Abstract: To understand the structure–property relationship of nanostructures, reliably quantifying parameters, such as the number of atoms along the projection direction, is important. Advanced statistical methodologies have made it possible to count the number of atoms for monotype crystalline nanoparticles from a single ADF STEM image. Recent developments enable one to simultaneously acquire multiple ADF STEM images. Here, we present an extended statistics-based method for atom counting from a combination of multiple statistically independent ADF STEM images reconstructed from non-overlapping annular detector collection regions which improves the accuracy and allows one to retrieve precise atom-counts, especially for images acquired with low electron doses and multiple element structures.

Abstract: CO2 exchange between terrestrial ecosystems and the atmosphere is key to understanding the feedbacks between climate change and the land surface. In regions with carbonaceous parent material, CO2 exchange patterns occur that cannot be explained by biological processes, such as disproportionate outgassing during the daytime or night-time CO2 uptake during periods when all vegetation is senescent. Neither of these phenomena can be attributed to carbonate weathering reactions, since their CO2 exchange rates are too small. Soil ventilation induced by high atmospheric turbulence is found to explain atypical CO2 exchange between carbonaceous systems and the atmosphere. However, by strongly altering subsurface CO2 concentrations, ventilation can be expected to influence carbonate weathering rates. By imposing ventilation-driven CO2 outgassing in a carbonate weathering model, we show here that carbonate geochemistry is accelerated and does play a surprisingly large role in the observed CO2 exchange pattern of a semi-arid ecosystem. We found that by rapidly depleting soil CO2 during the daytime, ventilation disturbs soil carbonate equilibria and therefore strongly magnifies daytime carbonate precipitation and associated CO2 production. At night, ventilation ceases and the depleted CO2 concentrations increase steadily. Dissolution of carbonate is now enhanced, which consumes CO2 and largely compensates for the enhanced daytime carbonate precipitation. This is why only a relatively small effect on global carbonate weathering rates is to be expected. On the short term, however, ventilation has a drastic effect on synoptic carbonate weathering rates, resulting in a pronounced diel pattern that exacerbates the non-biological behavior of soil-atmosphere CO2 exchanges in dry regions with carbonate soils.

Abstract: We investigate the performance of an atmospheric pressure glow discharge (APGD) reactor for CO2 conversion in three different configurations, through experiments and simulations. The first (basic) configuration utilizes the well-known pin-to-plate design, which offers a limited conversion. The second configuration improves the reactor performance by employing a vortex-flow generator. The third, “confined” configuration is a complete redesign of the reactor, which encloses the discharge in a limited volume, significantly surpassing the conversion rate of the other two designs. The plasma properties are investigated using an advanced plasma model.

Abstract: Daily and seasonal variations in dry and wet atmospheric nitrogen fluxes have been studied during four campaigns between 2004 and 2006 at a coastal site of the Southern North Sea at De Haan (Belgium) located at coordinates of 51.1723° N and 3.0369° E. Concentrations of inorganic N-compounds were determined in the gaseous phase, size-segregated aerosol (coarse, medium, and fine), and rainwater samples. Dissolved organic nitrogen (DON) was quantified in rainwater. The daily variations in N-fluxes of compounds were evaluated with air-mass backward trajectories, classified into the main air-masses arriving at the sampling site (i.e., continental, North Sea, and Atlantic/UK/Channel). The three, non-episodic campaigns showed broadly consistent fluxes, but during the late summer campaign exceptionally high episodic N-deposition was observed. The average dry and wet fluxes for non-episodic campaigns amounted to 2.6 and 4.0 mg N m−2 d−1, respectively, whereas during the episodic late summer period these fluxes were as high as 5.2 and 6.2 mg N m−2 d−1, respectively. Non-episodic seasons/campaigns experienced average aerosol fluxes of 0.91.4 mg N m−2 d−1. Generally, the contribution of aerosol NH4+ was more significant in the medium and fine particulate fractions than that of aerosol NO3−, whereas the latter contributed more in the coarse fraction, especially in continental air-masses. During the dry mid-summer campaign, the DON contributed considerably (15%) to the total N-budget. Exceptionally high episodic aerosol-N inputs have been observed for the late summer campaign, with especially high deposition rates of 3.6 and 2.9 mg N m−2 d−1 for Atlantic/UK/Channel and North Sea-continental (mixed) air-masses, respectively. During this pollution episode, the flux of NH4+ was dominating in each aerosol fraction/air-mass, except for coarse continental aerosols. High deposition of gaseous-N was also observed in this campaign with an average total N-flux of 22.5-times higher than in other campaigns.

