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At least 361 records · Page 20

Enhanced Manganese Oxidation at the Biofilm–Fluid Interface Drives Pore-Scale Patterns in Mineral Precipitation

Microbial oxidation of manganese (Mn) from aqueous Mn(II) to solid-phase Mn(III, IV) minerals catalyzes Mn(II) removal in natural and engineered porous systems. However, little is known about the spatiotemporal evolution of Mn biomineralization in confined spaces that experience simultaneous Mn(II) delivery and Mn oxide precipitation. Here, we combine time-lapse microscopy, image analysis, and mass spectrometry to quantify the extent and rate of Mn biomineralization by Pseudomonas putida GB-1 in an optically transparent two-dimensional porous medium. We found that Mn(II) oxidation initially occurred within biofilms but shifted over time toward the edges of biofilms in contact with pore fluid. Minerals precipitated outside of the initial biofilm footprint likely due to surface-mediated oxidation of Mn(II) by nascent biogenic Mn oxides, reinforcing a gradient in mineral accumulation from the Mn(II) source near the reactor inlet to the outlet. The rate of mineral precipitation outside the biofilm footprint surpassed the rate of mineral accumulation inside biofilms within 6 h and accounted for two-thirds of the total Mn oxide mass in the pore space at the end of the experiment. This work advances a mechanistic understanding of coupled biotic and abiotic Mn oxidation in porous environments while providing a novel platform to quantify microbe-mineral-fluid interactions.

Biofilms↗

The Value of Reversible Carbon Storage in a Zero-Emissions World

Atmospheric carbon dioxide removal (CDR) is required to stabilize global temperature. CDR can be achieved via ecosystem-based approaches that are cost-effective but reversible (e.g., soil and forest management) or by more durable but expensive approaches (e.g., direct air capture coupled with geologic storage). Here, we examine trade-offs between these approaches, focusing on timing, climate impacts, and cost. We simulated reversible carbon accrual for a range of CDR contract structures using a general minimalist model of ecosystem carbon cycling, and parameterized it to simulate US agricultural soil management─specifically cover cropping─as a case study. We then quantified the resulting impact on atmospheric carbon and global temperature using a climate model emulator. We find that maintaining a patchwork of reversible CDR projects by replacing lapsed projects with new projects can reduce warming by 22–195 μ°C in 2100 and that the magnitude of this cooling effect depends on how effectively the patchwork is maintained. Long-term maintenance of reversible CDR projects requires institutional stability that cannot be guaranteed over multiple decades. Consequently, effective CDR ultimately requires replacing reversible projects with durable projects. To address this problem, we modeled the cost of replacing reversible agricultural soil CDR with geologic CDR. We found that using reversible CDR as a bridge to durable CDR is potentially more cost-effective as a global cooling strategy (0.20–0.81 billion USD per μ°C avoided) than perpetual maintenance of reversible CDR (0.32–1.31 billion USD per μ°C avoided) or an immediate transition to durable CDR (1.37–2.19 billion USD per μ°C avoided). However, we emphasize that institutional commitments to maintain reversible CDR projects cannot be guaranteed. Reliance on reversible CDR as a bridge to durable CDR therefore carries an unknown amount of risk and will only function if efforts to maintain reversible CDR are robust.

carbon capture and storage↗

Methanol Decomposition on Copper Surfaces under Ambient Conditions: Mechanism, Surface Kinetics, and Structure Sensitivity

Here, we study the adsorption of methanol vapor under ambient pressure and temperature conditions on low-index Cu surfaces using surface-sensitive infrared (IR) and X-ray spectroscopy techniques. The first step of methanol decomposition, i.e. , breaking of the O—H bond to form surface-bound methoxy, readily occurs under ambient conditions. Time-lapse IR spectra clearly indicate a gradually decreasing methoxy coverage, which does not obey well established kinetic models. We rationalize the initial temperature-independent, high, nonequilibrium coverage of methoxy by a H-bonded methanol assembly in the precursor state. A temperature-dependent equilibrium coverage is achieved as the excess methoxy is eliminated gradually via further dehydrogenation to CO that desorbs to the gas phase. The kinetics of this process displays a significant structure sensitivity with considerably faster kinetics on the Cu(110) surface compared to Cu(111) and Cu(100) surfaces.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Immunotargeting of Nanocrystals by SpyCatcher Conjugation of Engineered Antibodies

