ASU Scholarship Showcase

This study explores the capabilities of the Coherent X-ray Imaging Instrument at the Linac Coherent Light Source to image small biological samples. The weak signal from small samples puts a significant demand on the experiment. Aerosolized Omono River virus particles of ∼40 nm in diameter were injected into the submicrometre X-ray focus at a reduced pressure. Diffraction patterns were recorded on two area detectors. The statistical nature of the measurements from many individual particles provided information about the intensity profile of the X-ray beam, phase variations in the wavefront and the size distribution of the injected particles. The results point to a wider than expected size distribution (from ∼35 to ∼300 nm in diameter). This is likely to be owing to nonvolatile contaminants from larger droplets during aerosolization and droplet evaporation. The results suggest that the concentration of nonvolatile contaminants and the ratio between the volumes of the initial droplet and the sample particles is critical in such studies. The maximum beam intensity in the focus was found to be 1.9 × 10¹² photons per µm² per pulse. The full-width of the focus at half-maximum was estimated to be 500 nm (assuming 20% beamline transmission), and this width is larger than expected. Under these conditions, the diffraction signal from a sample-sized particle remained above the average background to a resolution of 4.25 nm. The results suggest that reducing the size of the initial droplets during aerosolization is necessary to bring small particles into the scope of detailed structural studies with X-ray lasers.

Urban environments are the primary contributors to global anthropogenic carbon emissions. Because much of the growth in CO₂ emissions will originate from cities, there is a need to develop, assess, and improve measurement and modeling strategies for quantifying and monitoring greenhouse gas emissions from large urban centers. In this study the uncertainties in an aircraft-based mass balance approach for quantifying carbon dioxide and methane emissions from an urban environment, focusing on Indianapolis, IN, USA, are described. The relatively level terrain of Indianapolis facilitated the application of mean wind fields in the mass balance approach. We investigate the uncertainties in our aircraft-based mass balance approach by (1) assessing the sensitivity of the measured flux to important measurement and analysis parameters including wind speed, background CO₂ and CH₄, boundary layer depth, and interpolation technique, and (2) determining the flux at two or more downwind distances from a point or area source (with relatively large source strengths such as solid waste facilities and a power generating station) in rapid succession, assuming that the emission flux is constant. When we quantify the precision in the approach by comparing the estimated emissions derived from measurements at two or more downwind distances from an area or point source, we find that the minimum and maximum repeatability were 12 and 52%, with an average of 31%. We suggest that improvements in the experimental design can be achieved by careful determination of the background concentration, monitoring the evolution of the boundary layer through the measurement period, and increasing the number of downwind horizontal transect measurements at multiple altitudes within the boundary layer.

Modulated reflectance (contactless electroreflectance (CER), photoreflectance (PR), and piezoreflectance (PzR)) has been applied to study direct optical transitions in bulk MoS₂, MoSe₂, WS₂, and WSe₂. In order to interpret optical transitions observed in CER, PR, and PzR spectra, the electronic band structure for the four crystals has been calculated from the first principles within the density functional theory for various points of Brillouin zone including K and H points. It is clearly shown that the electronic band structure at H point of Brillouin zone is very symmetric and similar to the electronic band structure at K point, and therefore, direct optical transitions at H point should be expected in modulated reflectance spectra besides the direct optical transitions at the K point of Brillouin zone. This prediction is confirmed by experimental studies of the electronic band structure of MoS₂, MoSe₂, WS₂, and WSe₂ crystals by CER, PR, and PzR spectroscopy, i.e., techniques which are very sensitive to critical points of Brillouin zone. For the four crystals besides the A transition at K point, an A_H transition at H point has been observed in CER, PR, and PzR spectra a few tens of meV above the A transition. The spectral difference between A and A_H transition has been found to be in a very good agreement with theoretical predictions. The second transition at the H point of Brillouin zone (B_H transition) overlaps spectrally with the B transition at K point because of small energy differences in the valence (conduction) band positions at H and K points. Therefore, an extra resonance which could be related to the B_H transition is not resolved in modulated reflectance spectra at room temperature for the four crystals.

