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At least 1,333 records · Page 74

Satellite-Based Evaluation of AeroCom Model Bias in Biomass Burning Regions

Global models are widely used to simulate biomass burning aerosol (BBA). Exhaustive evaluations on model representation of aerosol distributions and properties are fundamental to assess health and climate impacts of BBA. Here we conducted a comprehensive comparison of Aerosol Comparisons between Observations and Models (AeroCom) project model simulations with satellite observations. A total of 59 runs by 18 models from three AeroCom Phase-III experiments (i.e., biomass burning emissions, CTRL16, and CTRL19) and 14 satellite products of aerosols were used in the study. Aerosol optical depth (AOD) at 550 nm was investigated during the fire season over three key fire regions reflecting different fire dynamics (i.e., deforestation-dominated Amazon, Southern Hemisphere Africa where savannas are the key source of emissions, and boreal forest burning in boreal North America). The 14 satellite products were first evaluated against AErosol RObotic NETwork (AERONET) observations, with large uncertainties found. But these uncertainties had small impacts on the model evaluation that was dominated by modeling bias. Through a comparison with Polarization and Directionality of the Earth’s Reflectances measurements with the Generalized Retrieval of Aerosol and Surface Properties algorithm (POLDER-GRASP), we found that the modeled AOD values were biased by −93 % to 152 %, with most models showing significant underestimations even for the state-of-the-art aerosol modeling techniques (i.e., CTRL19). By scaling up BBA emissions, the negative biases in modeled AOD were significantly mitigated, although it yielded only negligible improvements in the correlation between models and observations, and the spatial and temporal variations in AOD biases did not change much. For models in CTRL16 and CTRL19, the large diversity in modeled AOD was in almost equal measures caused by diversity in emissions, lifetime, and the mass extinction coefficient (MEC). We found that in the AeroCom ensemble, BBA lifetime correlated significantly with particle deposition (as expected) and in turn correlated strongly with precipitation. Additional analysis based on Cloud-Aerosol LIdar with Orthogonal Polarization (CALIOP) aerosol profiles suggested that the altitude of the aerosol layer in the current models was generally too low, which also contributed to the bias in modeled lifetime. Modeled MECs exhibited significant correlations with the Ångström exponent (AE, an indicator of particle size). Comparisons with the POLDER-GRASP-observed AE suggested that the models tended to overestimate the AE (underestimated particle size), indicating a possible underestimation of MECs in models. The hygroscopic growth in most models generally agreed with observations and might not explain the overall underestimation of modeled AOD. Our results imply that current global models contain biases in important aerosol processes for BBA (e.g., emissions, removal, and optical properties) that remain to be addressed in future research.

biomass burning aerosols↗

Theory of critical balance in plasma turbulence

Critical balance, a statement of the approximate equality of a timescale of motion parallel to the magnetic field with a timescale of turbulent motion perpendicular to the field, is analyzed from a statistical description of the relative motion of two particles consistent with two-point correlation in a nonlinear gyrokinetic system with collisions. Critical balance is understood from a premise that the fastest time to any spatial scale that encounters decorrelated motions sets an overall correlation time for both perpendicular and parallel scales. For a regime of weak collisionality, this leads to the approximate equality of the parallel streaming time and the perpendicular turbulent correlation time, which is a standard statement of critical balance. These two timescales are only approximately equal because of effects in parallel streaming dynamics and collisions, the former producing deviations tied to variations of perpendicular and parallel wavenumbers. Finally, analysis of a collisional regime shows that critical balance also applies in that limit with a modified relation between parallel and perpendicular spatial scales.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Spectral characteristics of background error covariance and multiscale data assimilation

The spatial resolutions of numerical atmospheric and oceanic circulation models have steadily increased over the past decades. Horizontal grid spacing down to the order of 1 km is now often used to resolve cloud systems in the atmosphere and sub-mesoscale circulation systems in the ocean. These fine resolution models encompass a wide range of temporal and spatial scales, across which dynamical and statistical properties vary. In particular, dynamic flow systems for small scales can become spatially localized and temporarily intermittent. An analysis shows that the background correlation length scale is larger than 75 km for streamfunctions, even for a 2-km resolution model, and larger than 25 km for water vapor mixing ratios. The theoretical analyses suggest that such correlation length scales prevent the currently used data assimilation schemes from constraining spatial scales smaller than 150 km for streamfunctions and 50 km for water vapor mixing ratios. These results highlight the necessity of fundamentally modifying the currently used data assimilation algorithm for assimilating high-resolution observations into the aforementioned fine resolution models. A multiscale methodology based on scale decomposition is suggested, and challenges are discussed.