Inorganic nanocrystals such as quantum dots (QDs) and upconverting nanoparticles (UCNPs) are uniquely suited for quantitative live-cell imaging and are typically functionalized with ligands to study specific receptors or cellular targets. Antibodies (Ab) are among the most useful targeting reagents owing to their high affinities and specificities, but common nanocrystal labeling methods may orient Ab incorrectly, be reversible or denaturing, or lead to Ab-NP complexes too large for some applications. Here, we report that SpyCatcher proteins, which bind and spontaneously form covalent isopeptide bonds with cognate SpyTag peptides, can conjugate engineered Ab to nanoparticle surfaces with control over stability, orientation, and stoichiometry. Compact SpyCatcher-functionalized QDs and UCNPs may be labeled with short-chain variable fragment Ab (scFv) engineered to bind urokinase-type plasminogen activator receptors (uPAR) that are overexpressed in many human cancers. Confocal imaging of anti-uPAR scFv-QD conjugates shows the antibody mediates specific binding and internalization by breast cancer cells expressing uPAR. Time-lapse imaging of photostable scFv-UCNP conjugates shows that Ab binding causes uPAR internalization with a ~20 min half-life on the cell surface, and uPAR is internalized to endolysosomal compartments distinct from general membrane stains and without significant recycling to the cell surface. The controlled and stable conjugation of engineered Ab to NPs enables targeting of diverse receptors for live-cell study of their distribution, trafficking, and physiology.

60 APPLIED LIFE SCIENCES↗

Facile synthesis of silver nanocubes with sharp corners and edges in an aqueous solution

It remains a challenge to synthesize Ag nanocubes in an aqueous system, although the polyol process was successfully adopted more than one decade ago. Here, we report an aqueous method for the synthesis of Ag nanocubes with an average edge length of 35–95 nm. It involves the formation of AgCl octahedra by mixing CF 3 COOAg with cetyltrimethylammonium chloride, followed by the nucleation and growth of Ag nanocrystals in the presence of ascorbic acid (AA) and FeCl 3 . The Fe 3+ /Fe 2+ redox pair is responsible for the removal of multiply twinned seeds through oxidative etching. Here, the Cl – ions play two critical roles in the nucleation and growth of Ag nanocubes with a single-crystal structure. First, the Cl – ions react with Ag + ions to generate nanometer-sized AgCl octahedra in the initial stage of a synthesis. In the presence of room light and a proper reducing agent such as AA, the AgCl can be reduced to generate Ag n nuclei followed by their evolution into single-crystal seeds and then Ag nanocrystals. Second, the Cl – ions can act as a specific capping agent toward the Ag(100) surface, enabling the formation of Ag nanocubes with sharp corners and edges. Based on the results from a set of time-lapse studies and control experiments, we formulate a plausible mechanism to account for the formation of Ag nanocubes that resembles the formation and development of latent image centers in silver halide grains in the photographic process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Development of Lipid-Coated Semiconductor Nanosensors for Recording of Membrane Potential in Neurons

In the past decade, optical imaging methods have significantly improved our understanding of the information processing principles in the brain. Although many promising tools have been designed, sensors of membrane potential are lagging behind the rest. Semiconductor nanoparticles are an attractive alternative to classical voltage indicators, such as voltage-sensitive dyes and proteins. Such nanoparticles exhibit high sensitivity to external electric fields via the quantum-confine Stark effect. Here we report the development of semiconductor voltage-sensitive nanorods (vsNRs) that self-insert into the neuronal membrane. To facilitate interaction of the nanorods with the membrane, we functionalized their surface with the lipid mixture derived from brain extract. We describe a workflow to detect and process the photoluminescent signal of vsNRs after widefield time-lapse recordings. We also present data indicating that vsNRs are feasible for sensing membrane potential in neurons at a single-particle level. This shows the potential of vsNRs for the detection of neuronal activity with unprecedentedly high spatial and temporal resolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Non-stoichiometry Governs the Pathway from Amorphous to Crystalline Calcium Carbonate