The valley degree of freedom in two-dimensional (2D) crystals recently emerged as a novel information carrier in addition to spin and charge. The intrinsic valley lifetime in 2D transition metal dichalcogenides (TMD) is expected to be markedly long due to the unique spin-valley locking behavior, where the intervalley scattering of the electron simultaneously requires a large momentum transfer to the opposite valley and a flip of the electron spin. However, the experimentally observed valley lifetime in 2D TMDs has been limited to tens of nanoseconds thus far. We report efficient generation of microsecond-long-lived valley polarization in WSe₂/MoS₂ heterostructures by exploiting the ultrafast charge transfer processes in the heterostructure that efficiently creates resident holes in the WSe₂ layer. These valley-polarized holes exhibit near-unity valley polarization and ultralong valley lifetime: We observe a valley-polarized hole population lifetime of more than 1 μs and a valley depolarization lifetime (that is, intervalley scattering lifetime) of more than 40 μs at 10 K. The near-perfect generation of valley-polarized holes in TMD heterostructures, combined with ultralong valley lifetime, which is orders of magnitude longer than previous results, opens up new opportunities for novel valleytronics and spintronics applications.

The ‘Hestia Project’ uses a bottom-up approach to quantify fossil fuel CO₂(FFCO₂) emissions spatially at the building/street level and temporally at the hourly level. Hestia FFCO₂ emissions are provided in the form of a group of sector-specific vector layers with point, line, and polygon sources to support carbon cycle science and climate policy. Application to carbon cycle science, in particular, requires regular gridded data in order to link surface carbon fluxes to atmospheric transport models. However, the heterogeneity and complexity of FFCO₂ sources within regular grids is sensitive to spatial resolution. From the perspective of a data provider, we need to find a balance between resolution and data volume so that the gridded data product retains the maximum amount of information content while maintaining an efficient data volume.

The Shannon entropy determines the minimum bits that are needed to encode an information source and can serve as a metric for the effective information content. In this paper, we present an analysis of the Shannon entropy of gridded FFCO₂ emissions with varying resolutions in four Hestia study areas, and find: (1) the Shannon entropy increases with smaller grid resolution until it reaches a maximum value (the max-entropy resolution); (2) total emissions (the sum of several sector-specific emission fields) show a finer max-entropy resolution than each of the sector-specific fields; (3) the residential emissions show a finer max-entropy resolution than the commercial emissions; (4) the max-entropy resolution of the onroad emissions grid is closely correlated to the density of the road network. These findings suggest that the Shannon entropy can detect the information effectiveness of the spatial resolution of gridded FFCO₂ emissions. Hence, the resolution-entropy relationship can be used to assist in determining an appropriate spatial resolution for urban CO₂ flux studies. We conclude that the optimal spatial resolution for providing Hestia total FFCO₂ emissions products is centered around 100 m, at which the FFCO₂ emissions data can not only fully meet the requirement of urban flux integration, but also be effectively used in understanding the relationships between FFCO₂ emissions and various social-economic variables at the U.S. census block group level.