Abstract: The major threat to clean air in developed and industrializing countries is now posed by traffic emissions. The effects of traffic road modifications on the air quality are, however, rarely reported in the literature. The aim of this study was to determine the influence of the modernization and renovation of a traffic artery in the region of Mortsel (Antwerp, Belgium) on the concentration of volatile organic compounds such as: benzene, toluene, ethylbenzene and m-, p-, o-xylenes (BTEX). The original goal of the reconstruction works was to reduce the traffic lanes of one of the busiest streets in Antwerp, in order to discourage the road traffic and in consequence also to improve the air quality in this region. The average concentrations of BTEX before these works in 2003 were: 1.6, 7.0, 0.9, 2.3, and 0.9 ìg/m3, for benzene, toluene, ethylbenzene, m + p xylenes, and o-xylene, respectively. However, after the completion of the works, in 2005, they were slightly higher: 2.5, 9.5, 1.6, 3.4, and 1.3 ìg/m3, respectively. The scatter plots of benzene against toluene, ethylbenzene and xylenes in 2003 and 2005 showed very good correlations. This fact indicated that all of the measured compounds originated from the same source, namely the road traffic. Moreover, the data obtained from an air-monitoring station at less than 6 km distance from the sampling site (operated by the Flemish Environment Agency, and located in Borgerhout, Antwerp), confirmed the lack of influence of background concentrations of BTEX. The obtained results led to the conclusion that the reduction of the number of traffic lanes had apparently increased the traffic jams and also increased the emission from cars. Therefore, these modernization works had even a negative impact on the local concentration of traffic-related pollutants as BTEX.

Abstract: In this letter, we address the bipolar resistive switching phenomenology in scaled TiN\HfO2\Hf cells. By means of stack engineering using a thin Al2O3 layer inserted either at the TiN\HfO2 or at the Hf\HfO2 interface, we demonstrate that the reset operation takes place close to the TiNanode. Due to the increase of the oxygen-vacancy profile from the TiN to the Hf interface, the filament-confining and wide band-gap Al2O3 layer should indeed be engineered at the interface with the TiN electrode in order to further improve the switching control and to allow reaching larger state resistances. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.003204ssl] All rights reserved.

Abstract: In the present work two different cold working and annealing schemes were utilized, and the asymmetric superelastic response of thermomechanically processed materials were then assessed through cyclic tensile and compressive modes of deformation. The values of transformation stress, transformation strain, and pseudoelastic strain were measured for each treated and solutionized specimens and the asymmetric response was compared. In the solution annealed state, the difference of these parameters at different deformation modes was negligible due to the weak texture of the material, while for thermomechanically treated ones, development of specific deformation and recrystallization texture components was identified to be one of the underlying reasons of intensified asymmetry. The evolved substructure during the thermomechanical processing also played a substantial role in determining the asymmetric response. The presence of fine grains and dense dislocation substructure could hinder the movement of the transformation front, thus limiting the range of transformation. In tensile mode, the transformation stress was lower, but higher transformation strain was achieved, which was discussed relying on the slip activity in specified oriented grains. The lower transformation strain in compression mode led to lower pseudoelastic strain due to the narrow transformation range which finally degraded superelastic response of the material. (C) 2021 Elsevier B.V. All rights reserved.

Abstract: The structural and magnetic properties of LaMnO₃/LaFeO₃(LMO/LFO) heterostructures are characterized using a combination of scanning transmission electron microscopy, electron energy-loss spectroscopy, bulk magnetometry, and resonant x-ray reflectivity. Unlike the relatively abrupt interface when LMO is deposited on top of LFO, the interface with reversed growth order shows significant cation intermixing of Mn³⁺and Fe³⁺, spreading ∼8 unit cells across the interface. The asymmetric interfacial chemical profiles result in distinct magnetic properties. The bilayer with abrupt interface shows a single magnetic hysteresis loop with strongly enhanced coercivity, as compared to the LMO plain film. However, the bilayer with intermixed interface shows a step-like hysteresis loop, associated with the separate switching of the “clean” and intermixed LMO sublayers. Our study illustrates the key role of interfacial chemical profile in determining the functional properties of oxide heterostructures.

