Soman. Therefore, its detection by Chemical Weapons Convention (CWC) inspection teams during on-site investigations is a strong indicator of the past or latent presence of Soman in the environment. Its small molecular weight (102), early elution time, and poor ionization profile make PA a challenging analyte to detect particularly at low concentrations (∼1–10 μg/g). In this work, 1,1′-carbonyldimidazole (CDI) has been used to effectively modify PA for the first time in two different soil matrices (Virginia type A soil and silt sediment) at two separate concentrations (1 and 10 μg/g) for its subsequent detection by EI-GC-MS and LC-HRMS methods. For the EI-GC-MS analysis, the PA carbamate derivative (PIC) exhibits improved chromatography relative to PA such as improved peak shape, increased molecular weight (196 for PIC and 102 for PA) and increased retention time (16.9 min for PIC and ∼4.1 min for PA). In addition, the derivatization also improves the detection of PA by LC-HRMS as the PIC product possesses protonation sites (i.e., imidazole ring) relative to none exhibited by PA. More importantly, the carbamoylation proceeds under mild conditions (55 °C, no base) and rapidly (3 h), characteristics that make it an appealing protocol for the analysis of PA during OPCW PTs or real case scenarios particularly in instances where it is present at low concentrations. It is anticipated that the protocol can be applied to the forensic analysis of this important Soman marker in various environmental matrices.

Chemistry↗