We assess the detectability of city emissions via a tower-based greenhouse gas (GHG) network, as part of the Indianapolis Flux (INFLUX) experiment. By examining afternoon-averaged results from a network of carbon dioxide (CO₂), methane (CH₄), and carbon monoxide (CO) mole fraction measurements in Indianapolis, Indiana for 2011–2013, we quantify spatial and temporal patterns in urban atmospheric GHG dry mole fractions. The platform for these measurements is twelve communications towers spread across the metropolitan region, ranging in height from 39 to 136 m above ground level, and instrumented with cavity ring-down spectrometers. Nine of the sites were deployed as of January 2013 and data from these sites are the focus of this paper. A background site, chosen such that it is on the predominantly upwind side of the city, is utilized to quantify enhancements caused by urban emissions. Afternoon averaged mole fractions are studied because this is the time of day during which the height of the boundary layer is most steady in time and the area that influences the tower measurements is likely to be largest. Additionally, atmospheric transport models have better performance in simulating the daytime convective boundary layer compared to the nighttime boundary layer. Averaged from January through April of 2013, the mean urban dormant-season enhancements range from 0.3 ppm CO₂ at the site 24 km typically downwind of the edge of the city (Site 09) to 1.4 ppm at the site at the downwind edge of the city (Site 02) to 2.9 ppm at the downtown site (Site 03). When the wind is aligned such that the sites are downwind of the urban area, the enhancements are increased, to 1.6 ppm at Site 09, and 3.3 ppm at Site 02. Differences in sampling height affect the reported urban enhancement by up to 50%, but the overall spatial pattern remains similar. The time interval over which the afternoon data are averaged alters the calculated urban enhancement by an average of 0.4 ppm. The CO₂ observations are compared to CO₂ mole fractions simulated using a mesoscale atmospheric model and an emissions inventory for Indianapolis. The observed and modeled CO₂ enhancements are highly correlated (r² = 0.94), but the modeled enhancements prior to inversion average 53% of those measured at the towers. Following the inversion, the enhancements follow the observations closely, as expected. The CH₄ urban enhancement ranges from 5 ppb at the site 10 km predominantly downwind of the city (Site 13) to 21 ppb at the site near the landfill (Site 10), and for CO ranges from 6 ppb at the site 24 km downwind of the edge of the city (Site 09) to 29 ppb at the downtown site (Site 03). Overall, these observations show that a dense network of urban GHG measurements yield a detectable urban signal, well-suited as input to an urban inversion system given appropriate attention to sampling time, sampling altitude and quantification of background conditions.

The INFLUX experiment has taken multiple approaches to estimate the carbon dioxide (CO₂) flux in a domain centered on the city of Indianapolis, Indiana. One approach, Hestia, uses a bottom-up technique relying on a mixture of activity data, fuel statistics, direct flux measurement and modeling algorithms. A second uses a Bayesian atmospheric inverse approach constrained by atmospheric CO₂ measurements and the Hestia emissions estimate as a prior CO₂ flux. The difference in the central estimate of the two approaches comes to 0.94 MtC (an 18.7% difference) over the eight-month period between September 1, 2012 and April 30, 2013, a statistically significant difference at the 2-sigma level. Here we explore possible explanations for this apparent discrepancy in an attempt to reconcile the flux estimates. We focus on two broad categories: 1) biases in the largest of bottom-up flux contributions and 2) missing CO₂ sources. Though there is some evidence for small biases in the Hestia fossil fuel carbon dioxide (FFCO2) flux estimate as an explanation for the calculated difference, we find more support for missing CO₂ fluxes, with biological respiration the largest of these. Incorporation of these differences bring the Hestia bottom-up and the INFLUX inversion flux estimates into statistical agreement and are additionally consistent with wintertime measurements of atmospheric ¹⁴CO₂. We conclude that comparison of bottom-up and top-down approaches must consider all flux contributions and highlight the important contribution to urban carbon budgets of animal and biotic respiration. Incorporation of missing CO₂ fluxes reconciles the bottom-up and inverse-based approach in the INFLUX domain.

The strong light-matter interaction and the valley selective optical selection rules make monolayer (ML) MoS₂ an exciting 2D material for fundamental physics and optoelectronics applications. But, so far, optical transition linewidths even at low temperature are typically as large as a few tens of meV and contain homogeneous and inhomogeneous contributions. This prevented in-depth studies, in contrast to the better-characterized ML materials MoSe₂ and WSe₂. In this work, we show that encapsulation of ML MoS₂ in hexagonal boron nitride can efficiently suppress the inhomogeneous contribution to the exciton linewidth, as we measure in photoluminescence and reflectivity a FWHM down to 2 meV at T = 4 K. Narrow optical transition linewidths are also observed in encapsulated WS₂, WSe₂, and MoSe₂ MLs. This indicates that surface protection and substrate flatness are key ingredients for obtaining stable, high-quality samples. Among the new possibilities offered by the well-defined optical transitions, we measure the homogeneous broadening induced by the interaction with phonons in temperature-dependent experiments. We uncover new information on spin and valley physics and present the rotation of valley coherence in applied magnetic fields perpendicular to the ML.