The controlled crystallization of calcium carbonate underlies the elaborate architectures of marine corals, the design of biomimetic materials, and the global carbon cycle. Despite its ubiquity, the chemical mechanisms that govern the crystallization of calcium carbonate from its amorphous precursor, amorphous calcium carbonate (ACC), remain elusive, largely due to the difficulty in resolving the structure and chemistry of this transient amorphous state. Here, we use time-lapse photography, image analysis, spatially resolved pH determination, in situ synchrotron pair distribution function (PDF) analysis, and dynamic nuclear polarization (DNP) solid-state nuclear magnetic resonance (NMR) spectroscopy to reveal pervasive compositional variability in ACC that underpins its metastability and crystallization. By evaluating the kinetics of the amorphous-to-crystalline transition across different solution chemistries, we demonstrate that ACC is non-stoichiometric and CO 3 -deficient. Counterions from the precursor (e.g., NO 3 - from Ca(NO 3 ) 2 ) substitute into the ACC network, displacing CO 3 ions and mediating both ACC stability and transformation. Crystallization proceeds through refinement of the stoichiometry toward CaCO 3 and uptake of free CO 3 2- anions. Furthermore, these findings are consistent across a wide range of concentrations and different carbonate sources, explaining the diverse behaviors observed for ACC and providing a chemical framework for controlling calcium carbonate crystallization.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Long Range Chiral Imprinting of Cu(110) by Tartaric Acid

Restructuring of metals by chiral molecules represents an important route to inducing and controlling enantioselective surface chemistry. Tartaric acid adsorption on Cu(110) has served as a useful system for understanding many aspects of chiral molecule adsorption and ordering on a metal surface, and a number of chiral and achiral unit cells have been reported. Herein, we show that given the appropriate annealing treatment, singly deprotonated tartaric acid monolayers can restructure the Cu metal itself, and that the resulting structure is both highly ordered and chiral. Molecular resolution scanning tunneling microscopy reveals that singly deprotonated tartaric acid extracts Cu atoms from the Cu(110) surface layer and incorporates them into highly ordered, chiral adatom arrays capped by a continuous molecular layer. Further evidence for surface restructuring comes from images of atom-deep trenches formed in the Cu(110) surface during the process. These trenches also run in low symmetry directions and are themselves chiral. Simulated scanning tunneling microscopy images are consistent with the appearance of the added atom rows and etched trenches. The chiral imprinting results in a long-range, highly ordered unit cell covering the whole surface as confirmed by low energy electron diffraction. Details of the restructuring mechanism were further investigated via time-lapse imaging at elevated temperature. This work reveals the stages of nanoscale surface restructuring and offers an interesting method for chiral modification of an achiral metal surface.

36 MATERIALS SCIENCE↗

Statistical Classification of Self-Organized Snow Surfaces

Wind-swept snow self-organizes into bedforms. These bedforms affect local and global energy fluxes but have not been incorporated into Earth system models because the conditions governing their development are not well understood. To address this difficulty, we created statistical classifiers, drawn from 736 hr of time-lapse footage in the Colorado Front Range, that predict bedform presence as a function of wind speed and time since snowfall. These classifiers provide the first quantitative predictions of bedform and sastrugi presence in varying weather conditions. We find that the likelihood that a snow surface is covered by bedforms increases with time since snowfall and with wind speed and that the likelihood that a surface is covered by sastrugi increases with time and with the highest wind speeds. Our observations will be useful to Earth system modelers and represent a new step toward understanding self-organized processes that ornament 8% of the surface of the planet.