Abstract: Background: It has been hypothesized that ambient particulate air pollution is able to modify the autonomic nervous control of the heart, measured as heart rate variability (HRV) . Previously we reported heterogeneous associations between particulate matter with aerodynamic diameter < 2.5 µm (PM2.5) and HRV across three study centers. Objective: We evaluated whether exposure misclassification, effect modification by medication, or differences in particle composition could explain the inconsistencies. Methods: Subjects with coronary heart disease visited clinics biweekly in Amsterdam, the Netherlands ; Erfurt, Germany ; and Helsinki, Finland for 68 months. The standard deviation (SD) of NN intervals on an electrocardiogram (ECG ; SDNN) and high frequency (HF) power of HRV was measured with ambulatory ECG during paced breathing. Outdoor levels of PM2.5 were measured at a central site. In Amsterdam and Helsinki, indoor and personal PM2.5 were measured during the 24 hr preceding the clinic visit. PM2.5 was apportioned between sources using principal component analyses. We analyzed associations of indoor/personal PM2.5, elements of PM2.5, and source-specific PM2.5 with HRV using linear regression. Results: Indoor and personal PM2.5 were not associated with HRV. Increased outdoor PM2.5 was associated with decreased SDNN and HF at lags of 2 and 3 days only among persons not using beta-blocker medication. Traffic-related PM2.5 was associated with decreased SDNN, and long-range transported PM2.5 with decreased SDNN and HF, most strongly among persons not using beta blockers. Indicators for PM2.5 from traffic and long-range transport were also associated with decreased HRV. Conclusions: Our results suggest that differences in the composition of particles, beta-blocker use, and obesity of study subjects may explain some inconsistencies among previous studies on HRV.

Abstract: Nano-sized ZnO particles with a narrow size distribution and high crystallinity were prepared from aqueous solutions with high concentrations of Zn2+ containing salts and citric acid in a conventional spray pyrolysis setup. Structure, morphology and size of the produced material were compared to ZnO material produced by simple spray pyrolysis of zinc nitrates in the same experimental setup. Using transmission electron microscopy and electron tomography it has been shown that citric acid-assisted spray pyrolysed material is made up of micron sized secondary particles comprising a shell of lightly agglomerated, monocrystalline primary ZnO nanoparticles with sizes in the 2030 nm range, separable by a simple ultrasonic treatment step.

Abstract: Sustainability guidelines can help to safeguard the sustainable use of biological materials. When these guidelines are legally prescribed, their influence on the economic viability of bioenergy, biofuel and bioliquid projects is increased substantially, through their impact on national subsidy regimes and international trade. One of the key examples is the European directive 2009/28/EC, or the Renewable Energy Directive (RED), and the related COM/2010/11 that integrate guidelines for calculating greenhouse gas impact for various bioenergy pathways. This paper looks further into the sustainability results when influenced by principal decisions that are legally open for debate. Therefore, a concise review is conducted of the legal state-of-the-art on whether a product is waste or not. The review pinpoints uncertainty, leading to four potential legal scenarios. The sustainability of a complex biorefinery is analysed for each scenario. The results show (i) a high sensitivity to the principal decisions on the nature of waste materials in the scenarios, and (ii) to the definition of boundaries between the processes. More detailed rules for the application of the RED guidelines are needed, and should be complemented with methods specifically targeting all relevant sustainability aspects, thereby enhancing the overall understanding of the sustainability of the process. (C) 2014 Elsevier Ltd. All rights reserved.

Abstract: The surface termination of MXenes greatly determines the electrochemical properties and ion kinetics on their surfaces. So far, hydroxyl-, oxygen-, and fluorine-terminated MXenes have been widely studied for energy storage applications. Recently, sulfur-functionalized MXene structures, which possess low diffusion barriers, have been proposed as candidate materials to enhance battery performance. We performed first-principles calculations on the structural, stability, electrochemical, and ion dynamic properties of Li-adsorbed sulfur-functionalized groups 3B, 4B, 5B, and 6B transition-metal (M)-based MXenes (i.e., M2CS2 with M = Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W). We performed phonon calculations, which indicated that all of the above M2CS2 MXenes, except for Sc, are dynamically stable at T = 0 K. The ground-state structure of each M2CS2 monolayer depends on the type of M atom. For instance, while sulfur prefers to sit at the FCC site on Ti2CS2, it occupies the HCP site of Cr-based MXene. We determined the Li adsorption configurations at different concentrations using the cluster expansion method. The highest maximum open-circuit voltages were computed for the group 4B element (i.e., Ti, Zr, and Hf)-based M2CS2, which are larger than 2.1 V, while their average voltages are approximately 1 V. The maximum voltage for the group 6B element (i.e., Cr, Mo, W)-based M2CS2 is less than 1 V, and the average voltage is less than 0.71 V. We found that S functionalization is helpful for capacity improvements over the O-terminated MXenes. In this respect, the computed storage gravimetric capacity may reach up to 417.4 mAh/g for Ti2CS2 and 404.5 mAh/g for V2CS2. Ta-, Cr-, Mo-, and W-based M2CS2 MXenes show very low capacities, which are less than 100 mAh/g. The Li surface diffusion energy barriers for all of the considered MXenes are less than 0.22 eV, which is favorable for high charging and discharging rates. Finally, ab initio molecular dynamic simulations performed at 400 K and bond-length analysis with respect to Li concentration verify that selected promising systems are robust against thermally induced perturbations that may induce structural transformations or distortions and undesirable Li release.