Megacities are major sources of anthropogenic fossil fuel CO₂(FFCO₂) emissions. The spatial extents of these large urban systems cover areas of 10 000 km² or more with complex topography and changing landscapes. We present a high-resolution land–atmosphere modelling system for urban CO₂ emissions over the Los Angeles (LA) megacity area. The Weather Research and Forecasting (WRF)-Chem model was coupled to a very high-resolution FFCO₂ emission product, Hestia-LA, to simulate atmospheric CO₂ concentrations across the LA megacity at spatial resolutions as fine as  ∼  1 km. We evaluated multiple WRF configurations, selecting one that minimized errors in wind speed, wind direction, and boundary layer height as evaluated by its performance against meteorological data collected during the CalNex-LA campaign (May–June 2010). Our results show no significant difference between moderate-resolution (4 km) and high-resolution (1.3 km) simulations when evaluated against surface meteorological data, but the high-resolution configurations better resolved planetary boundary layer heights and vertical gradients in the horizontal mean winds. We coupled our WRF configuration with the Vulcan 2.2 (10 km resolution) and Hestia-LA (1.3 km resolution) fossil fuel CO₂ emission products to evaluate the impact of the spatial resolution of the CO₂ emission products and the meteorological transport model on the representation of spatiotemporal variability in simulated atmospheric CO₂ concentrations. We find that high spatial resolution in the fossil fuel CO₂ emissions is more important than in the atmospheric model to capture CO₂ concentration variability across the LA megacity. Finally, we present a novel approach that employs simultaneous correlations of the simulated atmospheric CO₂ fields to qualitatively evaluate the greenhouse gas measurement network over the LA megacity. Spatial correlations in the atmospheric CO₂ fields reflect the coverage of individual measurement sites when a statistically significant number of sites observe emissions from a specific source or location. We conclude that elevated atmospheric CO₂ concentrations over the LA megacity are composed of multiple fine-scale plumes rather than a single homogenous urban dome. Furthermore, we conclude that FFCO₂ emissions monitoring in the LA megacity requires FFCO₂ emissions modelling with  ∼1 km resolution because coarser-resolution emissions modelling tends to overestimate the observational constraints on the emissions estimates.

Recent advances in fossil fuel CO₂ (FFCO₂) emission inventories enable sensitivity tests of simulated atmospheric CO₂ concentrations to sub-annual variations in FFCO₂ emissions and what this implies for the interpretation of observed CO₂. Six experiments are conducted to investigate the potential impact of three cycles of FFCO₂ emission variability (diurnal, weekly and monthly) using a global tracer transport model. Results show an annual FFCO₂ rectification varying from −1.35 to +0.13 ppm from the combination of all three cycles. This rectification is driven by a large negative diurnal FFCO₂ rectification due to the covariation of diurnal FFCO₂ emissions and diurnal vertical mixing, as well as a smaller positive seasonal FFCO₂ rectification driven by the covariation of monthly FFCO₂ emissions and monthly atmospheric transport. The diurnal FFCO₂ emissions are responsible for a diurnal FFCO₂ concentration amplitude of up to 9.12 ppm at the grid cell scale. Similarly, the monthly FFCO₂ emissions are responsible for a simulated seasonal CO₂ amplitude of up to 6.11 ppm at the grid cell scale. The impact of the diurnal FFCO₂ emissions, when only sampled in the local afternoon, is also important, causing an increase of +1.13 ppmv at the grid cell scale. The simulated CO₂ concentration impacts from the diurnally and seasonally varying FFCO₂ emissions are centered over large source regions in the Northern Hemisphere, extending to downwind regions. This study demonstrates the influence of sub-annual variations in FFCO₂ emissions on simulated CO₂ concentration and suggests that inversion studies must take account of these variations in the affected regions.