Li, Zhijin↗

Spatial Distribution of Resonance in the Velocity Field for Transonic Flow over a Rectangular Cavity

Pulse-burst particle image velocimetry (PIV) has been used to acquire time-resolved data at 37.5 kHz of the flow over a finite-width rectangular cavity at Mach 0.8. Power spectra of the PIV data reveal four resonance modes that match the frequencies detected simultaneously using high-frequency wall pressure sensors but whose magnitudes exhibit spatial dependence throughout the cavity. Spatio-temporal cross-correlations of velocity to pressure were calculated after bandpass filtering for specific resonance frequencies. Cross-correlation magnitudes express the distribution of resonance energy, revealing local maxima and minima at the edges of the shear layer attributable to wave interference between downstream- and upstream-propagating disturbances. Turbulence intensities were calculated using a triple decomposition and are greatest in the core of the shear layer for higher modes, where resonant energies ordinarily are lower. Most of the energy for the lowest mode lies in the recirculation region and results principally from turbulence rather than resonance. Together, the velocity-pressure cross-correlations and the triple-decomposition turbulence intensities explain the sources of energy identified in the spatial distributions of power spectra amplitudes.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Inverse problems-based maximum likelihood estimation of ground reflectivity for selected regions of interest from stripmap SAR data [Regularized maximum likelihood estimation of ground reflectivity from stripmap SAR data]

In this study, we derive a comprehensive forward model for the data collected by stripmap synthetic aperture radar (SAR) that is linear in the ground reflectivity parameters. It is also shown that if the noise model is additive, then the forward model fits into the linear statistical model framework, and the ground reflectivity parameters can be estimated by statistical methods. We derive the maximum likelihood (ML) estimates for the ground reflectivity parameters in the case of additive white Gaussian noise. Furthermore, we show that obtaining the ML estimates of the ground reflectivity requires two steps. The first step amounts to a cross-correlation of the data with a model of the data acquisition parameters, and it is shown that this step has essentially the same processing as the so-called convolution back-projection algorithm. The second step is a complete system inversion that is capable of mitigating the sidelobes of the spatially variant impulse responses remaining after the correlation processing. We also state the Cramer-Rao lower bound (CRLB) for the ML ground reflectivity estimates.We show that the CRLB is linked to the SAR system parameters, the flight path of the SAR sensor, and the image reconstruction grid.We demonstrate the ML image formation and the CRLB bound for synthetically generated data.

47 OTHER INSTRUMENTATION↗

Analysis of non-diffuse characteristics of the seismic noise field in southern California based on correlations of neighbouring frequencies

Non-diffuse characteristics of the ambient seismic noise wavefield recorded at 154 broad-band stations in southern California are analysed by computing the correlation matrix of power spectral values at neighbouring frequencies. The similarities of the derived correlation matrices are compared by choosing a different reference station at a time. The data recorded by the different stations are classified into five groups using a hierarchical clustering algorithm based on the similarity of the correlation matrices. Stations belonging to different groups are clustered spatially in the Los Angeles basin, mountains and regions farther from the coast. The deviations from diffuse wavefield in the correlation matrices of representative stations from the five groups are inverted for dominant cross-frequency components. These are used to derive power spectral ratios of non-diffuse noise and fully diffuse noise. The similarity maps for different reference stations and the inverted cross-frequency components provide information on properties of the noise sources and propagation/scattering characteristics in the different regions.

