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At least 1,207 records · Page 67

Measurements and modeling of contemporary radiocarbon in the stratosphere

Measurements of the 14 C content of carbon dioxide in air collected by high-altitude balloon flights in 2003–2005 reveal the contemporary radiocarbon distribution in the northern midlatitude stratosphere, four decades after the Limited Test Ban Treaty restricted atmospheric testing of nuclear weapons. Comparisons with results from a 3-D chemical-transport model show that the 14 CO 2 distribution is now largely governed by the altitude/latitude dependence of the natural cosmogenic production rate, stratospheric transport, and propagation into the stratosphere of the decreasing radiocarbon trend in tropospheric CO 2 due to fossil fuel combustion. From the observed correlation of 14 CO 2 with N 2 O mixing ratios, an annual global mean net flux of 14 CO 2 to the troposphere of 1.6(±0.4) × 10 17 ‰ mol CO 2 yr –1 and a global production rate of 2.2(±0.6) × 10 26 atoms 14 C yr –1 are empirically derived. Furthermore, the results also indicate that contemporary 14 CO 2 observations provide highly sensitive diagnostics for stratospheric transport and residence times in models.

54 ENVIRONMENTAL SCIENCES↗

A space-based, high-resolution view of notable changes in urban NO x pollution around the world (2005-2014)

Nitrogen oxides (NO x = NO + NO 2 ) are produced during combustion processes and, thus may serve as a proxy for fossil fuel-based energy usage and coemitted greenhouse gases and other pollutants. We use high-resolution nitrogen dioxide (NO 2 ) data from the Ozone Monitoring Instrument (OMI) to analyze changes in urban NO 2 levels around the world from 2005 to 2014, finding complex heterogeneity in the changes. We discuss several potential factors that seem to determine these NO x changes. First, environmental regulations resulted in large decreases. The only large increases in the United States may be associated with three areas of intensive energy activity. Second, elevated NO 2 levels were observed over many Asian, tropical, and subtropical cities that experienced rapid economic growth. Two of the largest increases occurred over recently expanded petrochemical complexes in Jamnagar (India) and Daesan (Korea). Third, pollution transport from China possibly influenced the Republic of Korea and Japan, diminishing the impact of local pollution controls. However, in China, there were large decreases over Beijing, Shanghai, and the Pearl River Delta, which were likely associated with local emission control efforts. Fourth, civil unrest and its effect on energy usage may have resulted in lower NO 2 levels in Libya, Iraq, and Syria. Fifth, spatial heterogeneity within several megacities may reflect mixed efforts to cope with air quality degradation. We also show the potential of high-resolution data for identifying NO x emission sources in regions with a complex mix of sources. Lastly, intensive monitoring of the world's tropical/subtropical megacities will remain a priority, as their populations and emissions of pollutants and greenhouse gases are expected to increase significantly.

59 BASIC BIOLOGICAL SCIENCES↗

A three-dimensional sectional representation of aerosol mixing state for simulating optical properties and cloud condensation nuclei

Light absorption by black carbon (BC) particles emitted from fossil fuel combustion depends on the how thickly they are coated with non-refractory species such as ammonium, sulfate, nitrate, organics, and water. The cloud condensation nuclei (CCN) activation property of a particle depends on its dry size and the hygroscopicities of all the individual species mixed together. It is therefore necessary to represent both size and mixing state of aerosols to reliably predict their climate-relevant properties in atmospheric models. Here we describe and evaluate a novel sectional framework in the Model for Simulating Aerosol Interactions and Chemistry, referred to as MOSAIC-mix, that represents the mixing state by resolving aerosol dry size (D dry ), BC dry mass fraction (w BC ), and hygroscopicity (κ). Using ten idealized urban plume scenarios in which different types of aerosols evolve over 24 hours under a range of atmospherically relevant environmental conditions, we examine errors in CCN concentrations and optical properties with respect to a more explicit aerosol mixing state representation. We find that only a small number of w BC and κ bins are needed to achieve significant reductions in the errors, and propose a configuration consisting of 24 D dry bins, 2 w BC bins, and 2 κ bins that gives 24-hour average errors of about 5% or less in CCN concentrations and optical properties, 3-4 times lower than those from size-only-resolved simulations. Here, these results show that MOSAIC-mix is suitable for use in regional and global models to examine the effects of evolving aerosol mixing states on aerosol-radiation-cloud feedbacks.