54 ENVIRONMENTAL SCIENCES↗

How Asymmetries Between Arctic and Antarctic Climate Sensitivity Are Modified by the Ocean

Abstract We investigate how the ocean response to CO 2 forcing affects hemispheric asymmetries in polar climate sensitivity. Intermodel comparison of Phase 5 of the Coupled Model Intercomparison Project CO 2 quadrupling experiments shows that even in models where hemispheric ocean heat uptake differences are small, Arctic warming still exceeds Antarctic warming. The polar climate impact of this evolving ocean response to CO 2 forcing is then isolated using slab ocean experiments in a state‐of‐the‐art climate model. Overall, feedbacks over the Southern Hemisphere more effectively dissipate top‐of‐atmosphere anomalies than those over the Northern Hemisphere. Furthermore, a poleward shift in ocean heat convergence in both hemispheres amplifies destabilizing ice albedo and lapse rate feedbacks over the Arctic much more so than over the Antarctic. These results suggest that the Arctic is intrinsically more sensitive to both CO 2 and oceanic forcings than the Antarctic and that ocean‐driven climate sensitivity asymmetry arises from feedback destabilization over the Arctic rather than feedback stabilization over the Antarctic.

54 ENVIRONMENTAL SCIENCES↗

Characteristics of Optically Thin Coastal Florida Cumuli Derived From Surface-Based Lidar Measurements

The optical depths and sizes of optically thin passive shallow cumuli are characterized with a micropulse lidar. The measurements are from a coastal south Florida location spanning a 10-week synoptically suppressed winter time period with almost no upper-level clouds present. Clouds are distinguished from aerosol through visual comparison to zenith-viewing time-lapse camera images, establishing an instrument-specific particle backscatter coefficient threshold. Sun photometers provide a continuous independent aerosol optical depth estimate applied within the lidar retrieval of cloud optical depth. The focus is on clouds that do not attenuate the lidar signal. Clouds with optical depths less than one constitute more than 13% of the sampled data set, with decreasing optical depths occurring more frequently. Most of the clouds are less than 60 m thick and are located below 1 km. The optically thin regions occur most frequently in individual 15-s samples, corresponding to a horizontal width of less than 100 m, with occasional stratiform segments extending up to 2 km. Many segments border optically thicker regions, but some are self-contained, reflecting small-scale humidity variations near-saturation. To our knowledge, this study is the first to apply micropulse lidar data toward characterizing these low, shallow, broken clouds, too small for robust characterization from space but whose ubiquitiousness renders them radiatively important.

54 ENVIRONMENTAL SCIENCES↗

Mechanisms Behind the Extratropical Stratiform Low-Cloud Optical Depth Response to Temperature in ARM Site Observations

Ground-based observations from three middle- and high-latitude sites managed by the U.S. Department of Energy's Atmospheric Radiation Measurement (ARM) program are used to determine the sensitivity of the low-cloud optical depth to temperature and to test whether observations support mechanisms previously proposed to affect the optical depth feedback. Analysis of cloud optical depth retrievals support previous satellite findings that the optical depth decreases or stays constant with increases in temperature when the cloud is warm but increases when the cloud is cold. The cloud liquid water path sensitivity to warming largely explains the optical depth sensitivity at all sites.Mechanisms examined in this study involve the temperature dependence of (a) the moist-adiabatic lapse rate, (b) cloud phase partitioning, (c) drying efficiency of cloud top mixing, (d) cloud top inversion strength,and (e) boundary layer decoupling. Mechanism (a) is present across all clouds and explains 30% to 50%of the increase in liquid water path with warming at temperatures below 0°C. However, the cloud's adiabaticity, the ratio between the liquid water path and its theoretical maximum, is at least as important and determines how the liquid water path sensitivity to temperature varies with temperature. At temperatures below 0°C, the adiabaticity increases with warming, and the data support mechanism (b).At warmer temperatures, the adiabaticity decreases with warming, overwhelming mechanism (a) and resulting in the liquid water path decreasing with warming. This adiabaticity decrease arises primarily because of mechanism (d), and to a lesser degree because of mechanism (e). No evidence is found supporting mechanism (c)