58 GEOSCIENCES↗

Predictability of tropical vegetation greenness using sea surface temperatures

Much research has examined the sensitivity of tropical terrestrial ecosystems to various environmental drivers. The predictability of tropical vegetation greenness based on sea surface temperatures (SSTs), however, has not been well explored. This study employed fine spatial resolution remotely-sensed Enhanced Vegetation Index (EVI) and SST indices from tropical ocean basins to investigate the predictability of tropical vegetation greenness in response to SSTs and established empirical models with optimal parameters for hindcast predictions. Three evaluation metrics were used to assess the model performance, i.e., correlations between historical observed and predicted values, percentage of correctly predicted signs of EVI anomalies, and percentage of correct signs for extreme EVI anomalies. Our findings reveal that the pan-tropical EVI was tightly connected to the SSTs over tropical ocean basins. The strongest impacts of SSTs on EVI were identified mainly over the arid or semi-arid tropical regions. The spatially-averaged correlation between historical observed and predicted EVI time series was 0.30 with its maximum value reaching up to 0.84. Vegetated areas across South America (25.76%), Africa (33.13%), and Southeast Asia (39.94%) were diagnosed to be associated with significant SST-EVI correlations (p < 0.01). In general, statistical models correctly predicted the sign of EVI anomalies, with their predictability increasing from ~60% to nearly 100% when EVI was abnormal (anomalies exceeding one standard deviation). These results provide a basis for the prediction of changes in greenness of tropical terrestrial ecosystems at seasonal to intra-seasonal scales. Furthermore, the statistics-based observational relationships have the potential to facilitate the benchmarking of Earth System Models regarding their ability to capture the responses of tropical vegetation growth to long-term signals of oceanic forcings.

54 ENVIRONMENTAL SCIENCES↗

Asymmetries in adaptive optics point spread functions

An explanation for the origin of asymmetry along the preferential axis of the point spread function (PSF) of an AO system is developed. When phase errors from high-altitude turbulence scintillate due to Fresnel propagation, wavefront amplitude errors may be spatially offset from residual phase errors. These correlated errors appear as asymmetry in the image plane under the Fraunhofer condition. In an analytic model with an open-loop AO system, the strength of the asymmetry is calculated for a single mode of phase aberration, which generalizes to two dimensions under a Fourier decomposition of the complex illumination. Other parameters included are the spatial offset of the AO correction, which is the wind velocity in the frozen flow regime multiplied by the effective AO time delay and propagation distance or altitude of the turbulent layer. In this model, the asymmetry is strongest when the wind is slow and nearest to the coronagraphic mask when the turbulent layer is far away, such as when the telescope is pointing low toward the horizon. A great emphasis is made about the fact that the brighter asymmetric lobe of the PSF points in the opposite direction as the wind, which is consistent analytically with the clarification that the image plane electric field distribution is actually the inverse Fourier transform of the aperture plane. Validation of this understanding is made with observations taken from the Gemini Planet Imager, as well as being reproducible in end-to-end AO simulations.

79 ASTRONOMY AND ASTROPHYSICS↗

Evaluating ecosystem water use efficiency under drought stress: a case study of the Helan Mountain region, northwest China

Context Water use efficiency (WUE) is a fundamental ecological indicator links carbon assimilation and water loss in terrestrial ecosystems. Understanding its responses to drought stress is essential for adaptive ecosystem management, particularly in climate-sensitive mountain landscapes. Objectives This study aimed to investigate drought-driven variations in WUE across major vegetation types in the Helan Mountain region of Northwest China. Specifically, we sought to identify dominant ecological drivers of WUE variability and to disentangle their relative importance and causal pathways. Methods We quantified WUE using the Moderate Resolution Imaging Spectroradiometer (MODIS) products and the Drought Severity Index (DSI) data from 2001 to 2020. To examine WUE – drought relationships across contrasting vegetation types, we employed a spatially explicit analytical framework integrating Random Forest (RF) modeling, partial correlation analysis, and structural equation modeling (SEM). Results Regional WUE exhibited relatively stable interannual dynamics, yet pronounced spatial heterogeneity that was strongly modulated by drought conditions. Vegetation properties, particularly Leaf Area Index (LAI) and Normalized Difference Vegetation Index (NDVI), emerged as the dominant determinants of WUE, with NDVI alone explaining over 20% of its spatial variance in forest and grassland during non-drought periods. SEM analyses revealed that climate forcing influenced WUE mainly through indirect pathways mediated by soil moisture availability and vegetation structural dynamics, rather than through direct climatic controls. Among all regulating factors, LAI acted as the central control node governing ecosystem carbon–water coupling. In contrast, short-term climatic stress, especially atmospheric demand and drought duration, exerted weak or negative direct effects on WUE. Ecosystem-specific responses were observed, with croplands mainly regulated by soil water availability, whereas forests and grasslands showed more sensitive to atmospheric drought stress. Together, these results reveal a hierarchical control framework where soil–vegetation interactions mediate climate impacts on WUE, driving strong spatial heterogeneity in drought responses across mountain landscapes. Conclusions Our findings highlight the pivotal role of indirect drought effects mediated by vegetation and soil processes in shaping ecosystem WUE. The identified soil–vegetation–climate regulatory hierarchy provides mechanistic insight into landscape–scale drought sensitivity and supports integrated modeling approaches for evaluating ecosystem resilience and sustainable management in arid mountain regions.