54 ENVIRONMENTAL SCIENCES↗

Bayesian-information-gap decision theory with an application to CO 2 sequestration

Decisions related to subsurface engineering problems such as groundwater management, fossil fuel production, and geologic carbon sequestration are frequently challenging because of an overabundance of uncertainties (related to conceptualizations, parameters, observations, etc.). Because of the importance of these problems to agriculture, energy, and the climate (respectively), good decisions that are scientifically defensible must be made despite the uncertainties. We describe a general approach to making decisions for challenging problems such as these in the presence of severe uncertainties that combines probabilistic and non-probabilistic methods. The approach uses Bayesian sampling to assess parametric uncertainty and Information-Gap Decision Theory (IGDT) to address model inadequacy. The combined approach also resolves an issue that frequently arises when applying Bayesian methods to real-world engineering problems related to the enumeration of possible outcomes. In the case of zero non-probabilistic uncertainty, the method reduces to a Bayesian method. Lastly, to illustrate the approach, we apply it to a site-selection decision for geologic CO 2 sequestration.

58 GEOSCIENCES↗

Geoengineering, marine microalgae, and climate stabilization in the 21st century

Abstract Society has set ambitious targets for stabilizing mean global temperature. To attain these targets, it will have to reduce CO 2 emissions to near zero by mid‐century and subsequently remove CO 2 from the atmosphere during the latter half of the century. There is a recognized need to develop technologies for CO 2 removal; however, attempts to develop direct air‐capture systems have faced both energetic and financial constraints. Recently, BioEnergy with Carbon Capture and Storage ( BECCS ) has emerged as a leading candidate for removing CO 2 from the atmosphere. However, BECCS can have negative consequences on land, nutrient, and water use as well as biodiversity and food production. Here, we describe an alternative approach based on the large‐scale industrial production of marine microalgae. When cultivated with proper attention to power, carbon, and nutrient sources, microalgae can be processed to produce a variety of biopetroleum products, including carbon‐neutral biofuels for the transportation sector and long‐lived, potentially carbon‐negative construction materials for the built environment. In addition to these direct roles in mitigating and potentially reversing the effects of fossil CO 2 emissions, microalgae can also play an important indirect role. As microalgae exhibit much higher primary production rates than terrestrial plants, they require much less land area to produce an equivalent amount of bioenergy and/or food. On a global scale, the avoided emissions resulting from displacement of conventional agriculture may exceed the benefits of microalgae biofuels in achieving the climate stabilization goals.

54 ENVIRONMENTAL SCIENCES↗

The Wintertime Covariation of CO 2 and Criteria Pollutants in an Urban Valley of the Western United States

Numerous mountain valleys experience wintertime particulate pollution events, when persistent cold air pools (PCAPs) develop and inhibit atmospheric mixing, leading to the accumulation of pollutants. Here we examine the relationships between trace gases and criteria pollutants during winter in Utah’s Salt Lake Valley, in an effort to better understand the roles of transport versus chemical processes during differing meteorological conditions as well as insights into how targeted reductions in greenhouse gases will impact local air quality in varying meteorological conditions. CO 2 is a chemically inert gas that is coemitted during fossil fuel combustion with pollutants. Many of these coemitted pollutants are precursors that react chemically to form secondary particulate matter. Thus, CO 2 can serve as a stable tracer and potentially help distinguish transport versus chemical influences on pollutants. During the winter of 2015–2016, we isolated enhancements in CO 2 over baseline levels due to urban emissions (“CO 2ex ”). CO 2ex was paired with similar excesses in other pollutant concentrations. These relationships were examined during different wintertime conditions and stages of pollution episodes: (a) Non-PCAP, (b) beginning, and (c) latter stages of an episode. We found that CO 2ex is a good indicator of the presence of gaseous criteria pollutants and a reasonable indicator of PM2.5. Additionally, the relationships between CO 2ex and criteria pollutants differ during different phases of PCAP events which provide insight into meteorological and transport processes. Lastly, we found a slight overestimation of CO:CO 2 emission ratios and a considerable overestimation of NO x :CO 2 by existing inventories for the Salt Lake Valley.

