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At least 685 records · Page 38

U.S. emissions of HFC-134a derived for 2008-2012 from an extensive flask-air sampling network: US emissions of HFC-134a

U.S. national and regional emissions of HFC-134a are derived for 2008-2012 based on atmospheric observations from ground and aircraft sites across the U.S. and a newly developed regional inverse model. Synthetic data experiments were first conducted to optimize the model assimilation design and to assess model-data mismatch errors and prior flux error covariances computed using a maximumlikelihood estimation technique. The synthetic data experiments also tested the sensitivity of derived national and regional emissions to a range of assumed prior emissions, with the goal of designing a system that was minimally reliant on the prior. We then explored the influence of additional sources of error in inversions with actual observations, such as those associated with background mole fractions and transport uncertainties. Estimated emissions of HFC-134a range from 52 to 61 Gg yr -1 for the contiguous U.S. during 2008-2012 for inversions using air transport from Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model driven by the 12km resolution meteorogical data from North American Mesoscale Forecast System (NAM12) and all tested combinations of prior emissions and background mole fractions. Estimated emissions for 2008-2010 were 20% lower when specifying alternative transport from Stochastic Time-Inverted Lagrangian Transport (STILT) model driven by the Weather Research and Forecasting (WRF) meteorology. Our estimates (for HYSPLIT-NAM12) are consistent with annual emissions reported by U.S. Environmental Protection Agency for the full study interval. The results suggest a 10-20% drop in U.S. national HFC-134a emission in 2009 coincident with a reduction in transportation-related fossil fuel CO 2 emissions, perhaps related to the economic recession. All inversions show seasonal variation in national HFC-134a emissions in all years, with summer emissions greater than winter emissions by 20-50%.

54 ENVIRONMENTAL SCIENCES↗

Uncertainty in gridded CO 2 emissions estimates

We are interested in the spatial distribution of fossil-fuel-related emissions of CO 2 for both geochemical and geopolitical reasons, but it is important to understand the uncertainty that exists in spatially explicit emissions estimates. Working from one of the widely used gridded data sets of CO 2 emissions, we examine the elements of uncertainty, focusing on gridded data for the United States at the scale of 1° latitude by 1° longitude. Uncertainty is introduced in the magnitude of total United States emissions, the magnitude and location of large point sources, the magnitude and distribution of non-point sources, and from the use of proxy data to characterize emissions. For the United States, we develop estimates of the contribution of each component of uncertainty. At 1° resolution, in most grid cells, the largest contribution to uncertainty comes from how well the distribution of the proxy (in this case population density) represents the distribution of emissions. In other grid cells, the magnitude and location of large point sources make the major contribution to uncertainty. Uncertainty in population density can be important where a large gradient in population density occurs near a grid cell boundary. Uncertainty is strongly scale-dependent with uncertainty increasing as grid size decreases. In conclusion, uncertainty for our data set with 1° grid cells for the United States is typically on the order of ±150%, but this is perhaps not excessive in a data set where emissions per grid cell vary over 8 orders of magnitude.

54 ENVIRONMENTAL SCIENCES↗

Increased influence of nitrogen limitation on CO 2 emissions from future land use and land use change

Abstract In the latest projections of future greenhouse gas emissions for the Intergovernmental Panel on Climate Change (IPCC), few Earth System Models included the effect of nitrogen limitation, a key process limiting forest regrowth. Few included forest management (wood harvest). We estimate the impacts of nitrogen limitation on the CO 2 emissions from land use and land use change (LULUC), including wood harvest, for the period 1900–2100. We use a land surface model that includes a fully coupled carbon and nitrogen cycle and accounts for forest regrowth processes following agricultural abandonment and wood harvest. Future projections are based on the four Representation Concentration Pathways used in the IPCC Fifth Assessment Report, and we account for uncertainty in future climate for each scenario based on ensembles of climate model outputs. Results show that excluding nitrogen limitation will underestimate global LULUC emissions by 34–52 PgC (20–30%) during the 20th century (range across three different historical LULUC reconstructions) and by 128–187 PgC (90–150%) during the 21st century (range across the four IPCC scenarios). The full range for estimated LULUC emissions during the 21st century including climate model uncertainty is 91 to 227 PgC (with nitrogen limitation included). The underestimation increases with time because (1) projected annual wood harvest rates from forests summed over the 21st century are 380–1080% higher compared to those of the 20th century, resulting in more regrowing secondary forests; (2) nitrogen limitation reduces the CO 2 fertilization effect on net primary production of regrowing secondary forests following wood harvest and agricultural abandonment; and (3) nitrogen limitation effect is aggravated by the gradual loss of soil nitrogen from LULUC disturbance. Our study implies that (1) nitrogen limitation of CO 2 uptake is substantial and sensitive to nitrogen inputs; (2) if LULUC emissions are larger than previously estimated in studies without nitrogen limitation, then meeting the same climate mitigation target would require an equivalent additional reduction of fossil fuel emissions; (3) the effectiveness of land‐based mitigation strategies will critically depend on the interactions between nutrient limitations and secondary forests resulting from LULUC; and (4) it is important for terrestrial biosphere models to consider nitrogen constraint in estimates of the strength of future land carbon uptake.