China↗

Optimal Fisher Discriminant Ratio for an Arbitrary Spatial Light Modulator

Optimizing the Fisher ratio is well established in statistical pattern recognition as a means of discriminating between classes. I show how to optimize that ratio for optical correlation intensity by choice of filter on an arbitrary spatial light modulator (SLM). I include the case of additive noise of known power spectral density.

Juday, Richard D.↗

On Digital Simulation of Multicorrelated Random Processes and Its Applications

Two methods are described to simulate, on a digital computer, a set of correlated, stationary, and Gaussian time series with zero mean from the given matrix of power spectral densities and cross spectral densities. The first method is based upon trigonometric series with random amplitudes and deterministic phase angles. The random amplitudes are generated by using a standard random number generator subroutine. An example is given which corresponds to three components of wind velocities at two different spatial locations for a total of six correlated time series. In the second method, the whole process is carried out using the Fast Fourier Transform approach. This method gives more accurate results and works about twenty times faster for a set of six correlated time series.

Sinha, A. K.↗

Spatial nematic fluctuation in BaFe 2 (As 1-x P x ) 2 revealed by spatially and angle-resolved photoemission spectroscopy

Nematicity, where rotational symmetry is broken while translational symmetry is conserved, is prevalent in higherature superconductors. In particular, nematic quantum critical point has been universally found near the optimum doping of the superconducting dome of several iron-based superconductor families. In such a regime, evidence for strong nematic fluctuations have been observed. As the precursor to this order, nematic fluctuations emerge before nematicity, providing favorable ground to study how nematic order modifies the electronic structure in the absence of structural distortion. Here we use spatially resolved angle-resolved photoemission spectroscopy to investigate the correlation between the onset of nematic fluctuations and electronic structure in an optimally doped BaFe 2 (As 1-x P x )2 (x ~ 0.3) superconductor. We reveal a strong spatially varying anisotropy of the Fermi surface on a length scale of tens of microns with strong correlation between the changes in the hole and electron Fermi pockets, consistent with the variations expected in the presence of fluctuating nematic order. These results provide direct evidence for spatial nematic fluctuations in the optimal doping regime of iron-based superconductors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Comparisons of Bispectral and Polarimetric Retrievals of Marine Boundary Layer Cloud Microphysics: Case Studies Using a LES-Satellite Retrieval Simulator

Many passive remote-sensing techniques have been developed to retrieve cloud microphysical properties from satellite-based sensors, with the most common approaches being the bispectral and polarimetric techniques. These two vastly different retrieval techniques have been implemented for a variety of polar-orbiting and geostationary satellite platforms, providing global climatological data sets. Prior instrument comparison studies have shown that there are systematic differences between the droplet size retrieval products (effective radius) of bispectral (e.g., MODIS, Moderate Resolution Imaging Spectroradiometer) and polarimetric (e.g., POLDER, Polarization and Directionality of Earth's Reflectances) instruments. However, intercomparisons of airborne bispectral and polarimetric instruments have yielded results that do not appear to be systematically biased relative to one another. Diagnosing this discrepancy is complicated, because it is often difficult for instrument intercomparison studies to isolate differences between retrieval technique sensitivities and specific instrumental differences such as calibration and atmospheric correction. In addition to these technical differences the polarimetric retrieval is also sensitive to the dispersion of the droplet size distribution (effective variance), which could influence the interpretation of the droplet size retrieval. To avoid these instrument-dependent complications, this study makes use of a cloud remote-sensing retrieval simulator. Created by coupling a large-eddy simulation (LES) cloud model with a 1-D radiative transfer model, the simulator serves as a test bed for understanding differences between bispectral and polarimetric retrievals. With the help of this simulator we can not only compare the two techniques to one another (retrieval intercomparison) but also validate retrievals directly against the LES cloud properties. Using the satellite retrieval simulator, we are able to verify that at high spatial resolution (50 m) the bispectral and polarimetric retrievals are highly correlated with one another within expected observational uncertainties. The relatively small systematic biases at high spatial resolution can be attributed to different sensitivity limitations of the two retrievals. In contrast, a systematic difference between the two retrievals emerges at coarser resolution. This bias largely stems from differences related to sensitivity of the two retrievals to unresolved inhomogeneities in effective variance and optical thickness. The influence of coarse angular resolution is found to increase uncertainty in the polarimetric retrieval but generally maintains a constant mean value.