54 ENVIRONMENTAL SCIENCES↗

Electric Vehicles and the Electric Grid

In response to the need for the decarbonization of the transport sector and to reduce the reliance on fossil fuels, it is expected that large fleets of plug-in electric vehicles (PEVs) will constitute an important share of the electricity demand in the not so distant future. These devices can, and would behave as any regular demand if they are allowed to charge as soon as they are connected to the electric grid. If such charging process is allowed, then several adverse impacts on the power grids such as increased system-wide peak demand, and early reinforcements of the distribution, transmission and/or generation systems would be required. However, as opposed to conventional demands, these new devices are equipped with a battery that enables them deferring their needs for electric energy in time. If the pliant nature of this demand is exploited in such a way that the charging of these devices takes place when it is more convenient for the power system, then not only would the adverse impacts to the system would be avoided, but also, a new stream of services could be offered to the electric power grid in the form of demand response, power injections in V2G and regulating reserves. This article discusses the consequences of integrating significant volumes of PEVs into power systems, in both, uncontrolled and controlled manners.

Ortega Vazquez, Miguel A.↗

Role of Interfaces at Nano-Architectured Photocatalysts for Hydrogen Production from Water Splitting

Hydrogen has been nominated as an ideal energy carrier to replace the heavily engaged fossil fuels. Photocatalytic hydrogen production from the splitting of water is the most energy effective and environmentally preservative strategy. This chapter summarizes the basic principles of the photocatalytic hydrogen evolution reaction (HER) from the splitting of water with focus on the role of interfaces in nanostructured photocatalysts. We review the historical development of photocatalytic water splitting systems consisting of various types of heterojunctions that benefit the photogenerated charge carrier separation during photocatalytic processes. These “interfaces” are generally found in metal–semiconductor and semiconductor–semiconductor composite catalysts built upon nano-architectures made possible with recent advances in nanomaterial synthesis. The mechanisms are also discussed for the enhanced photocatalytic HER yield over the various interfaces in the composite photocatalysts.

Peng, Rui↗

Effect of Laser Shock Peening on the Microstructures and Properties of Oxide-Dispersion-Strengthened Austenitic Steels

Oxide-dispersion-strengthened (ODS) austenitic steels are promising materials for next-generation fossil and nuclear energy systems. In this study, laser shock peening (LSP) has been applied to ODS 304 austenitic steels, during which a high density of dislocations, stacking faults, and deformation twins are generated in the near surface of the material due to the interaction of laser-driven shock waves and the austenitic steel matrix. The dispersion particles impede the propagation of dislocations. The compressive residual stress generated by LSP increases with successive LSP scans and decreases along the depth, with a maximum value of -369MPa. The hardness on the surface can be improved by 12% using LSP. In situ transmission electron microscopy (TEM) irradiation studies reveal that dislocations and incoherent twin boundaries induced by LSP serve as effective sinks to annihilate irradiation defects. Furthermore, these findings suggest that LSP can improve the mechanical properties and irradiation resistance of ODS austenitic steels in nuclear reactor environments.

36 MATERIALS SCIENCE↗

Materials Science and Materials Chemistry for Large Scale Electrochemical Energy Storage: From Transportation to Electrical Grid

Large-scale electrical energy storage has become more important than ever for reducing fossil energy consumption in transportation and for the widespread deployment of intermittent renewable energy in electric grid. However, significant challenges exist for its applications. Here, the status and challenges are reviewed from the perspective of materials science and materials chemistry in electrochemical energy storage technologies, such as Li-ion batteries, sodium (sulfur and metal halide) batteries, Pb-acid battery, redox flow batteries, and supercapacitors. Perspectives and approaches are introduced for emerging battery designs and new chemistry combinations to reduce the cost of energy storage devices.

Environmental Molecular Sciences Laboratory↗

Hierarchically Controlled Inside-Out Doping of Mg Nanocomposites for Moderate Temperature Hydrogen Storage

Demand for pragmatic alternatives to carbon–intensive fossil fuels is growing more strident. Hydrogen represents an ideal zero–carbon clean energy carrier with high energy density. For hydrogen fuel to compete with alternatives, safe and high capacity storage materials that are readily cycled are imperative. Here, development of such a material, comprised of nickel–doped Mg nanocrystals encapsulated by molecular–sieving reduced graphene oxide (rGO) layers, is reported. While most work on advanced hydrogen storage composites to date endeavor to explore either nanosizing or addition of carbon materials as secondary additives individually, methods to enable both are pioneered: “dual–channel” doping combines the benefits of two different modalities of enhancement. Specifically, both external (rGO strain) and internal (Ni doping) mechanisms are used to efficiently promote both hydriding and dehydriding processes of Mg nanocrystals, simultaneously achieving high hydrogen storage capacity (6.5 wt% in the total composite) and excellent kinetics while maintaining robustness. Furthermore, hydrogen uptake is remarkably accomplished at room temperature and also under 1 bar—as observed during in situ measurements—which is a substantial advance for a reversible metal hydride material. In conclusion, the realization of three complementary functional components in one material breaks new ground in metal hydrides and makes solid–state materials viable candidates for hydrogen–fueled applications.