54 ENVIRONMENTAL SCIENCES↗

Geophysical Monitoring of Moisture-Induced Landslides: A Review

Geophysical monitoring of landslides can provide insights into spatial and temporal variations of subsurface properties associated with slope failure. Recent improvements in equipment, data analysis, and field operations have led to a significant increase in the use of such techniques in monitoring. Geophysical methods complement intrusive approaches, which sample only a very small proportion of the subsurface, and walk-over or remotely sensed data, which principally provide information only at the ground surface. In particular, recent studies show that advances in geophysical instrumentation, data processing, modeling, and interpretation in the context of landslide monitoring are significantly improving the characterization of hillslope hydrology and soil and rock hydrology and strength and their dynamics over time. This review appraises the state of the art of geophysical monitoring, as applied to moisture-induced landslides. Here we focus on technical and practical uses of time-lapse methods in geophysics applied to monitoring moisture-induced landslide. The case studies identified in this review show that several geophysical techniques are currently used in the monitoring of subsurface landslide processes. These geophysical contributions to monitoring and predicting the evolution of landslide processes are currently underrealized. Hence, the further integration of multiple-parametric and geotechnically coupled geophysical monitoring systems has considerable potential. The complementary nature of certain methods to map the distribution of subsurface moisture and elastic moduli will greatly increase the predictive and monitoring capacity of early warning systems in moisture-induced landslide settings.

58 GEOSCIENCES↗

Authigenic Mineral Texture in Submarine 1979 Basalt Drill Core, Surtsey Volcano, Iceland

Micrometer-scale maps of authigenic microstructures in submarine basaltic tuff from a 1979 Surtsey volcano, Iceland, drill core acquired 15 years after eruptions terminated describe the initial alteration of oceanic basalt in a low-temperature hydrothermal system. An integrative investigative approach uses synchrotron source X-ray microdiffraction, microfluoresence, micro-computed tomography, and scanning transmission electron microscopy coupled with Raman spectroscopy to create finely resolved spatial frameworks that record a continuum of alteration in glass and olivine. Microanalytical maps of vesicular and fractured lapilli in specimens from 157.1-, 137.9-, and 102.6-m depths and borehole temperatures of 83, 93.9, and 141.3 °C measured in 1980, respectively, describe the production of nanocrystalline clay mineral, zeolites, and Al-tobermorite in diverse microenvironments. Irregular alteration fronts at 157.1-m depth resemble microchannels associated with biological activity in older basalts. By contrast, linear microstructures with little resemblance to previously described alteration features have nanocrystalline clay mineral (nontronite) and zeolite (amicite) texture. The crystallographic preferred orientation rotates around an axis parallel to the linear feature. Raman spectra indicating degraded and poorly ordered carbonaceous matter of possible biological origin are associated with nanocrystalline clay mineral in a crystallographically oriented linear microstructure in altered olivine at 102.6 m and with subcircular nanoscale cavities in altered glass at 137.9-m depth. Although evidence for biotic processes is inconclusive, the integrated analyses describe the complex organization of previously unrecognized mineral texture in very young basalt. In conclusion, they provide a foundational mineralogical reference for longitudinal, time-lapse characterizations of palagonitized basalt in oceanic environments.

58 GEOSCIENCES↗

Modeling Frequency–Independent Q Viscoacoustic Wave Propagation in Heterogeneous Media