Miller, Daniel J.↗

Publisher Correction: Imaging the square of the correlated two-electron wave function of a hydrogen molecule

The tool box for imaging molecules is well-equipped today. Some of the techniques visualize the mean geometrical structure, others image the single electron density or single electron orbitals. Molecules, however, are many-body systems for which the correlation between the constituents is often decisive and the spatial and the momentum distribution of one electron depend on the positions and momenta of the other electrons and the nuclei. Such correlations have escaped direct observation by imaging techniques so far. We implement an imaging scheme which visualizes correlations between electrons by coincident detection of the electronic and nuclear fragments after high energy photofragmentation. We use this technique to examine parts of the H 2 two-electron wave function in which electron-electron correlation beyond the mean-field level is prominent and we visualize the dependence of the correlated two-electron wave function on the internuclear distance. High energy photoelectrons are shown to be a powerful tool for molecular imaging and our study paves the way for future time resolved imaging of electron correlations at free electron lasers and laser based X-ray sources. (The original version of this Article contained an error in the fifth sentence of the first paragraph of the 'Application on H 2 ' section of the Results, which incorrectly read 'The role of electron correlation is quite apparent in this presentation: Fig. 1a is empty for the uncorrelated Hartree-Fock wave function, since projection of the latter wave function onto the 2pσ u orbital is exactly zero, while this is not the case for the fully correlated wave function (Fig. 1d); also, Fig. 1b, c for the uncorrelated description are identical, while Fig. 1e, f for the correlated case are significantly different.' The correct version replaces 'Fig. 1e, f' with 'Fig. 2e and f'. This has been corrected in both the PDF and HTML versions of the Article.)

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Time scales of pattern evolution from cross-spectrum analysis of advanced very high resolution radiometer and coastal zone color scanner imagery

We have selected square subareas (110 km on a side) from coastal zone color scanner (CZCS) and advanced very high resolution radiometer (AVHRR) images for 1981 in the California Current region off northern California for which we could identify sequences of cloud-free data over periods of days to weeks. We applied a two-dimensional fast Fourier transformation to images after median filtering, (x, y) plane removal, and cosine tapering. We formed autospectra and coherence spectra as functions of a scalar wavenumber. Coherence estimates between pairs of images were plotted against time separation between images for several wide wavenumber bands to provide a temporal lagged coherence function. The temporal rate of loss of correlation (decorrelation time scale) in surface patterns provides a measure of the rate of pattern change or evolution as a function of spatial dimension. We found that patterns evolved (or lost correlation) approximately twice as rapidly in upwelling jets as in the 'quieter' regions between jets. The rapid evolution of pigment patterns (lifetime of about 1 week or less for scales of 50-100 km) ought to hinder biomass transfer to zooplankton predators compared with phytoplankton patches that persist for longer times. We found no significant differences between the statistics of CZCS and AVHRR images (spectral shape or rate of decorrelation). In addition, in two of the three areas studied, the peak correlation between AVHRR and CZCS images from the same area occurred at zero lag, indicating that the patterns evolved simutaneously. In the third area, maximum coherence between thermal and pigment patterns occurred when pigment images lagged thermal images by 1-2 days, mirroring the expected lag of high pigment behind low temperatures (and high nutrients) in recently upwelled water. We conclude that in dynamic areas such as coastal upwelling systems, the phytoplankton cells (identified by pigment color patterns) behave largely as passive scalars at the mesoscale and that growth, death, and sinking of phytoplankton collectively play at most a mariginal role in determining the spectral statistics of the pigment patterns.

Denman, Kenneth L.↗

Fan Noise Source Diagnostic Test: Vane Unsteady Pressure Results

To investigate the nature of fan outlet guide vane pressure fluctuations and their link to rotor-stator interaction noise, time histories of vane fluctuating pressures were digitally acquired as part of the Fan Noise Source Diagnostic Test. Vane unsteady pressures were measured at seven fan tip speeds for both a radial and a swept vane configuration. Using time-domain averaging and spectral analysis, the blade passing frequency (BPF) harmonic and broadband contents of the vane pressures were individually analyzed. Significant Sound Pressure Level (SPL) reductions were observed for the swept vane relative to the radial vane for the BPF harmonics of vane pressure, but vane broadband reductions due to sweep turned out to be much smaller especially on an average basis. Cross-correlation analysis was used to establish the level of spatial coherence of broadband pressures between different locations on the vane and integral length scales of pressure fluctuations were estimated from these correlations. Two main results of this work are: (1) the average broadband level on the vane (in dB) increases linearly with the fan tip speed for both the radial and swept vanes, and (2) the broadband pressure distribution on the vane is nearly homogeneous and its integral length scale is a monotonically decreasing function of fan tip speed.