08 HYDROGEN↗

CO 2 –Based Dual–Tone Resists for Electron Beam Lithography

The increasing global environmental and energy crisis has urgently motivated the advancement of sustainable materials. Significant effort has been focused on developing new materials to replace the fossil-based resists in the semiconductor industry based on greener sources such as ice, dry ice, small organic molecules, and proteins. Such resist materials, however, have yet to meet the stringent requirements of high sensitivity, high resolution, reliable repeatability, and good compatibility with the current protocols. To this end, CO 2 -based polycarbonates (CO 2 -PCs) obtained from the copolymerization of CO 2 and epoxides are demonstrated as sustainable dual-tone (positive & negative tone) resists for electron beam lithography. By adjusting the chemical structure, developing agent, and molecular weight, the CO 2 -PCs present high sensitivities to electron beam (1.3/120 μC cm -2 ), narrow critical dimensions (29/58 nm), and moderate line edge roughness (4.6/26.7 nm) for negative and positive resists, respectively. Here, a deep understanding of the exposure mechanism of CO 2 -PC resists is provided on the basis of the Fourier transform infrared, Raman, and electron ionization mass spectroscopy. 2D photonic crystal devices are fabricated using the negative and positive CO 2 -PC resists, respectively, and both devices show distinct colors derived from their well-defined nanostructures, indicating the great practical potential of CO 2 -derived electron beam resists.

nanofabrication↗

Advanced Electrocatalysis for Energy and Environmental Sustainability via Water and Nitrogen Reactions

Abstract Clean and efficient energy storage and conversion via sustainable water and nitrogen reactions have attracted substantial attention to address the energy and environmental issues due to the overwhelming use of fossil fuels. These electrochemical reactions are crucial for desirable clean energy technologies, including advanced water electrolyzers, hydrogen fuel cells, and ammonia electrosynthesis and utilization. Their sluggish reaction kinetics lead to inefficient energy conversion. Innovative electrocatalysis, i.e., catalysis at the interface between the electrode and electrolyte to facilitate charge transfer and mass transport, plays a vital role in boosting energy conversion efficiency and providing sufficient performance and durability for these energy technologies. Herein, a comprehensive review on recent progress, achievements, and remaining challenges for these electrocatalysis processes related to water (i.e., oxygen evolution reaction, OER, and oxygen reduction reaction, ORR) and nitrogen (i.e., nitrogen reduction reaction, NRR, for ammonia synthesis and ammonia oxidation reaction, AOR, for energy utilization) is provided. Catalysts, electrolytes, and interfaces between the two within electrodes for these electrocatalysis processes are discussed. The primary emphasis is device performance of OER‐related proton exchange membrane (PEM) electrolyzers, ORR‐related PEM fuel cells, NRR‐driven ammonia electrosynthesis from water and nitrogen, and AOR‐related direct ammonia fuel cells.

Li, Yi↗

3D-Printable Fluoropolymer Gas Diffusion Layers for CO 2 Electroreduction

The electrosynthesis of value-added multicarbon products from CO 2 is a promising strategy to shift chemical production away from fossil fuels. Particularly important is the rational design of gas diffusion electrode (GDE) assemblies to react selectively, at scale, and at high rates. However, the understanding of the gas diffusion layer (GDL) in these assemblies is limited for the CO 2 reduction reaction (CO 2 RR): particularly important, but incompletely understood, is how the GDL modulates product distributions of catalysts operating in high current density regimes > 300 mA cm -2 . Here, 3D-printable fluoropolymer GDLs with tunable microporosity and structure are reported and probe the effects of permeance, microstructural porosity, macrostructure, and surface morphology. Under a given choice of applied electrochemical potential and electrolyte, a 100× increase in the C 2 H 4 :CO ratio due to GDL surface morphology design over a homogeneously porous equivalent and a 1.8× increase in the C 2 H 4 partial current density due to a pyramidal macrostructure are observed. Overall, these findings offer routes to improve CO 2 RR GDEs as a platform for 3D catalyst design.