Quantifying the attenuation of seismic waves propagating in the Earth interior is critical to study the subsurface structure. Previous studies have proposed fractional anelastic wave equations to model the frequency–independent Q seismic wave propagation. Such wave equations involve fractional derivatives that pose computational challenges for the numerical schemes in terms of accuracy and efficiency when dealing with heterogeneous Earth media. To tackle these challenges, here we derive a new viscoacoustic wave equation, where the power terms of the fractional Laplacian operators are spatially independent, thus accurate and efficient methods (e.g., the Fourier pseudospectral method) can be adopted. Our derivation enables the resultant equation to capture both amplitude and phase signatures of the anelastic wave propagation by matching the complex wave numbers for all the frequencies of interest. We verify the derivation by comparing the dispersion curves of both the attenuation factor and the phase velocity produced by the new wave equation with their theoretical values as well as the Pierre Shale in situ measurements. Following that, we use a synthetic attenuating gas chimney model to demonstrate the attenuation effects on seismic waveforms and then construct the Q–compensated reverse time migration to undo these effects for seismic image enhancement. Finally, we find that our forward modeling results can characterize the spatiotemporal attenuation effects revealed in the Frio–II CO2 injection time–lapse seismic monitoring data. Here, we expect this proposed equation to be useful to quantify the attenuation in seismic data to push the resolution limits of seismic imaging and inversion.

25 ENERGY STORAGE↗

Episodes of Warm-Air Advection Causing Cloud-Surface Decoupling During the MARCUS

It has been understood for decades that advection of a cloud-topped marine boundary layer (CTBL) over warmer sea surface causes the stratification (or decoupling) of the CTBL via the entrainment feedback, a mechanism commonly known as “deepening-warming” decoupling that is typical in subtropics. This study focuses on the opposite direction of advection, that is, low-level warm air advection (LLWAA), and its impacts on the decoupling degree of a CTBL. Our hypothesis is that LLWAA stabilizes a CTBL, causing a decoupling of the CTBL. It is tested for three LLWAA episodes observed during the Measurements of Aerosols, Radiation, and CloUds over the Southern Ocean (MARCUS) field campaign between the Hobart (43°S, 147°E), Australia, and several Antarctic coast stations. By synthesizing the shipborne measurements of CTBL structure, Himawari-8 satellite imagery of cloud fields, and reanalysis of meteorological field, four common characteristics of CTBLs under the LLWAA are found: (1) CTBLs are highly stratified to the extent that penetrations of cumulus into main temperature inversions, which are common for subtropical decoupled CTBLs, do not exist; (2) sea surface temperature is 1–2 K lower than the near-surface air temperature; (3) clouds manifest stratiform with lifetime as long as several tens of hours; and (4) they locate in warm sectors of middle-latitude cyclones. Possible mechanisms for the maintenance of decoupled clouds under LLWAA are discussed in terms of dynamic and thermodynamic factors. Lapse rates of the decoupled CTBLs are markedly lower than those commonly used for passive satellite estimation of cloud top heights.

54 ENVIRONMENTAL SCIENCES↗

Insights into Permafrost and Seasonal Active-Layer Dynamics from Ambient Seismic Noise Monitoring

Widespread permafrost thaw in response to changing climate conditions has the potential to dramatically impact ecosystems, infrastructure, and the global carbon budget. Ambient seismic noise techniques allow passive subsurface monitoring that could provide new insights into permafrost vulnerability and active–layer processes. Using nearly 2 years of continuous seismic data recorded near Fairbanks, Alaska, we measured relative velocity variations that showed a clear seasonal cycle reflecting active–layer freeze and thaw. Relative to January 2014, velocities increased up to 3% through late spring, decreased to –8% by late August, then gradually returned to the initial values by the following winter. Velocities responded rapidly (over ~2 to 7 days) to discrete hydrologic events and temperature forcing and indicated that spring snowmelt and infiltration events from summer rainfall were particularly influential in propagating thaw across the site. Velocity increases during the fall zero–curtain captured the re–freezing process and incremental ice formation. Looking across multiple frequency bands (3–30 Hz), negative relative velocities began at higher frequencies earlier in the summer then shifted lower when active–layer thaw deepened, suggesting a potential relationship between frequency and thaw depth; however, this response was dependent on interstation distance. Bayesian tomography returned 2–D time–lapse images identifying zones of greatest velocity reduction concentrated in the western side of the array, providing insight into the spatial variability of thaw progression, soil moisture, and drainage. Furthermore, this study demonstrates the potential of passive seismic monitoring as a new tool for studying site–scale active–layer and permafrost thaw processes at high temporal and spatial resolution.

58 GEOSCIENCES↗