Envia, Edmane↗

From BASE-ASIA Toward 7-SEAS: A Satellite-Surface Perspective of Boreal Spring Biomass-Burning Aerosols and Clouds in Southeast Asia

In this paper, we present recent field studies conducted by NASA's SMART-COMMIT (and ACHIEVE, to be operated in 2013) mobile laboratories, jointly with distributed ground-based networks (e.g., AERONET, http://aeronet.gsfc.nasa.gov/ and MPLNET, http://mplnet.gsfc.nasa.gov/) and other contributing instruments over northern Southeast Asia. These three mobile laboratories, collectively called SMARTLabs (cf. http://smartlabs.gsfc.nasa.gov/, Surface-based Mobile Atmospheric Research & Testbed Laboratories) comprise a suite of surface remote sensing and in-situ instruments that are pivotal in providing high spectral and temporal measurements, complementing the collocated spatial observations from various Earth Observing System (EOS) satellites. A satellite-surface perspective and scientific findings, drawn from the BASE-ASIA (2006) field deployment as well as a series of ongoing 7-SEAS (2010-13) field activities over northern Southeast Asia are summarized, concerning (i) regional properties of aerosols from satellite and in situ measurements, (ii) cloud properties from remote sensing and surface observations, (iii) vertical distribution of aerosols and clouds, and (iv) regional aerosol radiative effects and impact assessment. The aerosol burden over Southeast Asia in boreal spring, attributed to biomass burning, exhibits highly consistent spatial and temporal distribution patterns, with major variability arising from changes in the magnitude of the aerosol loading mediated by processes ranging from large-scale climate factors to diurnal meteorological events. Downwind from the source regions, the tightly coupled-aerosolecloud system provides a unique, natural laboratory for further exploring the micro- and macro-scale relationships of the complex interactions. The climatic significance is presented through large-scale anti-correlations between aerosol and precipitation anomalies, showing spatial and seasonal variability, but their precise cause-and-effect relationships remain an open-ended question. To facilitate an improved understanding of the regional aerosol radiative effects, which continue to be one of the largest uncertainties in climate forcing, a joint international effort is required and anticipated to commence in springtime 2013 in northern Southeast Asia.

biomass burning aerosols↗

Quantifying the Influence of Defects on Selectivity of Electrodes Encapsulated by Nanoscopic Silicon Oxide Overlayers

Encapsulation of electrocatalysts and photocatalysts with semipermeable nanoscopic oxide overlayers that exhibit selective transport properties is an attractive approach to achieve high redox selectivity. However, defects within the overlayers-such as pinholes, cracks, or particle inclusions-may facilitate local high rates of parasitic reactions by creating pathways for facile transport of undesired reactants to exposed active sites. Scanning electrochemical microscopy (SECM) is an attractive method to determine the influence of defects on macroscopic performance metrics thanks to its ability to measure the relative rates of competing electrochemical reactions with high spatial resolution over the electrode. Here, we report the use of SECM to determine the influence of overlayer defects on the selectivity of silicon oxide (SiOx) encapsulated platinum thin-film electrocatalysts operated under conditions where two competing reactions-the hydrogen evolution and Fe(III) reduction reactions-can occur. After an SECM methodology is described to determine spatially resolved selectivity, representative selectivity maps are correlated with the location of defects that are characterized by optical, electron, and atomic force microscopies. This analysis reveals that certain types of defects in the oxide overlayer are responsible for ∼60-90% of the partial current density toward the undesired Fe(III) reduction reaction. By correcting for defect contributions to Fe(III) reduction rates, true Fe(III) permeability values for the SiOxoverlayers were determined to be over an order of magnitude lower than permeabilities determined from analyses that ignore the presence of defects. Lastly, different types of defects were studied revealing that defect morphology can have varying influence on both redox selectivity and calculated permeability. This work highlights the need for spatially resolved measurements to evaluate the performance of oxide-encapsulated catalysts and understand their performance limits.

25 ENERGY STORAGE↗