36 MATERIALS SCIENCE↗

Toward High Conversion Efficiency of Thermoelectric Modules through Synergistical Optimization of Layered Materials

Abstract Waste‐heat electricity generation using high‐efficiency solid‐state conversion technology can significantly decrease dependence on fossil fuels. Here, a synergistical optimization of layered half‐Heusler (hH) materials and module to improve thermoelectric conversion efficiency is reported. This is realized by manufacturing multiple thermoelectric materials with major compositional variations and temperature‐gradient‐coupled carrier distribution by one‐step spark plasma sintering. This strategy provides a solution to overcome the intrinsic concomitants of the conventional segmented architecture that only considers the matching of the figure of merit ( zT ) with the temperature gradient. The current design is dedicated to temperature‐gradient‐coupled resistivity and compatibility matching, optimum zT matching, and reducing contact resistance sources. By enhancing the quality factor of the materials by Sb‐vapor‐pressure‐induced annealing, a superior zT of 1.47 at 973 K is achieved for (Nb, Hf)FeSb hH alloys. Along with the low‐temperature high‐ zT hH alloys of (Nb, Ta, Ti, V)FeSb, the single stage layered hH modules are developed with efficiencies of ≈15.2% and ≈13.5% for the single‐leg and unicouple thermoelectric modules, respectively, under Δ T of 670 K. Therefore, this work has a transformative impact on the design and development of next‐generation thermoelectric generators for any thermoelectric material families.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Shapeshifting Nanocatalyst for CO2 Conversion

The conversion of CO2 into high-value chemicals through a photoreduction reaction in water is a promising route to reduce the dependence on fossil fuels. Enhancing selectivity toward hydrocarbons or alcohols can be achieved by Ag-Cu alloys. However, the stabilized surface state created by Ag-Cu interactions is still poorly understood. In this work, multi-modal in situ X-ray experiments reveals underlying mechanisms and the evolution of Ag-Cu nanoparticles under CO2 reduction reaction (CO2RR) conditions. Both morphological and chemical changes of Ag and Cu species induced by diffusion mechanics are tracked during nanocatalyst operation. The initial spheroid Ag-Cu nanoparticles are composed of a Cu-rich shell and Ag-rich core. The reduction treatment promotes Ag migration toward the surface. During photocatalytic CO2 reduction reaction, Cu atoms migrate back to the surface, forming Ag-Cu-O species. The study observes the surface oxidation of Cu(0) to Cu+ and the presence of Ag at the sub-surface region. Furthermore, nanoparticles change their shape, decreasing their specific surface area, driven by Cu diffusion during the CO2 photoreduction reaction. The results provide invaluable insights into the dynamic restructuring of the catalyst under reaction conditions and into the active species responsible for CO2 conversion.

CO2 reduction reaction↗

Solvent‐Templated Block Ionomers for Base‐ and Acid‐Gas Separations: Effect of Humidity on Ammonia and Carbon Dioxide Permeation

Abstract As energy needs continue to drive the development of biogas and fossil‐fuel technologies, methods by which to selectively remove basic (NH 3 ) and acidic (CO 2 ) gases are becoming increasingly important, especially in light of global climate change. Block copolymers are considered as suitable membrane candidates in gas separations due to the ability of such copolymers to microphase‐separate and spontaneously form nanoscale morphologies that exhibit spatially modulated chemical specificity. Incorporation of charged moieties along the midblock of a thermoplastic elastomeric multiblock copolymer yields an amphiphilic block ionomer possessing a flexible molecular network stabilized by rigid endblocks. The presence of hydrophilic microdomains introduces an important consideration regulating molecular transport: humidity. In this study, solvent‐templating paradigms are employed to control the morphologies of midblock‐sulfonated pentablock ionomers, as discerned by electron microscopy and X‐ray scattering. The effect of humidity on the permeation of NH 3 , CO 2 , and N 2 is then investigated through the resulting membranes. As expected, NH 3 permeates significantly faster than N 2 , especially under humid conditions. Although not as pronounced, similar behavior is observed for CO 2 , thereby establishing that this block ionomer is generally selective to humidified polar gases.

Ansaloni, Luca↗