Meiyappan, Prasanth↗

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 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↗

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↗

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↗

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↗

Strategies for Semiconductor/Electrocatalyst Coupling toward Solar‐Driven Water Splitting

Abstract Hydrogen (H 2 ) has a significant potential to enable the global energy transition from the current fossil‐dominant system to a clean, sustainable, and low‐carbon energy system. While presently global H 2 production is predominated by fossil‐fuel feedstocks, for future widespread utilization it is of paramount importance to produce H 2 in a decarbonized manner. To this end, photoelectrochemical (PEC) water splitting has been proposed to be a highly desirable approach with minimal negative impact on the environment. Both semiconductor light‐absorbers and hydrogen/oxygen evolution reaction (HER/OER) catalysts are essential components of an efficient PEC cell. It is well documented that loading electrocatalysts on semiconductor photoelectrodes plays significant roles in accelerating the HER/OER kinetics, suppressing surface recombination, reducing overpotentials needed to accomplish HER/OER, and extending the operational lifetime of semiconductors. Herein, how electrocatalyst coupling influences the PEC performance of semiconductor photoelectrodes is outlined. The focus is then placed on the major strategies developed so far for semiconductor/electrocatalyst coupling, including a variety of dry processes and wet chemical approaches. This Review provides a comprehensive account of advanced methodologies adopted for semiconductor/electrocatalyst coupling and can serve as a guideline for the design of efficient and stable semiconductor photoelectrodes for use in water splitting.

Thalluri, Sitaramanjaneya Mouli↗

A Global Methane Observation System to Reduce Uncertainty for Anthropogenic and Natural Sources and Sinks for Detecting and Attributing Climate Feedbacks

Atmospheric methane (CH4) concentrations are accelerating global warming as net emissions increase. Observing systems that quantify sources remain too sparse and fragmented to detect trends—especially in remote regions where climate‐driven natural emissions may be rising. We provide a framework for quantifying uncertainty reductions through the implementation of a global ecosystem‐methane observing system designed to: (i) substantially lower uncertainty in sectoral and regional emissions, (ii) separate co‐occurring anthropogenic and natural fluxes, and (iii) trend detection at regional scales to verify mitigation progress and provide early warning of natural feedbacks. Using bottom‐up inventories and process‐model ensembles for 2014–2023, we show that anthropogenic emissions remain uncertain by ∼32% globally, while natural sources—tropical and boreal‐arctic wetlands, fires, and inland waters—carry far larger uncertainties (+ 70%) and trend uncertainties reaching ∼200%. Additional observations must match spatial emission structure to increase observability of emissions: high‐resolution satellite constellations for point sources combined with expanded flux networks and wetland mapping for diffuse sources, and denser ground‐based atmospheric column measurements to restore observability in under‐sampled tropics and high latitudes. Notional analyses indicate that targeted additions of flux towers and ∼20 in situ atmospheric column concentration instruments per key tropical region could reduce continental‐scale uncertainties at modest cost. Conceptual illustration of a Global Ecosystem Methane Observing System (GEM‐OS) integrating satellites, aircraft, atmospheric networks, and ecosystem measurements to quantify methane emissions from anthropogenic and natural sources. The multi‐scale observing framework improves source attribution, reduces uncertainty in regional methane budgets, and enables early detection of climate‐driven feedbacks from wetlands, fires, permafrost, agriculture, and fossil‐fuel emissions.

Ciais, P↗

Sustainable Electric Vehicle Batteries for a Sustainable World: Perspectives on Battery Cathodes, Environment, Supply Chain, Manufacturing, Life Cycle, and Policy

Abstract Li‐ion batteries (LIBs) can reduce carbon emissions by powering electric vehicles (EVs) and promoting renewable energy development with grid‐scale energy storage. However, LIB production and electricity generation still heavily rely on fossil fuels at present, resulting in major environmental concerns. Are LIBs as environmentally friendly and sustainable as expected at the current stage? In the past 5 years, a skyrocketing growth of the EV market has been witnessed. LIBs have garnered huge attention from academia, industry, government, non‐governmental organizations, investors, and the general public. Tremendous volumes of LIBs are already implemented in EVs today, with a continuing, exponential growth expected for the years to come. When LIBs reach their end‐of‐life in the next decades, what technologies can be in place to enable second‐life or recycling of batteries? Herein, life cycle assessment studies are examined to evaluate the environmental impact of LIBs, and EVs are compared with internal combustion engine vehicles regarding environmental sustainability. To provide a holistic view of the LIB development, this Perspective provides insights into materials development, manufacturing, recycling, legislation and policy, and beyond. Last but not least, the future development of LIBs and charging infrastructures in light of emerging technologies are envisioned.

36 MATERIALS SCIENCE↗